Carbon Capture Technology Compendium 2020
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Barış GürelCarbon Capture Technology Compendium 2020
Uploaded by
Barış Gürel2020
CARBON CAPTURE PROGRAM R&D
COMPENDIUM
of
CARBON CAPTURE
TECHNOLOGY
MAY 2020
05.2020–1000
DOE/NETL CARBON CAPTURE PROGRAM R&D
Preface
DISCLAIMER
This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal lia-
bility or responsibility for the accuracy, completeness, or usefulness
of any information, apparatus, product, or process disclosed, or
represents that its use would not infringe privately owned rights.
Reference herein to any specific commercial product, process, or
service by trade name, trademark, manufacturer, or otherwise does
not necessarily constitute or imply its endorsement, recommenda-
tion, or favoring by the United States Government or any agency
thereof. The views and opinions of authors expressed herein do not
necessarily state or reflect those of the United States Government
or any agency thereof.
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
Table of Contents
TABLE OF CONTENTS
OVERVIEW 1
RESEARCH AND INNOVATION CENTER TECHNOLOGIES............................... 10
NETL-Research and Innovation Center – Transformational Solvents...................................................................................................... 11
NETL-Research and Innovation Center – Microwave Assisted Sorbent Regeneration............................................................................. 15
NETL-Research and Innovation Center – Transformational Membranes.................................................................................................21
NETL-Research and Innovation Center – Systems Engineering & Analysis.............................................................................................31
NETL-Research and Innovation Center – Carbon Capture Simulation for Industry Impact...................................................................... 36
POST-COMBUSTION SOLVENT TECHNOLOGIES.............................................. 40
URS Group, Inc. – Piperazine Solvent with Flash Regeneration.............................................................................................................41
University of Kentucky Research Foundation – Advanced Solvents, Heat Integration, and Membrane Separation.................................. 49
University of Notre Dame – Microencapsulated CO 2 Capture Materials................................................................................................ 66
Carbon Engineering, Ltd. – Direct Air Capture from Dilute CO 2 Sources................................................................................................ 74
Pacific Northwest National Laboratory – CO 2 -Binding Organic Liquid Solvents......................................................................................79
Massachusetts Institute of Technology – Electrochemical Regeneration of Amine Solvents.................................................................. 85
University of Illinois at Urbana-Champaign – Linde-BASF CO 2 Capture Process................................................................................... 93
University of Illinois at Urbana-Champaign – Biphasic Solvents for CO 2 Absorption.............................................................................100
Pacific Northwest National Laboratory – Molecular Refinement of Water-Lean Solvents...................................................................... 107
SRI International – Advanced Mixed-Salt Solvent Process.................................................................................................................. 113
University of North Dakota Energy and Environmental Research Center (UNDEERC) – KM-CDR Process Retrofit.................................120
SRI International – Ammonia- and Potassium Carbonate-Based Mixed Salt Solvent............................................................................ 125
Research Triangle Institute – Water-Lean Solvent...............................................................................................................................134
Pacific Northwest National Laboratory – CO 2 -Binding Organic Liquid Solvents.................................................................................... 141
Gas Technology Institute – Rotating Packed Bed with Advanced Solvent............................................................................................. 147
Liquid Ion Solutions, LLC – Novel Additives for Water-Lean Amines.................................................................................................... 152
Research Triangle Institute – Water-Lean Solvent Emissions Mitigation...............................................................................................157
University of Kentucky – Fog and Froth Solvent Process.....................................................................................................................162
ION Clean Energy, Inc. – Water-Lean Amine-Based Solvent for CO 2 Capture......................................................................................168
University of Illinois at Urbana-Champaign – Advanced KM CDR Process Retrofit............................................................................... 172
ION Clean Energy, Inc. – Water-Lean Solvent Technology Retrofit....................................................................................................... 175
Electric Power Research Institute, Inc. – Econamine FG Plus (EFG+) Retrofit to NGCC........................................................................ 179
University of Texas at Austin – Piperazine Solvent with Advanced Stripper Retrofit to NGCC................................................................182
Minnkota Power Cooperative, Inc. – Econamine FG Plus (EFG+) Retrofit to Coal Plant........................................................................188
Bechtel National, Inc. – Amine-Based Solvent Technology Retrofit to NGCC........................................................................................193
Southern Company Services, Inc. – Linde-BASF Amine Solvent-Based Technology Retrofit to NGCC..................................................198
Enchant Energy LLC – KM CDR Process Retrofit............................................................................................................................... 207
POST-COMBUSTION SORBENT TECHNOLOGIES........................................... 210
TDA Research, Inc. – Alkalized Alumina Solid Sorbent....................................................................................................................... 211
Research Triangle Institute – Fluidizable Solid Sorbents.....................................................................................................................216
Georgia Tech Research Corporation – Pressure Swing Adsorption Process with Novel Sorbent.......................................................... 223
Texas A&M University – Porous Polymer Networks............................................................................................................................ 229
InnoSepra, LLC – Structured Sorbent-Based Process for Low-Concentration Sources....................................................................... 232
Precision Combustion, Inc. – Metal Organic Framework Nanosorbent................................................................................................ 237
Lawrence Berkeley National Laboratory – Amine-Appended Metal-Organic Framework Sorbent.........................................................242
TDA Research, Inc. – Amine-Functionalized Resin Sorbent.................................................................................................................248
TDA Research, Inc. – Membrane-Sorbent Hybrid System.................................................................................................................. 252
Electricore, Inc. – Advanced Structured Adsorbent Architectures....................................................................................................... 259
InnoSepra, LLC – Microporous Sorbent............................................................................................................................................ 264
TDA Research, Inc. – Metal-Organic Framework (MOF)-Based Sorbent............................................................................................ 270
Rensselaer Polytechnic Institute – Size-Sieving Sorbent Integrated with Pressure Swing Adsorption.................................................... 274
NATIONAL ENERGY TECHNOLOGY LABORATORY
DOE/NETL CARBON CAPTURE PROGRAM R&D
Table of Contents
POST-COMBUSTION MEMBRANE TECHNOLOGIES....................................... 282
American Air Liquide, Inc. – Sub-Ambient Temperature Membrane................................................................................................... 283
Ohio State University – Selective Membranes for <1% CO 2 Sources.................................................................................................. 290
Luna Innovations – Membrane Support Materials.............................................................................................................................. 296
Membrane Technology and Research, Inc. – Large Pilot Polymer Membrane System......................................................................... 303
Electric Power Research Institute, Inc. – Polymeric Membrane-Based Process Retrofit...................................................................... 308
Membrane Technology and Research, Inc. – Polymeric Membranes................................................................................................... 313
Gas Technology Institute – Graphene Oxide Membranes.................................................................................................................... 318
Membrane Technology and Research, Inc. – Polymeric Membranes...................................................................................................324
State University of New York – Mixed Matrix Membranes.................................................................................................................. 330
The Ohio State University – Polymer Composite Membranes............................................................................................................. 334
Membrane Technology and Research, Inc. – Polaris Polymeric Membrane-Based Process Retrofit..................................................... 338
POST-COMBUSTION NOVEL CONCEPTS....................................................... 350
Lawrence Livermore National Laboratory – Encapsulation of Solvents in Permeable Membrane for CO2 Capture.................................351
Altex Technologies Corporation – Molecular Basket Sorbents on Microchannel Heat Exchangers....................................................... 360
Liquid Ion Solutions, LLC – Solvent-Membrane Hybrid Capture System............................................................................................. 366
Dresser-Rand Company – Supersonic Compression...........................................................................................................................376
Sustainable Energy Solutions, LLC – Cryogenic Carbon Capture Process........................................................................................... 380
Oak Ridge National Laboratory – Additively Manufactured Intensified Device for Solvent-Based CO 2 Capture..................................... 385
Lawrence Livermore National Laboratory – Additively Manufactured High-Efficiency Reactors
for Sorbents, Solvents, and Membranes............................................................................................................................................ 389
ION Clean Energy, Inc. – Gas-Liquid Contacting Devices for Post-Combustion CO 2 Capture............................................................... 392
University of Kentucky – Integrated Advanced Solvent Process.......................................................................................................... 397
Linde, LLC – Flue Gas Aerosol Pretreatment..................................................................................................................................... 406
LumiShield Technologies Incorporated – Corrosion-Resistant Coated Carbon Steel Components in CO 2 Capture Processes................ 413
University of Kentucky – Solvent Enabling Techniques........................................................................................................................ 419
PRE-COMBUSTION SORBENT TECHNOLOGIES.............................................. 424
TDA Research, Inc. – High Capacity Regenerable Sorbent................................................................................................................. 425
PRE-COMBUSTION MEMBRANE TECHNOLOGIES......................................... 434
Arizona State University – Zeolite Membrane Reactor........................................................................................................................ 435
State University of New York - Buffalo – Mixed Matrix Membranes.................................................................................................... 443
Bettergy Corporation – Water-Gas Shift Catalytic Membrane Reactor................................................................................................ 450
Membrane Technology and Research, Inc. – Polymeric Membranes.................................................................................................. 455
SRI International – PBI Polymer Membrane....................................................................................................................................... 462
Arizona State University – Ceramic-Carbonate Dual-Phase Membrane Reactor..................................................................................472
Ohio State University – Amine-Containing Polymeric Membranes...................................................................................................... 481
State University of New York, Buffalo – Carbon Molecular Sieve Hollow Fiber Membranes................................................................. 487
PRE-COMBUSTION NOVEL CONCEPTS......................................................... 496
University of Southern California – Combined CMS Membrane/WGS Reactor and Adsorption Reactor................................................ 497
Southern Research Institute – Combined CO2 Sorbent/WGS Reactor................................................................................................. 507
R&D COLLABORATIONS................................................................................. 516
Southern Company Services, Inc. – Carbon Capture Testing Center................................................................................................... 517
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
Table of Contents
APPENDIX: COMPLETED PROJECTS 522
POST-COMBUSTION SOLVENT TECHNOLOGIES............................................ 523
General Electric Company – Phase-Changing Absorbent....................................................................................................................524
Pacific Northwest National Laboratory – CO2 -Binding Organic Liquid (CO 2BOL) Solvents................................................................... 529
General Electric Company – Aminosilicone Solvent........................................................................................................................... 535
Southern Company Services, Inc. – Waste Heat Integration............................................................................................................... 542
Southern Company Services, Inc. – Amine-Based Solvent and Process Improvements...................................................................... 545
Linde, LLC – Slipstream Novel Amine-Based Post-Combustion Process............................................................................................ 550
GE Power – Chilled Ammonia Process Improvements........................................................................................................................ 558
Akermin, Inc. – Carbonic Anhydrase Catalyzed Advanced Carbonate and Non-Volatile Salt Solution (“Solvents”)................................ 563
Neumann Systems Group, Inc. – Carbon Absorber Retrofit Equipment............................................................................................... 569
Rice University – Novel Absorption/Stripper Process......................................................................................................................... 576
Carbon Capture Scientific, LLC – Gas-Pressurized Stripping............................................................................................................. 584
Novozymes North America, Inc. – Solvent + Enzyme and Vacuum Regeneration Technology.............................................................. 589
Babcock & Wilcox Company – Optimized Solvent Formulation........................................................................................................... 595
University of Illinois at Urbana-Champaign – Hot Carbonate Absorption with Crystallization-Enabled High-Pressure Stripping............. 598
3H Company, LLC – CO 2 Capture with Self-Concentrating Amine Absorbent..................................................................................... 604
University of Notre Dame – Ionic Liquids........................................................................................................................................... 607
Illinois State Geological Survey – Novel Integrated Vacuum Carbonate Process................................................................................... 614
Siemens Energy, Inc. – POSTCAP Capture and Separation................................................................................................................ 620
Lawrence Berkeley National Laboratory – Chemical Additives for CO 2 Capture.................................................................................. 623
Georgia Tech Research Corporation – Reversible Ionic Liquids.......................................................................................................... 628
Hampton University – Phase Transitional Absorption......................................................................................................................... 633
POST-COMBUSTION SORBENT TECHNOLOGIES........................................... 638
SRI International – Novel Solid Sorbent............................................................................................................................................. 639
Aspen Aerogels, Inc. – Advanced Aerogel Sorbents.......................................................................................................................... 645
NRG Energy, Inc. – Temperature Swing Adsorption with Structured Sorbent.......................................................................................651
W.R. Grace and Company – Rapid Pressure Swing Adsorption.......................................................................................................... 654
ADA-ES, Inc. – Cross-Heat Exchanger for Sorbent-Based CO 2 Capture............................................................................................. 660
RTI International – Advanced Solid Sorbents and Processes for CO 2 Capture..................................................................................... 667
TDA Research, Inc. – Low-Cost, High-Capacity Regenerable Sorbent................................................................................................ 672
Georgia Tech Research Corporation – Rapid Temperature Swing Adsorption...................................................................................... 678
University of North Dakota Energy and Environmental Research Center (UNDEERC) – Solid Sorbent-Based CO 2 Capture.................... 685
University of Akron – Metal Monolithic Amine-Grafted Zeolites.......................................................................................................... 689
UOP – CO 2 Removal from Flue Gas Using Microporous MOFs............................................................................................................ 694
Research Triangle Institute – A Dry Sorbent-Based Post Combustion CO 2 Capture............................................................................. 700
POST-COMBUSTION MEMBRANE TECHNOLOGIES....................................... 704
Ohio State University – Inorganic/Polymer Composite Membrane...................................................................................................... 705
General Electric Company – Composite Hollow Fiber Membranes....................................................................................................... 710
Membrane Technology and Research, Inc. – Low-Pressure Membrane Contactors (Mega-Module)..................................................... 715
Research Triangle Institute – Hollow-Fiber, Polymeric Membrane....................................................................................................... 719
Carbozyme – Biomimetic Membrane................................................................................................................................................. 725
University of New Mexico – Dual Functional, Silica-Based Membrane................................................................................................ 729
POST-COMBUSTION NOVEL CONCEPTS....................................................... 734
Orbital ATK, Inc. – Supersonic Inertial CO2 Extraction System........................................................................................................... 735
Southwest Research Institute – Evaluation of Compression Efficiency Improvements......................................................................... 739
NATIONAL ENERGY TECHNOLOGY LABORATORY
DOE/NETL CARBON CAPTURE PROGRAM R&D
Table of Contents
PRE-COMBUSTION SOLVENT TECHNOLOGIES.............................................. 748
SRI International – CO2 Capture Using AC-ABC Process..................................................................................................................... 749
PRE-COMBUSTION SORBENT TECHNOLOGIES.............................................. 756
URS Group, Inc. – Sorbent Development for WGS............................................................................................................................. 757
PRE-COMBUSTION MEMBRANE TECHNOLOGIES......................................... 764
Media and Process Technology, Inc. – Two-Stage Membrane Separation: Carbon Molecular Sieve Membrane Reactor
followed by Pd-Based Membrane...................................................................................................................................................... 765
Los Alamos National Laboratory – High-Temperature Polymer-Based Membrane............................................................................... 772
Arizona State University – Dual-Phase Ceramic-Carbonate Membrane Reactor................................................................................. 779
Pall Corporation – Pd-Alloys for Sulfur/Carbon Resistance................................................................................................................. 784
University of Minnesota – Hydrogen-Selective Zeolite Membranes..................................................................................................... 789
New Jersey Institute of Technology – Pressure Swing Membrane Absorption Device and Process...................................................... 793
Gas Technology Institute – Nanoporous, Superhydrophobic Membrane Contactor Process................................................................. 799
R&D COLLABORATIONS................................................................................. 804
University of North Dakota Energy and Environmental Research Center (UNDEERC) – Partnership for CO 2 Capture............................ 805
Argonne National Laboratory – Analysis of CCS Technology Adoption................................................................................................ 809
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 1
Overview
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
OVERVIEW
NATIONAL ENERGY TECHNOLOGY LABORATORY
2 DOE/NETL CARBON CAPTURE PROGRAM R&D
Overview
The U.S. Department of Energy’s (DOE) Fossil Energy Program has adopted a comprehensive, multi-pronged approach to the research and develop-
ment (R&D) of advanced carbon dioxide (CO2) capture technologies for today’s fossil fuel-based power platforms, as well as for industrial systems.
The National Energy Technology Laboratory (NETL) is implementing the Carbon Capture R&D Program to develop the next generation of advanced
CO2 capture concepts. The success of this research will enable cost-effective implementation of carbon capture and storage (CCS) technologies
throughout the power generation sector and ensure the United States will continue to have access to safe, reliable, and affordable energy from
fossil fuels.
DOE’s CCS R&D effort is conducted as part of the CCS and Power Systems Program under the Office of Clean Coal and Carbon Management
(OCCM). OCCM is implemented by NETL through contracted research activities and onsite research at NETL. Research projects are carried out
under various award mechanisms — including partnerships, cooperative agreements, and financial assistance grants — with corporations, small
businesses, universities, nonprofit organizations, and other national laboratories and government agencies.
DOE/NETL’s Carbon Capture Program consists of two core research areas — Post-Combustion Capture and Pre-Combustion Capture — com-
posed of projects with Technology Readiness Levels (TRLs) ranging from conceptual engineering and materials design (i.e., TRL 2) to 25-mega-
watt-electrical (MWe) equivalent pilot testing (i.e., TRL 5-7). These two core areas are focused on creating technological improvements providing
a step-change in both cost and performance as compared to current state-of-the-art solvent-based capture systems. Post-combustion systems
separate CO2 from the flue gas stream produced by conventional fossil fuel-fired power plants after fuel combustion in air. In this approach, CO2
is separated from nitrogen (N2), the primary constituent of the flue gas. Pre-combustion systems are designed to separate CO2 and hydrogen (H2)
from the syngas stream produced by the gasifier in integrated gasification combined cycle (IGCC) power plants. In both cases, R&D is underway to
develop technologies based on advanced solvents, sorbents, membranes, hybrid systems, and other novel concepts.
This Technology Compendium provides a technical summary of DOE/NETL’s Carbon Capture Program, assembling CO2 capture technology R&D
descriptions for 132 projects in a single document. As of October 1, 2019, there were 80 active projects and 52 completed projects. Active projects
listed were active at some point between September 1, 2017, and October 1, 2019, some of which may have ended during that time frame. De-
scriptions of the completed projects are provided in Appendix A. It should be noted that some of the previously completed projects may differ slightly
in format as they were developed for a prior version of the compendium. The following tables list the CO2 capture technologies summarized in this
Compendium as developed under DOE/NETL’s onsite and external R&D projects.
National Energy Technology Laboratory – Research and Innovation Center Technologies
Onsite research at NETL in CO2 capture leverages cutting-edge research facilities, world-class scientists and engineers, state-of-the-art compu-
tational modeling and simulation tools, and strategic collaborations to foster the discovery, development, and testing of transformational materials
and high-throughput computational tools. Through the Carbon Capture Simulation for Industry Impact (CCSI2), DOE’s core strengths in modeling and
simulation are partnered with industry to scale-up new and innovative carbon capture technologies.
Project Focus Participant Performance Period
ACTIVE
National Energy Technology Laboratory –
Transformational Solvents 04.01.2019 – 03.31.2022
Research and Innovation Center Technologies
National Energy Technology Laboratory –
Microwave Assisted Sorbent Regeneration 04.01.2019 – 03.31.2022
Research and Innovation Center Technologies
National Energy Technology Laboratory –
Transformational Membranes 04.01.2019 – 03.31.2022
Research and Innovation Center Technologies
National Energy Technology Laboratory –
Systems Engineering & Analysis 04.01.2019 – 03.31.2022
Research and Innovation Center Technologies
National Energy Technology Laboratory –
Carbon Capture Simulation for Industry Impact 04.01.2019 – 03.31.2022
Research and Innovation Center Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 3
Overview
Post-Combustion Solvent Technologies
High levels of CO2 capture are possible with chemical solvent-based systems, but these systems also require significant amounts of energy for re-
generation, which involves a temperature swing to break the absorbent-CO2 chemical bond. Advanced solvents that have lower regeneration energy
requirements, lower volatility, and lower degradation rates than commercially available amine systems, combined with high CO2 capture capacity
and tolerance to flue gas impurities, are being developed through DOE/NETL-sponsored research. Water-lean solvents are particularly promising for
CO2 capture processes, providing significant reductions in energy requirements, corrosion, and solvent losses.
Project Focus Participant Performance Period
ACTIVE
Piperazine Solvent with Flash Regeneration URS Group 10.01.2010 – 12.31.2018
Advanced Solvents, Heat Integration, and Membrane
University of Kentucky 10.01.2011 – 03.31.2019
Separation
Microencapsulated CO2 Capture Materials University of Notre Dame 10.01.2015 – 03.31.2019
Direct Air Capture from Dilute CO2 Sources Carbon Engineering LTD 09.19.2016 – 06.30.2019
CO2-Binding Organic Liquid Solvents Pacific Northwest National Laboratory 07.01.2017 – 03.31.2021
Electrochemical Regeneration of Amine Solvents Massachusetts Institute of Technology 08.01.2017 – 07.31.2020
Linde/BASF CO2 Capture Process University of Illinois at Urbana-Champaign 04.04.2018 – 12.31.2020
Biphasic Solvents for CO2 Absorption University of Illinois at Urbana-Champaign 04.06.2018 – 04.05.2021
Molecular Refinement of Water-Lean Solvents Pacific Northwest National Laboratory 05.01.2018 – 01.31.2021
Advanced Mixed-Salt Solvent Process SRI International 06.01.2018 – 11.30.2021
University of North Dakota Energy and
Pre-FEED Study for Retrofit 06.25.2018 – 12.31.2019
Environmental Center
Ammonia- and Potassium Carbonate-Based Mixed Salt Solvent SRI International 07.01.2018 – 07.31.2021
Water-Lean Solvent Research Triangle Institute 08.08.2018 – 06.30.2021
CO2-Binding Organic Liquid Solvents Pacific Northwest National Laboratory 10.01.2018 – 09.30.2020
Rotating Packed Bed with Advanced Solvent Gas Technology Institute 10.01.2018 – 03.31.2021
Novel Additives for Water-Lean Amines Liquid Ion Solutions, LLC 10.01.2018 – 09.30.2021
Water-Lean Solvent Emissions Mitigation Research Triangle Institute 10.01.2018 – 09.30.2021
Fog and Froth Solvent Process University of Kentucky 05.01.2019 – 04.30.2021
Water-Lean Amine-Based Solvent for CO2 Capture ION Clean Energy, Inc. 06.01.2019 – 05.31.2021
Advanced KM CDR Process FEED University of Illinois at Urbana-Champaign 09.30.2019 – 09.30.2021
FEED Study for Carbon Capture System Retrofit ION Clean Energy, Inc. 10.01.2019 – 03.31.2021
Econamine FG Plus (EFG+) Retrofit to NGCC FEED Electric Power Research Institute, Inc. 10.01.2019 – 03.31.2021
Piperazine Solvent with Advanced Stripper FEED University of Texas at Austin 10.01.2019 – 06.30.2021
Fluor’s Econamine FG Plus Technology FEED Minnkota Power Cooperative, Inc. 10.01.2019 – 09.30.2020
Amine-Based Capture Retrofit to NGCC FEED Bechtel National, Inc. 10.01.2019 – 09.30.2020
Linde-BASF Amine Solvent-Based Technology Retrofit
Southern Company Services, Inc. 10.01.1029 – 09.30.2021
for NGCC
KM CDR Process FEED Enchant Energy LLC 10.15.2019 – 03.31.2021
COMPLETED (in Appendix)
Phase-Changing Absorbent GE Global Research 11.01.2014 – 09.30.2017
CO2-Binding Organic Liquid Solvents Pacific Northwest National Laboratory 04.01.2014 – 09.30.2017
NATIONAL ENERGY TECHNOLOGY LABORATORY
4 DOE/NETL CARBON CAPTURE PROGRAM R&D
Overview
Project Focus Participant Performance Period
Aminosilicone Solvent GE Global Research 10.01.2015 – 06.30.2017
Waste Heat Integration Southern Company Services, Inc. 10.01.2011 – 03.31.2017
Amine-Based Solvent and Process Improvements Southern Company Services, Inc. 10.01.2015 – 03.31.2017
Slipstream Novel Amine-Based Post-Combustion Process Linde LLC 12.01.2011 – 11.30.2016
Chilled Ammonia Process Improvements GE Power 10.01.2015 – 09.30.2016
Carbonic Anhydrase Catalyzed Advanced Carbonate and Non-
Akermin, Inc. 10.01.2013 – 09.30.2016
Volatile Salt Solution (“Solvents”)
Carbon Absorber Retrofit Equipment Neumann Systems Group 01.02.2012 – 12.31.2015
Novel Absorption/Stripper Process William Marsh Rice University 10.01.2011 – 12.31.2015
Gas-Pressurized Stripping Carbon Capture Scientific LLC 10.01.2011 – 06.30.2015
Solvent + Enzyme and Vacuum Regeneration Technology Novozymes North America, Inc. 10.01.2011 – 06.30.2015
Optimized Solvent Formulation Babcock & Wilcox 10.01.2011 – 04.30.2014
Hot Carbonate Absorption with Crystallization-Enabled High-
University of Illinois at Urbana-Champaign 01.01.2011 – 03.31.2014
Pressure Stripping
Self-Concentrating Amine Absorbent 3H Company, LLC 10.01.2010 – 01.31.2013
Ionic Liquids University of Notre Dame 03.01.2007 – 09.30.2012
Novel Integrated Vacuum Carbonate Process Illinois State Geological Survey 10.01.2008 – 04.30.2012
POSTCAP Capture and Sequestration Siemens Energy Inc. 10.01.2010 – 02.29.2012
Chemical Additives for CO2 Capture Lawrence Berkeley National Laboratory 06.01.2008 – 09.30.2011
Reversible Ionic Liquids Georgia Tech Research Corporation 10.01.2008 – 09.30.2011
Phase Transitional Absorption Hampton University 06.15.2005 – 06.30.2009
Post-Combustion Sorbent Technologies
DOE/NETL’s R&D objectives for post-combustion sorbents include development of low-cost, durable sorbents that have high selectivity, high CO2
adsorption capacity, and can withstand multiple regeneration cycles with little to no attrition.
Project Focus Participant Performance Period
ACTIVE
Alkalized Alumina Solid Sorbent TDA Research, Inc. 02.03.2014 – 01.31.2020
Fluidizable Solid Sorbents Research Triangle Institute 10.01.2015 – 06.30.2018
Pressure Swing Adsorption Process with Novel Sorbent Georgia Tech Research Corporation 10.01.2015 – 09.30.2019
Porous Polymer Networks Texas A&M University 10.01.2015 – 03.31.2019
Structured Sorbent-Based Process
InnoSepra, LLC 02.22.2016 – 04.09.2019
for Low-Concentration Sources
High Efficiency Post Combustion Carbon Capture System Precision Combustion, Inc. 02.21.2017 – 05.20.2020
Amine-Appended Metal-Organic Framework Sorbent Lawrence Berkeley National Laboratory 08.31.2017 – 07.31.2021
Amine-Functionalized Resin Sorbent TDA Research, Inc. 07.02.2018 – 08.18.2021
Membrane-Sorbent Hybrid System TDA Research, Inc. 08.15.2018 – 08.14.2021
Bi-Layer Structured Sorbent Electricore, Inc. 05.01.2019 – 04.30.2021
Microporous Sorbent InnoSepra, LLC 05.01.2019 – 04.30.2022
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 5
Overview
Project Focus Participant Performance Period
Metal-Organic Framework (MOF)-Based Sorbent TDA Research, Inc. 06.01.2019 – 05.31.2022
Size-Sieving Sorbent Integrated with Pressure Swing Adsorption Rensselaer Polytechnic Institute 10.01.2019 – 09.30.2022
COMPLETED (in Appendix)
Novel Solid Sorbent SRI International 10.01.2013 – 09.30.2018
Advanced Aerogel Sorbents Aspen Aerogels, Inc. 10.01.2013 – 12.31.2016
Temperature Swing Adsorption with Structured Sorbent NRG Energy Inc. 10.01.2015 – 09.30.2016
Rapid Pressure Swing Adsorption W.R. Grace and Co. 10.01.2011 – 07.31.2016
Cross-Heat Exchanger for Sorbent-Based CO2 Capture ADA-ES, Inc. 10.01.2013 – 12.31.2015
Advanced Solid Sorbents and Processes for CO2 Capture RTI International 10.01.2011 – 12.31.2015
Low-Cost, High-Capacity Regenerable Sorbent TDA Research, Inc. 10.01.2011 – 09.30.2015
Rapid Temperature Swing Adsorption Georgia Tech Research Corporation 10.01.2011 – 03.31.2015
Hybrid Sorption Using Solid Sorbents University of North Dakota 10.01.2011 – 12.31.2014
Metal Monolithic Amine-Grafted Zeolites University of Akron 02.21.2007 – 03.31.2011
CO2 Removal from Flue Gas Using Microporous MOFs UOP 03.12.2007 – 06.30.2010
Dry Sorbent-Based Post Combustion CO2 Capture Process Research Triangle Institute 03.07.2007 – 12.31.2009
Post-Combustion Membrane Technologies
DOE/NETL’s R&D objectives for post-combustion membrane technologies include the development of low-cost, durable membranes that have
improved permeability and selectivity, thermal and physical stability, tolerance to contaminants in combustion flue gas, and are integrated into low
pressure drop modules.
Project Focus Participant Performance Period
ACTIVE
Sub-Ambient Temperature Membrane American Air Liquide, Inc. 10.01.2015 – 12.31.2019
Selective Membranes for <1% CO2 Sources Ohio State University 03.01.2016 – 08.31.2019
Solid Phase Supports for Flue Gas CO2 Separation
Luna Innovations 02.21.2017 – 05.20.2020
with Molten Electrolytes
Large Pilot Polymer Membrane System Membrane Technology and Research, Inc. 04.01.2018 – 12.31.2020
Polymeric Membrane-Based Post Combustion
Electric Power Research Institute, Inc. 04.06.2018 – 03.31.2020
Engineering Design
Polymeric Membranes Membrane Technology and Research, Inc. 06.01.2018 – 09.30.2021
Graphene Oxide Membranes Gas Technology Institute 06.01.2018 – 09.30.2021
PolarisTM Membrane CO2 Capture System Membrane Technology and Research, Inc. 08.01.2018 – 07.31.2021
Mixed Matrix Membranes State University of New York 07.01.2019 – 06.30.2020
Inorganic/Polymer Composite Membranes Ohio State University 07.01.2019 – 06.30.2022
Polaris Membrane Technology FEED Membrane Technology and Research, Inc. 10.01.2019 – 09.30.2021
COMPLETED (in Appendix)
Inorganic/Polymer Composite Membrane Ohio State University 10.01.2011 – 12.31.2015
Composite Hollow Fiber Membranes GE Global Research 10.01.2011 – 12.31.2014
Low-Pressure Membrane Contactors (Mega-Module) Membrane Technology & Research, Inc. 10.01.2011 – 09.30.2014
NATIONAL ENERGY TECHNOLOGY LABORATORY
6 DOE/NETL CARBON CAPTURE PROGRAM R&D
Overview
Project Focus Participant Performance Period
Hollow-Fiber, Polymeric Membrane Research Triangle Institute 09.26.2008 – 09.30.2011
Biomimetic Membrane Carbozyme 03.28.2007 – 07.31.2009
Dual Functional, Silica-Based Membrane University of New Mexico 08.23.2004 – 04.30.2009
Post-Combustion Novel Concepts
DOE/NETL is evaluating various post-combustion novel concepts for large-scale CO2 capture or compression. Novel concepts include hybrid sys-
tems that combine attributes from multiple technologies, electrochemical membranes, and advanced manufacturing to enable enhanced processes.
Several concepts were evaluated using computational fluid dynamics and laboratory testing, leading to prototype development and field testing.
Project Focus Participant Performance Period
ACTIVE
Encapsulation of Solvents in Permeable Membrane
Lawrence Livermore National Laboratory 03.01.2015 – 04.30.2019
for CO2 Capture
Integrated Temperature and Pressure Swing
Altex Technologies Corporation 06.08.2015 – 08.18.2018
Carbon Capture System
ICE Membrane for Post-Combustion CO2 Capture Liquid Ion Solutions LLC 10.01.2015 – 09.30.2018
Supersonic Compression Dresser-Rand Company 03.01.2016 – 06.30.2018
Cryogenic Carbon Capture Process Sustainable Energy Solutions, LLC 10.01.2016 – 06.30.2019
Additive Manufacturing for CO2 Capture Oak Ridge National Laboratory 07.01.2017 – 09.20.2019
Additively Manufactured High-Efficiency Reactors for Sorbents,
Lawrence Livermore National Laboratory 08.01.2017 – 07.31.2021
Solvents, and Membranes
Gas-Liquid Contacting Devices for Post-Combustion
ION Clean Energy, Inc. 01.19.2018 – 05.31.2020
CO2 Capture
Decoupled Absorber Kinetics and Solvent Regeneration through
University of Kentucky 05.01.2018 – 04.30.2021
Membrane Dewatering and In-Column Heat Transfer
Aerosol Flue Gas Pretreatment Linde, LLC 06.01.2018 – 02.28.2021
Corrosion-Resistant Coated Carbon Steel Components
LumiShield Technologies Incorporated 10.01.2018 – 09.30.2020
in CO2 Capture Processes
Solvent Enabling Techniques University of Kentucky 10.01.2018 – 09.30.2021
COMPLETED (IN APPENDIX)
Supersonic Inertial CO2 Extraction System Orbital ATK, Inc. 10.01.2013 – 03.31.2017
Evaluation of Compression Efficiency Improvements Southwest Research Institute 10.01.2005 – 06.30.2014
Pre-Combustion Solvent Technologies
Pre-combustion solvent R&D activities focus on addressing solvent technology challenges, including increasing CO2-loading capacity and reaction
kinetics coupled with decreasing regeneration energy.
Project Focus Participant Performance Period
COMPLETED (in Appendix)
CO2 Capture Using AC-ABC Process SRI International 10.01.2009 – 09.30.2016
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 7
Overview
Pre-Combustion Sorbent Technologies
DOE/NETL is developing solid sorbents for pre-combustion CO2 capture aimed at improving the cost and performance of IGCC CO2 separation.
These sorbents must maintain a high adsorption loading capacity, be resistant to attrition over multiple regeneration cycles, and exhibit good perfor-
mance at the high temperatures encountered in IGCC systems to avoid the need for syngas cooling and reheating.
Project Focus Participant Performance Period
ACTIVE
High Capacity Regenerable Sorbent TDA Research, Inc. 10.01.2013 – 03.31.2021
COMPLETED (in Appendix)
Sorbent Development for WGS URS Group, Inc. 01.01.2010 – 09.30.2013
Pre-Combustion Membrane Technologies
Several advanced membrane technology options are under development by DOE/NETL to separate CO2 and H2 in coal-derived syngas. Membrane
designs include metallic, polymeric, or ceramic materials operating at elevated temperatures and using a variety of chemical and/or physical mech-
anisms for separation. Successful membranes must have high permeability and selectivity with low pressure drop, tolerance to contaminants (e.g.,
sulfur), and be capable of operation at system temperatures up to 500°F.
Project Focus Participant Performance Period
ACTIVE
Zeolite Membrane Reactor Arizona State University 10.01.2015 – 12.31.2018
Mixed Matrix Membranes State University of New York, Buffalo 10.01.2015 – 09.30.2018
WGS Catalytic Membrane Reactor Bettergy Corporation 07.02.2018 – 08.18.2021
Composite Polymeric Membranes for H2 Separation
Membrane Technology and Research, Inc. 10.01.2018 – 09.30.2021
from Coal Syngas
PBI Polymer Membrane SRI International 10.01.2018 – 09.30.2021
Ceramic-Carbonate Membrane Reactor Arizona State University 10.01.2018 – 09.30.2021
Amine-Containing Polymeric Membrane Ohio State University 10.01.2018 – 09.30.2021
Carbon Molecular Sieve Hollow Fiber Membranes State University of New York, Buffalo 10.01.2018 – 09.30.2021
COMPLETED (in Appendix)
Two-Stage Membrane Separation: Carbon Molecular Sieve
Media and Process Technology, Inc. 10.01.2013 – 09.30.2017
Membrane Reactor followed by Pd-Based Membrane
High-Temperature Polymer-Based Membrane Los Alamos National Laboratory 03.01.2013 – 03.31.2016
Dual-Phase Ceramic-Carbonate Membrane Reactor Arizona State University 10.01.2009 – 09.30.2014
Pd-Alloys for Sulfur/Carbon Resistance Pall Corporation 10.01.2009 – 09.30.2014
Hydrogen-Selective Zeolite Membranes University of Minnesota 10.01.2009 – 09.30.2014
Pressure Swing Membrane Absorption Device and Process New Jersey Institute of Technology 10.01.2009 – 03.31.2013
Nanoporous, Superhydrophobic Membrane Contactor Process Gas Technology Institute 10.01.2009 – 03.31.2012
NATIONAL ENERGY TECHNOLOGY LABORATORY
8 DOE/NETL CARBON CAPTURE PROGRAM R&D
Overview
Pre-Combustion Novel Concepts
DOE/NETL is developing various novel concepts for the integration of CO2 removal processes with other systems, including water-gas shift and
adsorption reactors, to efficiently and cost-effectively separate CO2 from produced syngas streams.
Project Focus Participant Performance Period
ACTIVE
Combined CMS Membrane/WGS Reactor
University of Southern California 06.01.2019 – 05.31.2022
and Adsorption Reactor
Combined CO2 Sorbent/WGS Reactor Southern Research Institute 10.01.2015 – 09.30.2018
R&D Collaborations
DOE/NETL also participates in R&D collaborations exploring multiple approaches to CO2 capture for coal-based power plants and modeling the
economic and emissions reduction impact of carbon capture R&D.
Project Focus Participant Performance Period
ACTIVE
Carbon Capture Testing Center Southern Company 06.06.2014 – 05.31.2020
COMPLETED (in Appendix)
University of North Dakota Energy and
Partnership for CO2 Capture 09.28.2011 – 12.31.2014
Environmental Research Center
Analysis of CCS Technology Adoption Argonne National Laboratory 02.01.2011 – 03.31.2014
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 9
Overview
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NATIONAL ENERGY TECHNOLOGY LABORATORY
10 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
RESEARCH AND
INNOVATION CENTER
TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
11
Research and Innovation Center Technologies
Transformational Solvents technology maturity:
Laboratory-Scale; Pilot-
Scale, Actual Syngas
primary project goals
project focus:
The National Energy Technology Laboratory’s (NETL) Research and Innovation Pre-Combustion Solvents
Center (RIC) is developing advanced solvents for pre-combustion carbon dioxide
(CO2) capture that can reduce both the energy penalty and the cost of CO2 participant:
separation compared with conventional technologies. Novel advanced solvents National Energy Technology
are optimized through designing, synthesizing, characterizing, modeling, and Laboratory – Research and
performance-testing these materials. Innovation Center
project number:
technical goals FwP-1022402
• Design and synthesize low-cost hydrophobic solvents with high CO2 uptake, predecessor project:
low hydrogen (H2) uptake, low viscosity, and low vapor pressure. 2018 Carbon Capture FwP
• Measure the crucial properties of these solvents, which are needed in order to
conduct economic comparisons with commercially available physical solvents. NETL technical portfolio
lead:
• Measure corrosion rates for both commercially available solvents and NETL-
designed solvents. Generally, hydrophobic physical solvents have significantly David Hopkinson
[email protected]
lower corrosion rates compared with aqueous and hydrophilic solvents under
acidic conditions inside a pre-combustion CO2 capture absorber and flash tanks.
NETL principal
• Develop a method for operating the existing continuous stirred tank reactor investigator:
(CSTR) under mixed gas conditions. While quantifying gas uptake into solvents Nicholas Siefert
under mixed gas conditions is challenging compared with measuring gas [email protected]
uptake under pure gas conditions, such data are crucial for predicting the real-
world performance of a pre-combustion carbon capture solvent, especially partners:
water absorption from the gas stream effects on CO2 and H2 solubilities. University of Pittsburgh,
• Conduct economic comparisons for 30 different physical solvents, which will University of North Dakota
Energy & Environmental
include both commercially available solvents and NETL-synthesized solvents.
Research Center
• Conduct long-term experimental testing at the University of North Dakota’s (UNDEERC),
Energy and Environment Research Center (UNDEERC) on the most promising Carbon Capture Scientific
physical solvent based on economic comparisons of 30 physical solvents.
• Conduct a hybrid solvent-membrane test at UNDEERC, demonstrating the
synergies of a hybrid solvent-membrane system at modular-scale gasifiers.
technical content
Liquid solvent processes are the most well-developed technology for CO2
separation. In these processes, a liquid solvent circulates between an absorption
column and a series of desorption flash tanks. The energy required to separate
CO2 from the gas stream can either come in the form of electricity or low-
grade/waste heat.
The current state-of-the-art pre-combustion CO2 capture solvents are Selexol®
(Union Carbide, Houston, Texas, United States) and Rectisol® (Lurgi AG, Frankfurt
am Main, Germany). Unfortunately, both solvents are hydrophilic, have high vapor
pressure, and can cause significant corrosion at elevated temperatures. To avoid
water uptake and solvent evaporation, the syngas temperature for both processes
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
12 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
is typically lowered to sub-ambient conditions (10°C for Selexol and -10°C for Rectisol) and then raised back up to roughly
200°C for combustion. This process is both inefficient and costly. Instead, hydrophobic solvents with low vapor pressures
could be operated at higher temperatures to avoid the energy and cost penalties associated with cooling the syngas to
below ambient conditions. The ideal pre-combustion carbon capture solvent would be operated above room temperature
and regenerated using waste heat, which would minimize the electricity and cost penalties associated with CO2 separation
from syngas.
Accordingly, this research is focused on finding materials that are hydrophobic so that they can be operated at
temperatures between 40 and 150°C and in the presence of water vapor and contaminants. A particular focus has been
placed on the testing solvents to determine their CO2 solubility, kinetics, mass transfer, regeneration energy, stability, and
corrosion rates on common steels. Each of these properties is a parameter that may be tuned in solvent development, so
their effect on CO2 separation energetics, and ultimately cost, serves to guide materials development. Equally important,
system and economic studies are being conducted to determine how these material properties affect the overall
performance of the pre-combustion capture system. NETL-RIC is currently conducting economics comparisons on 30
solvents (both commercially available and NETL-synthesized). Subsequently, a regression analysis will be conducted to
determine the ideal combination of these properties (i.e., the trade-offs between viscosity, CO2 uptake, H2 uptake, and
vapor pressure).
Improvements in material performance can be achieved through modifications to the structure or formulation of the
solvent material. When appropriate, computational methods have been used to guide structure and formulation
modifications. For example, NETL has developed several hydrophobic physical solvents with promising performance for
pre-combustion CO2 capture by combining high absorption capacity of polyethylene glycol (PEG) and the hydrophobicity
and low viscosity of poly(dimethylsiloxane) (PDMS). Using hydrophobic solvents avoids the necessity to remove water
vapor from the syngas stream, which increases efficiency and decreases capital cost. To date, several solvents that were
invented by NETL show improvements, and one in particular, PEGPDMS-3, has shown exceptional performance for low
energy and low capital cost of CO2 removal from fuel gas. Another exciting solvent, which came from a computational
screening of more than 100,000 physical solvents, is titled CASSH-1. This solvent is extremely low cost and hydrophobic,
and has reasonably low vapor pressure, high CO2 uptake, and high CO2/H2 selectivity.
NETL has tested both PEGPDMS-3 and CASSH-1 under real syngas generated at a fluidized-bed gasifier at UNDEERC.
Both solvents performed well compared against the two commercially available solvents, which were also tested at
UNDEERC under the same operating conditions. (See references below for experimental results.)
technology advantages
NETL’s PEGPDMS-3 and CASSH-1 solvents have several advantages for pre-combustion CO2 capture:
• Simple synthesis procedure using low-cost reagents.
• Hydrophobic nature allows pre-combustion capture at higher temperatures when water vapor is present in syngas,
eliminating the need to lower the syngas temperature to below 40ºC to remove the water vapor and minimizing the
energy and cost penalties of cooling the syngas.
• High CO2/H2 selectivity.
• No foaming tendency.
• Can operate above room temperature due to lower vapor pressure, reducing energy penalty for chilling syngas.
R&D challenges
Challenges for physical solvent process for pre-combustion CO2 capture include:
• Achieving balance between required physical properties, such as viscosity, density, vapor pressure, CO2 capacity,
CO2/H2 selectivity, and cost.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
13
Research and Innovation Center Technologies
• Identifying chemical functionalities for the optimal mix of physical properties and performance.
• Increasing the CO2/H2 selectivity of the solvent, increasing hydrophobicity, decreasing viscosity, and optimizing
solvents for temperature, pressure, and gas mixture conditions specific to its application.
• Measuring uptake of gases into the solvent phase under real/mixed gas conditions (CO2, H2, water [H2O], and other
impurities)
status
In previous work, NETL developed several promising physical solvents based on PEG/PDMS with comparable CO2 capacity,
higher CO2/H2 selectivity, and improved vapor pressure compared to Selexol, along with improved hydrophobicity and
lower viscosity. Two NETL-developed solvents were tested in actual syngas at UNDEERC.
available reports/technical papers/presentations
Siefert, N. and Hopkinson, D., “Physical Solvent Development for Pre -Combustion Carbon Capture,” Presented at 2019
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019.
Shi, W., Thompson, R., Macala, M., Resnik, K., Steckel, J., Siefert, N., Hopkinson, D., "Molecular Simulations of CO2 and H2
Solubility, CO2 Diffusivity, and Solvent Viscosity at 298 K for 27 Commercially Available Physical Solvents," Journal of
Chemical & Engineering Data, 2019, 64, 9, 3682-3692.
Thompson, R., Culp, J., Tiwari, S., Basha, O., Shi, W., Damodaran, K., Resnik, K., Siefert, N., Hopkinson, D., "Effect of
Molecular Structure on the CO2 Separation Properties of Hydrophobic Solvents Consisting of Grafted Poly Ethylene Glycol
and Poly Dimethyl Siloxane Units,” Energy & Fuels, 2019, 33, 5, 4432-4441.
Hopkinson, D., Siefert, N., Thompson, R., Macala, M., and Lei, M., “Di-Substituted Siloxane Solvents for Gas Capture,” US
Non-provisional Patent Application No. 15/989,444.
Wei Shi, Megan Macala, Robert L. Thompson, Surya Tiwari, Kevin P. Resnik, Nicholas Siefert and David Hopkinson "The
Development of Machine Learning, Group Contribution and Molecular Modeling Approach to Screen Physical Solvents for
Gas Separation," 2018 AIChE Conference, Pittsburgh, PA, October 2018.
Luebke, D., Nulwala, H., Kail, B., Shi, F. Thompson, R., and Siefert, N., “Sulfur Tolerant Hydrophobic Ionic Liquid Solvent,”
US Patent 9,975,080, May 2018.
O. Basha, I. Gamwo, N.S. Siefert, and B. Morsi, "Computational Fluid Dynamics Modeling and Optimization of Absorber
Design for Pre-combustion CO2 Capture," International Pittsburgh Coal Conference, September 2017.
Nicholas Siefert, “Experimental Materials Development and Bench-Scale System Design for Pre-Combustion Solvents,”
Presented at 2017 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2017.
Nulwala, H. and Luebke, D., “High Performance Hydrophobic Solvent, Carbon Dioxide Capture,” US Patent 9,643,123,
May 2017.
Shi, W., Siefert, N.S.S., and Morreale, B.D., “Molecular Simulations of CO2, H2, H2O, and H2S Gas Absorption into
Hydrophobic Poly(dimethylsiloxane) (PDMS) Solvent: Solubility and Surface Tension,” J. Phys. Chem. C, 119 (33), pp
19253–19265 (July 2015).
Siefert, N.S, Agarwal, S., Shi, F., Shi, W., Roth, E.A., Hopkinson, D., Kusuma, V.A., Thompson, R.L., Luebke, D.R., and
Nulwala, H.B., “Hydrophobic physical solvents for pre-combustion CO2 capture: Experiments, Computational simulations,
and Techno-economic analysis,” International Journal of Greenhouse Gas Control, Volume 49, June 2016, Pages 364-371.
Fan Shi, Nicholas Siefert, and David Hopkinson, “Anti-foaming Study for Physical Solvents for Pre-Combustion CO2
Capture,” 2015 AIChE Annual Meeting, Salt Lake City, November 8-13, 2015.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
14 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Nicholas Siefert, Hunaid Nulwala, Wei Shi, Fan Shi, Jeffrey Culp, Elliot Roth, Victor Kusuma, David Hopkinson, “Warm Gas
Pre-combustion CO2 Capture Using Hydrophobic Solvents,” 2015 International Pittsburgh Coal Conference, Pittsburgh,
PA, October 5-8, 2015.
Fan Shi, Brian Kail, Hunaid Nulwala, Nicholas Siefert, David Luebke, "Effects of Contaminants on Pre-combustion CO2
Capture Solvents," 18th Annual Energy, Utility & Environment Conference (EUEC), San Diego, CA, Feb 16-18, 2015.
Siefert, N., Sweta, A., Nulwala, H., Roth, E., Kusuma, V., Shi, F., Shi, W., Culp, J., Miller, D., Hopkinson, D., Luebke, D.,
“Hydrophobic, Physical Solvents for Pre-combustion CO2 Capture: Experiments and System Analysis,” Fourteenth Annual
CCUS Conference, Pittsburgh, PA, April 30, 2015.
Siefert, N., Sweta, A., Nulwala, H., Roth, E., Kusuma, V., Shi, F., Shi, W., Culp, J., Narburgh, S., Miller, D., Hopkinson, D.,
“Hydrophobic, Physical Solvents for Pre-combustion CO2 Capture,” Presented at 2015 NETL CO2 Capture Technology
Meeting, Pittsburgh PA, June 25, 2015.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
15
Research and Innovation Center Technologies
Microwave-Assisted Sorbent technology maturity:
Laboratory/Bench-Scale,
Regeneration Simulated Flue Gas
project focus:
primary project goals Microwave-Assisted Sorbent
Regeneration for Carbon
The objective of this project is to evaluate microwave-assisted sorbent Capture
regeneration for carbon dioxide (CO2) capture processes as an alternative for the
current state-of-the-art methods. A novel sorbent material that is optimal for participant:
electromagnetic fields will be designed, synthesized, optimized, and evaluated. National Energy Technology
Laboratory–Research and
Innovation Center
technical goals
project number:
• Develop a novel microwave-assisted slurry process for post-combustion carbon FwP-1022402
capture that has a CO2 desorption flux 10 times faster in comparison with
thermal heating and consumes much less energy for CO2 desorption, even at predecessor project:
process temperatures of 65 to 85oC. 2018 Carbon Capture FwP
• Assess microwave-assisted sorbent regeneration for some known in-house
sorbent materials. NETL technical portfolio
lead:
• Develop highly active, thermally and chemically stable materials to achieve
sorbent regeneration at relatively lower temperatures (i.e., as low as 85oC) than David Hopkinson
[email protected]
the conventional processes.
• Provide a fundamental understanding of phenomena leading to the NETL principal
development of novel materials and processes for carbon capture technologies. investigators:
• Develop and optimize a novel reactor system for carbon capture technologies. Dushyant Shekhawat
[email protected]
McMahan Gray
technical content [email protected]
Carbon capture using solid sorbents has many benefits compared to state-of-the-
partners:
art solvent systems, including the inherent ability to circulate less moisture than N/A
solvent systems, which results in lower heat duties. However, solid sorbents are
more difficult to heat than solvents and generally require direct heating, in which
the use of steam or recirculated CO2 for regeneration results in slow kinetics.
Regeneration temperatures can be reached at extremely fast rates using the
method of rapid heating through microwave radiation. This rapid regeneration
leads to a smaller size regenerator, potentially reducing capital costs. Sorbent
regeneration rates can be enhanced by applying high-frequency electromagnetic
fields to the sorbent regeneration zone, which can selectively stimulate targeted
sites on the sorbent through dielectric and magnetic interactions without
increasing the bulk gas temperature and solid medium. These conditions result in
significantly higher sorbent regeneration rates at relatively lower temperatures
than predicted by thermodynamics, which can provide savings in both energy and
feed costs. Further, due to the selective input of energy, microwave heating is more
efficient and more rapid than conventional heating, which requires heating of the
entire reactor system and is limited by conventional heat transfer mechanisms. The
basis of these effects lies in the fundamental physics by which radiation at
microwave frequencies interact with matter.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
16 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
The National Energy Technology Laboratory’s (NETL) basic immobilized amine sorbent (BIAS) slurry has demonstrated
the removal of CO2 from a dry or humidified post-combustion flue gas, along with fast CO2 desorption kinetics. The
adsorption data shown in Figure 1 verify that the amount of CO2 adsorbed by sorbent-1 is the same as the amount of
CO2 adsorbed by a slurry of the same sorbent dispersed in solvent-1 (when normalized to the mass of sorbent in the
slurry). The equal uptake in the sorbent and slurry verify that the silicone oil dispersant does not interfere with CO2 uptake
in the suspended sorbent. The microwave desorption data showed a regeneration time of only a few minutes for releasing
a CO2 gas stream from the slurry compared to several hours using the conventional thermal regeneration method. As
Figure 2 shows, microwave (MW) irradiation delivered up to 10 times more accumulated CO2 than thermal heating (TH)
within the first 20 minutes. The enhanced CO2 desorption rate under microwave heating is especially pronounced during
the first few minutes of microwave Time on Stream (mTOS) due to the lag in the thermal heating ramp resulting from the
thermal inertia of the system. Thermal images, as shown in Figure 3, also demonstrated that microwave energy can be
selectively absorbed by polarized components with a high dielectric loss factor (i.e., CO2-adsorbed BIAS) in slurry. The
other major advantage is a high-pressure pure CO2 product, as indicated in Table 1 – as high as 30 pounds per square
inch gauge (psig) of pressure was observed.
Slurry (normalized to sorbent weight)
Sorbent
Figure 1: Comparing CO2 uptake normalized to the mass of sorbent for the pure sorbent-1 (red)
and a slurry of the same sorbent dispersed in solvent-1 (black).
Figure 2: Comparison of microwave and thermal regeneration of the basic immobilized amine slurry.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
17
Research and Innovation Center Technologies
Figure 3. Thermal images of (a) silica, (b) silicone oil, (c) fresh BIAS, (d) CO2-loaded BIAS, and (e) CO2-adsorbed BIAS in silicone oil,
respectively, at 1 min mTOS under 200-W microwave irradiation.
TABLE 1: MICROWAVE REGENERATION OPERATION PARAMETERS
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
18 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Since traditional carbon capture materials may not be optimal for electromagnetic field regeneration, there is a need for
proof-of-concept runs on proven sorbents that are also active in an electromagnetic field. Zeolite-based sorbents have
been shown to absorb microwave radiation, and when properly functionalized, zeolite can capture CO2. Using zeolite-
based material as a capture material also allows for high surface area and tunable surface chemistry. In this project,
zeolite-based materials are being investigated and optimized to improve regeneration using a semi-continuous fixed-
bed microwave reactor. As microwave interactions with materials depend on the particle geometry, zeolite-based
materials can be optimized by adjusting physical properties, including particle size, pore size, number of active surface
sites, etc. Proof-of-concept testing on microwave-assisted regeneration of zeolite 13X have shown rapid regeneration
rates with greater than 50% faster regeneration times compared to conventional regeneration (Figure 4). Zeolite 13X is
an excellent microwave absorber and heats to a desorption temperature of 100°C in 30 seconds under microwave
irradiation. Conventionally, heating times are on the order of 15 minutes.
Figure 4. CO2 desorption curves and temperature profiles during microwave and conventional regeneration of zeolite 13X.
In addition, computational modeling techniques, such as a finite difference time domain (FDTD), are being used to
optimize interactions between the microwave field and material and to minimize any thermal losses in the system. Poor
interaction between the microwave field and material, thermal losses, and coupling with interior features of the reactor
cavity versus material contribute in making microwave technology inefficient for certain materials; therefore, it is
important to target sorbent materials that can heat efficiently under microwave irradiation. In addition to zeolites, amine-
based materials or carbon hybrid materials that can be heated with microwaves can also be evaluated. A basic kinetic
study on the regeneration of CO2 using these materials is required to confirm rapid release of CO2. Furthermore, a system
study will determine the energy savings associated with the process and will reveal what type of reactor is suitable for
larger-scale application.
In this project, new formulas of microwave-stable slurry are being designed, synthesized, optimized, and evaluated in
electromagnetic fields for carbon capture. The effects of reaction conditions (regeneration temperature; microwave
power, pulse, and frequency) on slurry regeneration are being investigated. The formulated slurry is being tested in a
laboratory environment (absorption at 60°C and desorption at no more than 100°C) at NETL using a Discover SP
microwave reactor with simulated flue gas. Promising materials are further investigated in a bench-scale environment. In
parallel to the slurry studies, an optimal sorbent material is also being designed, characterized, and evaluated for the
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
19
Research and Innovation Center Technologies
microwave-assisted carbon capture technologies. A systems engineering and analysis assessment for microwave-assisted
regeneration process is being prepared based on experimental results, including an evaluation of kinetics and activation
energy of desorption, to determine the energy and cost savings compared to using steam for regeneration. A survey will
be performed to explore the application of microwave technology used for any industrial scaled-up processes and the
scalability of the technology.
The scale-up of the microwave-assisted slurry process for carbon capture involves testing in a slurry reactor (1-liter scale)
with a microwave regeneration unit and the establishment of operating conditions and procedures to further
commercialize the process. Computational efforts focus on screening and optimizing non-aqueous solvents and sorbents
for use of microwave regeneration. This involves studying the interactions between CO2 and the non-aqueous solvent or
sorbent under microwave conditions and then determining the materials that will be most responsive to microwaves at
certain wavelengths. Information gathered from experimental tests and modeling is used to design and improve
microwave-assisted slurry carbon capture systems that can be scaled-up and tested with a slipstream of flue gas at the
National Carbon Capture Center (NCCC) in Wilsonville, Alabama.
technology advantages
• Selective heating via microwave radiation is extremely rapid, allowing regeneration temperatures to be attained at very
fast rates.
• Rapid regeneration allows for smaller regenerator size in a commercial application, lowering capital costs.
• Applying electromagnetic fields to sorbent or slurry regeneration zone enhances sorbent regeneration rates at
relatively low temperature (i.e., at 85oC), providing energy and cost savings.
• Microwave regeneration of sorbent and non-aqueous slurry are steam-free processes, which substantially lowers the
cooling and regeneration energy duties while eliminating the need for reboilers and steam extractors.
• NETL is established as a premier institute in the microwave area and has commissioned a variable frequency microwave
reactor that is a one-of-a-kind system that does not exist in any other research laboratories in the world.
R&D challenges
• Addressing issues associated with microwave technology, such as poor interaction between the microwave field and
material, thermal losses, and coupling with interior features of the reactor cavity versus material.
• Scale-up of microwave-based slurry or sorbent regeneration process.
status
NETL’s Research and Innovation Center (RIC) has demonstrated significantly higher sorbent regeneration rates (at least
50% faster) for releasing a CO2 gas stream from a zeolite sorbent or BIAS slurry compared to using the conventional
thermal regeneration method (steam). A conceptual systems engineering and analysis assessment for the microwave-
assisted regeneration process was also performed based on the measured regeneration kinetics. The scalability of the
microwave-assisted slurry process is being evaluated.
available reports/technical papers/presentations
Patents
F. Shi, McMahan Gray, Yee Soong, Yuhua Duan, Tuo Ji, Microwave-Accelerated Regeneration of Graphene-Amine
(MARGA) Aqueous Solution for Carbon Capture, S-163,989 (19N-30), 2019.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
20 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
F. Shi, J. Culp, M. Gray, etc., Regenerable Non-Aqueous Basic Immobilized Amine Slurries for Removal of CO2 from a
Gaseous Mixture and a Method of Use Thereof, 2019, PCT International Patent Application No. PCT/US19/47047.
F. Shi, J. Culp, M. Gray, etc., Regenerable Non-Aqueous Basic Immobilized Amine Slurries for Removal of CO2 from a
Gaseous Mixture and a Method of Use Thereof, 2018, 16/110,352.
Technical Paper
T. Ji, H. Zhai, J. Culp, C.M. Marin, H. P. Paudel, B. Kail, W.C. Wilfong, Q. Wang, Y. Duan, Y. Soong, F. Shi, M. Gray, A Non-
Aqueous Microwave-Accelerated Regeneration of a Slurry (MARS) Process for Carbon Capture, Science, 2020 (under
review).
Presentations
F. Shi, T. Ji, H. Paudel, Y. Duan, J. Culp, C. Marin, M. Gray, Novel Microwave-Accelerated Regeneration of a Non-aqueous
Slurry (MARS) for Post-combustion Carbon Capture, 2019 AIChE meeting, Orlando, FL, Nov. 10, 2019.
F. Shi, T. Ji, Y. Soong, M. Gray, A study of ultra-fast CO2 desorption kinetics for Microwave-Enhanced Regeneration
Process, 2019 Carbon Management Technology Conference, Houston, TX. July 2019.
Ellison, C.; Shekhawat, D. Microwave-assisted Regeneration of Zeolite 13X for CO2 Capture. In Proceedings of IMPI’s 53rd
Annual Microwave Power Symposium, Las Vegas, NV, June 18-20, 2019.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 21
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Transformational Membranes technology maturity:
Bench-Scale, Actual Flue
Gas
primary project goals
project focus:
The National Energy Technology Laboratory’s (NETL) Research and Innovation Post-Combustion
Center (RIC) is developing new, ultra-high-performance membranes and Membrane Materials
membrane modules for post-combustion carbon dioxide (CO2) capture.
Membrane types under investigation include polymer membranes and mixed participant:
matrix membranes (MMMs); also, high-permeance flat sheet and hollow fiber National Energy Technology
supports are being fabricated on which thin-film coatings of the polymers can be Laboratory–Research and
Innovation Center
demonstrated. Development efforts are consistent with overall goals of reducing
the energy penalty and cost of CO2 separation relative to conventional
project number:
technologies.
FWP-1022402
technical goals predecessor project:
2018 Carbon Capture FWP
• For polymer membranes, selectivity/permeability performance for
CO2/nitrogen (N2) gas separations lying on or above the Robeson upper bound. NETL technical portfolio
• Polymeric materials must overcome the practical difficulty of poor mechanical lead:
properties that are often associated with high-performance experimental David Hopkinson
[email protected]
polymers.
• Viable membrane module performance given the low-pressure driving force NETL principal
available in post-combustion flue gas. investigator:
• Progression from proven performance in simulated flue gas to validation on David Hopkinson
actual flue gas slipstream at pilot scale. [email protected]
• Determination of cost effectiveness of membranes/modules for post-
combustion CO2 capture in techno-economic analyses (TEAs), consistent with
partners:
approach to a cost of carbon capture at $30/tonne CO2 by 2030. Compact Membrane
Systems, University of
Pittsburgh, Penn State
technical content University, Texas A&M
Membrane technology poses an exciting option for large-scale gas separations
due to the small footprint, simplicity of the device and process, ease of operation,
modularity and bolt-on installation, and typically low parasitic energy
requirements. Industrially, polymer-type membranes have a well-established role
in gas separation technology, and are commonly used in applications such as
separation of hydrogen from gas mixtures, purifying natural gas, etc. However,
extremely high-permeability membrane materials are needed to make this
technology an economically viable option for post-combustion CO2 capture. While
there are multiple experimental membranes reported in the literature that appear
to meet the performance requirements, most have practical drawbacks, such as
poor mechanical strength, poor thin film forming ability, reduced performance
with aging, or complex and expensive synthesis procedures. Therefore, there is a
need to develop new membranes that have high performance but also meet the
practical requirements of post-combustion CO2 capture.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
22 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Advanced Polymer Membranes
Fundamentally, polymer membranes are bounded by their performance, known as the Robeson upper bound (gas
permeability must be sacrificed for species selectivity and vice versa). This intrinsic trade-off between permeability and
selectivity is a significant limitation of using polymer membranes in the challenging application of capture of relatively
dilute CO2 from flue gas. Incremental improvements in polymer performance continue to advance the trade-off curve
towards more selective, more permeable materials, but a step-change over current technology would facilitate wider
implementation of membrane technology.
Recently, NETL-RIC has been investigating two polymers of interest for CO2 capture: PIM-1 and MEEP80-polyposphazene
(MEEP80-PPZ), as illustrated in Figure 1. PIM-1 has high permeability, but has low selectivity, forms brittle films, and aging
tends to reduce its permeability. MEEP-PPZ has only moderate permeability but has high selectivity and forms gummy
films.
Figure 1: High-performance polymers.
NETL has found that blends of PIM-1/MEEP-PPZ have high permeability and excellent mechanical properties in terms of
forming strong and flexible films. The performance of the neat polymers and the better performing blends are shown in
Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 23
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Figure 2: Polymer blend performance.
Also, in the area of advanced polymers, NETL has been combining MEEP-PPZ and PPOP-PPZ and adding a crosslinking
agent to form crosslinked MEEP (XL MEEP). MEEP-PPZ has excellent gas separation performance, but is a flowing semi-
solid material, while PPOP-PZ has poor gas separation performance but excellent mechanical robustness. The resultant
XL MEEP has excellent gas separation performance and is a solid with good mechanical robustness. NETL testing and
analyses have shown that crosslinking of MEEP dramatically improves film durability with some decrease in gas
permeability, and that crosslinked MEEP gas separation performance can be optimized based on composition and
crosslinker. Crosslinked MEEP is stable in real flue gas, shows little performance degradation in the presence of humidity,
and thin films suffer no significant degradation from aging.
Mixed Matrix Membranes
MMMs are a technology that could potentially achieve a step-change in gas separation performance. MMMs are
composite structures that make use of a polymer matrix and a porous filler particle. Metal-organic frameworks (MOFs)
are commonly used as the filler particle because of their high CO2 uptake and the tunability of their pores for achieving
selective mass transfer of CO2 relative to the other species in post-combustion flue gas (primarily N2). In general, MOFs
will have more desirable gas transport properties than a polymer but are very difficult to form into a free-standing and
defect-free membrane film. By integrating MOFs into a polymer film, the selectivity and permeance of the film are
enhanced. This makes the system more capable of dealing with a low partial pressure driving force than conventional
polymers, while also retaining the processability of a polymer. The MMM concept, challenges, and development are
depicted in Figure 3.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
24 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Advantages of MMM Problems in preparation of MMM Engineering the materials resulted
in defect-free membranes
Mixed matrix
Pure
inorganics
Performance
Polymers
Cost ($/sq.meter)
Polymer Inorganic filler
Figure 3: MMMs characteristics and development.
MMMs often suffer from poor contact between the polymer matrix and MOF crystallites. This phenomenon, known as
the sieve-in-a-cage effect, can cause gas streams to bypass the MOFs without separation, thus dramatically reducing
selectivity. Overcoming this problem and identifying a polymer-MOF pair with the capability to form a highly permeable
and selective membrane is a technology development focus.
Figure 4 shows the performance of various MMMs on the Robeson plot, showing their potential to exceed the
characteristic performance limits of ordinary polymeric membranes.
Figure 4: MMMs performance.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 25
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Most recently, NETL has taken a unique approach to MMM design by using high-throughput computational tools to
predict the gas permeability of a large database of MOF materials and make predictions of the gas permeation behavior
of more than a million hypothetical MMMs. The model was expanded by coupling it with process analysis tools to
calculate the cost of capture for the hypothetical MMMs. This represents the first known attempt at a true rational design
of MMMs for post-combustion carbon capture. It was found that a well-designed MMM can lead to dramatic
improvement of performance over a neat polymer and reduce the cost of capture by $15/tonne.
Several screened candidates were experimentally demonstrated, showing excellent agreement with model results. Figure
5 shows these candidates, which exceed the Robeson upper bound.
Figure 5: NETL’s recent MMM results.
NETL has investigated incorporating MOFs into the already high-performance advanced polymers PIM-1/MEEP and XL
MEEP, as discussed previously. The MMMs formed show improved performance over the base advanced polymers, as
illustrated in Figure 6.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
26 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Figure 6: Improved performance of NETL MMMs from XL MEEP and PIM-1/MEEP advanced polymers.
Supports and Thin-Film Coatings
Carbon capture using membranes depends on much more than the development of an effective selective layer. The
selective layer must be extremely thin, and thus it must be reinforced by a strong, highly permeable support layer. In
order to prevent the selective material from flowing into the pores of the support layer, a thin “gutter” layer can be
introduced between the support and the thin selective layer. The combination of these various layers is called a thin-film
composite (TFC). NETL has recently made significant advances in TFC membranes, particularly in the development of
high-flux porous supports. NETL’s current hollow fiber membrane supports have N2 permeance greater than 100,000 gas
permeation units (GPU), CO2/N2 selectivity ~0.8 (Knudsen diffusion), surface pore size ~20 nm, and are resistant to mild
solvents. These have been fabricated as both high-flux hollow fiber supports and high-flux flat sheet supports. The two
panels on the top of Figure 7 show PIM-1/MEEP/10% MOF MMM selective layer on a hollow fiber support, while the
bottom two panels show a XL MEEP selective layer on a flat sheet support.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 27
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Figure 7: PIM-1/MEEP MMMs and XL MEEP in thin-film composites.
technology advantages
• Membranes separate mixed gas streams according to differences in gas permeability across a membrane film, enabling
steady-state operation with no energy-intensive regeneration step required. This creates potential for energy savings
using this technology.
• Higher-permeability membranes lead to a reduced membrane area requirement, smaller capital cost, and a smaller
equipment footprint.
• NETL-developed polymers have enhanced mechanical stability.
• High-throughput computational methods have identified MMMs capable of breaking the Robeson upper bound.
R&D challenges
• Increasing membrane permeability and selectivity for CO2.
• Identifying compositions that have durable mechanical properties and good thin-film forming properties.
• Maintaining low cost of fabrication, particularly in membranes that involve complex synthesis procedures.
• Maintaining robust performance under harsh operating conditions, such as elevated temperature or pressure.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
28 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
• Increasing the resistance of membranes and membrane materials to contaminants including water, sulfur species, or
particulates.
• Increasing the compatibility between composite membrane materials.
• Realizing good membrane separation performance, even under low driving forces for separation associated with
energy-saving configurations.
• Achieving defect-free thin-film selective layer coatings that are less than 1 µm in thickness.
available reports/technical papers
“Membrane Development for Post-Combustion CO2 Capture,” Dave Hopkinson, NETL Research and Innovation Center,
presentation at the 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting
- Capture and Utilization Sessions, August 2019.
“The effect of poly(ethylene oxide) cross-linking structure on the mechanical properties and CO2 separation
performance of an ion gel membrane,” Victor Kusuma, Christina Chen, James S. Baker, Megan K. Macala, David
Hopkinson, Polymer, 2019.
“High-throughput computational prediction of the cost of carbon capture using mixed matrix membranes,” Samir
Budhathoki, Olukayode Ajayi, Janice Steckel, Christopher Wilmer, Energy & Environmental Science 4 (2019) 1111-1430.
“Defect-Free MOF-Based Mixed-Matrix Membranes Obtained by Corona Cross-Linking,” Katayama, Y.; Bentz, K. C.;
Cohen, S. M., ACS Applied Materials & Interfaces 2019, 11 (13), 13029-13037 DOI: 10.1021/acsami.9b02539.
“Ionic Liquid Compatibility in Polyethylene Oxide/Siloxane Ion Gel Membranes,” Victor A. Kusuma, Megan Macala, Jian
Liu, Anne M. Marti, Rebecca Hirsch, Lawrence J. Hill, David Hopkinson, Journal of Membrane Science, 545 (2018) 292-
300.
“Interfacial Engineering in Metal–Organic Framework-Based Mixed Matrix Membranes Using Covalently Grafted
Polyimide Brushes,” Wang, H.; He, S.; Qin, X.; Li, C.; Li, T., Journal of the American Chemical Society 2018, 140 (49),
17203-17210 DOI: 10.1021/jacs.8b10138.
“Ionic Cross-Linked Polyether and Silica Gel Mixed Matrix Membranes for CO2 Separation from Flue Gas,” Ali K.
Sekizkardes, Xu Zhou, Hunaid B. Nulwala, David Hopkinson, Surendar R. Venna, Separation and Purification Technology,
191 (2018) 301-306.
“Incorporation of benzimidazole linked polymers into Matrimid to yield mixed matrix membranes with enhanced
CO2/N2 selectivity,” Tsemre Dingel M. Tessema, Surendar R. Venna, Ganpat Dahe, David P. Hopkinson, Hani M. El-Kaderi,
Ali K. Sekizkardes, Journal of Membrane Science, 554 (2018).
“A Simple Fabrication Method for Mixed Matrix Membranes with In-situ MOF Growth for Gas Separation,” Anne M.
Marti, Surendar R. Venna, Elliot A. Roth, Jeffrey T. Culp, and David P. Hopkinson, ACS Applied Materials and Interfaces,
10-29 (2018) 24784-24790.
“Layer-by-Layer Assembled Polymer/Metal-Organic Framework (MOF) Composite Membrane with Individually
Dispersed Filler Particles and Strong Filler-Matrix Interaction,” Fangming Xiang, Anne Marti, David Hopkinson, Journal of
Membrane Science, 556 (2018).
“Microporous polymeric composite membranes with advanced film properties: pore intercalation yields excellent CO2
separation performance,” Ali K. Sekizkardes, Victor A. Kusuma, Joshua S. McNally, David W. Gidley, Kevin Resnik,
Surendar R. Venna, and David Hopkinson, Journal of Materials Chemistry A, 6 (2018) 22472-22477.
“Cross-linked Poly(ethylene oxide) Ion Gels Containing Functionalize Imidazolium Ionic Liquids as Carbon Dioxide
Separation Membranes,” Kusuma, Victor; Macala, Megan; Baker, James; Hopkinson, David, Industrial & Engineering
Chemistry Research, 2018 57 (34), pp. 11658-11667.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 29
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
“Active Response of Six-Coordinate Cu2+ on CO2 Uptake in Cu(dpa)2SiF6-i from In Situ X-Ray Absorption Spectroscopy,”
Jeffrey B. Kortright, Anne M. Marti, Jeffrey Culp, Surendar Venna, David Hopkinson, Journal of Physical Chemistry Part C,
121 (2017) 11519-11523.
“An Automated Lab-Scale Flue Gas Permeation Membrane Testing System at the National Carbon Capture Center,”
Victor Kusuma, David Hopkinson, Journal of Membrane Science, 533 (2017) 28-37.
“Polyphosphazene polymer development for mixed matrix membranes using SIFSIX-Cu-2i as performance
enhancement filler particles,” Alex Spore, Zhicheng Tian, Erik Albenze, Hunaid Nulwala, Nathaniel Rosi, Anne Marti,
David Luebke, David Hopkinson, Harry Allcock, Journal of Membrane Science, 535 (2017) 103-112.
“Continuous Flow Processing of ZIF-8 Membranes on Polymeric Porous Hollow Fiber Supports for CO2 Capture,” Anne
M. Marti, Shan Wickramanayake, Ganpat Dahe, Ali Sekizkardes, Tracy Banks, David Hopkinson, and Surendar Venna, ACS
Applied Materials & Interfaces, 9 (2017) 5678-5682.
“Interactions at the Interface of Polymer Matrix-Filler Particle Composites,” Jie Feng, Surendar Venna, and David
Hopkinson, Polymer, 103 (2016) 189-195.
“Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation,” Lin, R.; Ge, L.; Diao, H.;
Rudolph, V.; Zhu, Z., ACS Applied Materials & Interfaces 2016, 8 (46), 32041-32049 DOI: 10.1021/acsami.6b11074.
“Improved Interfacial Affinity and CO2 Separation Performance of Asymmetric Mixed Matrix Membranes by
Incorporating Postmodified MIL-53(Al).” Zhu, H.; Wang, L.; Jie, X.; Liu, D.; Cao, Y., ACS Applied Materials & Interfaces
2016, 8 (34), 22696-22704 DOI: 10.1021/acsami.6b07686.
“Interfacial Design of Mixed Matrix Membranes for Improved Gas Separation Performance,” Wang, Z.; Wang, D.; Zhang,
S.; Hu, L.; Jin, J., Advanced Materials 2016, 28 (17), 3399-3405 DOI: 10.1002/adma.201504982.
“Carbon Dioxide Separation from Flue Gas by Mixed Matrix Membranes using Dual Phase Microporous Polymeric
Constituents,” Ali K. Sekizkardes, Victor A. Kusuma, Ganpat Dahe, Elliot A. Roth, Lawrence J. Hill, Anne Marti, Megan
Macala, Surendar R. Venna, and David Hopkinson, Chemical Communications, 52 (2016) 11768-11771.
“Ultra-Micro Porous Organic Polymer for High Performance Carbon Dioxide Capture and Separation,” Ali Sekizkardes,
Jeff Culp, Anne Marti, Christina Myers, David Hopkinson, Hunaid Nulwala, Chemical Communications, 51 (2015) 13393-
13396.
“Characterization of hollow fiber supported ionic liquid membranes using microfocus X-ray computed tomography,”
Sheng Dai, Shan Wickramanayake, Yongkoo Seol, David Hopkinson, Journal of Membrane Science, 492 (2015) 497-504.
“Cross-linked Poly(ethylene oxide) containing siloxanes fabricated through thiol-ene photochemistry,” Victor A. Kusuma,
Elliot A. Roth, William P. Clafshenkel, Steven S. Klara, Xu Zhou, Surendar R. Venna, Erik Albenze, David R. Luebke,
Meagan S. Mauter, Richard R. Koepsei, Alan J. Russell, David Hopkinson, and Hunaid B. Nulwala, Journal of Polymer
Chemistry A, 2015.
“Fabrication of MMMs with improved gas separation properties using externally-functionalized MOF particles,” S. R.
Venna, M. Lartey, T. Li, A. Spore, S. Kumar, H. Nulwala, D. R. Luebke, N. L. Rosi and E. Albenze, J. Mater. Chem. A, 3 (2015)
5014.
“The upper bound revisited,” Robeson, L. M., Journal of Membrane Science, 320 (2008) 390-400.
“Layer-by-layer assembly of metal-organic framework nanosheets with polymer,” by Fangming Xiang, Eric J. Popczun,
and David P. Hopkinson, accepted to Nanotechnology, 4/9/2019.
“A cost and performance analysis of polymeric membrane-based post-combustion carbon capture,” Dale Keairns, Tim
Fout, David Hopkinson (in pre-publication and to be submitted to Journal of Membrane Science).
“Multicomponent Mixed-Matrix Membranes as a Next-Generation Post-Combustion Carbon Capture Technology,”
Sameh K. Elsaidi, Surendar Venna, Ali Sekizkardes, Mona H. Mohamed, Janice A. Steckel, James Baker, Michael J. Gipple,
John Baltrus, David Hopkinson (under preparation).
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
30 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
“Cross-linked polyphosphazene blends as robust, highly permeable gas separation membranes,” Victor A. Kusuma,
Joshua S. McNally, James S. Baker, Zi Tong, Lingxiang Zhu, Christopher J. Orme, Frederick F. Stewart David Hopkinson, in
preparation.
CARBON CAPTURE TECHNOLOGY SHEETS TRANSFORMATIONAL MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
31
Research and Innovation Center Technologies
Carbon Capture Retrofit technology maturity:
Systems Engineering and
Database – v.2019.1 Analysis
project focus:
primary project goals Carbon Capture Retrofit
Database Tools
The U.S. Department of Energy’s (DOE) National Energy Technology Laboratory
(NETL) has developed three carbon capture retrofit database (CCRD) tools that participant:
provide high-level analysis on the incremental cost for retrofitting point sources National Energy Technology
with carbon dioxide (CO2) capture and/or compression systems. The tools also Laboratory – Research and
provide options to include the cost of implementing other plant emissions Innovation Center
reduction technology improvements that may be required to comply with various
regulations (e.g., Mercury and Air Toxic Standards [MATS][1] and New Source
project number:
Performance Standards [NSPS][2]) when installing CO2 scrubbing technology, or aid FwP-1022402
in maximizing the efficiency of the installed CO2 removal technology.
predecessor projects:
N/A
technical goals
NETL technical portfolio
• Provide a tool that allows for the quick approximation of the cost to retrofit an lead:
existing power or industrial plant with CO2 capture equipment, grounded in Alexander Zoelle
sound techno-economic analysis (TEA) fundamentals and methodology [email protected]
approaches.
• Provide sufficient technology options for selection, upstream of the capture NETL principal
system, to maximize the applicability of the tool. investigator:
Timothy Fout
o For example, if a candidate plant for retrofit does not remove sulfur from
[email protected]
the flue gas at adequate levels to meet the inlet flue gas specifications of
the capture system to be added, the tool provides additional technology partners:
options for selection and inclusion to frame all requirements for the N/A
addition of CO2 capture.
technical content
Techno-economic evaluation of the impacts that post-combustion CO2 capture
systems impart on power and industrial plants is key to determination of
technology viability. Performing a TEA of an individual technology can provide
insights into the key process parameters for a given capture system and identify
areas for improvement that offer the most return by way of performance
improvement and cost reduction. Practitioners of TEAs generally operate using
their preferred set of assumptions, modeling and cost estimating methodologies,
and sensitivity analysis approaches, and these standards may vary across
organizations. In addition, there may be limitations regarding data availability and
approaches for filling these gaps may vary widely. These factors can contribute to
assessments that may or may not be developed on equivalent bases, and thus may
not be comparable without sufficient definition of all assumptions and
methodologies.
At NETL, systems analysis of power and power-related technologies, particularly
post-combustion carbon capture, has been a focus for many years, and a key
output of that work has been publicly available guidelines for conducting a TEA
CARBON CAPTURE TECHNOLOGY SHEETS SYSTEMS ENGINEERING AND ANALYSIS
NATIONAL ENERGY TECHNOLOGY LABORATORY
32 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
that are normalized, consistent, and transparent. However, even with the detailed guidance available for technology
developers seeking to assess their systems, differences can still arise that lead to incompatible studies and results. To
alleviate this issue, NETL has developed numerous tools for public use that build on the extensive systems analysis
guidelines developed by NETL and simplify the process of systems analysis to allow for a broader range of engineers and
scientists to take advantage of techno-economic evaluations.
NETL has developed three separate CCRD tools:
• Two power-related tools:
o One assessing coal-fired pulverized coal (PC) and atmospheric fluidized bed (AFB) units (the PC CCRD) and another
assessing natural gas units (the natural gas combined cycle [NGCC] CCRD).
• A third focused on industrial source (IND) sectors.
The IND CCRD contains data on facilities from the ammonia, cement, ethanol, hydrogen, and natural gas processing
industries. The tools allow for a user to quickly screen, at a high level, the impact of adding carbon capture to a plant by
calculating the incremental cost for retrofitting point sources with CO2 capture and/or compression systems.
The reference costs for all CCRDs are predicated on baseload operation, so no cost or performance considerations are
rendered for turn-down capability. In addition, the reference cost data sourced from NETL reports, and applied in the
CCRDs, has been developed for a target plant size; therefore, scaling cost and performance data to units of significantly
differing sizes, compared to the reference data, will introduce inaccuracies due to the nature of process design. Calculation
of cost results follows NETL’s guidance[3] and utilizes capital charge factors that will be contingent on a number of financial
parameter assumptions, including interest rate, return on equity, economic life of the plant, debt and equity split, debt
term, and others.
Similar to reference costs, the performance basis for the reference systems considered in the CCRD were developed for
International Organization for Standardization (ISO) ambient conditions[4][5], and no cost or performance adjustments are
made in the CCRD to account for the operating ambient conditions.
In order to reflect the expected but undefined costs associated with the retrofit of existing plants, a retrofit cost factor is
applied to all sites with no consideration given to the amount of retrofit equipment required, the available space, or other
site-specific conditions. As the plant configuration will have a significant impact on the actual installation costs and design
(and therefore equipment costs) of each system, the site-specific retrofit factor would be expected to deviate significantly
from the average value applied in the CCRDs.
The PC and NGCC CCRDs do not provide a library of existing U.S. fleet power plants for which calculations may be applied
to. If this type of analysis is desired, the individual user must obtain and import this data into the CCRD. The CCRD does
come pre-populated with cases that derive from legacy NETL systems analysis studies of representative coal and natural
gas power plants. These cases can be used without further adjustment if appropriate for the analysis desired.
In the case of a user importing U.S. fleet plant data, the CCRD offers several options to allow the user to bring the plant
into compliance with air emissions regulations, such that the plant is suitable for the addition of post-combustion capture
equipment. For example, if an existing unit does not meet the nitrogen oxides (NOX) environmental regulatory limit, a
selective catalytic reducer (SCR) can be included in the retrofit configuration, and the cost of adding the SCR unit is
calculated by the CCRD based on the CO2 capture rate. There are cost result accuracy considerations given the approach
employed by the CCRD to include addition of the SCR. The scaling approach of CO2 flow rate provides a short-cut method
reasonable for a screening-level assessment to approximate costs, but does not take into account site-specific
considerations of the existing plant, such as boiler type, coal type, removal efficiency requirements, and other factors, and
thus could result in an over- or under-sized SCR. Similar to NOX, if an existing unit does not meet the sulfur dioxide (SO2)
regulatory limit, wet flue gas desulfurization (FGD) can be included in the retrofit configuration, and the cost of FGD is
calculated by the CCRD based on the CO2 capture rate. The same cost result accuracy considerations listed for addition
of SCR apply to the addition of FGD.
CARBON CAPTURE TECHNOLOGY SHEETS SYSTEMS ENGINEERING AND ANALYSIS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
33
Research and Innovation Center Technologies
While scaling the CO2 removal system on the rate of CO2 captured is significantly more accurate than for either FGD or
SCR (discussed above) for similarly designed plants, regardless of coal type, considerable deviations can occur due to
various process design choices, such as excess air to the boiler, infiltration air, air leakage, efficiency of existing gas cleanup
systems, and operating temperature and pressure. Using solvent-based CO2 removal systems as an example, additional
air in the flue gas will not only increase the volumetric flow rate, but will also have a diluting effect on the CO2
concentration of the flue gas. These factors will affect the sizing of both the pre-scrubber and absorption columns
(impacting capital costs), as well as the solvent circulation rate (impacting the operating and maintenance [O&M] costs,
capital cost, and auxiliary load). The same cost result accuracy considerations listed for addition of SCR and FGD apply to
the retrofit of the CO2 removal system, and the user should take these considerations into account when interpreting the
results.
The reference CO2 compression system considered in the CCRD is an integrally geared centrifugal type, designed for
baseload operation[4], which may not be suitable for all unit sizes. For small units, reciprocating compressors may be more
appropriate, but the current CCRD does not offer this technology selection option.
In instances where the user provides U.S. plant fleet data, the CCRD charting tools allow for generation of an array of
scenario results plots. In Figure 1, the fleet-of-entries level view is presented for the breakeven CO2 sales price. In this
scenario, which is based on a particular user-defined set of assumptions, the plot shows that 80% of the total plant
capacity input into the CCRD tool and retrofitted could return a cost of $125/tonne or less. Figure 2 presents a different
scenario, where the nameplate capacity of the unit retrofitted, based on the user-defined fleet data, is plotted against the
calculated breakeven CO2 sales price. The trend shows that as the unit size increases, the breakeven CO2 sales price
decreases.
Figure 1: Breakeven CO2 sales price versus cumulative portion of capacity retrofitted.
CARBON CAPTURE TECHNOLOGY SHEETS SYSTEMS ENGINEERING AND ANALYSIS
NATIONAL ENERGY TECHNOLOGY LABORATORY
34 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Figure 2: Unit capacity retrofitted versus breakeven CO2 sales price.
technology advantages
• The tool allows for a first-cut screening of the potential impact of technology options, ranging from developing to
commercially available CO2 capture technologies, on the existing fleet of coal and gas power plants (when fleet data
is provided by the user), as well as industrial sources.
R&D challenges
• Lack of detailed energy and mass balance diagrams for each plant in the U.S. fleet reduces absolute accuracy of single
point results.
• Lack of comprehensive publicly available U.S. fleet plant data for pre-population of the tool database.
• The user must provide their own plant data or use the pre-populated cases that derive from legacy NETL systems
analysis studies of representative coal and natural gas power plants.
• The individual plant level accuracy of results is subject to the underlying performance and cost approximation
methodologies and plant data. While the underlying methodologies are sound, an individual plant-level model and
capital cost estimate is not developed for each case. Thus, the most useful application of the tool results is to compare
case outputs based on varying user inputs (e.g., power plant inputs, capture technology inputs, etc.) rather than
assessing an individual case’s absolute result.
status
NETL has developed three CCRD tools that allow for a quick approximation of the cost to retrofit an existing power or
industrial plant with CO2 capture equipment.
CARBON CAPTURE TECHNOLOGY SHEETS SYSTEMS ENGINEERING AND ANALYSIS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
35
Research and Innovation Center Technologies
available reports/technical papers/presentations
Kuehn, Norma. “Natural Gas Combined Cycle Carbon Capture Retrofit Database.” April 2, 2019.
https://netl.doe.gov/energy-analysis/details?id=2950.
Kuehn, Norma. “Industrial Sources Carbon Capture Retrofit Database.” April 2, 2019. https://netl.doe.gov/energy-
analysis/details?id=2951.
Kuehn, Norma. “Pulverized Coal Carbon Capture Retrofit Database.” April 2, 2019. https://netl.doe.gov/energy-
analysis/details?id=2949.
references
Environmental Protection Agency, "40 CFR Part 63: National Emission Standards for Hazardous Air Pollutants for
[1]
Source Categories," [Online]. Available: http://www.ecfr.gov/cgi-bin/text-
idx?tpl=/ecfrbrowse/Title40/40cfr63_main_02.tpl. [Accessed 5 January 2016].
Environmental Protection Agency, "40 CFR Part 60: Standards of Performance for New Stationary Sources," [Online].
[2]
Available: http://www.ecfr.gov/cgi-bin/textidx?tpl=/ecfrbrowse/Title40/40cfr60_main_02.tpl. [Accessed 5 January 2016].
National Energy Technology Laboratory, "Cost Estimation Methodology for NETL Assessments of Power Plant
[3]
Performance," Department of Energy, Pittsburgh, PA, 2011.
[4]
National Energy Technology Laboratory, "Cost and Performance Baseline for Fossil Energy Plants, Volume 1a:
Bituminous Coal (PC) and Natural Gas to Electricity," Department of Energy, Pittsburgh, 2015.
National Energy Technology Laboratory, "Cost of Capturing CO2 from Industrial Sources – Revision 2," Department of
[5]
Energy, Pittsburgh, PA, 2014.
CARBON CAPTURE TECHNOLOGY SHEETS SYSTEMS ENGINEERING AND ANALYSIS
NATIONAL ENERGY TECHNOLOGY LABORATORY
36 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
Carbon Capture Simulation For technology maturity:
Practical Application of
Industry Impact (CCSI2) Modeling to all TRLs
project focus:
primary project goals Carbon Capture Simulation
The primary project goals are to utilize the computational tools and models developed participant:
under the Carbon Capture Simulation Initiative (CCSI), in partnership with industry, to National Energy Technology
scale-up new and innovative carbon capture technology. The Carbon Capture Simulation Laboratory–Research and
for Industry Impact (CCSI2) operates in conjunction with and in support of the U.S. Innovation Center
Department of Energy’s (DOE) Office of Fossil Energy’s (FE) Carbon Capture Program to
focus on advancing promising technologies. project number:
In 2010, DOE initiated CCSI to help reduce the amount of time that it historically takes to FwP-1022422
develop and scale-up new technologies in the energy sector, which traditionally takes up
to 15 years to move from the laboratory to pre-deployment, and another 20 to 30 years predecessor project:
for mature, industrial-scale deployment. Advanced modeling and simulation is developed 2018 Carbon Capture FwP
and applied to enable more rapid and lower-cost capture technology development at
reduced risk during the commercialization process. NETL project leads:
Parrish Galusky
[email protected]
technical goals
Michael Matuszewski
[email protected]
The team assists the Carbon Capture Program and technology developers by:
• Providing more detailed understanding of capture materials through system
performance under parametric uncertainty. NETL technical portfolio
• Enabling improved designs for high performance and intensified unit operations.
lead:
Benjamin Omell
• Indicating synthesis of processes optimized for novel materials. [email protected]
• Characterizing dynamic system behavior.
• Providing more informed design, operating, and control decisions.
partners:
• Optimizing processes with intrinsic uncertainty.
Los Alamos National
• Providing a framework for intelligent design of experiments at all Technology Laboratory, Lawrence
Readiness Levels (TRLs) for model refinement and system optimization. Berkeley National
Laboratory, Pacific
CCSI2 has released the CCSI Toolset to the public as open-source and continues to
Northwest National
maintain the tools, including document capabilities and instructions for use, as well as
Laboratory, Lawrence
the public repository. In addition, CCSI2 also continues to provide improvements to better
Livermore National
support the Carbon Capture Program. The CCSI2 website can be found at:
Laboratory, Oak Ridge
https://www.acceleratecarboncapture.org/ and the CCSI Toolset is available at:
National Laboratory, west
https://github.com/CCSI-Toolset/.
virginia University, University
CCSI2 is led by the National Energy Technology Laboratory (NETL) and leverages the DOE of Texas-Austin, University of
national laboratories’ core strengths in modeling and simulation. CCSI2 integrates the Toledo, University of Notre
best modeling and simulation capabilities at NETL and complements them with relevant, Dame, University of
world-class expertise at Lawrence Berkeley National Laboratory (LBNL), Lawrence Pittsburgh
Livermore National Laboratory (LLNL), Los Alamos National Laboratory (LANL), Pacific
Northwest National Laboratory (PNNL), and Oak Ridge National Laboratory (ORNL) in
pursuit of the overarching vision of CCSI2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
37
Research and Innovation Center Technologies
technical content
Carbon capture is critical to significantly reducing domestic and global carbon dioxide (CO2) emissions. However, the energy and
capital cost associated with carbon capture systems is prohibitive for deployment. Today’s cost to capture CO2 using state-of-the-
art carbon capture technologies must be reduced to competitive levels more rapidly and at lower risk. FE goals are for technologies
under development to be ready for commercial deployment by 2030 and must be on a pathway to achieve a price of $30/tonne of
CO2 captured, or a reduction in cost of electricity (COE) of a state-of-the-art supercritical pulverized coal plant with carbon capture
and storage (CCS; excluding transportation and storage) by 30%. Balancing capital cost reduction and performance improvements
with a level of CO2 capture meaningful enough to contribute to climate change mitigation is critical in this approach, yet this balance
introduces a great deal of additional complexity. CCSI2, with world-class expertise in process modeling and proven cost-performance
optimization frameworks, is ideally positioned to provide well-informed perspective on the most impactful areas of research and
development (R&D) to most cost-effectively mitigate CO2 in electrical and industrial sectors.
The CCSI2 team provides fundamental analysis, modeling, and optimization of carbon capture technology by working closely with
industry partners. The CCSI2 team efficiently identifies data collection needs, characterizes carbon capture materials, designs and
optimizes devices and processes, and fully propagates uncertainty in model predictions for a complete perspective on model
accuracy.
The work is organized under several tasks, including the Discovery of Carbon Capture Substances and Systems (DOCCSS) Support,
the Computational Support for the Capture Portfolio, and the Open-Source Toolset Community Support.
The DOCCSS Initiative has three projects that explore the integrated development and optimization of devices and systems for the
following transformational concepts:
• LBNL Metal-Organic Framework (MOF) Sorbent Materials
• PNNL CO2-Binding Organic Liquids (CO2BOL)
• LLNL Advanced Device Manufacturing
The Computational Support for the Capture Program task focuses on increasing the impact of R&D across the Carbon Capture
Program by generating and applying computational frameworks to support carbon capture technology research. The subtasks for
this task include:
• Sequential Design of Experiments
• Multi-Scale Modeling and Optimization
• Guiding R&D for Carbon Capture in the Industrial Sector
An Open-Source Toolset Community Support task manages the open-source CCSI Toolset, which was released March 30, 2018. A
centralized open-source repository was created and is maintained to facilitate public access to the CCSI Toolset. Prior to release,
the CCSI computational tools were conditioned and documented to reduce the need for ongoing support of the public release. This
task developed a software and management framework for interoperability of the underlying simulation tools, ongoing
development of the software and management of public tools for CCSI2, and information access (i.e., CCSI2 website management).
technology advantages
CCSI developed and deployed a suite of multi-scale computational tools that find use in multiple carbon capture technology
development applications. Overall, this CCSI Toolset: (1) enables promising concepts to be more quickly identified through rapid
computational screening of processes and devices; (2) reduces the time to design and troubleshoot new devices by using detailed,
device-scale models to better understand and improve the internal behavior of complex equipment; (3) streamlines process design
by using state-of-the-art optimization techniques that focus development on the best overall operating conditions and process
configurations; and (4) provides quantitative predictions of device and process performance during scale-up based on rigorously
validated simulations that take into account model and parameter uncertainty.
With open-source licensing of the CCSI Toolset available, the CCSI2 team is poised to rapidly engage carbon capture technology
developers for direct and widespread support within the Capture Program. Moreover, the CCSI2 team is also currently in multiple
negotiations/agreements with technology developers outside the FE Carbon Capture Program; some are interested in
complementary R&D via Cooperative Research and Development Agreements (CRADAs) for maximum collaborative impact, and
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
38 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Research and Innovation Center Technologies
others are interested in directly funding the CCSI2 team via Contributed Funds Agreements (CFAs) to apply their expertise to specific
problems of interest. Both mechanisms will strengthen CCSI2 capabilities and ability to extend application of the developed
knowledge to future capture technology development efforts.
R&D challenges
Identification and rigorous quantification of scale-up uncertainty and model enhancement to reduce such uncertainties.
status
The tasks of CCSI2 have four thrusts:
1. Provide direct, low-TRL support to the projects awarded under the DOCCSS Initiative. The DOCCSS Initiative integrates
contributions from national laboratory developers and industrial stakeholders to accelerate the commercialization process of
advanced carbon capture materials, requiring a multi-hierarchical characterization that embodies materials through systems-
level performance. Specifically, this work ensures advanced materials development efforts are integrated with advanced systems
design, analysis, and optimization. Work first focused on CO2BOL and MOF-based modeling frameworks to enable multi-scale,
integrated materials and device and process optimization. Work continues to address generalized solvent and sorbent
frameworks for execution year (EY) 2020 and beyond.
2. Develop a formalized Sequential Design of Experiments (SDoE) methodology that strives for data generation at all TRLs that is
optimized for a variety of objectives, including model refinement, process optimization, etc. In EY 2018, this thrust worked
towards developing a methodology to optimize the experimentation required at any scale, maximizing learning while reducing
the time and cost of experimental testing at lab- through pilot-scale. In EY 2019, to reduce time and personnel required to
implement SDoE, the project teams worked to build additional capability for computational Design of Experiments into the
Framework for Optimization and Quantification of Uncertainty and Sensitivity (FOQUS)—a validated computational fluid
dynamics (CFD) model to wetted area in a packed column—which covered computational experimental design, maximizing
learning while reducing the time and computational cost of generating results from computationally-intense simulations;
developed constrained Design of Experiments to consider operational and/or safety restrictions in the Design of Experiments;
and investigated the feasibility of Design of Experiments generation based on output-based requirements. In EY 2020, the
initiative will work to implement dynamic Design of Experiments, which will substantially increase the speed and amount of data
that can be generated at pilot-scale.
3. Inform R&D efforts in projects supported by the Carbon Capture Program through fundamental modeling, analysis, and
optimization, including an Advanced Flash Stripper (AFS) modeling framework capable of rapid design and operational
optimization to minimize COE, and demonstration of an Advanced Process Control (APC) strategy predicted to reduce settling
time by 80%. The efforts expanded in EY 2019 to work on accurate wetted area framework for estimating advanced packing and
generic solvents to inform device performance, as well as the support of large-scale pilots through modeling and uncertainty
quantification. The EY 2020 focus will shift to advance solvent system configurations by developing models for packed-column
intensification and optimization, a framework for techno-economic analysis (TEA) taking into account flexibility of solvent-based
capture systems, and reducing emissions from industrial sources.
4. Prepared and released the full CCSI Toolset to the open domain, namely to complete a fully operational toolset release and
launch of a repository for both open-source and internal CCSI2 modeling products. Then focus shifted to launch of the system
for evaluation, testing, and release management of open-source contributions to the CCSI Toolset. In EY 2020, the project seeks
to improve the toolset for continued Carbon Capture Program support. The CCSI2 team continues to work to develop the
management system as a fully operational open-source community with toolset revision evaluation and distributed toolset
management in EY 2020.
available reports/technical papers/presentations
CCSI2 Website: https://www.acceleratecarboncapture.org.
CCSI Toolset: https://github.com/CCSI-Toolset/.
CCSI2 Publications List: https://www.acceleratecarboncapture.org/publications.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
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NATIONAL ENERGY TECHNOLOGY LABORATORY
40 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
POST-COMBUSTION
SOLVENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
41
Post-Combustion Solvent Technologies
Evaluation of Concentrated technology maturity:
Piperazine for CO2 Capture
Pilot-Scale (0.5 MWe),
Simulated Flue Gas and
from Coal-Fired Flue Gas
Coal-Derived Flue Gas
Slipstream
project focus:
primary project goals Piperazine Solvent with Flash
Regeneration
URS Group, Inc. (URS) investigated the use of a concentrated aqueous piperazine
(PZ) solvent combined with novel solvent regeneration systems to capture carbon participant:
dioxide (CO2) from coal-fired flue gas more economically. Methods for URS Group, Inc.
measurement, generation, and control of amine aerosols were also explored. Pilot
tests and analyses were conducted at the 0.1-megawatt-electric (MWe) scale, and project number:
then scaled to the 0.5-MWe scale for testing at the National Carbon Capture FE0005654
Center (NCCC). Results were used to evaluate the technical and economic
feasibility of a full-scale implementation of this process. NETL project manager:
Bruce Lani
[email protected]
technical goals
principal investigator:
Quantify and demonstrate the robustness of concentrated PZ with coal-fired Gary T. Rochelle
flue gas in an integrated absorption/stripping system with solvent regeneration The University of Texas at
at 150°C. Austin
[email protected]
Optimize equipment design and energy performance for the innovative solvent
regeneration configurations. partners:
Identify and resolve other potential operational and design issues, including University of Texas at Austin,
amine aerosol emissions, process control, corrosion, foaming, and solids Trimeric Corporation
precipitation.
Evaluate the technical and economic feasibility of a full-scale implementation start date:
of this process. 10.01.2010
percent complete:
technical content
100%
URS, in collaboration with the University of Texas (UT) and Trimeric Corporation,
studied the use of concentrated PZ as a solvent for absorbing CO 2 from coal-fired
power plant flue gas. Concentrated PZ has a faster CO2 absorption rate, higher CO2
capacity, lower volatility, and negligible thermal and oxidative degradation
compared with conventional amine solvents. Evaluations of concentrated PZ for
CO2 removal have previously been performed through laboratory investigations,
process modeling, and short-term testing in a 0.1-MWe unit with synthetic flue
gas. Results indicated greater than 90% CO2 capture. This project continued the
development of the PZ-based CO2 absorption process through a series of four test
campaigns at pilot scale to gain operational experience with the solvent in coal-
fired flue gas, while employing a novel, high-temperature flash regeneration
design. The process parameters of the PZ solvent are listed in Table 1.
The project team addressed the project objectives in two phases. In the first phase,
the PZ absorption process was combined with a novel regeneration scheme—a
high-temperature two-stage flash (2SF), shown in Figure 1. This configuration was
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
42 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
installed in UT’s Separations Research Program (SRP) plant and tested at 0.1-MWe scale with synthetic flue gas using PZ
in the SRP plant absorption column.
Figure 1: Diagram of PZ CO2 absorption process with high-temperature two-stage flash.
The results from the SRP test program and the techno-economic analysis (TEA) demonstrated the benefits of using PZ as
a solvent-of-choice for CO2 capture. The results from the SRP test program revealed that 2SF regeneration is a viable
alternative regeneration process to simple stripping; however, the TEA showed only a marginal economic benefit of the
2SF process. Therefore, additional testing at the 0.1-MWe scale was performed on an advanced flash stripper (AFS) (Figure
2) regeneration design to validate a significant reduction in energy requirement and capital cost. The improvement in
energy performance is achieved through use of the cold rich bypass and warm rich bypass streams in the AFS
configuration. Compared to previous campaigns with the 2SF, the AFS reduced the heat duty by more than 25%. Testing
at the SRP plant also confirmed that PZ with a 5 molal concentration is a superior solvent to PZ with an 8 molal
concentration. The reduced viscosity of 5 molal PZ results in an enhanced CO 2 absorption rate in the absorber and
improved heat transfer performance in the cross-exchanger, which reduces heat duty. Combining the 5 molal PZ solvent
with the AFS, as shown in Figure 2, decreases the cost of CO 2 capture to less than $40/tonne.
Figure 2: 5 molal PZ CO2 absorption with the advanced flash stripper.
Since one of the main objectives of this project was to address operational and design issues of the PZ process, the project
team recommended to the U.S. Department of Energy (DOE)/National Energy Technology Laboratory (NETL) that project
resources be allocated toward investigating and solving critical solvent management issues that are common to amine
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
43
Post-Combustion Solvent Technologies
solvents, particularly the formation and control of aerosols. DOE/NETL approved the project team to use the project
resources remaining in Phase I to study aerosol formation in the absorber. Aerosols have been implicated in high amine
emissions from absorbers at several pilot plants. The project team conducted further tests at UT’s SRP facility to investigate
possible mechanisms for aerosol formation and concluded that aerosol and solid precipitation could be managed with 5
molal PZ.
In Phase II, the optimized technology including the AFS and 5 molal PZ was scaled to 0.5-MWe scale for a single test
campaign at the NCCC with coal-fired flue gas. The existing NCCC Pilot Solvent Test Unit (PSTU) system was modified to
change the existing lean solvent storage tank to a rich solvent storage tank. The second bed intercooler was not used,
and the third bed was piped so that it could be used as an additional stage of water wash during a portion of testing.
Testing at the NCCC provided operational experience with PZ in coal-fired flue gas and demonstrated that the AFS process
configuration provides significant improvements in energy performance over the conventional simple stripper (SS)
configuration with PZ and has the potential to improve the energy performance of other solvents. Additionally, the
campaign investigated the effect of flue gas sulfur trioxide (SO 3) concentration on amine aerosol emissions and evaluated
the technology for other operational and design issues, such as the solvent stability, degradation, and corrosion.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 86.14 86.14
Normal Boiling Point °C 146 146
Normal Freezing Point °C 106 106
Vapor Pressure @ 15°C bar 0.000206 0.000206
Manufacturing Cost for Solvent $/kg $60/lb $60/lb
Working Solution
Concentration kg/kg 30% 30%
Specific Gravity (15°C/15°C) — 1.02 1.02
Specific Heat Capacity @ STP kJ/kg-K 3.2 3.2
Viscosity @ STP cP 7 7
Absorption
Pressure bar 0.05 0.05
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.8 0.8
Heat of Absorption kJ/mol CO2 70 70
Solution Viscosity cP 3.2 3.2
Desorption
Pressure bar 6 6
Temperature °C 150 150
Equilibrium CO2 Loading mol/mol 0.44 0.44
Heat of Desorption kJ/mol CO2 70 70
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,662,000
CO2 Recovery, Purity, and Pressure % / % / bar 90% 95% 153
Absorber Pressure Drop bar 0.013
Estimated Absorber/Stripper Cost of __$__
Manufacturing and Installation kg/hr
─
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
44 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO 2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal (PC) power plant, the
total pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2%. Therefore, the partial pressure
of CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H 2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The reaction of PZ with CO2 involves formation of the following four PZ
species:
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
45
Post-Combustion Solvent Technologies
Figure 3: Molecular structure of piperazine species.
These reactions are as follows:
1. PZH+ + H2O ↔ PZ + H3O+
2. PZ + CO2 + H2O ↔ PZCOO- + H3O+
3. H2O + H+PZCOO- ↔ H3O+ + PZCOO-
4. PZCOO- + CO2 + H2O ↔ PZ(COO-)2 + H3O+
TABLE 2: EQUILIBRIUM CONSTANTS FOR ABOVE REACTIONS
ln K = A + B/T + C lnT
Eq. No Equilibrium Constant
A B C
1
-11.91 -4,351 ─
2
-29.31 5,615 ─
3
-8.21 -5,286 ─
4
-30.78 5,615 ─
This speciation and solubility model has been used to predict the partial pressure of CO 2 and mole fraction of species in
solution as a function of PZ loading; the results show a good match between the model and the experimental data.
Solvent Contaminant Resistance – 5 molal PZ is thermally stable at 150°C with negligible oxidative (Freeman, 2011)
degradation. The total amine loss is estimated to be 0.5% per week when stripping at 150°C. At 135°C, the estimated total
amine loss of PZ is 0.3% as compared to 3.0% in the case of an MEA solvent. PZ forms nitrosamines and other nitro
products with nitrogen dioxide (NO2). Both pilot-scale flue gas testing and bench-scale testing have confirmed that
nitrosamines decompose at temperatures of 150°C and greater. The main degradation products of PZ are formate (0.04
mM/hr) and ammonia (0.09 mM/hr) (Freeman, 2011).
Solvent Foaming Tendency – Pilot plant tests of PZ with two different sources of coal-fired flue gas and with air/CO 2
have experienced no persistent problems with foaming. However, bench-scale experiments have shown the possibility
for PZ to foam under certain conditions (e.g., after undergoing oxidation degradation). In the bench-scale tests, foaming
of PZ was greatly reduced with use of an oxidation inhibitor or with use of 1 part per million (ppm) of silicone antifoam
(Chen, 2011).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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Post-Combustion Solvent Technologies
Flue Gas Pretreatment Requirements – Tests at UT’s SRP plant were performed on synthetic flue gas composed of air
and CO2. NCCC tests were conducted on medium-sulfur bituminous coal flue gas cleaned by FGD. Commercial
applications would likely need sulfur oxides (SOX) to be removed to levels below 10 ppm.
Solvent Makeup Requirements – Including an estimate for additional amine lost in the reclaiming process, the required
makeup rate is estimated to be 0.76 kg of 30 wt% PZ per metric ton (MT) of CO 2 captured for PZ regenerated at 150°C.
The estimated makeup rate for 30 wt% MEA at 120°C is approximately 2.0 kg/MT CO 2.
Waste Streams Generated – The major amine solid/liquid waste streams come from reclaimer waste. There could be
fugitive liquid amine emissions, which can be controlled by incorporating seamless valves, rupture disks, closed-loop
ventilation systems, pumps with dual mechanical seals, minimum welds, and correct gasket material selection. Gas-phase
amine emissions from the absorber can be minimized by controlling aerosol formation and aerosol emissions from the
absorber. Gas-phase amine emissions from the stripper can be minimized by controlling temperature of the CO 2 outlet
gas and via operating conditions of the condenser.
Process Design Concept – Flowsheet/block flow diagram shown above in Figure 2.
Proposed Module Design – The design is based on the flue gas assumptions stated above.
technology advantages
As compared to conventional amine solvents, the advantages of PZ are:
Faster CO2 absorption rate, higher working capacity, higher thermal stability, and less oxidative degradation—all of
which point toward 10 to 20% less energy use.
Lower capital costs due to reduced energy use, greater stripper pressure (reduced compressor size), and faster kinetics.
Additional savings in cost of electricity (COE) may be achieved by optimization of absorber packing, flue gas pre-
treating, compressors, heat exchangers, and design improvements realized as part of this project.
R&D challenges
Similar to other amines, PZ may absorb on aerosols in flue gas leading to poor amine collection in the water wash after
CO2 absorption and thus high amine emissions. Aerosol formation needs to be managed.
PZ reacts with dissolved or entrained oxygen (O2) at temperatures exceeding 150°C, potentially leading to greater than
expected solvent makeup, but still less than MEA.
PZ forms as a solid phase with water (PZ • 6H2O) and also with CO2 (H+PZCOO- • H2O). Process robustness to excursions
in CO2 loading, temperature, and water balance is being demonstrated by quantifying their effects on solids
precipitation and plant operation.
status
Testing was conducted on synthetic flue gas at the UT’s SRP facility to investigate CO 2 capture with 5 and 8 molal PZ and
2SF and AFS regeneration designs. The testing showed that the AFS represents an optimized amine regeneration system
with superior energy performance and simple operability over the 2SF or a simple stripper, that 5 molal PZ provides an
economic and operability advantage over 8 molal, and that phase doppler interferometry can provide useful particle size
information on amine aerosol. An extended test campaign resulted in more than 2,000 hours of operation at 0.5-MW
scale on coal-fired flue gas at the NCCC to investigate CO 2 capture with 5 molal PZ and the AFS. The pilot plant testing
verified reliable long-term operation of the novel regeneration technology and solvent combination. Results were used
to evaluate the technical and economic feasibility of the full-scale implementation of this process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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47
Post-Combustion Solvent Technologies
available reports/technical papers/presentations
Chen, E., et al. “Evaluation of Concentrated Piperazine for CO 2 Capture from Coal-Fired Flue Gas,” Final Report, Rev. 0,
March 2019. https://www.osti.gov/servlets/purl/1512446.
Rochelle, G., “Piperazine with Advanced Flash Stripper (AFS): NCCC Pilot Plant Results,” presented at the 2018 NETL CO 2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018. https://netl.doe.gov/sites/default/files/netl-
file/G-Rochelle-UTA-Piperazine-Flash-Regeneration.pdf.
Rochelle, G., “Pilot Plant Testing of Piperazine with Advanced Flash Regeneration,” presented at the 2017 NETL CO 2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-Thursday/G-Rochelle-UTA-Evaluation-of-
Piperazine.pdf.
Rochelle, G., “Pilot Plant Testing of Piperazine with Advanced Flash Regeneration,” presented at the 2016 NETL CO 2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/G-Rochelle-UTAustin-
Piperazine-with-Flash-Regeneration.pdf.
Dombrowski, K., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2015 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/K-Dombrowski-AECOM-Concentrated-
Piperazine.pdf.
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2014 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/G-Rochelle-UTAustin-
Evaluation-Of-Concentrated-Piperazine.pdf.
Nielsen, P. T.; Li, L.; Rochelle, G. T., “Piperazine Degradation in Pilot Plants.” GHGT-11; Energy Proc. 2013.
Fulk, S. M.; Rochelle, G. T., “Modeling Aerosols in Amine-Based CO 2 Capture,” GHGT-11, Energy Proc. 2013.
Fine, N. A.; Goldman, M. J.; Nielsen, P. T.; Rochelle, G. T., “Managing N-nitrosopiperazine and Dinitrosopiperazine,”
presented at GHGT-11 Kyoto, Japan. November 18–22, 2012. Energy Procedia, 2013.
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2013 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2013. https://netl.doe.gov/sites/default/files/event-
proceedings/2013/co2%20capture/G-Rochelle-UTA-Concentrated-Piperazine-for-CO2-Capture.pdf.
Madan, T.; “Stripper Configurations and Modeling for CO 2 Capture Using Piperazine.” M. S. Thesis. The University of
Texas at Austin, May 2013.
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2012 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2012. https://netl.doe.gov/sites/default/files/event-
proceedings/2012/CO2%20Capture%20Meeting/G-Rochelle-UT-Austin-Piperazine.pdf.
Sexton, A., “Evaluation of Concentrated Piperazine for CO 2 Capture from Coal-Fired Flue Gas,” presented at the 2011
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2011.
https://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/23Aug11-Sexton-Trimeric-Concentrated-
Piperazine-for-CO2-Capt.pdf.
Freeman, S.A., “Thermal Degradation and Oxidation of Aqueous Piperazine for Carbon Dioxide Capture,” Ph.D. Thesis,
University of Texas at Austin, May 2011.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
48 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Dombrowski, K., “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” presented at the
2010 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, September 2010.
https://netl.doe.gov/projects/files/Katherine-Dombrowski---URS-Corporation.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
49
Post-Combustion Solvent Technologies
UKy-CAER Heat-Integrated
technology maturity:
Large Pilot-Scale, Actual
Transformative CO2 Capture Flue Gas (10 Mwe)
project focus:
Process for Pulverized Coal Transformative Process Using
Power Plants
Advanced Solvents, Heat
Integration, and Membrane
Separation
primary project goals participant:
University of Kentucky
The University of Kentucky Center for Applied Energy Research (UKy-CAER) Research Foundation
team is developing a post-combustion carbon dioxide (CO2) capture technology project number:
using advanced solvents and incorporating innovative heat integration methods to
utilize heat typically rejected to the environment via a two-stage solvent FE0031583
regeneration configuration, thereby ultimately improving power plant efficiency. predecessor projects:
UKy-CAER has prepared a pre-front-end engineering design (pre-FEED) study for FE0007395
a 10-megawatt-electric (MWe) large pilot plant (FE0026497) based on the FE0012926
technology demonstrated at the 0.7-MWe scale. FE0026497
UKy-CAER is performing the design, construction, and operation of a 10-MWe NETL project manager:
capture system based on the UKy-CAER heat-integrated transformational CO2 Isaac Aurelio
capture technology at a coal-fired power plant. Phase I has been completed and [email protected]
consisted of: (1) selection of a host site for Phases II and III; (2) creation of Aspen
Plus® model simulation; (3) completion of an environmental information volume principal investigator:
(EIV); and (4) determination of Phase II team and cost-share commitments. Phase Kunlei Liu
II efforts are underway, consisting of a detailed FEED study, National University of Kentucky
Environmental Policy Act (NEPA) permitting and documentation, and Phase III [email protected]
cost-share commitments. If selected for Phase III, the project will support
construction and operation of the large-scale pilot facility. The Fossil Fuel Large- partners:
Scale Pilots effort supports the design, construction, and operation of large test Carbon Clean Solutions,
facilities for transformational CO2 capture technologies aimed at enabling step- USA (CCSUS), Smith
change improvements in coal-powered system performance, efficiency, and cost Management Group (SMG),
of electricity (COE). Carbon Management
Research Group (CMRG),
Electric Power Research
technical goals
Institute (EPRI), Huaneng
Clean Energy Research
Phase I objectives were to: Institute (HCERI), Koch
• Reinforce the formation of a cohesive project team covering technology Modular Process Systems
development; solvent development; environmental, health, and safety (EH&S); (KMPS), worley, Membrane
engineering design, fabrication, and construction management; technology Technology Research (MTR),
commercialization; and end-user utilities. University of Texas at Austin
(UTA), Trimeric Corporation,
• Select and secure a host site and carbon capture system location.
Louisville Gas and Electric
• Update heat and material balances with the most recent small-scale and Kentucky Utilities (LG&E
experimental data and chemical composition to complete and improve and KU), Integrated Test
accuracy of an EIV and process design package for the proposed UKy-CAER Center (ITC), Carnegie
CO2 capture technology, including the cost and schedule. Mellon University (CMU)
• Secure commitments from an engineering design firm, NEPA contractor,
technology partners, and vendors. start date:
• Update preliminary costs and schedules for Phases II and III. 04.01.2018
• Secure commitments for Phases II and III cost share. percent complete:
55%
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
50 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Phase II objectives are to:
• Complete a FEED study for the proposed large-scale pilot, including a detailed cost and schedule estimate for Phase
III for the installation of the 10-MWe pilot at the host site, followed by commissioning, start-up, testing, operations, and
data collection for performance validation.
• Complete the NEPA process at the host site.
• Submit permitting documentation to appropriate authorities and obtain the air permits for the steam generator and
carbon capture system units.
• Document secured cost share for Phase III.
• Secure commitments for all necessary Phase III team members, including an engineering, procurement, and
construction (EPC) vendor or equivalent to complete construction.
• Update the techno-economic analysis (TEA) for the UKy-CAER technology integrated with a 550-MWe net
supercritical pulverized coal power plant based on the most recent system design and cost information.
technical content
UKy-CAER’s four-pronged CO2 capture approach that includes process intensification, two-stage solvent regeneration,
heat integration, and an advanced solvent has evolved over a series of projects in recent years. Currently, the proposed
capture process system incorporates several energy-saving and performance-increasing features, among which the most
notable are as follows:
• A two-stage solvent regeneration configuration, consisting of a steam-driven, first-stage primary stripper removing
most of the CO2, followed by a secondary stage designed as an air stripper powered by recovered heat from the
carbon capture system block, CO2 compressor intercoolers, and the primary stripper overhead stream. The two-
stage stripping reduces the carbon loading in the lean solvent to very low levels, and the exiting CO2-laden air is fed
into the boiler as secondary combustion air to boost CO2 concentration at the absorber inlet. The system integration
and heat recovery scheme has been demonstrated through experimentation and simulation. The secondary stripper
also provides direct cooling to the lean solution returning to the absorber, significantly reducing the duty of the
indirect-cooled lean solvent polishing exchanger; therefore, the additional capital cost of the second stripping column
is offset by heat exchanger and cooling tower savings. Another advantage of the two-stage solvent regeneration
scheme is that ion-free water carried by saturated air from the up-stream water evaporator is added to the solvent
loop in the secondary stripper, eliminating the complexity, equipment, chemicals, and power needed to produce de-
ionized water for amine loop makeup.
• Applied process intensification technologies, including:
o Three discrete packing sections in the absorber with random packing included as in-situ gas-liquid distributors
at every 5 to 10 feet of structured packing for high volumetric effectiveness and less gas-liquid channel flow.
o Membrane CO2 pre-concentration prior to the absorber inlet applied as needed to boost carbon loading in the
rich solvent. Outputs from membrane consist of retentate enriched in CO2 and permeate depleted in CO2.
These two flue gas streams are introduced at different levels in the absorber column, with the lean stream
injected higher in the column where fresher solvent is present, and the rich stream injected farther down.
o A split rich feed to the primary stripper to reduce the reboiler steam requirement and decrease the water
content in the exit gas stream. The rich amine stream is split with a portion being heated to ~175 to 180°F
(solvent- and stripping-dependent), and fed to the top of the stripper packing, acting as a heat sink to condense
the water vapor and reduce the exit gas water (H2O)/CO2 ratio. The remaining rich flow is further heated to
220 to 239°F past the vaporization point, and two-phase flow is fed to the middle of the stripper packing, acting
as a second source of carrier gas for CO2 stripping.
o Extracted steam exergy loss minimization through splitting of the feed water after the boiler feed water pump
into two streams. While the main portion of the feed water maintains the normal flow path, 20 to 25% of the
flow is heated to the same parameters as the boiler economizer in a split, last-stage feed water heater powered
by steam extracted for the carbon capture system reboiler.
o Solids incorporated in the absorber exit gas wash stream to minimize solvent entrainment and aerosols. By
adding particles (up to 2 wt%) within the water wash stream, the solvent emission at the exhaust of the solvent
recovery system is demonstrated to be less than the instrument detection limit.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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51
Post-Combustion Solvent Technologies
• Has been demonstrated with various advanced solvents at the bench- and pilot-scales. Notably, the commercial
Hitachi H3-1 and Carbon Clean Solutions, USA (CCSUS) CDRMax solvents have been under investigation and
have figured prominently in small-pilot testing. Corporate restructuring has resulted in H3-1 becoming commercially
unavailable, but CCSUS is partnering with UKy-CAER at the large-pilot scale. To balance the cost of commercial
solvents and the gain in performance benefits, the advisable approach to solvent development focuses on striking a
good balance of moderate solvent cost with CO2 absorption performance and kinetics, including, but not limited to,
cyclic capacity, solvent emissions, and degradation. This can be achieved by blending amines that are functionalized
to prevent the formation of nitrosamine, and using additives with catalytic kinetic function and inhibitors to reduce
solvent degradation and corrosion.
• Advanced process controls; UKy-CAER has developed two computing blocks, integrated with process control
software such as Emerson DeltaV, to determine the alkalinity and carbon loading of the solvent first by using
conventional instrumentation such as temperature and density signals, and then to manipulate the most effective
control variables, such as lean solution circulation rate, lean loading, and liquid/gas temperature, in prompt response
to external changes while ensuring minimum stream extraction is maintained.
Figure 1 depicts the general process arrangement of the UKy-CAER technology (most of these features are depicted
here).
Figure 1: UKy-CAER carbon capture system process flow diagram.
Note: Black oval indicates the CO2 pre-concentrating membrane unit investigated in FE0012926, which is not included in the large-pilot carbon
capture system.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
52 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
UKy-CAER’s Advanced Solvents
UKy-CAER solvent development focuses on low-cost, enhanced CO2 absorption kinetics; low emissions; and low
degradation, considering both chemical and physical properties and the interactions between amine components of
solvent blends and the additives. The overwhelming majority of research and development (R&D) in CO2 capture solvents
has focused on the amine chemistry, with little thought to the impact of additives on gas-liquid interface characterization.
Understanding the impact of additives on key solvent properties – including surface tension and elasticity, wettability, and
whether these impacts play a significant role in CO2 capture characteristics such as adsorption rate, degradation, and
aerosol formation – are an important focus of R&D in this context.
The UKy-CAER novel catalytic amine solvents utilize organometallic homogeneous catalyst chemistry to enhance CO2
absorption kinetics. Mass transfer rate increases of 15 to 40% are possible by using a catalytic advanced amine solvent
over an uncatalyzed amine solvent, resulting in more efficient absorption of CO2, increased rich stream CO2
concentration, and decreased absorber size requirements. Improved solvent thermal stability allows the solvent to be
used in the high-temperature stripper conditions utilized in this process. Additional improvements from the catalytic
solvent include increased cyclic capacity, reduced solvent loss and makeup requirements, and lower energy regeneration
demand.
UKy-CAER designates catalytic solvents currently under investigation with codes to maintain confidentiality, reflecting
permutations of proprietary commercial amine solvents (Solvent A, Solvent B, etc.). One of the solvents much
investigated of late is CAER-B3.
Discretized Packing in Absorber
For any advanced solvent, the absorber temperature bulge typically occurs 10 to 15% from the top of a uniformly packed
section when operated under a low liquid/gas ratio. UKy-CAER bench experimental data has shown that with a discretized
packing arrangement, the temperature profile is modified, moving the bulge down the column and resulting in a 5 to 11%
increase in rich loading for the same heights of packing, depending on the solvent lean loading. With an ideal column
temperature profile, significant CO2 absorption rate improvements (2 to 4x) will result in a small absorber (25 to 50% size
reduction).
Pressurized Primary Stripper with Split Rich Solvent Feeds
UKy-CAER developed a rich solvent split configuration using the traditional lean/rich heat exchanger with one additional
warm rich solvent extraction port. During operation, up to 50% of the total rich flow is extracted at a temperature of
approximately 170°F (solvent- and stripping-dependent) and fed to the top of the stripper packing. This acts as a heat
sink to condense the water vapor and reduce the exit gas H2O/CO2 ratio. The remaining rich flow is further heated past
the vaporization point and a two-phase flow, with 5 to 6% vapor concentration, enters the middle of stripper packing at a
temperature of 220 to 239°F depending on stripper pressure and solvent properties. The produced vapor acts as a second
source of carrier gas for CO2 stripping. Combined with solvent regeneration under pressure, UKy-CAER modelling results
indicate the H2O/CO2 ratio in the stripper exhaust is significantly reduced from conventional 0.8 to 1.0, to 0.3 to 0.4 at 45
pounds per square inch (psi) stripper pressure, resulting in a steam consumption reduction of ~26%. This feature, in
combination with CO2 recycling, will result in a reboiler-specific energy of 950 British thermal units (Btu)/lb (2.2 gigajoules
[GJ]/tonne) CO2 captured for advanced solvents.
CO2 Pre-Concentrating Membrane
Experimental results show that using a CO2 pre-concentrating membrane to split the absorber gas feed into two streams
(the permeate stream, with an enriched CO2 concentration of 30 vol %, and the rejection stream, with a CO2 concentration
of ~10 vol %) yields a 30% energy savings compared to the conventional non-membrane configuration. Figure 2 shows
the membrane separator for enriching CO2 in the flue gas, and an actual polymeric membrane unit produced by
Membrane Technology and Research (MTR), which was used in pilot-scale testing.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
53
Post-Combustion Solvent Technologies
Figure 2: MTR CO2 pre-concentrating membrane, internals on left and housing on right.
Membrane-Based Dewatering of Rich Amine Solvent
Related bench-scale project work (FE0012926) has extended the technology to include a membrane dewatering unit
installed in the solvent rich stream. This feature is an integrated membrane concentrator unit intended to provide
dewatering of the CO2-rich amine solvent/solution exiting from the CO2 absorber, either before or after the lean/rich heat
exchanger. The membrane separator would selectively permeate water from the stream for recycle to the absorber
through a zeolite-based membrane, as shown in Figure 3, effectively concentrating the CO2-rich stream and increasing
the CO2 partial pressure, which can further reduce process energy demand. This membrane should be designed to
maximize water permeability and carbon/amine rejection while maintaining stable performance over time. UKy-CAER
has investigated zeolites as the material of choice for this membrane. Currently, given the membrane surface area
required and the high cost of zeolite membranes, it is not practical to include it in process scenarios as envisioned.
However, through the use of lower-cost hollow fiber support materials and increasing the packing density of the active
membrane surface area up to >200 m2/m3, the economics of this enrichment process can be improved. In addition,
through modifications to the active membrane layer and the permeability of the support layer, water flux through the
membrane can be enhanced to further reduce the cost and implementation of this system in a CO2 capture process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
54 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 3: Solvent membrane dewatering for CO2 enrichment.
Findings from Slipstream Testing
Small pilot testing at 0.7 MWe has been performed at the Kentucky Utilities E.W. Brown Generating Station in
Harrodsburg, Kentucky, using a process configuration including much of the scheme depicted in Figure 1. Performance
of the capture system was baselined using a generic 30-wt% monoethanolamine (MEA) solvent to obtain data for direct
comparison with the National Energy Technology Laboratory (NETL) Reference Case 10 (RC10). Also, Hitachi’s
proprietary solvent H3-1, CCSUS’ proprietary solvent CDRMax, and the CAER blended solvent were tested. Parametric
test campaigns, system transient dynamic studies, and long-term continuous verification tests of the heat integration
process enabled characterization of the system response in terms of load-demand following, varying flue gas conditions,
and individual component operation. Evaluation of solvent degradation, process emissions, and corrosion studies of
materials in the circulating solvent were accomplished. See below, and also in the Other Parameters section following
Table 2 for findings in these areas. Data were collected to support a full techno-economic and EH&S analysis for a 550-
MW commercial-scale carbon capture plant.
Notable findings are as follows:
• The process can easily capture 90% of CO2 in flue gas using either MEA, H3-1, CDRMax, or CAER solvent as the
working capture solvent.
• MEA solvent regeneration energy was determined to be 1,200 to 1,750 Btu/lb CO2 captured, ~13% lower than RC10.
• H3-1 solvent regeneration energy was determined to be 900 to 1,600 Btu/lb CO2 captured,~36% lower than RC10.
Overall, low-regeneration energies are possible over a range of solvent concentrations.
• CDRMax solvent regeneration energy was determined to be 1,150 to 1,400 Btu/lb CO2 captured,~8 to 25% lower
than RC10.
• The secondary air stripper is capable of regenerating >10% of the CO2 captured, as depicted in Figure 4. At the
commercial scale, the exhaust CO2-laden air (8 to 12 vol% CO2, dry) will be recycled back to the boiler as combustion
secondary air, yielding a higher absorber inlet CO2 concentration (15 to 17 vol%), which has been observed to
always correspond to a low-solvent regeneration energy.
• A high rich carbon loading (2.3 to 2.4 mol/kg solution), corresponding to a low-solvent regeneration energy, can be
achieved with a pump around to the bottom section of the absorber packing with assistance of interstage cooling.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
55
Post-Combustion Solvent Technologies
Figure 4: UKy-CAER secondary air stripper CO2 regeneration.
• Varying ambient conditions have an impact on CO2 capture, attributable to cooling water temperature variations that
impact the capture system process stream temperatures at any point where heat exchange with cooling water is
involved, including flue gas temperature, lean solvent return, and absorber interstage cooling.
• Adequate absorber liquid/gas distribution is required to maintain high absorber efficiency.
• Lean/rich exchanger performance is critical to the energy efficiency of the cycle: if the approach temperature in the
exchanger is not kept low, the efficiency suffers. This is depicted in Figure 5, showing that an increase in approach
temperature to 35°F from 20°F increases the solvent regeneration energy demand by about 400 Btu/lb CO2.
Figure 5: Effect of lean/rich heat exchanger approach temperature on solvent regeneration energy demand.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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• Use of deionized water for makeup is not necessary in the UKy-CAER two-stage stripping technology when
scrubbing coal combustion flue gases, helping to reduce the cost and complexity of constructing and operating CO2
capture systems. The measured accumulation of chloride from the service water and heat-stable salt (HSS)
contaminants from coal flue gas is depicted in Figure 6. While elemental accumulation in the solvent still needs to
be monitored, this shows that the majority of accumulating contaminants originate in the coal flue gas, not the service
water source. Because accumulating species can cause various deleterious impacts, including solvent degradation
and loss of absorption performance, corrosion of materials in the process circuit, etc., this is an area to continue
investigating in future technology scale-up.
Figure 6: Accumulation of contaminants in solvent.
• Process emissions in the scrubbed flue gas from solvent degradation (as ammonia) were found to be related to
increasing iron content in the solvent from corrosion, as depicted in Figure 7. Corrosion and solvent degradation can
be controlled by adding a proprietary multi-functional additive to the solvent. Figure 8 shows that when the multi-
functional additive concentration in the solvent is above the operating level of 100 parts per million (ppm), the
ammonia emissions are low, but when the additive is depleted, solvent degradation and ammonia emissions
increase.
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Figure 7: Ammonia emissions and iron.
Figure 8: Ammonia emissions versus additive in the solvent.
Techno-Economic Analysis Findings
The preliminary TEA conducted and experimentally validated under FE0007395 shows that application of the improved
process cycle (with MEA as the solvent) would reduce the COE by about 8% over the conventional 90% capture case,
and that use of H3-1 in the improved process cycle would reduce COE 12%. The TEA was updated to include discretized
packing for absorber temperature control, a solids-incorporated solvent recovery system, split rich primary stripper feeds
to reduce H2O/CO2 ratio in the stripper outlet, and de-superheating the carbon capture and storage (CCS) extracted
steam with a feed water heater. In this case, the overall reduction in COE is 19%. Figure 9 shows that the cost of CO2
capture (excluding transportation, storage, and monitoring) is reduced from $56.52 to $34.51 per tonne of CO2 captured,
a reduction of 38.9% with coal being the sole energy source. The cost of CO2 capture could be further reduced to $25.26
per tonne of CO2 captured when all auxiliary electricty and steam required for the carbon capture system are from natural
gas-fuel by taking advantage of the low capital cost of natural gas combined electricity and heat unit.
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Figure 9: Cost of CO2 capture estimates from techno-economic analysis.
However, additional cost reductions will be necessary to attain ultimate U.S. Department of Energy (DOE) program
targets. For this, UKy-CAER estimates that a combination of a further-improved third-generation solvent will be critical,
combined with absorption enhancement technologies via optimal absorber temperature profile and gas-liquid interface
mixing. To illustrate the issue, the current second-generation solvents are simply too expensive compared to conventional
MEA, as shown in Table 1 (Solvent B is 10 times the cost of MEA on a unit basis). In these cases with solvents A and B
being commercially available, the energy savings are less than the additional solvent makeup cost.
TABLE 1: SOLVENT COST COMPARISON
30 wt% MEA Solvent A Solvent B
Make-up Rate (kg/ton CO2) 1.5 0.5 0.5
Energy Consumption Compared to 30 wt% MEA 30% less 40% less
Unit Cost ($/kg) 1.5 9 15
Solvent Cost ($/tonne CO2 Captured) 2.25 4.5 7.5
COE ($/MWh) 106.5 93.3 91.2
TABLE 2: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 <90 <90
Normal Boiling Point °C 160–165 160–220
Normal Freezing Point °C -2 -2–5
Vapor Pressure @ 15°C bar 6.3x10-4 6.3x10-4-6.3x10-3
Manufacturing Cost for Solvent $/kg 4–6 (estimated) 3–5
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Post-Combustion Solvent Technologies
Working Solution
Concentration kg/kg <0.4 <0.45
Specific Gravity (15°C/15°C) - 1.01 1.01
Specific Heat Capacity @ STP kJ/kg-K 3.7 3.7
Viscosity @ STP cP 3.04 3.5
Surface Tension @ STP dyn/cm <55 <55
Absorption
Pressure bar 1 1
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.42 0.51–0.65
Heat of Absorption kJ/mol CO2 74 <60
Solution Viscosity cP 4.88 8-10
Desorption
Pressure bar 3.1 3.0
Temperature °C 125 120
Equilibrium CO2 Loading mol/mol 0.23 0.30
Heat of Desorption kJ/mol CO2 84 <75
Proposed Module Design (for equipment developers)
Flue Gas Flowrate @ 10 MWe equivalent kg/hr 43,000
CO2 Recovery, Purity, and Stripper Pressure %/%/bar 90 99.9 3.0
Absorber Pressure Drop bar <0.1–0.15
Estimated Absorber/Stripper Cost of __$__
~200
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Surface Tension – The tension of the surface film of a liquid caused by the attraction of the particles in the surface layer
by the bulk of the liquid, which tends to minimize surface area. This is measured in force per unit length (dyn/cm).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
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pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted otherwise, flue gas pressure, temperature, and composition leaving the flue
gas desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The absorption reactions for any amine-based system can be broken into
two primary reactions, as depicted in Figure 10. The absorption of CO2 is primarily dictated by the reactions of primary
amine (SC) to form carbamates. The reaction second order rate constant for these species can vary, but is generally on
the order of (103 l/mol·s), with similar rate constants observed for CAER-B3. The SC reaction generates a mole of proton
for each mole of CO2 capture, leading to primary amines being generally limited on a molar basis to 0.5 CO2:1N. The
CAER-B3 amine solvent utilizes a primary amine as the main component. Additionally, another minor component is
added to the solvent to principally act as a proton receiver (PC) in the solution to balance the bicarbonate formation. The
pKa of this proton receiver is higher (more basic) than that of the main component. The reaction from the proton receiver
to directly form bicarbonate is much slower (100x). It is expected to function similarly to those enzymes in directly
catalyzing the reaction of dissolved CO2 in solution to form bicarbonate. A third reaction to form bicarbonate directly from
hydroxide present in solution can generally be excluded from consideration despite the fast rate constant (104 l/mol·s)
because hydroxide concentration is limited by the base dissociation constant in typical amine solutions (<1 x 10-4).
Figure 10: Schematic for reactions occurring in the CO2 capture cycle.
Solvent Contaminant Resistance – The CAER-B3 solvent shows behavior analogous to MEA towards oxidation and
flue gas components. Similar levels or less of oxidation and degradation due to flue gas components are anticipated.
Solvent Foaming Tendency – The addition of anti-foam to solvent can help control foaming tendencies by lowering the
solvent surface tension. Any new solvent additive will need to be evaluated for its foaming potential and any that may
increase foaming tendency should be avoided. The CAER-B3 solvent has very low foaming tendencies (less than 30%
MEA) due to a low surface tension of <40 dyn/cm.
Flue Gas Pretreatment Requirements – At the UKy-CAER bench-scale CO2 capture facility, flue gas from the boiler
goes through a solid separator where particulate matter is initially removed before being treated in a wet desulfurization
process to lower sulfur dioxide (SO2) concentration typically below 100 ppm using conventional limestone-based wet flue
gas desulfurization (WFGD). After SO2 removal, the flue gas goes through a knock-out drum for final particulate and
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liquid droplet removal before it is sent to the CO2 capture unit. In practice, power generation flue gas exiting from existing
environmental controls is further polished to below 10 ppm SO2 through an additional pretreatment step to slow the
accumulation of sulfate in the solvent. Sulfate is an HSS, meaning it cannot be thermally removed from the solvent. Its
accumulation will slowly reduce the CO2 capture capacity of the solvent.
Solvent Makeup Requirements – Long-term stability is an ever-present concern of all solvent developers. The CAER
solvent is composed of amines that are inherently more stable than MEA and has a higher thermal stability than MEA.
As seen in Figure 11, a 50 to 70% decrease in rate-of-amine loss as a percent of initial is observed at the high
temperatures associated with stripper conditions over a two-week period. Regression of the data compared to reference
MEA predicts a thermal degradation rate similar to MEA at a 10°C higher stripper operating temperature. It is expected
that the makeup requirements will be similar to that of MEA under the proposed process conditions of a higher stripper
temperature/pressure.
Figure 11: Rate of amine loss as total percent amine under stripper conditions of 30 wt% MEA (blue) and various combinations of CAER-
B3.
Waste Streams Generated – The waste streams generated from the process are the spent soda ash solution and CAER-
B3 solvent, used for SO2 removal and the absorption of CO2, respectively. The loss of performance and how quickly the
solvent is spent is impacted by the rate of degradation and HSS formation in the solvent. In practice, the solvent will be
treated in a thermal reclaimer to remove HSSs and metal species, which will also produce a waste that is likely hazardous
in nature.
Process Design Concept – The process flow is shown in Figure 1. In brief, the SO2-polished flue gas (from the
pretreatment tower) enters the CO2 pre-concentrating membrane to produce two streams that are injected into the CO2
absorber at separate locations. After gaseous CO2 is converted into aqueous carbon species, the carbon-rich solution
exits the absorber bottom, is pressurized, and sent to the rich-lean solution heat exchanger (Crossover HXER) with split
rich outlets to primary stripper or the hot rich stream from lean/rich heat exchanger entering to the dewatering membrane
unit for solution pre-concentration, which is not shown in Figure 1. The permeate stream of the dewatering membrane
unit with low amine concentration combines with the regenerated lean solution stream exiting at the outlet of the stripper.
The reject stream, which has higher carbon loading than the feed stream, is sent to the middle of pressurized stripper for
solvent regeneration. This stage will require an energy source to drive the reboiler. At the stripper exit, the gas stream
consists primarily of CO2 and water vapor at a pressure of approximately 3 bar. After exiting the heat recovery unit at the
top of stripper, the CO2 gas stream has a purity of 99.9% and will be pressurized to about 135 bar and intercooled for
downstream utilization or storage. The carbon-lean solution exiting the primary stripper is sent to the Crossover EHX,
where heat will be recovered with the carbon-rich solution. After the Crossover EHX, this heat depleted stream will be
cooled to approximately 40°C and recycled to the absorber.
technology advantages
• The two-stage stripping unit, including the deployment of an air-based secondary stripper, will regenerate an
exceptionally CO2-lean solvent, increasing the rate of CO2 absorption and solvent cyclic capacity, will eliminate the
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need for deionized water for amine loop makeup, and will provide a direct cooling effect on lean solvent prior to
returning to the absorber.
• Low capital cost resulting from a discretized packing arrangement and in-situ gas-liquid distribution to minimize the
liquid maldistribution.
• High system efficiency resulting from carbon capture system internal heat integration, rich solvent split to the primary
stripper, and de-superheating extracted steam by splitting the feed water.
• The solvent recovery column, at the outlet of the gas stream leaving the CO2 absorber, with solid particle assistance
to minimize the solvent emissions, minimizing solvent makeup requirements.
• The advanced solvent used in this system has: (1) a higher mass-transfer flux; (2) a higher net cyclic carbon capacity;
(3) less energy demand for CO2 stripping; and (4) lower corrosion rates than a 30 wt% MEA solution, leading to
lower capital and operational costs.
• The advanced solvent also has a 15 to 20% lower degradation rate compared to 30 wt% MEA, leading to lower
solvent makeup volume.
• Potential for reduced capital cost for post-combustion CO2 capture, chiefly through increased absorption kinetics
that allow for a smaller absorber and regeneration columns coupled with a lower solvent circulation rate and smaller
associated equipment (blowers, pumps, and piping systems).
• Potential for reduced energy consumption compared to conventional MEA-based scrubbing, chiefly attributable to:
o High cyclic capacity.
o High stripper pressure: the primary CO2 stripper can be operated at approximately 3 bar in order to maximize
the energy benefit while minimizing system capital and solvent degradation, which could lead to low
compressor capital and operating costs.
o Heat integration to power air-based secondary stripper.
R&D challenges
To achieve the targets set forth by DOE/NETL, several R&D challenges remain to be met.
• Due to the low CO2 absorption driving force in utility flue gas and the highly viscous nature of second-generation +
solvents, the low-pressure drop structured packing suffers from a lack of macro-mixing/turbulence between the bulk
solvent and the gas-liquid interface, which results in localized channel flow and significantly reduces column
effectiveness. The application of short sections (3 to 6 inches) of high-pressure drop random packing could re-adjust
the pressure and redistribute the liquid within a section of structured packing.
• Two-stage solvent regeneration has been successfully demonstrated at the small pilot scale, but intensification in
the absorber and strippers can be applied to reduce the column height and steam requirement.
• The UKy-CAER solvent recovery from the absorber exit gas stream has been demonstrated at lab, bench, and pilot
scale.
• Use of a CO2 pre-concentrating membrane in the absorber flue gas feed has been demonstrated at bench scale,
and been tested at the pilot scale.
• Implementation of a smart process control scheme needs to be demonstrated to reduce the solvent regeneration
energy while also responding quickly to the dynamic load and ambient conditions.
• Waste minimization techniques need to be demonstrated at the large pilot scale. Accumulation of elements such as
selenium (Se) and arsenic (As) in the CO2 capture solvent can result in a hazardous classification of the material.
• The relationship between thermal compression and lean/rich heat exchanger size needs to be understood and
included when reporting solvent and process performance. It is generally accepted that the stripper is equilibrium-
controlled, and in-situ thermal compression via high-temperature operation will drop the H2O/CO2 ratio at the stripper
outlet, lowering the specific reboiler duty. The 0.7-MWe small pilot experimental data indicate this holds true only for
systems with a relatively large lean/rich heat exchanger (low ΔT between hot lean from stripper and hot rich to
stripper).
• Long-term, low-cost advanced solvent performance needs to be demonstrated. While several solvents are currently
in use at the commercial scale, they are costly, and improved performance may not justify this cost.
• Lower-cost corrosion-resistant materials of construction need to be demonstrated. In general, most amine solvents
have the tendency to corrode metal surfaces, especially in high carbon loading and/or high temperature locations.
Sections of the CCS that are specifically impacted are the absorber bottom, lean/rich heat exchanger, and the top
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of the stripper. Currently, most CCS systems deployed in the utility environment use stainless steel for locations
where wetted surfaces are expected, while some are using concrete with a plastic/polymer or ceramic liner for the
CO2 absorber, which results in a higher capital investment.
status
Small pilot-scale (0.7-MWe) testing results and identification of process improvements have shown the promise of UKy-
CAER’s process-intensified and heat-integrated post-combustion CO2 capture technology to attain DOE program goals.
Additional advancement to meet ultimate performance and cost goals will rely on identification of a third-generation
advanced solvent that can be produced at reasonable cost, and subsequent large-pilot demonstration at the proposed
10-MWe plant scale.
UKy-CAER is designing a pilot-scale (10-MWe) post-combustion carbon capture system for installation at the Wyoming
Integrated Test Center (ITC). The ITC is located at Basic Electric Power Cooperative’s Dry Fork Station near Gillette,
Wyoming, wherein flue gas from the plant is diverted to the testing facility. In Phase I, Wyoming ITC coal-fired power
plant in Gillette, Wyoming, was selected as the host site for the large capture pilot and cost-share commitments were
finalized. Preliminary engineering and cost estimates were prepared for the equipment inside the battery limit (ISBL) and
outside the battery limit (OSBL). A NEPA contractor was also selected as part of the Phase I effort. A plan was developed
for securing cost-share commitments for Phase III. Phase II efforts are underway and will conclude with completion of a
FEED study, NEPA process, permitting documentation, and team member commitments.
available reports/technical papers/presentations
FE0031583
Liu, K., et. al., UKy-CAER Heat-integrated Transformative CO2 Capture Process in Pulverized Coal Power Plants,”
presented at the 2019 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/K-Liu-UKY-CAER-Heat-Integrated-Capture_r1.pdf.
Nikolic, H., et. al., “UKy-CAER Heat-integrated Transformative CO2 Capture Process in Pulverized Coal Power Plants,”
presented at the 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://netl.doe.gov/sites/default/files/netl-file/H-Nikolic-UKCAER-Heat-Integrated-CO2-Capture.pdf.
“UKy-CAER Heat-integrated Transformative CO2 Capture Process in Pulverized Coal Power Plants,” Project kickoff
meeting presentation, May 2018. https://www.netl.doe.gov/project-information?p=FE0031583.
FE0007395
Nikolic, H., et. al., “Application of a Heat Integrated Post-Combustion Carbon Dioxide Capture System with Hitachi
Advanced Solvent into Existing Coal-Fired Power Plant,” presented at the 2019 NETL CO2 Capture Technology Project
Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/H-Nikolic-UKY-CAER-
Integrated-Postcombustion-Capture.pdf.
Thompson, J., et. al., “Application of a Heat Integrated Post-Combustion Carbon Dioxide Capture System with Hitachi
Advanced Solvent into Existing Coal-Fired Power Plant,” presented at the 2018 NETL CO2 Capture Technology Project
Review Meeting, Pittsburgh, PA, August 2018. https://netl.doe.gov/sites/default/files/netl-file/J-Thompson-UKCAER-
Heat-Integrated-Post-Combustion-Capture.pdf.
Wei Li, James Landon, Bradley Irvin, Liangfu Zheng, Keith Rugh, Liang Kong, Jonathan Pelgen, David Link, Jose D.
Figueroa, Jesse Thompson, Heather Nikolic, Kunlei Liu. “Use of Carbon Steel for Construction of Post-Combustion CO2
Capture Facilities: A Pilot-Scale Corrosion Study,” Industrial & Engineering Chemistry Research. 56. 16. 4792-4803.
2017.
Jesse G. Thompson, Megan Combs, Keemia Abad, Saloni Bhatnagar, Jonathan Pelgen, Matt Beaudry, Gary Rochelle,
Scott Hume, David Link, Jose Figueroa, Heather Nikolic, Kunlei Liu. “Pilot Testing of a Heat Integrated 0.7 MWe CO2
Capture System with Two-stage Air-stripping: Degradation and Amine Emissions,” International Journal of Greenhouse
Gas Control. 64. 267-275. 2017.
Jesse Thompson, Keemia Abad, Heather Nikolic, Jonathan Pelgen, Jose Figueroa, Davis Link, Saloni Bhatnagar,
Megan Combs, Femke Onneweer, Kunlei Liu. “Pilot testing of a heat integrated 0.7 MWe CO2 capture system with two-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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64 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
stage air-stripping: Amine degradation and metal accumulation,” International Journal of Greenhouse Gas Control. 64.
22-33. 2017
J.R. Heberle, Heather Nikolic, Jesse Thompson, Kunlei Liu, Lora L. Pinkerton, David Brubaker, James C. Simpson,
Song Wu, Aboyjit S. Bhown. “Techno-Economic Analysis of a Secondary Air Stripping Process. 13th International
Conference on Greenhouse Gas Control Technologies,” GHGT-13, 14-18 November 2016, Lausanne, Switzerland.
Energy Procedia. 114. 2017.
Jesse Thompson, Heather Nikolic, Megan Combs, Saloni Bhatnagar, Jonathan Pelgen, Keemia Abad, Kunlei Liu.
“Solvent degradation and emissions from a 0.7 MWe pilot CO2 capture system with two-stage stripping. 13th
International Conference on Greenhouse Gas Control Technologies,” GHGT-13, 14-18 November 2017, Lausanne,
Switzerland. Energy Procedia. 114. 2017.
Widger, L. R.; Sarma, M.; Bryant, J. J.; Mannell, D. S.; Thompson, J. G.; Lippert, C. A.; Liu, K., “Enhancements in Mass
Transfer for Carbon Capture Solvents Part I: Homogeneous Catalyst” Int. J. Greenhouse Gas Control, 2017, 63, 249-
259.
Mannel, D. S.; Qi, G.; Widger, L. R.; Bryant, J.; Liu, K.; Fegenbush, A.; Lippert, C. A.; Liu, K.,“ Enhancements in Mass
Transfer for Carbon Capture Solvents Part II: Micron-Sized Solid Particles” Int. J. Greenhouse Gas Control, 2017, 61,
138-145.
Leland Widger, Cameron Lippert, Moushumi Sarma, and Kunlei Liu “Method of Development and Use of Catalyst-
Functionalized Catalytic-Particles to Increase the Mass Transfer Rate of Solvents Used in Acid Gas Cleanup” Patent
Pending (Published August 17, 2017, 2017/0232380)
Nikolic, H., et al.,“Application of a Heat Integrated Post-Combustion Carbon Dioxide Capture System with Hitachi
Advanced Solvent into Existing Coal-Fired Power Plants,” presented at the 2017 NETL CO2 Capture Technology
Project Review Meeting, Pittsburgh, PA, August 2017. https://netl.doe.gov/sites/default/files/event-
proceedings/2017/co2%20capture/1-Monday/K-Liu-UK-Hitachi-SolventCatalytic-Solvent.pdf.
Liu, K., et. al.,”Application of a Heat Integrated Post-combustion CO2 Capture System with Hitachi Advanced Solvent
into Existing Coal-Fired Power Plants,” presented at the 2016 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2016. https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/2-
Tuesday/H-Nikolic-UKCAER-Hitachi-Advanced-Solvent.pdf.
Thompson, J., et. al.,”Application of a Heat Integrated Post-combustion CO2 Capture System with Hitachi Advanced
Solvent into Existing Coal-Fired Power Plants,” presented at the 2015 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, June 2015. https://netl.doe.gov/sites/default/files/event-proceedings/2015/co2captureproceedings/J-
Thompson-CAER-UK-Heat-Integrated-Capture.pdf.
“Application of a Heat Integrated Post-combustion CO2 Capture System with Hitachi Advanced Solvent into Existing
Coal-Fired Power Plants,” BP3 review presentation, March 2015. https://netl.doe.gov/projects/files/FE0007395-Review-
March-2015.pdf.
Heather Nikolic, Kun Liu, James Landon, Cameron Lippert, and Kunlei Liu, “UKY-CAER Carbon Capture Research
Projects,” EM Magazine, a publication of the Air, Waste Management Association, March 2015, 13-17
Liu, K. et. al., “Nitrosamines and Thermal Degradation: Exploring Solvent Degradation with Mass Spectrometry,” UT
Review Meeting, October 2014.
Liu, K. et.al., “Application of a Heat Integrated Post-Combustion CO2 Capture System with Hitachi Advanced Solvent
into Existing Coal-Fired Power Plants,” presented at the 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA,
July 2014. https://netl.doe.gov/sites/default/files/event-proceedings/2014/2014%20NETL%20CO2%20Capture/H-
Nikolic-CAER-UK-Heat-Integrated-Post-Combustion-CO2.pdf.
Lippert, C. A.; Widger, L. R.; Sarma, M.; Liu, K., “Catalyst Development for Rate Enhanced Acid Gas (CO2) Scrubbing”
Energy Procedia, 2014, 63, 273-278
Liu, K., “Application of a Heat Integrated Post-Combustion CO2 Capture System,” presented at the 2013 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2013 https://netl.doe.gov/sites/default/files/event-
proceedings/2013/co2%20capture/K-Liu-UKCAER-Heat-Integrated-Post-Combustion-CO2.pdf.
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Post-Combustion Solvent Technologies
Neathery, J. and Liu K., “Slipstream Demonstration of a Heat Integrated CO2 Capture System,” presented at the 2012
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2012. https://netl.doe.gov/sites/default/files/event-
proceedings/2012/CO2%20Capture%20Meeting/J-Neathery-UKy-Slipstream-Heat-integrated.pdf.
“Application of A Heat-Integrated Post-Combustion CO2 Capture System with Hitachi Advanced Solvent into Existing
Coal-Fired Power Plant,” Project Fact Sheet, May 2012. https://netl.doe.gov/projects/files/fe0007395.pdf.
Liu, K., et al., “Application of A Heat-Integrated Post-Combustion CO2 Capture System with Hitachi Advanced Solvent
into Existing Coal-Fired Power Plant,” Project Kickoff Meeting Presentation, October 2011.
https://netl.doe.gov/projects/files/application-heat-integrated-oct2011.pdf.
FE0012926
Liu, K., “An Advanced Catalytic Solvent for Lower Cost Post-Combustion CO2 Capture in a Coal-Fired Power Plant,”
Final Scientific Report, July 2017, https://www.osti.gov/servlets/purl/1425200.
Nikolic, H. et. al., “An Advanced Catalytic Solvent for Lower Cost Post-combustion CO2 Capture in a Coal-fired Power
Plant,” presented at the 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://netl.doe.gov/sites/default/files/event-proceedings/2017/co2%20capture/1-Monday/K-Liu-UK-Hitachi-
SolventCatalytic-Solvent.pdf.
Lippert, C. et. al., “An Advanced Catalytic Solvent for Lower Cost Post-combustion CO2 Capture in a Coal-fired Power
Plant,” presented at the 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/3-Wednesday/C-Lippert-
UKCAER-Advanced-Catalytic-Solvent.pdf.
Lippert, C., “An Advanced Catalytic Solvent for Lower Cost Post-combustion CO2 Capture in a Coal-fired Power Plant,”
presented at the 2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://netl.doe.gov/sites/default/files/event-proceedings/2015/co2captureproceedings/C-Lippert-CAER-UK-Advanced-
Catalytic-Solvent.pdf.
Cameron, L., “An Advanced Catalytic Solvent for Lower Cost Post-Combustion CO2 Capture in a Coal-Fired Power
Plant,” presented at the 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
https://netl.doe.gov/sites/default/files/event-proceedings/2014/2014%20NETL%20CO2%20Capture/C-Lippert-CAER-
UK-Advanced-Catalytic-Solvent.pdf.
FE0026497
Placido, A. et. al., “Large Pilot CAER Heat Integrated Post-Combustion CO2 Capture Technology for Reducing the Cost of
Electricity,” presented at the 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/2-Tuesday/A-Placido-UKCAER-
CAER-Heat-Integrated-CO2-Capture.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
66 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Hybrid Encapsulated Ionic technology maturity:
Liquids for Post-Combustion
Laboratory-Scale, Simulated
Flue Gas (3.3 liters per
Carbon Dioxide Capture
minute)
project focus:
Microencapsulated CO2
primary project goals Capture Materials
The University of Notre Dame, in collaboration with Lawrence Livermore National participant:
Laboratory (LLNL) and colleagues at the University of Texas, has been developing University of Notre Dame
technology for hybrid encapsulated ionic liquid (IL) and phase-change ionic liquid
(PCIL) materials for post-combustion carbon dioxide (CO2) capture. Although ILs
project number:
have many favorable properties as CO2-absorbing solvents, their typically high
viscosities directly correlate with poor mass transfer rates and prohibit their FE0026465
practicable application in large-scale commercial operation when configured in
conventional absorption/regeneration systems. Researchers’ work in identifying predecessor projects:
ILs and PCILs with high capacity and low regeneration energy that, when DE-FC26-07NT43091
combined with their technology for microencapsulation of the ILs or PCILs in DE-AR0000094
polymer shells, may enable synthesis of high surface area IL- and PCIL-based
materials well-suited for CO2 capture from post-combustion flue gas. The goal of NETL project manager:
the project is successful synthesis of the microencapsulated ILs and/or PCILs and
validated CO2 removal from simulated flue gas in a laboratory-scale unit, with David Lang
demonstration of dramatically improved mass transfer rates. [email protected]
principal investigator:
technical goals Mark McCready
University of Notre Dame
Encapsulated ILs/PCILs structural integrity: microcapsules in fluidized beds [email protected]
able to contain the ILs without leaking.
Uptake of CO2 by encapsulated ILs/PCILs: greater than 50% CO2 absorption partners:
from a humid nitrogen (N2)-CO2 gas mixture in laboratory-scale testing. University of Texas at Austin
Durability/recyclability of the encapsulated ILs/PCILs: less than 20% decline in Lawrence Livermore
absorption capacity of CO2 after five cycles in humid N2-CO2 gas mixture. National Laboratory
Solvent regeneration: at least 80% of the absorbed CO 2 removed by hot vapor
(steam) without significant damage to the particles. start date:
Substantial technology progress towards a capture system enabling 90% CO 2 10.01.2015
capture with 95% CO2 purity at a cost of electricity 30% less than baseline
aqueous amine technologies. percent complete:
100%
technical content
Conventional solvent-based carbon capture methods typically employ amines
such as monoethanolamine (MEA) as the capture solvent. However, amines are
corrosive, degrade over time, and have relatively high vapor pressures, making
their leakage into the environment more likely. ILs are a class of ionic salts tending
to have large nitrogen or phosphorous-bearing cations with alkyl chain
substituents. ILs are anhydrous, liquid at ambient temperatures, have low vapor
pressures, are thermally stable and relatively non-corrosive, and certain ILs have
a considerable affinity for absorption of CO2 and selectivity towards CO2 in gas
mixtures. For example, the hexafluorophosphate (PF6–) and tetrafluoroborate
(BF4–) anions have been shown to be amenable to CO2 capture.
ILs might be used in a similar process to amine gas treating to effect carbon
capture from flue gas, where the flue gas is contacted with the solvent in an
absorption column, and the rich solvent is regenerated in a stripper column at
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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67
Post-Combustion Solvent Technologies
higher temperature through use of steam heating. ILs consistently show CO 2 absorption behavior of decreasing solubility
with increasing temperature, enabling conventional temperature swing absorption cycling. Because they have increasing
CO2 solubility with increasing pressure, ILs could also be stripped using pressure swing or swept with inert gases, possibly
reducing the process energy requirement.
A current issue with ILs for carbon capture is that they have a lower working capacity than amines. Another pressing
concern with their use is their high viscosity compared with that of commercial solvents. ILs that employ chemisorption
depend on a chemical reaction between solute and solvent for CO2 separation. The rate of this reaction is dependent on
the diffusivity of CO2 in the solvent and is thus inversely proportional to viscosity. The self-diffusivity of CO 2 in ILs is
generally on the order of 10−10 m2/s, approximately an order of magnitude less than similarly performing commercial
solvents used for CO2 capture. This represents a problematic mass transfer barrier for ILs and overcoming it would
constitute a significant advance in IL-based carbon capture technology.
However, encapsulating ILs/PCILs in small spherical shells and suspending these in a low-viscosity medium would create
a high-surface area IL/PCIL-based material into which CO 2 could much more easily diffuse and react, potentially
overcoming the mass transfer barriers caused by the inherently high viscosities of the stand-alone ILs/PCILs. Therefore,
the technologic development approach being explored here involves combining IL and PCIL materials having high CO 2
absorption capacity and low regeneration energy, and microencapsulation of these in polymer shells, with significant
potential for resulting in high surface area materials to be very well-suited for CO 2 capture from post-combustion flue gas.
Selection of Suitable ILs and PCILs
Strongly performing ILs and PCILs would have several favorable properties/characteristics, such as:
Chemical complexation strong enough to increase capacity and to decrease required IL circulation rates.
Chemical complexation weak enough to keep regeneration energies (and temperatures) down.
High equimolar absorption capacity: value of 1 mol CO 2/mol IL at absorption conditions is favorable.
No viscosity increases of the IL upon reaction with CO 2. Such increases occur because of the formation of hydrogen
bonding networks.
It has been observed that ILs containing aprotic heterocyclic anions are favorable on these points. They enable relatively
high absorption capacity. It is possible to tailor/tune heat of reaction of these ILs, guided by experience and previous
density functional theory, in order to enable an optimal chemical complexation strength (this happens to be between
about -45 and -60 kJ/mole enthalpy of reaction with CO2). Also, they retain amine in the ring structure, and further
reduction of free hydrogens to reduce hydrogen bonding is possible, avoiding the viscosity increase problem. Figure 1
depicts some types of these aprotic heterocyclic anions.
Figure 1: Several types of aprotic heterocyclic anions.
The researchers have evaluated a number of possibilities for ILs and PCILs prepared by LLNL, and settled on one IL and
one PCIL for continued development in this technology. The IL (NDIL0230) is triethyl(octyl)phosphonium 2-cyanopyrrolide
([P2228][2CNPyr]), and the PCIL (NDIL0309) is tetraethylphosphonium benzimidazolide ([P2222][BnIm]), which was
developed in an Advanced Research Projects Agency-Energy (ARPA-E) project. The PCIL will undergo a phase change
to and from liquid and solid at the varying temperatures it experiences during regeneration and absorption. This is
expected to confer certain energy efficiency advantages as discussed below in process implementation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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68 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Microencapsulation
The central innovation of this developmental technology involves encapsulating ILs and PCILs in thin CO 2-permeable
polymeric shells to produce particles of approximately 100 to 600 μm in diameter. It is thought that this approach will
create a high volumetric surface area material that can put ILs within easy diffusion range of CO 2-containing flue gas in
a fluidized-bed or moving-bed absorber in a post-combustion CO2 capture cycle. This idea is depicted in Figure 2. The
typical tower packing in amine absorption columns is either structured packing or random packing fill, which in either case
establishes a surface area for liquid-gas contacting in the range of hundreds of m2 surface per m3 of column volume.
However, note the microcapsules would generally establish surface areas near or above 10,000 m 2 per m3.
Figure 2: Surface area benefit of microencapsulation.
The technology for creating polymer-shell-encased IL microcapsules is now well established by LLNL. The microcapsules
are produced in a microfluidic device where the solvent and uncured shell material are flowed together in a third, inert
carrier fluid through a junction to create double emulsions – drops of solvent inside drops of shell material precursor,
suspended in the carrier fluid. The apparatus is diagrammed in Figure 3. The shell material is subsequently cured by
exposure to ultraviolet (UV) light. In project work, capsules are produced in single-junction devices assembled from glass
capillaries, but the process can be parallelized for large-scale production.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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69
Post-Combustion Solvent Technologies
Figure 3: Diagram of the capsule production apparatus (Inner Fluid is the IL; Middle Fluid is the shell material precursor; and Outer Fluid is
an aqueous, inert, carrier solution).
The polymer shell of the microcapsules must satisfy several conditions, including ability to reliably contain the IL contents
and maintain general physical stability, provide negligible diffusion resistance to CO 2, and to not adversely affect the IL
absorption reaction. Initially, issues were experienced with incompatibility of the ILs with the polymer material forming the
polymer shell, but these have since been overcome. LLNL settled on their in-house developed and refined Thiolene-Q
shell material formulation for NDIL0309, given its chemical compatibility and for which an alternative crosslinker for
improved microcapsule production and in-air production was found. Figure 4 depicts this formulation. For NDIL0230, a
different polymer SiTRIS was found to be compatible; Figure 5 is a magnified image of the microcapsules that have been
successfully fabricated using these combinations.
Figure 4: Thiolene-Q shell material.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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70 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Figure 5: Successful microcapsules: A: NDIL0231/water-in-SiTRIS; B: NDIL0230/water-in-SiTRIS; C: NDIL0309/water-in-Thiolene-Silica; D:
NDIL0309/water-in-Thiolene-Q.
Testing of the encapsulated ILs/PCILs in simulated flue gas showed the following:
Effects of impurities: the IL and PCIL under consideration both react irreversibly with sulfur dioxide (SO 2) and nitrogen
oxides (NOX), whether free or encapsulated. Accordingly, CO2 capture with these would need to follow the flue gas
desulfurization (FGD) and NOX reduction units in the flue gas cleanup system.
Reaction of water with the IL or PCIL in the presence of CO2 is completely reversible and recyclable. Therefore,
water does not need to be excluded from the cores of the microcapsules. This is greatly advantageous given the
inevitable presence of water vapor in flue gas.
PCIL Process Implementation
Process advantages result from the inherent characteristics of PCILs in temperature swing absorption cycles, as depicted
in Figure 6. In the absorption column on the left, a PCIL slurry containing encapsulated PCILs at low temperature (at
which the PCILs are in the solid phase) is contacted counter-currently with CO 2-containing flue gas passing up the
column. The PCIL reacts exothermically with CO2, creating heat that is absorbed by the PCIL particles, causing them to
melt. The PCIL-CO2 liquid leaving the column is sprayed into a dryer shown on the right, which serves as the regenerator
in this process cycle. The PCIL is heated in the dryer, causing it to release CO 2 in relatively pure gaseous form, which is
withdrawn and compressed for transport or storage. The heat duty of the stripper is reduced somewhat by the heat of
fusion of the PCIL as it goes from liquid to solid phase. Also, the cooling duty of the PCILs on the absorption side is
reduced by the phase change from solid to liquid phase.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
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Post-Combustion Solvent Technologies
Figure 6: CO2 capture cycling with phase-change material.
The result of this is that the overall heat duties on either side of the process cycle are moderated somewhat by the phase
changes occurring. This is more clearly depicted in Figure 7, which accounts how the phase changes of the PCILs reduce
the total molar heat duty on either side by 20 kJ/mol. Instead of needing to supply the entire 50 kJ/mol by external heating
of the dryer/regenerator, only the net amount of 30 kJ/mol needs to be supplied; the other 20 kJ/mol being contributed
by the PCIL phase-changes. This should lessen the parasitic energy demand for operating the process relative to a non-
phase-change scenario.
Figure 7: Heat duties for CO2 capture with PCILs.
Project Summary Findings
Small quantities (~1 g) of microcapsules with good integrity of both the IL and the PCIL have been successfully produced.
The CO2 uptake by these capsules is the same as for the free IL and PCIL and the capacity of the capsules decreases
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
72 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
only slightly after five absorption and desorption cycles. Over five cycles of absorption and regeneration, the CO 2 capacity
has been consistently measured at 0.64 to 0.68 moles CO 2/mol PCIL.
Large samples (~70 g and 100 g) of encapsulated PCIL were produced in a parallel microfluidic device and in an in-air
device, respectively. These capsules have been tested in a laboratory-scale unit (LSU) at 3.3 liters per minute simulated
flue gas flow rate to demonstrate uptake capacity in a fluidized bed. The LSU also allowed determination of recyclability
and mass transfer coefficients. Equivalent experiments with the IL were not possible due to difficulties with producing
large samples of the encapsulated IL. This IL encapsulation “scale-up” problem was not solved during the course of the
project. Nonetheless, testing of the PCIL microcapsules verified that the mass transfer is internally controlled. In concert
with a new rate-based model of a microcapsule fluidized-bed absorber, it was found that productivity is increased by a
factor of 4.75 in the microcapsule fluidized-bed absorber compared to a conventional liquid-gas packed-bed absorber.
An initial techno-economic model (assuming a process design as depicted in Figure 8) shows that the capital cost for the
microcapsule IL continuous fluidized-bed process is similar to that of an aqueous amine process (specifically, the
Econamine FG Plus technology). However, the stripping heat requirements are about 35% less for the model IL
microcapsule case compared to the MEA case. Thus, encapsulated ILs/PCILs in a continuous fluidized-bed absorber for
post-combustion CO2 capture are a significant improvement over the free IL/PCIL case and represent a major reduction
in the parasitic energy requirements compared to an aqueous amine process.
Figure 8: Process flow diagram for CO2 capture in a full-scale plant using PCILs.
technology advantages
The encapsulation of ILs and PCILs in micrometer-sized shells is projected to increase the mass transfer area by an
order of magnitude or more.
Significant reduction of the capital costs of the absorber and regenerator in CO 2 capture systems.
Lowered energy demands to operate absorption/regeneration cycle with the encapsulated solvents.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
73
Post-Combustion Solvent Technologies
R&D challenges
IL absorption capacities decrease with lower partial pressures of CO2, and CO2 concentration in flue gas is low at only
about 0.15 bar.
Viscosities of ILs generally increase upon reaction with CO 2, occurring because of the formation of hydrogen bonding
networks.
ILs tend to degrade strongly in the presence of typical flue gas contaminants, such SO 2 and SOX.
Encapsulation of ILs in polymer shells: getting sufficiently high loadings of the IL/PCIL in the shells, possible
compatibility issues or unfavorable effects of the IL and polymer material on each other, and viscosity and surface
tension issues in microencapsulation.
Solids handling issues that arise from encapsulating liquids in shells, essentially turning a liquid into a finely granular
solid material, and the necessity of reliably circulating this material around a complicated absorption-regeneration
cycle.
The shells themselves must withstand damage and reliably contain the ILs; leakage of the IL/PCIL if shell polymeric
cross-linking is insufficient.
status
The project has been completed.
available reports/technical papers/presentations
Final Scientific/Technical Report, “Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide (CO 2)
Capture,” June 29, 2019.
“Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide Capture,” presented by Mark McCready,
University of Notre Dame, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August, 2018.
“Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide Capture,” presented by Mark McCready,
University of Notre Dame, 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August, 2017.
“Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide (CO 2) Capture,” Topical Report, November
2016.
“Hybrid Encapsulated Ionic Liquids for Post-Combustion CO2 Capture,” presented by Joan Brennecke, University of
Notre Dame, 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
“Hybrid Encapsulated Ionic Liquids for Post Combustion CO2 Capture,” Project kickoff meeting presentation, November
2015.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
74 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Dilute-Source Carbon Dioxide technology maturity:
Pilot-Scale
(CO2) Capture: Management project focus:
of Atmospheric Coal- Direct Air Capture from Dilute
Produced Legacy Emissions
CO2 Sources
participant:
Carbon Engineering Ltd.
primary project goals
project number:
Carbon Engineering Ltd. is developing advancements for their Direct Air Capture
FE0026861
(DAC) technology to capture carbon dioxide (CO2) from dilute CO2 sources,
including evaluating DAC for other coal-relevant sources, such as post-carbon predecessor projects:
capture and storage (CCS) flue gas, and to re-capture legacy atmospheric coal-
N/A
based emissions. The DAC process uses a wet scrubbing air contactor, along with
chemical processing steps, to produce pure CO2 and remake the capture solution. NETL project manager:
The project will focus on applied research and development (R&D) at their pilot
Andrew jones
facility, along with a commercial readiness and cost-estimation evaluation. [email protected]
technical goals principal investigator:
jenny McCahill
Carbon Engineering Ltd.
• Use Carbon Engineering’s existing research pilot facility to perform component
[email protected]
testing, sensitivity analysis, and sub-system optimization of the DAC
technology. partners:
• Conduct performance analysis and technology optimization based on N/A
laboratory, simulated, and pilot operations.
• Develop key engineering inputs for scale-up of DAC technology. start date:
• Perform a techno-economic assessment (TEA) and applicability to coal stream 09.19.2016
study.
percent complete:
100%
technical content
Carbon Engineering Ltd. has been developing this dilute-source CO2 capture
technology since 2009 to scrub CO2 from atmospheric air present at
concentrations of 400 parts per million (ppm). This project is aimed to further
advance this DAC technology for atmospheric CO2 concentrations, as well as
evaluating the system’s performance as applied to other coal-relevant dilute CO2
sources, including post-CCS flue gas and re-capturing legacy atmospheric coal-
based emissions.
The DAC process, shown in Figure 1, is based on the use of a wet scrubbing air
contactor followed by several chemical processing steps. The chemistry of the
process is shown in Figure 2. The aqueous potassium hydroxide (KOH) used in the
air contactor is converted into aqueous potassium carbonate (K2CO3) when
reacted with the CO2 from the air. In the pellet reactor, the aqueous K2CO3 reacts
with solid calcium hydroxide (Ca(OH)2) from the slaker to regenerate the aqueous
hydroxide, which is sent back to the air contactor, and calcium carbonate (CaCO3)
to be used in the calciner. In the calciner, at elevated temperature, the CaCO3
decomposes into solid calcium oxide (CaO), releasing pure CO2 from the process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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75
Post-Combustion Solvent Technologies
The CaO goes to the slaker where water is introduced, forming the Ca(OH)2, which is sent to the pellet reactor, completing
the cycle.
Figure 1: Schematic of the DAC process.
Figure 2: Chemistry of the DAC process.
Carbon Engineering has a DAC research pilot facility in Squamish (British Colombia, Canada), which has been used to
support the testing in this project (Figure 3).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
76 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 3: Pilot plant in Squamish, British Columbia.
The project team formulated a heat and mass balance for an industrial-scale plant scrubbing CO2 directly from ambient
air. Carbon Engineering’s process scales-up to plant sizes capable of capturing 1,000,000 tonnes/year (t/yr) of CO2, which
are the most cost-effective due to economies of scale. Carbon Engineering’s efforts were focused on taking results from
the research pilot in Squamish, British Columbia, and utilizing them to design a first-of-a-kind plant that is expected to
capture on order of 1,000,000 t/yr. The key items in the heat and mass balance are:
• All the power required by the equipment in the DAC plant is provided by a turbine.
• Steam to drive this turbine is partially generated by the hot flue gasses and CaO pellets leaving the calciner, and partially
from the combustion of natural gas.
• All the CO2 produced by the combustion of natural gas is also captured and delivered as product CO2.
• Only fugitive emissions of CO2 are lost to the atmosphere.
• The amount of CO2 delivered is 50% larger than the CO2 that was captured from the air, with the extra from the
combustion of natural gas.
• The water that enters the system and is used to wash the pellets and fines is balanced by the amount of water that the
absorber evaporates into the atmosphere.
The scope of work for the TEA included a design and cost estimate of a modified Carbon Engineering DAC plant used as
a polishing unit on a modern commercial supercritical pulverized coal power plant that already removed 90% of the CO2
produced using a conventional liquid amine-based CCS system.
The TEA indicates that using DAC technology to remove an additional 1 Mt/yr CO2 (~9% of total CO2 emitted) from the
point source stack gases of a conventional coal-fired power plant equipped with a CO2 removal (CDR) system increases
the total cost of electricity (COE) by 16%.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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77
Post-Combustion Solvent Technologies
TABLE 1: PROCESS PARAMETERS
Capture Solution Units value
Nominal Concentrations – K+/OH-/CO32- mol/L 2.0/1.0/0.5
CO2 Capture
Delivered Feedstock (Upstream Air) (CO2) ppm 400
Downstream Air (CO2) ppm ~100
Air Contactor Mass Transfer Rate mm/sec 1.0-1.3
Pressure Drop Pa ~130
Air Velocity m/s 1.4-1.7
CO2 Release
Pressure bar 1
Temperature (Calcination) °C ~900
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
CO2 Laden Air (feed) Assumptions – Unless noted, gas pressure, temperature, and composition of feed (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 32–68 0.04 variable 78.09 20.95 0.93 trace trace
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Strong aqueous hydroxide solution reacts with large volumes of atmospheric
CO2 across an extremely large, dispersed air contactor. The reaction forms K2CO3 in an aqueous, liquid solution that can
easily be transported from the contactor to a central processing location. In addition, strong hydroxide solutions have
fast reaction kinetics with CO2, are robust against fouling, and have negligible volatility, meaning there is little risk when
using it with atmospheric air.
Gas Pretreatment Requirements – No treatment of atmospheric air required.
Solvent Makeup Requirements – CaCO3 (seed material) and small quantities of KOH makeup.
Waste Streams Generated – Minimal quantities of lime mud (CaCO3) as fines and inerts.
Proposed Module Design – The DAC plant draws air through an air contactor, where it contacts a strong aqueous KOH
solution. The CO2 in the air reacts with the KOH to form a solution of K2CO3 and water, absorbing about three-quarters
of the available CO2.
The carbonate solution is transferred to a pellet reactor, where it contacts Ca(OH)2, also known as hydrated lime, and
precipitates CaCO3 pellets through a process known as causticization.
The pellets are fed into a circulating fluidized bed and treated at ~900°C through a process known as calcination. The
heat releases the CO2 as a pure, gaseous stream, leaving CaO as byproduct. Heat for the calciner is provided by
combusting natural gas with oxygen (known as “oxy-firing”), so that the combustion exhaust is pure CO2 and water vapor,
which can be combined with the CO2 stream leaving the calciner. The resultant CaO from the calciner is fed into the slaker,
where it combines with water to regenerate hydrated lime, which is then fed into the pellet reactor for reuse.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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78 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
technology advantages
• Negative emission technology.
• Technology can manage CO2 emissions from any dilute source.
• Highly scalable technology.
R&D challenges
• Compared to standard CCS, there is a higher thermodynamic barrier for dilute-source capture.
• Compared to standard CCS, a larger air volume must be processed for dilute-source capture.
• Controlling/minimizing aerosol emissions is a challenge.
status
Carbon Engineering has concluded TEA activities by working closely with BBA (Engineering company), and an external
consultant (Keith Patch). The project has concluded.
available reports/technical papers/presentations
McCahill, J., “Dilute Source Carbon Dioxide (CO2) Capture: Management of Atmospheric Coal-Produced Legacy
Emissions,” Final Briefing, Pittsburgh, PA, September 2019. https://www.netl.doe.gov/projects/plp-
download.aspx?id=16805&filename=FE0026861_Final%20Briefing_09-27-19.pdf.
Souza, R., “Dilute Source Carbon Dioxide (CO2) Capture: Management of Atmospheric Coal-Produced Legacy
Emissions,” 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13378&filename=R-Souza-CarbonEng-Dilute-Source-CO2-
Capture.pdf.
Ritchie, J., “Dilute Source Carbon Dioxide (CO2) Capture: Management of Atmospheric Coal-Produced Legacy
Emissions,” Project Continuation Application Review Meeting Presentation, September 2017.
Kahn, D., “Dilute Source Carbon Dioxide (CO2) Capture: Management of Atmospheric Coal-Produced Legacy Emissions,”
2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-Tuesday/D-Kahn-Carbon-Engrg-Dilute-Source-
Carbon-Capture.pdf.
Ritchie, J., “Dilute Source Carbon Dioxide (CO2) Capture: Management of Atmospheric Coal-Produced Legacy
Emissions,” Project Kick-Off Meeting Presentation, March 2017.
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Post-Combustion Solvent Technologies
Low-Viscosity, Water-Lean technology maturity:
Bench-Scale, Simulated Flue
CO2-Binding Organic Liquids Gas
(CO2BOL) with Polarity-Swing project focus:
Assisted Regeneration (PSAR)
CO2-Binding Organic Liquid
Solvents
participant:
primary project goals Pacific Northwest National
Laboratory
This project is an extension to the Pacific Northwest National Laboratory’s (PNNL)
initial Discovery of Carbon Capture Substances and Systems (DOCCSS) project, project number:
which is aimed at advancing the promising Carbon Dioxide-Binding Organic Liquid FwP-70924
(CO2BOL) single-component derivative N-(2-ethoxyethyl)-3-morpholinopropan-
1-amine (EEMPA) to assess this solvent’s viability towards meeting the U.S. predecessor project:
Department of Energy’s (DOE) cost and performance targets for carbon capture. FE0007466
This DOCCSS extension will allow programmatic involvement by industrial
participants to evaluate the CO2BOL derivative on a bench-scale platform and to NETL project manager:
aid in the development of a novel system. The final process design, along with the Sai Gollakota
solvent, will include integrated (simultaneous absorption and regeneration) testing [email protected]
at the bench-scale on synthetic flue gas at an industrial participant facility. The
participants will also lead key techno-economic analyses (TEAs), targeted testing,
principal investigator:
and broader industry outreach to assure subsequent transfer of the technology to David Heldebrant
Pacific Northwest National
industry.
Laboratory
[email protected]
technical goals
partners:
• Test the DOCCSS CO2BOL solvent EEMPA using an integrated (simultaneous Carbon Capture Simulation
absorption and regeneration) carbon capture system at bench-scale on for Industry Impact
synthetic flue gas at an industrial participant facility.
start date:
• Perform independent solvent durability testing.
07.01.2017
• Provide inputs of viability of laboratory-scale testing to acquire adequate data
for a quantitative TEA to assess full-scale performance and project process costs percent complete:
at or below DOE’s cost and performance targets. 60%
• Provide guidance on scale-up routes; help engage with other industrial entities
that represent key scale-up pathways.
technical content
PNNL is performing this project to test their most advanced single-component
water-lean CO2BOL solvent, EEMPA. This solvent was developed through discrete
placement and orientation of hydrogen bonds at the molecular level. The control
over hydrogen bond orientation and strength resulted in the development of a
derivative that is greater than 90% lower in viscosity than the reference compound.
The low regeneration temperature of EEMPA provides a solvent system with
potential for a minimal temperature swing between absorption and regeneration
cycles. This project was designed to measure the critical data needed to project
performance of EEMPA for post-combustion carbon dioxide (CO2) capture,
ultimately enabling slip stream testing and subsequent industry adoption. Key
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efforts include comprehensive data collection and process modeling, as well as engagement with collaborators from Carbon
Capture Simulation for Industry Impact (CCSI2) and industry to determine viability of EEMPA for slip stream testing and
subsequent industry handoff.
The project team performed chemical durability measurements with individual components, CO2, water (H2O), oxygen (O2),
sulfur dioxide (SO2), and nitric oxide (NO). These tests showed that EEMPA is stable under thermal, oxidative, and hydrolysis
test conditions. In the presence of sulfur oxides (SOX) and nitrogen oxides (NOX), EEMPA forms heat-stable salts similar to
other amine-based solvents.
Forty hours of continuous operation on PNNL’s laboratory continuous flow system (LCFS) test loop at greater than 90% CO2
capture was completed with a simulated flue gas and EEMPA in a configuration without Polarity-Swing Assisted
Regeneration (PSAR). The LCFS test system was configured with an absorber column loaded with Pro-Pak packing, a high
surface area laboratory random packing. A compact absorber section was used (7.62 cm x 50.8 cm). A forced circulation
reboiler was used for the stripper.
Before the flue gas enters a CO2 capture unit, it is typically passed through a pre-scrubber and/or direction contact cooler
to reduce SO2 and NOX levels and reduce temperature. In the current CO2BOL-based capture unit, the flue gas is chilled to
about 16°C to reduce water content. It is assumed that a pre-scrubber will also be used to reduce SO2 and NOX to about 5
parts per million (ppm) and 50 ppm, respectively. For the LCFS flue gas simulant, NOX was delivered in form of NO. In some
preliminary work (routine testing), a simpler simulant without the O2/SO2/NO components was also used. In all tests, the
simulated flue gas was humidified to a 16°C dew point. The target simulated flue gas compositions are summarized in Table
1.
TABLE 1: TARGET SIMULATED FLUE GAS COMPOSITION
For the 40-hour duration testing, the dry flue gas rate was chosen as 12.5 standard liters per minute (slm) to target a greater
than 90% capture efficiency. The remaining test conditions chosen were 0.24 liters per minute (L/min) for solvent circulation,
40°C absorber column temperature, and 115°C reboiler temperature.
An Aspen simulation of the LCFS test loop was performed at the measured absorber and stream conditions. The Pro-Pak
absorber section was specified according to manufacturer-provided data, such as specific area, void fraction, and Stichlmair
correlation parameters for pressure drop. The packing-specific area was scaled from manufacturer data based on the actual
packed mass to account for the wall effects of the relatively small diameter of the LCFS absorber column. The EEMPA solvent
properties were calculated using the same thermodynamic package developed from vapor liquid equilibrium (VLE) and
wetted-wall column (WWC) data for the process flowsheet and TEA.
The Aspen simulation was compared with the measured outlet stream properties and the capture efficiency in Table 2. The
data are close to the Aspen prediction. The largest relative error is seen on the flue gas outlet CO2 mole fraction, which is
expected because this quantity is very small in absolute value. The deviation in capture efficiency, 1.5%, is small. Considering
the uncertainties in the Aspen thermodynamic package, as well as in the effective area of the packing section, there is good
agreement between the Aspen simulation and experimental data.
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Post-Combustion Solvent Technologies
TABLE 2: COMPARISON OF LCFS 40-HOUR TEST AND ASPEN SIMULATION RESULTS
EEMPA showed no visible evidence of degradation, foaming, or solid precipitation during the LCFS testing for the 40 hours
on stream. The solvent maintained its ability to capture CO2 and be regenerated thermally as expected, indicating EEMPA
can proceed to larger-scale testing.
The project team has been revising the TEA. The best system configuration as modeled is a combination of an inter-heated
column (IHC), advanced heat integration (AHI), and lean-vapor compression (LVC) together, giving a heat rate of 2.0
gigajoules (GJ)/tonne CO2, and a CO2 capture cost of $50.6/tonne CO2. These results are still preliminary based on the
thermodynamic package developed on previously collected VLE. Additional data from PTxy and reboiler heat duty will further
refine the energetics of EEMPA, while formal costing from Fluor will provide a more rigorous costing analysis for the final
process configuration.
The project team has started a preliminary assessment on how the units of operation for EEMPA with and without a PSAR
would be incorporated into RTI International’s slip stream test system. Engineers are assessing whether, how, and where
units such as a two-stage flash stripper, intercooling, and PSAR infrastructure would be incorporated. Preliminary discussions
have started on sizing and configurations for each unit.
TABLE 3: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 216.3 -
Normal Boiling Point °C 181.0 -
Normal Freezing Point °C <0 -
Vapor Pressure @ 15°C bar 5E-5 -
Manufacturing Cost for Solvent $/kg 13 10
Working Solution
Concentration kg/kg 0.98 (hydrated) -
Specific Gravity (15°C/15°C) - 0.94 -
Specific Heat Capacity @ STP kJ/kg-K 1.95 -
Viscosity @ 15°C cP 11.3 -
Absorption
Pressure bar 1 -
Temperature °C 40 -
Equilibrium CO2 Loading mol/mol 0.29 -
Heat of Absorption kJ/mol CO2 75 -
Solution Viscosity cP 25 -
Desorption
Pressure bar 1.8 -
Temperature °C 117 -
Equilibrium CO2 Loading mol/mol 0.05 -
Heat of Desorption kJ/mol CO2 75 -
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2.6E6
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 150
Absorber Pressure Drop bar <0.1
Estimated Absorber/Stripper Cost of __$__
pending
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical.
Solvent Contaminant Resistance – EEMPA appears to be relatively stable towards oxidative and thermal degradation
and hydrolysis in the absence of steel, while SOX and NOX form heat-stable salts.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Solvent Foaming Tendency – EEMPA showed no evidence of foaming during 40 continuous hours of testing with
simulated flue gas.
Flue Gas Pretreatment Requirements – It is assumed that a pre-scrubber will be used to reduce SO2 and NOX to about
5 ppm and 50 ppm, respectively.
Solvent Makeup Requirements – Solvent makeup rates are expected to be at worst comparable to 5M MEA, though
preliminary degradation studies indicate higher chemical durability of EEMPA under absorber and stripper conditions.
Waste Streams Generated – Sulfur oxides and NOX form heat-stable salts, which will need treatment to recover EEMPA
in a working process. Preliminary results indicate the addition of PSAR can facilitate regeneration of heat-stable salts,
releasing NOX and SOX from EEMPA at 60°C and 130°C, respectively.
Process Design Concept –
Figure 1: CO2BOL/PSAR conceptual configuration.
technology advantages
• No diluent: 100% active solvent.
• Low solvent volatility.
• Lower CO2-rich viscosity than early versions of CO2BOL solvents.
• PSAR decreases the regeneration temperature by destabilizing the acid gas carrier.
• Significantly lower regeneration energy compared to aqueous amines.
R&D challenges
• PSAR regeneration of heat-stable salts as part of solvent reclamation process.
• Reducing the cost of solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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status
The project team has continued its efforts in testing EEMPA for CO2 capture from simulated flue gas. The primary focus
of FY19 Q4 was continuous flow testing of EEMPA. Other efforts included revising the TEA with industrial partners and
CCSI2 collaborators. The project team successfully completed 40 hours steady-state performance of CO2 capture on
simulated flue gas. The project team has also identified the chemical tolerance of EEMPA towards heat-stable salt
formation, oxidative degradation, thermal degradation, and hydrolysis.
The project team upgraded and retrofitted the PVT cell to enable PTxy capability. The project team installed a chilled
mirror and CO2 sensor within the cell to enable gas-phase analysis during isotherm measurements. These upgrades will
enable CO2 and water partial pressures to be measured, enabling more accurate and robust thermodynamic models that
will provide higher-fidelity modeling results of solvent performance. The cell will be used to analyze EEMPA at varied
loadings of water.
available reports/technical papers/presentations
Heldebrant, D. “Low-Viscosity, Water-Lean CO2BOLs with Polarity-Swing Assisted Regeneration,” NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/sites/default/files/event-
proceedings/2018/co2%20capture/monday/D-Heldebrant-PNNL-Polarity-Swing-Regeneration.pdf.
Heldebrant, D. “Low-Viscosity, Water-Lean CO2BOLs with Polarity-Swing Assisted Regeneration,” project kickoff
meeting, Pittsburgh, PA, September 2017. https://www.netl.doe.gov/sites/default/files/netl-file/FWP-70924-PNNL-
DOCCSS-kickoff.pdf.
D. Malhotra, D. C. Cantu, P. K. Koech, D. J. Heldebrant, A. Karkamkar, F. Zheng, M. D. Bearden, R. Rousseau, and V. A.
Glezakou, “Directed Hydrogen Bond Placement: Low Viscosity Amine Solvents for CO2 Capture.” ACS Sustainable Chem.
Eng., (2019), 7 (8), pp 7535–7542.
D. Malhotra, J. P. Page, M. E. Bowden, A. Karkamkar, D. J. Heldebrant, V. A. Glezakou, R. Rousseau, P. K. Koech. “Phase
change aminopyridines as carbon dioxide capture solvents.” Ind. Eng. Chem. Res., (2017), 56, (26), 7534-7540.
D. Malhotra, P. K. Koech, D. J. Heldebrant, D. C. Cantu, F. Zheng, V. A. Glezakou, R. Rousseau, “Reinventing design
principles for developing low-viscosity carbon dioxide binding organic liquids (CO2BOLs) for flue gas clean up.”
ChemSusChem. (2017), 10, 636 –642.
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85
Post-Combustion Solvent Technologies
Electrochemically Mediated technology maturity:
Laboratory-Scale, Simulated
Amine Regeneration in CO2 Flue Gas (0.01 kg/day CO2
captured)
Scrubbing Processes project focus:
Electrochemical
primary project goals Regeneration of Amine
Solvents
The Massachusetts Institute of Technology (MIT) is advancing a novel carbon
dioxide (CO2) capture technology using traditional amine-based solvents, but with participant:
the key innovation of using electrochemical regeneration of the solvent instead of Massachusetts Institute of
conventional thermal regeneration. By utilizing cost-effective reduction/oxidation Technology
of metal ions to electrochemically enable the capture and release of CO2 by
traditional amine sorbents and thereby eliminating the demand for steam project number:
characteristic of conventional amine regeneration technology, the parasitic power FE0026489
requirement for operating the process is expected to be markedly less than that
of conventional methods. This should enable substantial savings in the cost of predecessor projects:
electricity (COE) for carbon capture process scenarios, with promise to meet N/A
programmatic U.S. Department of Energy (DOE) carbon capture goals.
NETL project manager:
David Lang
technical goals [email protected]
• Develop an optimized electrochemical cell configuration/design and size, principal investigator:
allowing best efficiency and cost performance for scalable carbon capture Trevor A. Hatton
processes for commercial-scale coal-fired plants. Massachusetts Institute of
• Validate system using electrochemically mediated amine regeneration in a CO2 Technology
[email protected]
scrubbing cycle for capture of at least 90% of CO2 from coal-derived flue gas
while demonstrating significant progress toward achievement of the DOE target partners:
of less than 35% increase in levelized cost of electricity (less than $40/tonne
N/A
CO2).
• Reduce energy requirements 20 to 40% relative to that of baseline start date:
monoethanolamine (MEA) capture. Achieve specific regeneration energy of 0.91 08.01.2017
gigajoules (GJ)/tonne CO2.
• Demonstrate electrochemical cell stability over 15 days continuous operation, percent complete:
at simulated flue gas flow rate enabling capture of 0.01 kg CO2 per day. 70%
technical content
MIT terms their technology as Electrochemically Mediated Amine Regeneration
(EMAR). In conventional amine regeneration-based capture processes, a standard
amine solvent such as MEA is contacted in countercurrent flow with CO2-
containing flue gas in an absorption column at relatively low temperature (less
than 60°C). At lower temperatures, CO2 readily reacts with the amine forming an
amine-CO2 complex, and given suitable contact time and solvent flow in the
absorption column, high levels of CO2 removal (greater than 90%) can be attained.
The rich amine solvent (containing elevated levels of absorbed CO2) exiting the
absorber column is preheated in a countercurrent heat exchanger and introduced
into the desorber column, where it is further heated with low-pressure steam
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withdrawn from the power plant’s steam cycle, to reach temperatures greater than 110°C. At elevated temperatures, the
CO2 is released from the solvent as a relatively pure stream of CO2 that can be recovered. Hot lean solvent is cooled and
returned to the absorption column. This conventional thermal regeneration-based process is depicted in the top half of
Figure 1.
Figure 1: Electrochemically mediated versus thermal amine regeneration.
In EMAR (depicted in the bottom half of Figure 1), the process uses the same type of absorption column and operating
conditions therein. However, the rest of the process is significantly different. Instead of regenerating the rich solvent by
increasing its temperature, the solvent passes sequentially through the anodic and cathodic sides of an electrochemical
cell. On the anodic side, certain metal ions enter solution and react with the amine/CO2 complexes in the rich solvent. If
the metal ions have sufficiently strong binding with the amines, they displace the CO2 and cause it to be liberated in pure
gaseous form, enabling its separation. On the cathodic side, the amine metal compound remaining behind is stripped of
the metal ions, resulting in lean amine solvent ready to return to the absorber. Temperature remains essentially constant
throughout the process, eliminating heat exchange operations and their associated energy losses and capital costs.
Because the EMAR process requires only a limited amount of electrical power to operate the electrochemical processes
in the cells, it avoids the need to use steam withdrawn from the power plant’s steam cycle, minimizing parasitic energy
consumption. This is depicted in Figure 2, which compares the amounts of CO2 capture work (units of kilojoule [kJe]/mol
CO2 captured) associated with the EMAR system, and those of comparative thermal amine systems. Note the EMAR system
advantage in respect of steam withdrawals.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Figure 2: Comparison of capture work of thermal amine systems and EMAR systems.
This process concept has been proven at lab-scale, and ongoing work has been refining/optimizing the technology in
terms of optimal selection of amine and metal ions, improving electrochemical kinetics, and optimizing cell design as
discussed below.
Amine Selection—Binding energies of metal ions with amines are specific to the amine. The binding energies must be
strong enough to overcome the amine/CO2 complexation, but higher binding energies demand high power consumption
in the electrochemical cell to remove metal ions from the amine/metal complexes. Therefore, amine selection is important
in optimizing the process. Adequate amine stability in the process is required. Candidate amines evaluated have included
the following:
• MEA
• Diethanolamine (DEA)
• Diethylenetriamine (DETA)
• 2-Amino-2-methyl-1-propanol (AMP)
• Ethylenediamine (EDA)
• Pentamethyldiethylenetriamine (PMDTA)
• Aminoethylethanolamine (AEEA)
• Triethylenetetramine (TETA)
• Piperazine (PZ)
Metal Ions—Ion species, including Co2+, Fe3+, Fe2+, Cr2+, Cu2+, Zn2+, and Ni2+, have been evaluated as possibilities for the
optimal choice for metal/amine complex according to the following essential criteria:
• No precipitation in alkaline solvent.
• Redox active on metal electrode.
• Stability.
Screening of amine/metal complexes considering the candidates above has been performed. The screening methodology
considered metal/amine stability in EMAR operating conditions, measurement of CO2 capacity, testing of electrochemical
reversibility, and validation of the CO2 separation via electrolysis in batch reactors. Via the stability measurement, MIT
concluded that only copper (Cu), zinc (Zn), and nickel (Ni) are plausible candidates to form metal-ligand complexes using
off-the-shelf aqueous amine solvents. Nevertheless, only Cu-EDA can be modulated with electrochemical methods
without incurring hydrogen evolution (i.e., water splitting). Therefore, MIT concluded that Cu-EDA is the most suitable
candidate to be integrated into the envisioned EMAR process.
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Electrochemical Kinetics—Rapid reaction rates of the complexes in the electrochemical cells are needed to
accommodate the high solvent throughputs typical of large-scale post-combustion capture process scenarios. The EMAR
cathode ideally operates in the absence of CO2, but in practice CO2 is present and tends to hinder the kinetics. Chlorides
in solution have been found to improve performance significantly.
MIT investigated the thermodynamic potential of Cu-EDA and provided detailed speciation modeling of the Cu-EDA-
water (H2O) electrolyte. Results are informing modeling of the EMAR process, which will enable estimates of the energy
consumption of an EMAR process in context of a post-combustion carbon capture cycle. The kinetics of the
electrochemical reactions have been examined via deposition and dissolution experiments performed with rotating disk
electrodes. The cathodic deposition of Cu is the slower process of the two Faradaic reactions and would require higher
overpotential to drive out the desired reaction rate (i.e., current density). Suitable electrolyte combinations (with
supporting salt) to decrease ohmic resistances and to minimize unwanted reactions have been identified. Both the Cu-
EDA-H2O-sodium (Na)-sulfate (SO4) and Cu-EDA-H2O-Na-chloride (Cl) systems were identified as stable electrolyte
formulations. These electrolyte combinations have been further implemented in a bulk electrolysis setup that validates
the electrochemical-thermal separation of CO2. Results from systematic study and experimental validation of the CO2
solubility constants have aided ongoing revision/improvement of the proposed thermodynamic cycle.
Cell Design—Ongoing work is optimizing cell architectures for fluid flow configuration and operational efficiency.
Because CO2 bubbles are formed in the cells, the design needs to efficiently accommodate removal of the gas. Prototype
architectures are being developed for continuous CO2 gas removal by utilizing gas/liquid separation membranes. In
addition, cell stacking strategies to optimize volumetric efficiency and fluid flow will be investigated. Figure 3 gives an
idea of the present configuration of cell engineering, showing metallic electrodes, channels, seals, etc. Figure 4 depicts a
cell stacking concept.
Figure 3: Electrochemical single-cell engineering.
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U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
89
Post-Combustion Solvent Technologies
Figure 4: Cell stacking.
Process and Costs—MIT has created a process model accounting for all process unit operations (e.g., absorbers, heat
exchangers, compressors), as well as additional energy efficiency losses (e.g., kinetic overpotentials) associated with an
EMAR system in a full-scale power plant context. Figure 5 depicts the flowsheet for this model.
Figure 5: Detailed flowsheet simulated for EMAR process for carbon capture.
A range of operating conditions and operation schemes were varied parametrically to identify reasonable overall
energetics in the EMAR system process. Interesting findings of the process simulations include the realization that net
energy demands can be significantly reduced if waste heat is available at temperatures below 90°C, and that the EMAR
process is able to desorb CO2 at pressures up to 20 bar with negligible additional energy penalty. Preliminary cost analysis
of a full-scale EMAR process indicates a cost of around $60 per ton of CO2 avoided ($40 per ton of CO2 captured) in
capture from post-combustion flue gas from a 550-megawatt (MW) coal-fired power plant. It is postulated that further
reduction in cost should emerge from advanced process design, process optimization, and improved solvent formulation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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90 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
MIT has preliminary estimates of capital and operating costs of an EMAR system, as well as comparisons to baselines.
Figure 6 shows the expected breakdown of equipment costs and offers COE comparisons to a no-capture case and
conventional amine-based capture cases.
Figure 6: Capital cost breakdown and COE estimates/comparisons.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight g mol-1 60.2172 60.2172
Normal Boiling Point °C 116 116
Normal Freezing Point °C 11 11
Vapor Pressure @ 15°C bar 0.037 0.037
Manufacturing Cost for Solvent $/kg <50 <50
Working Solution
Concentration kg/kg water 0.06 0.24
Specific Gravity (15°C/15°C) - 1 <1
Specific Heat Capacity @ STP kJ/kg-K 4 4
Viscosity @ STP cP 1.3
Absorption
Pressure bar 1 1
Temperature °C 50 50
Equilibrium CO2 Loading mol/mol 1 1
Heat of Absorption kJ/mol CO2 85 85
Solution Viscosity cP 1.3
Desorption
Pressure bar 1 1-10
Temperature °C 50 50
Equilibrium CO2 Loading mol/mol <0.2 <0.2
Heat of Desorption kJ/mol CO2 89
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
91
Post-Combustion Solvent Technologies
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 466
CO2 Recovery, Purity, and Pressure
%/%/bar 90%/99%/1–10bar
Absorber Pressure Drop bar <0.1
Estimated Absorber/Stripper Cost of Manufacturing __$__
and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column (or in the case of EMAR, at the exit of the electrochemical cell). Operating
pressure and temperature for the desorber/stripper are process-dependent (e.g., an MEA-based absorption system has a
typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120°C). Measured data at other conditions are
preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted otherwise, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% Ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – EDA readily forms carbamate upon contact with CO2 in water. The solvent
exhibits a strong affinity to CO2 in the absence of chelating metal ions, and no affinity for CO2 in the presence of these
metal ions.
Flue Gas Pretreatment Requirements – Sulfur removal.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
92 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Process Design Concept – See Figures 1 and 5 above.
technology advantages
• Amine scrubbing with electrochemically mediated amine regeneration offers a combination of fast kinetics, low
parasitic energy requirements, and process flexibility.
• CO2 gas recovered from the regenerator is at elevated pressure (up to 20 bar), lessening downstream compression
requirements and saving energy.
• An initial techno-economic analysis (TEA) indicates that the electrochemically mediated capture technology could have
a significant economic advantage over state-of-the-art thermal amine processes, cutting capture costs by 30 to 60%.
R&D challenges
• Possible sensitivity of the process to disturbances and long-term operation viability. Since the system needs to switch
the polarity of the electrodes and the corresponding process stream, this requires implementation of an automation
system that can accomplish both tasks for long-term operation stability.
• Validation of the basis for scale-up of the process to commercial-scale capability.
• Cell fluid flow channeling. Gas trapping in the fluid channel will reduce effective ionic conductivity, leading to reduced
CO2 separation. High velocities of liquid on the surface of the electrode will need to be ensured to minimize boundary
layer thickness.
status
MIT’s electrochemically mediated amine regeneration technology has been previously developed from concept to a
proof-of-concept lab-scale device, validating the feasibility and potential of the approach. Additional lab-scale work has
been underway to further optimize the performance of the technology, with a Cu-EDA amine/metal complex identified
as preferred. Cell architecture, cell operation and kinetics, and process optimization are being worked on currently.
available reports/technical papers/presentations
“Electrochemically Mediated Amine Regeneration in CO2 Scrubbing Processes,” Budget Period 2 project review
presentation by T. Alan Hatton of MIT, at NETL Pittsburgh on November 14, 2019.
“Electrochemically Mediated Amine Regeneration in CO2 Scrubbing Processes,” presented by T. Alan Hatton, 2019 NETL
CCUS Integrated Project Review Meeting, August 2019.
“Electrochemically-Mediated Sorbent Regeneration in CO2 Scrubbing Processes,” presented by T. Alan Hatton, Kickoff
meeting presentation, December 2017.
“Electrochemically-Mediated Sorbent Regeneration in CO2 Scrubbing Processes,” presented by T. Alan Hatton,
Massachusetts Institute of Technology, 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA,
August 2017.
Wang, M.; Rahimi, M.; Kumar, A.; Hariharan, S.; Choi, W.; Hatton, T. A. Flue Gas CO2 Capture via Electrochemically
Mediated Amine Regeneration: System Design and Performance. Applied Energy 2019, 255, 113879.
Wang, M.; Hariharan, S.; Shaw, R. A.; Hatton, T. A. Energetics of Electrochemically Mediated Amine Regeneration Process
for Flue Gas CO2 Capture. International Journal of Greenhouse Gas Control 2019, 82, 48–58.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
93
Post-Combustion Solvent Technologies
Large Pilot Testing of Linde- technology maturity:
Large Pilot-Scale (10 Mwe),
BASF Advanced Post- Actual Flue Gas Slipstream
Combustion Carbon Dioxide project focus:
Capture Technology at a
Linde-BASF CO2 Capture
Process
Coal-Fired Power Plant participant:
University of Illinois at
Urbana-Champaign
primary project goals
project number:
The University of Illinois is evaluating the design, construction, and operation of a
FE0031581
10 megawatt-electric (MWe) capture system based on the Linde-BASF advanced
amine-based post-combustion capture technology at a coal-fired power plant. Predecessor projects:
The project consists of three phases. Phase I has been completed and consisted of
FE0026588
a feasibility study that (1) outlined preliminary engineering designs; (2) conducted FE0007453
preliminary analysis of National Environmental Policy Act (NEPA)-related issues;
and (3) concluded selection of a host site for Phases II and III. Phase II efforts are NETL project manager:
underway, consisting of a detailed front-end engineering design (FEED) study, Andrew jones
NEPA permitting and documentation, and cost-share commitments. If selected for [email protected]
Phase III, the project will support construction and operation of the large-scale
pilot facility. The Fossil Fuel Large-Scale Pilots effort supports the design, principal investigator:
construction, and operation of large test facilities for transformational carbon Kevin O’Brien
dioxide (CO2) capture technologies aimed at enabling step-change improvements University of Illinois at
in coal-powered system performance, efficiency, and cost of electricity (COE). Urbana-Champaign
[email protected]
technical goals partners:
Linde, LLC, Affiliated
Phase I objectives were to: Construction Services,
Affiliated Engineers, Inc.
• Establish the feasibility of installing a 10-MWe capture facility at one of three
potential pilot host sites. start date:
• Select a host site based on the feasibility studies. 04.04.2018
• Complete an Environmental Information Volume for each potential host site.
percent complete:
• Obtain necessary commitments from the selected site.
55%
• Update the preliminary cost and schedule estimates provided in this Phase I
proposal.
• Secure cost-share commitments for Phase II (Design) and develop a plan for
securing cost-share commitments for Phase III (Construction/Operation).
Phase II objectives are to:
• Complete a FEED study for the proposed large-scale pilot, including a detailed
cost and schedule estimate for Phase III for the installation of the 10-MWe pilot
plant at the host site, followed by commissioning, start-up, operations, testing,
and data collection for performance validation.
• Complete NEPA process at the host site.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
94 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
• Draft permitting documentation to be submitted to appropriate authorities to initiate the permitting process and
develop a clear understanding of timelines that will support Phase III.
• Document secured cost share for Phase III.
• Secure commitments for all necessary Phase III team members, including an engineering, procurement, and
construction (EPC) firm to complete construction.
• Update the techno-economic analysis (TEA) for the Linde-BASF technology integrated with a 550-MWe net supercritical
pulverized coal power plant based on the most recent system design and cost information.
technical content
The Linde-BASF advanced CO2 capture process incorporating BASF’s novel amine-based solvent, OASE® blue, with
Linde’s process and engineering innovations allows for a significant increase in energy efficiency and reduced cost for
CO2 recovery from coal-based power plants. In addition to a reduction in regeneration energy and a lower solvent
circulation rate enabled by the BASF solvent, Linde has achieved significant improvements in process design, as shown in
Figure 1, featuring an advanced stripper inter-stage heater design to optimize heat recovery in the process. This results
in lower capital and operating costs for the CO2 capture system. The Linde-BASF technology addresses all the major
challenges for solvent-based carbon capture, including: (1) high specific energy for regeneration, (2) lack of stability due
to thermal and oxidative degradation, (3) increased corrosiveness with increased CO2 loading, and (4) lack of tolerance to
impurities from coal combustion products.
Previous testing of a 0.45-MWe pilot plant incorporating the Linde-BASF technology and utilizing lignite-fired power
plant flue gas has shown that the OASE® blue solvent is stable, with little degradation observed over 55,000 hours,
whereas the reference monoethanolamine (MEA) solvent started to degrade appreciably under the same conditions after
2,000 hours. The Linde-BASF CO2 capture process was also previously tested at 1.5-MWe-scale at the National Carbon
Capture Center (NCCC) under project DE-FE0007453, supported by the U.S. Department of Energy (DOE). The study
validated solvent stability and demonstrated a cyclic capacity 20% higher than MEA and regenerator steam consumption
25% lower than MEA. These results confirmed the ability of this technology to be cost-effective, energy efficient, and
compact. This project leverages work done previously through a DOE Phase I grant (DE-FE0026588), in which a 15-MWe
pilot plant of the Linde-BASF advanced CO2 capture technology was designed to be integrated with the University of
Illinois’ Abbott Power Plant on the campus of the University of Illinois at Urbana-Champaign (UIUC), with the goal of
capturing ~300 tonnes per day (tpd) of CO2 at a 90% capture rate. The 15-MWe pilot project aimed to optimize the
process at larger scale and gather performance data under realistic conditions to enable a robust commercial design.
Phase I of the project resulted in the completion of a preliminary plant design with basic engineering and cost estimates;
establishment of permitting needs; identification of approaches to address environmental, health, and safety concerns
related to pilot plant installation and operation; and completion of a detailed TEA, demonstrating that the implementation
of Phase II (Detailed Design, Construction, and Operation) of the project is feasible. The project also established strategies
for workforce development for the operation and maintenance of carbon capture systems based on the Linde-BASF
technology that are retrofitted to existing power plants.
The design and costing of the 10-MWe capture plant for installation at the selected host site – City, Water, Light, and
Power (CWLP) coal-fired power plant in Springfield, Illinois – was based on the estimate for the 15-MWe pilot in the
previous DOE-funded project and established industry-scaling factors. The capture system would be installed in the
Dallman 4 unit, which is a nominal 200-MWe pulverized coal-fired unit that became operational in 2009. The unit employs
a Foster Wheeler front and rear wall-fired pulverized coal boiler equipped with low-nitrogen oxide (NOX) burners; a
selective catalytic reduction (SCR) unit for NOX removal; a hydrated lime injection (HLI) system for sulfur trioxide (SO3)
removal; a fabric baghouse to capture particles; a flue gas desulfurization (FGD) system to mitigate sulfur dioxide (SO2)
emissions; and a wet electrostatic precipitator (ESP) to remove liquid droplets, such as sulfuric acid mist. For the 10-MWe
capture pilot, a slipstream flue gas from the Dallman 4 unit will be utilized as a feed gas for CO2 capture.
Based on results from small pilot studies and the TEA, the technology will achieve high CO2 capture (~90%) and generate
high-purity (greater than 99.9%) captured CO2 in a cost-effective manner. TEA results indicated that when the proposed
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
95
Post-Combustion Solvent Technologies
advanced Linde-BASF technology is integrated with a 550-MWe net supercritical pulverized coal power plant there will
be an increase in power plant efficiency of approximately 3% (relative), a nominal 11.4% reduction in COE, and an 18%
reduction in capital costs compared to the latest DOE/National Energy Technology Laboratory (NETL) base case (Case
B12B reference).
A. Flue gas blower provides enough pressure to overcome the
pressure drop across the pre-scrubber and absorber. The blower
location will be adjusted to host site-specific equipment in the most
cost-effective manner.
B. Integrated pre-scrubber and direct contact cooler to reduce SOX
content below 5 ppm and simultaneously cool the flue gas stream to
~35 -40°C.
C. Innovative and patented water wash section at the top of the
column to reduce amine losses, even in the presence of aerosols.
D. A gravity-driven inter-stage cooler for the absorber that eliminates
the pump and the controls.
E. High capacity structured packing reduces the absorber diameter,
thereby enabling a larger single-train plant construction.
F. Solvent-based heat exchanger designed to operate over a wide
range of temperature approaches, which provides the opportunity to
optimize the performance and capital cost trade-off.
G. Regenerator designed for operation at pressures up to 3.4 bar(a),
significantly reducing CO2 compression energy and eliminating the
bulky first stage of the CO2 compressor train, resulting in capital cost
savings.
H. Innovative plate and frame design of the reboiler minimizes
thermal degradation of solvent and provides for a lower solvent
inventory and faster dynamics to respond to power plant load
changes.
I. Stripper Inter-Stage Heater (SIH) enhances energy-efficient CO2
stripping from the solvent by recovering heat from the lean solvent to
provide intermediate reboil, thereby reducing energy consumption of
solvent regeneration.
J. Variations of the stripper-reboiler flashing configuration, which are
being evaluated for an ultimate reduction of solvent regeneration
Figure 1: Large pilot process configuration for Linde-BASF technology with highlighted energy.
design improvements.
K. Optional CO2 recycle stream, provided to evaluate the effect of
plant loading and variable CO2 concentration in the flue gas on overall
energy consumption, and to limit the effects of power plant loading
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 proprietary proprietary
Normal Boiling Point °C proprietary proprietary
Normal Freezing Point °C proprietary proprietary
Vapor Pressure @ 15°C bar(a) proprietary proprietary
Manufacturing Cost for Solvent $/kg — —
Working Solution
Concentration kg/kg proprietary proprietary
Specific Gravity (15°C/15°C) — proprietary proprietary
Specific Heat Capacity @ STP kJ/kg-K proprietary proprietary
Viscosity @ STP cP proprietary proprietary
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
96 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Absorption
Pressure bar(a) 1.0 0.9-1.1
Temperature °C 30-70 30-60
Equilibrium CO2 Loading mol/mol proprietary proprietary
Heat of Absorption kJ/mol CO2 proprietary proprietary
Solution Viscosity cP proprietary proprietary
Desorption
Pressure bar(a) 1.6-3.4 1.6-3.4
Temperature °C 124-140 124-140
Equilibrium CO2 Loading mol/mol proprietary proprietary
Heat of Desorption kJ/mol CO2 proprietary proprietary
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr LB1 Case: 2,718,270 SIH Case: 2,674,784
CO2 Recovery, Purity, and Pressure % / % / bar(a) 90%, 99.98% (dry), 3.4 bar(a)90%, 99.98% (dry), 3.4 bar(a)
Absorber Pressure Drop bar 0.1
Estimated Absorber/Stripper Cost of __$__
Manufacturing and Installation kg/hr
proprietary
Definitions:
Bar(a) – Unit used to indicate absolute pressure, where the reference pressure is absolute zero, i.e. not taking into account
atmospheric pressure.
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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97
Post-Combustion Solvent Technologies
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD unit (wet
basis) should be assumed as:
Composition
Pressure Temperature mol% ppmv
psig °F CO2 H2O N2 O2 Ar SOX NOX
0 135 9.8 17 67 5.3 0.80 34 30
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – CO2 in the flue gas chemically binds to the OASE blue® aqueous amine-based
solvent via an exothermic absorption step and this chemical bond is broken in the endothermic desorption step via heat
provided by steam in the reboiler of the regenerator column, generating pure CO2.
Solvent Contaminant Resistance – The OASE® blue solvent is highly resistant against many contaminants in the flue
gas, as shown in both parametric and long-term continuous tests (see Electric Power Research Institute [EPRI] report[1] for
additional information).
Solvent Foaming Tendency – During the pilot plant operation, although anti-foaming injection was included in the
design, its use was not found necessary.
Flue Gas Pretreatment Requirements – The pretreatment requirement includes reducing sulfur oxide (SOX) in the flue
gas to 2 to 5 parts per million (ppm) in order to limit solvent degradation and is implemented in a direct contact cooler
in conjunction with flue gas cooling, typically by adding appropriate amount of sodium hydroxide corresponding to the
SOX present in the flue gas.
Solvent Makeup Requirements – The OASE blue® solvent makeup rate is determined by the sum of the amine losses in
the treated gas leaving the absorber column and the rate of solvent degradation during operation over time. Low makeup
rates were observed during long-term testing well below an operationally manageable threshold. Low solvent makeup is
expected at scale when processing flue gas from power plants with a baghouse filter for particulate removal or with
upstream flue gas pretreatment for aerosol mitigation.
Waste Streams Generated – The main waste liquid stream is from the direct contact cooler where SOX and NOX are
removed; this stream is typically handled in the power plant waste water treatment facility. A small amount of solid waste
is removed using an activated carbon filter and mechanical cartridge filter that are replaced at regular intervals. Since the
solvent degradation observed in the pilot testing is small, no solvent reclamation unit is envisioned in the large scale.
Process Design Concept – See Figure 1.
Proposed Module Design – Free standing absorber and stripper columns will be tied into a modularized process skid.
There will be associated containers for electrical equipment, analytical equipment, and process control.
technology advantages
• Significant reduction in specific regeneration steam consumption (24 to 40% lower), electrical power (14 to 26% lower),
and cooling water duty (32 to 43% lower) compared to a reference MEA plant.
• Increased higher heating value efficiency (HHV) for power production (up to ~31.7% efficiency) and lower thermal load
compared to a reference MEA plant (28.4% efficiency) due to a combination of advanced solvent and process
improvements, including integrated pre-scrubber and direct contact cooler, downstream gas blower, higher desorber
pressure, and interstage gravity-flow cooler.
• The total plant costs are ~20% lower compared to a reference MEA plant, with significantly lower post-combustion
capture plant capital costs.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
98 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
• The Linde-BASF technology is readily scalable to large capacities with a single-train system, offering the potential to
further reduce costs by utilizing economies of scale.
• BASF is the producer of the OASE blue® solvent and the owner of the solvent technology. A major global player in the
chemical industry, BASF has the capabilities to reliably produce and supply the OASE blue® solvent in sufficient
volumes needed for commercialization, thereby enabling application at scale by avoiding issues related to solvent
manufacturing for large-scale commercial plants.
• The Linde-BASF partnership combines the necessary capabilities and experience to deliver the complete CO2 capture
technology value chain from solvent production to full-scale CO2 capture plant EPC, commercial deployment, and
long-term, continuous operations.
R&D challenges
• Scale-up of absorber column at low cost, maintaining uniform vapor and liquid distribution.
• Optimizing operation of the stripper to reduce steam utilization and increase energy efficiency of the CO2 capture
process using advanced stripper configurations and stripper inter-stage heating.
• Managing flue gas impurities and aerosol formation to reduce amine losses.
• Testing of new process units for energy optimization.
• Integration with operations at the CWLP host site.
status
In Phase I, the CWLP coal-fired power plant in Springfield, Illinois, was selected as the host site for the large pilot (10
MWe) capture plant and Phase II cost-share commitments were finalized. Preliminary engineering and cost estimates
were prepared for the equipment inside the battery limit (ISBL) and outside the battery limit (OSBL). A NEPA contractor
(ICF Jones & Stokes, Inc.) was also selected as part of the Phase I effort. A plan was developed for securing cost-share
commitments for Phase III. Phase II efforts are underway and will conclude with completion of a FEED study, NEPA process,
permitting documentation, and team member commitments.
available reports/technical papers/presentations
O’Brien, K. C., “PHASE II: Large Pilot Testing of Linde-BASF Advanced Post-Combustion CO2 Capture Technology at a
Coal-Fired Power Plant (FE0031581),” Phase II Kick-off Meeting, October 2019. https://www.netl.doe.gov/projects/plp-
download.aspx?id=16815&filename=FE0031581_Phase II Kickoff_10-02-19.pptx.
O’Brien, K. C., “PHASE II: Large Pilot Testing of Linde-BASF Advanced Post-Combustion CO2 Capture Technology at a
Coal-Fired Power Plant (FE0031581),” presented at the 2019 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/K-O'Brien-UIUC-Linde-BASF-Capture.pdf.
O’Brien, K. C., “Large Pilot Testing of Linde-BASF Advanced Post-Combustion CO2 Capture Technology at a Coal-Fired
Power Plant,” presented at the 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August
2018. https://netl.doe.gov/sites/default/files/netl-file/K-OBrien-ISTC-Linde-BASF-Post-Combustion-CO2-Capture.pdf.
“Large Pilot Testing of Linde-BASF Advanced Post-Combustion CO2 Capture Technology at a Coal-Fired Power Plant,”
Phase I Kick-off Meeting, May 2018. https://netl.doe.gov/projects/files/FE0031581-Kick-off-Presentation-05-10-18.pdf.
O’Brien, K. C., “Large Pilot Scale Testing of Linde/BASF Post-Combustion CO2 Capture Technology at the Abbott Coal-
Fired Power Plant,” Final Report, August 2017. https://www.osti.gov/servlets/purl/1375438.
O’Brien, K. C., “Phase I Results: Large Pilot Scale Testing of Linde/BASF Post-Combustion CO2 Capture Technology at the
Abbott Coal-Fired Power Plant,” presented at the 2016 NETL CO2 Capture Technology Project Review Meeting,
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
99
Post-Combustion Solvent Technologies
Pittsburgh, PA, August 2016. https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/2-
Tuesday/K-OBrien-UIllinois-Testing-at-Abbott-Power-Plant.pdf.
Krishnamurthy, K. R., “Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Technology for
Carbon Dioxide Capture from Coal-Fired Power Plant Flue Gas,” Final Scientific/Technical Report, February 2017.
https://www.osti.gov/servlets/purl/1342508.
Bostick, D., et al., “Final Techno-Economic Analysis of 550 MWe Supercritical PC Power Plant with CO2 Capture using the
Linde-BASF Advanced PCC Technology,” Topical Report of final techno-economic analysis, January 2017.
https://www.osti.gov/servlets/purl/1338328.
Krishnamurthy, K. R., “Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology
for CO2 Capture from Coal-Fired Power Plant Flue Gas,” presented at the 2016 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, August 2016. https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/2-
Tuesday/K-Krishnamurthy-Linde-Amine-Based-Process-Technology.pdf.
Krishnamurthy, K. R., “Development and Scale-up of an Advanced Aqueous Amine-Based Post-Combustion CO2 Capture
Utilizing BASF’s OASE® Blue Technology,” presented at the 2016 Carbon Capture, Utilization, and Storage Conference,
Tysons, VA, June 2016.
Krishnamurthy, K. R., “Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology
for CO2 Capture from Coal-Fired Power Plant Flue Gas,” presented at the 2015 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, June 2015. https://netl.doe.gov/sites/default/files/event-proceedings/2015/co2captureproceedings/K-
Krishnamurthy-Linde-Pilot-Novel-Amine.pdf.
Stoffregen, T., et al., “Pilot Plant Demonstration of an Advanced Amine-Based Post-Combustion Capture Technology for
CO2 Capture from Power Plant Flue Gases,” presented at the 12th Greenhouse Gas Control Technologies (GHGT-12)
Conference,” Austin, TX, October 2014.
Krishnamurthy, K. R., “Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology
for CO2 Capture from Coal-Fired Power Plant Flue Gas,” presented at the 2014 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2014. https://netl.doe.gov/sites/default/files/event-
proceedings/2014/2014%20NETL%20CO2%20Capture/K-Krishnamurthy-Linde-Slipstream-Pilot-Scale-Demonstration.pdf.
Jovanovic, S., et. al., “Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Technology for
Carbon Dioxide Capture from Coal-Fired Power Plant Flue Gas,” Topical Report: Techno-Economic Analysis of 550 MWe
subcritical PC power plant with CO2 capture, May 2012. https://netl.doe.gov/sites/default/files/2017-12/techno-economic-
analysis-topical-rpt-may2012.pdf.
Krishnamurthy, K. R., “Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology
for CO2 Capture from Coal-Fired Power Plant Flue Gas,” presented at the 2013 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2013. https://netl.doe.gov/sites/default/files/event-proceedings/2013/co2%20capture/K-
Krishnamurthy-Linde-Slipstream-Demo-of-Novel-Amine-Based-P.pdf.
Krishnamurthy, K. R., “Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology
for CO2 Capture from Coal-Fired Power Plant Flue Gas,” presented at the 2012 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2012. https://netl.doe.gov/sites/default/files/event-proceedings/2012/CO2%20Capture%20Meeting/K-
Krishnamurthy-Linde-Pilot-scale-Amine.pdf.
references
BASF-Linde Post Combustion Carbon Capture Pilot Plant at the National Carbon Capture Center, 2016 Test Campaign
[1]
Results, EPRI, February 2017.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
100 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Development and Bench- technology maturity:
Bench-Scale (40 kwe),
Scale Testing of a Novel Simulated Flue Gas and
Actual Flue Gas Slipstream
Biphasic Solvent-Enabled project focus:
Absorption Process for Post- Biphasic Solvents for CO2
Combustion Carbon Capture
Absorption
participant:
University of Illinois at
primary project goals Urbana-Champaign
The University of Illinois at Urbana-Champaign (UIUC) will advance the project number:
development of a novel biphasic carbon dioxide (CO2) absorption process (BiCAP) FE0031600
and validate its technical advantages by testing an integrated system at a 40-
kilowatt-electric (kWe) bench scale with actual coal-derived flue gas. The proposed predecessor project:
novel water-lean biphasic solvents have previously demonstrated (FE0026434) the FE0026434
desired vapor-liquid equilibrium (VLE) behavior, rapid absorption kinetics, and
high stability in lab-scale characterization experiments, and individual major NETL project manager:
process steps have been tested on the lab-scale equipment or assessed by Andrew jones
modeling studies. This project will move the technology development forward via [email protected]
fully integrated bench-scale testing in a relevant flue gas environment.
principal investigator:
Yongqi Lu
technical goals
Illinois State Geological
Survey, University of Illinois at
• To develop process simulations using an Aspen Plus model to determine the Urbana-Champaign
optimal process configuration and operating conditions. [email protected]
• Investigate biphasic solvent losses, emission control, and reclamation of the
degradation products. partners:
Trimeric Corporation
• Design, fabricate, and test a 40-kWe integrated bench-scale biphasic solvent-
based capture unit with simulated flue gas. A subsequent test will use a flue gas
start date:
slipstream from a coal-fired power plant.
4.06.2018
• Assess the techno-economic performance of the technology integrated into a
net 550-megawatt-electric (MWe) coal-fired power plant. percent complete:
• Analyze technology gaps and potential environmental, health, and safety 35%
(EH&S) risks to advance the technology toward further scale-up and
commercialization.
technical content
The BiCAP utilizes biphasic solvents, which are water-lean solvent blends, that can
form and develop dual liquid phases, with the absorbed CO2 highly enriched in
one of the phases and lean solvent in the other. The phase transition behavior of
a biphasic solvent is illustrated in Figure 1. The process features multiple stages of
liquid-liquid phase separation (LLPS) during CO2 absorption to maximize the CO2
absorption kinetics and minimize the increase in solvent viscosity.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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101
Post-Combustion Solvent Technologies
Figure 1: Phase transition behavior of a biphasic solvent.
A schematic diagram of the BiCAP is shown in Figure 2. The flue gas, after the desulfurization and sulfur dioxide (SO2)
polishing stages, enters the absorption column, which contains multiple stages of packed beds, and the CO2 is absorbed
into a biphasic solvent. At each stage, upon CO2 loading, the biphasic solvent undergoes a phase transition and forms
dual liquid phases. The CO2-enriched phase is separated and collected in a rich solvent tank. The CO2-lean phase then
flows to a heat exchanger to reduce the solvent temperature before entering the next stage of the packed bed. At the
last stage, the solvent exiting the absorber is sent to an LLPS tank, in which the CO2-enriched phase is pumped into the
rich solvent tank. Both the hot and cold rich solvents are fed to a flash/stripper to remove CO2, while the CO2-lean phase
is mixed with the regenerated solvent from the CO2 stripper before recycling to the absorber. The CO2 product streams
from both the flash and stripper are cooled and compressed.
Key features of the BiCAP include: (1) a unique process configuration of multi-stage CO2 absorption and phase transition
allows continual separation and removal of the CO2-enriched liquid phase, maintaining rapid kinetics and low solvent
viscosity throughout CO2 absorption; (2) only the CO2-enriched liquid phase is used for CO2 desorption, thus lowering
the mass flow of solvent required for regeneration; (3) a combination of flash and CO2 stripping operations allows the
high pressure of CO2 desorption to further improve the energy efficiency; and (4) a portion of cold feed stream enters the
stripping column bypassing the cross heat exchanger further reduces the stripping heat requirement.
In a previous U.S. Department of Energy (DOE)-funded project (FE0026434), the BiCAP was tested at laboratory scale (10
kWe) and exhibited a 34% reduction in parasitic power requirements and twice the CO2 working capacity for desorption
when compared with a process using the amine-based solvent, monoethanolamine (MEA). After determining the optimal
process configuration and operating conditions, the team will design and fabricate the 40-kWe integrated bench-scale
capture unit. Parametric testing for two of the best performing biphasic solvents identified from previous research
(FE0026434) will be conducted with simulated flue gas at UIUC’s Abbott power plant. One selected solvent will be further
evaluated with a slipstream of coal-derived flue gas at the power plant. The team will use the test results to prepare a
techno-economic analysis (TEA), as well as an analysis of the technology gaps and potential EH&S risks, to advance the
technology for further scale-up and commercialization.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
102 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Figure 2: Schematic diagram of the BiCAP with multiple stages of LLPS.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 60-240 <230
Normal Boiling Point °C 140-300 >140
Normal Freezing Point °C -30 to 110 <20
Vapor Pressure @ 20 °C bar 1x 10-5 to 4 x 10-3 <1.0 x 10-3
Manufacturing Cost for Solvent $/kg 3-10 <15
Working Solution
Concentration kg/kg 0.6-0.8 >0.5
Specific Gravity (15 °C/15 °C) - ~1.0 0.9–1.4
Specific Heat Capacity @ STP kJ/kg-K 2.5–3.5 <3.5
Viscosity @ STP cP 2-15 <20
Absorption
Pressure*
0.05 (equilibrium PCO2 at
bar <0.07
absorber bottom)
Temperature °C 40 30–50
Equilibrium CO2 Loading 0.375-0.625
mol/mol >0.375
(0.7-1.0 in rich phase)
Heat of Absorption kJ/mol CO2 65-85 ~75
Solution Viscosity 5–10/30–50 (upper/lower <100
cP phases) (CO2-enriched phase)
Desorption
Flash
Pressure** bar 4-9 (5-11 in total) ≥7 (10 in total)
Temperature °C 100-140 <140
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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103
Post-Combustion Solvent Technologies
Equilibrium CO2 Loading mol/mol 0.4-0.7
Stripping (lean solution)
Pressure*** bar 2-5 (3-7 in total) ≥3 (≥4 in total)
Temperature °C 120-150 <150
Equilibrium CO2 Loading mol/mol 0.05-0.35 <0.25
Heat of Desorption (flash + stripping) kJ/mol CO2 65-85 ~75
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr not available
CO2 Recovery, Purity, and Pressure %/%/bar 90% / >99% / >4
Absorber Pressure Drop Bar 0.14
Estimated Absorber/Stripper Cost of __$__
not available
Manufacturing and Installation kg/hr
*CO2 partial pressure in the flue gas; **CO2 partial pressure exiting flash; ***CO2 partial pressure exiting stripper
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
104 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The developed solvent belongs to a new class of biphasic solvents. The solvent
is a blend of amines or the like and is a water-lean system containing less than 30 wt% water. The solvent absorbs CO2
through chemical reactions between amines and CO2. The solvent undergoes a phase transition to form dual liquid phases
based on the difference of hydrophobicity between different species.
Solvent Contaminant Resistance – The developed biphasic solvent is highly resistant to oxygen and heat. Experiments
revealed that the oxidative degradation of the biphasic solvent was eight times slower than the benchmark MEA under
similar absorption conditions and its thermal stability at 150°C was comparable to the benchmark MEA at 120°C.
Solvent Foaming Tendency – No foaming issue was observed for the biphasic solvent, either in a gas bubbler tested
continually for two weeks or in a laboratory absorption column operated intermittently for several months.
Flue Gas Pretreatment Requirements – The flue gas leaving the FGD needs be further polished to reduce the content
of SO2 below 10 parts per million volume (ppmv).
Solvent Makeup Requirements – Laboratory solvent stability experiments indicate that the makeup requirement of the
biphasic solvent is lower than the benchmark MEA (i.e., less than 2 kg/ton CO2 captured).
Waste Streams Generated – Waste streams from the BiCAP are similar to those from amine-based processes, including
flue gas condensate, water wash blowdown, cooling water blowdown, heat stable salts, spent solvent wastes, and spent
solvent reclamation materials (e.g., activated carbon).
Process Design Concept – See Figure 2.
technology advantages
• BiCAP maintains rapid kinetics throughout the CO2 absorption process and thus can reduce the footprint and cost of
absorption equipment compared with either MEA or other biphasic solvent-based processes.
• BiCAP is able to maintain the solvent at a lower viscosity and thus retain rapid mass transfer in the absorber, potentially
increasing the CO2 working capacity of the solvent and reducing the footprint and capital cost of the absorber.
• The combination of flash and stripping operations achieves high-pressure CO2 desorption and thus lowers the energy
use for CO2 separation and compression.
• BiCAP desorption configuration with a cold rich solvent stream directly fed to the top of the stripper results in reduced
water vapor in the CO2 stream and thus further reduces the stripping heat duty.
• The energy efficiency advantages of the BiCAP coupled with reduced equipment sizes when scaled-up for commercial
systems leads to reductions in both capital and operating expenses compared with the benchmark MEA process.
R&D challenges
• Develop methods for controlling solvent losses caused by volatility of the selected biphasic solvents.
• Identifying the optimal process design and operating conditions for the proposed BiCAP.
• Developing methods for solvent reclamation with high efficiency and low environmental impact.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
105
Post-Combustion Solvent Technologies
• Demonstrating reliable operation and stable performance of the bench-scale unit in an actual power plant
environment.
status
The solvent volatility and losses studies on the two biphasic solvents were completed, and a preliminary assessment of
water wash option and performance completed to provide inputs for equipment design. The host site agreement was
finalized with Abbot Power. Also, the 40-kWe bench-scale capture equipment design was completed with the optimal
process identified. The design calculations show that the unit can meet the performance targets (e.g., heat duty less than
or equal to 2,100 kJ/kg of CO2 and stripping pressure greater than or equal to 4 bar). The experimental studies of solvent
degradation reclamation were conducted, and a suitable method for biphasic solvent reclamation was identified. The
bench-scale unit fabrication process is underway, with multiple vendors under consideration.
available reports/technical papers/presentations
Lu, Y. “Development and Bench-Scale Testing of a Novel Biphasic Solvent-Enabled Absorption Process for Post-
Combustion Carbon Capture, Aug 2019, 2019 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA.
https://netl.doe.gov/sites/default/files/netl-file/Y-Li-UIUC-Novel-Biphasic-Solvent.pdf.
Nielsen, P. “Development and Bench-Scale Testing of a Novel Biphasic Solvent-Enabled Absorption Process for Post-
Combustion Carbon Capture, Aug 2018, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA.
https://www.netl.doe.gov/projects/files/P-Nielsen-UIUC-Biphasic-Solvent-Enabled-Absorption-Process.pdf.
Lu, Y., “Development and Bench-Scale Testing of a Novel Biphasic Solvent-Enabled Absorption Process for Post-
Combustion Carbon Capture, May 2018, kick-off meeting presentation.
https://www.netl.doe.gov/projects/files/FE0031600-Kick-off-Presentation-051018.pdf.
Du, Y., et al., “A Novel Water-Lean Biphasic Solvent System for CO2 Capture,” presented at the 4th University of Texas
Conference on Carbon Capture and Storage, Austin, Texas, February 2018.
Sachde, D., et al., “Economic Analysis of a Water-Lean Biphasic Solvent,” presented at the 4th University of Texas
Conference on Carbon Capture and Storage, Austin, Texas, February 2018.
Du, Y., et al., “A Novel Biphasic Solvent for Post-Combustion CO2 Capture,” presented at the 4th Post-Combustion
Capture Conference, Birmingham, Alabama, September 2017.
Lu, Y., “Development of a Novel Biphasic CO2 Absorption Process with Multiple Stages of Liquid-Liquid Phase
Separation for Post-Combustion Carbon Capture,” presented at the 2017 NETL CO2 Capture Technology Project Review
Meeting, Pittsburgh, PA, August 2017. https://www.netl.doe.gov/projects/files/Y-Lu-ISGS-Biphasic-CO2-Absorption-
Process_2017.pdf.
Lu, H., et al., “Bench-Scale Testing of CO2 Absorption with a Biphasic Solvent in an Absorption Column with Staged
Phase Separations,” presented at the 2017 Carbon Capture, Utilization & Storage Conference, Chicago, IL, April 2017.
Lu, Y., “Development of a Novel Biphasic CO2 Absorption Process with Multiple Stages of Liquid-Liquid Phase
Separation for Post-Combustion Carbon Capture,” Budget Period 1 Project Review Meeting presentation, Pittsburgh,
PA, June 2017. https://www.netl.doe.gov/projects/files/FE0026434-BP1-Review-Presentation-06-08-17.pdf.
Lu, Y., “Development of a Novel Biphasic CO2 Absorption Process with Multiple Stages of Liquid-Liquid Phase
Separation for Post-Combustion Carbon Capture,” presented at the 2016 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, August 2016. https://www.netl.doe.gov/sites/default/files/event-
proceedings/2016/c02%20cap%20review/4-Thursday/Y-Lu-ISGS-Biphasic-CO2-Absorption-Process.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
106 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
“Development of a Novel Biphasic CO2 Absorption Process with Multiple Stages of Liquid-Liquid Phase Separation for
Post-Combustion Carbon Capture,” Project Kickoff Meeting presentation, Pittsburgh, PA, December 2015.
https://www.netl.doe.gov/projects/files/FE0026434-Kick-off-Presentation-12-11-15.pdf.
Ye, Q., et al., “Screening and Evaluation of Novel Biphasic Solvents for Energy-Efficient Post-Combustion CO2 Capture,”
International Journal of Greenhouse Gas Control, Volume 39, August 2015, pp. 205-214.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
107
Post-Combustion Solvent Technologies
Molecular Refinement of technology maturity:
Laboratory-Scale
Transformational Solvents for project focus:
CO2 Separations Molecular Refinement of
water-Lean Solvents
primary project goals participant:
Pacific Northwest National
Pacific Northwest National Laboratory (PNNL) aims to perform molecular Laboratory
refinement of third-generation water-lean solvents during this project. The
objectives are to reduce volatility while retaining desirable physical and project number:
thermodynamic properties, study the molecular underpinnings of solvent FwP-72396
degradation (e.g., hydrolysis, nitration, oxidation), design new molecules that are
resistant to these chemical degradations, and decrease infrastructure capital predecessor project:
expenditures (CAPEX) while increasing longevity by replacing steel with cheaper FwP-65872
and more durable plastics. This proposal builds on PNNL’s integrated solvent
development approach, with an integrated effort combining the elements of NETL project manager:
computation, advanced synthesis and testing capabilities, and comprehensive Isaac Aurelio
material property testing to refine advanced solvent performance while also [email protected]
reducing the CAPEX of these third-generation solvents.
principal investigator:
David Heldebrant
technical goals Pacific Northwest National
Laboratory
• Refine third-generation carbon dioxide (CO2)-binding organic liquid (CO2BOL) [email protected]
solvents (aminopyridines [APs], diamines [DAs]) to reduce volatility while
retaining favorable viscosity and CO2 bonding enthalpy.
partners:
N/A
• Learn the molecular underpinnings of chemical degradation and develop
strategies to mitigate or remove solvent decomposition with flue gas impurities,
start date:
such as sulfur oxides (SOX), nitrogen oxides (NOX), oxygen (O2), and hydrolysis.
05.01.2018
• Measure the contact angles of water-lean solvents at varied CO2 and water
loadings on plastic surfaces and assess whether plastic infrastructure could be percent complete:
used in place of steel. 55%
• Assess the reduction in CAPEX by substituting steels with fiber-reinforced
plastic to determine progress towards $30/tonne CO2 target.
• Disseminate all findings to the U.S. Department of Energy (DOE), Carbon
Capture Simulation for Industry Impact (CCSI2), and peer-reviewed publications.
technical content
The PNNL team aimed to refine the secondary and tertiary properties that are
limiting for water-lean CO2BOL solvents. It was anticipated that the vapor pressure
of third-generation solvents, such as APs or DAs, would be reduced to sub-parts-
per-million (ppm) levels, effectively negating evaporative losses of solvent. PNNL
expected to learn the reaction mechanisms of chemical degradations of carbamate
and alkylcarbonate solvent molecules and learn how to redesign new molecules that
are resistant to oxidation, nitration, and hydrolysis. PNNL aimed to demonstrate that
new formulations will exhibit an increase in solvent lifetime by two to four times.
PNNL also expected that water-lean solvents under operating conditions (~ less
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
108 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
than 10 wt% water, 40°C, 0 to 50 mol% CO2 loading) will be able to adequately wet plastics, enabling the substitution of
cheaper and more chemically durable plastic to be used in place of steel. The removal of steel will effectively cease corrosion,
improving solvent lifetime while negating the need for costly corrosion inhibitors. The substitution for fiber-reinforced
plastics like polyethylene or polypropylene are estimated to provide an estimated 50% reduction in CAPEX for absorbers,
strippers, and piping. These cost reductions are anticipated to help reduce CAPEX of carbon capture and storage (CCS) to
enable third-generation solvents to meet DOE’s prior $40/tonne cost metric, with the potential to achieve the revised
$30/tonne metric.
PNNL was tasked with resolving three key problems associated with aminosilicone solvents: (1) susceptibility to
disproportionation and hydrolysis; (2) significantly high CO2-rich viscosity of the solvents; and (3) the need for co-solvent,
thereby leading to increased capital and operational costs. To address all these challenges, the team has been working
towards developing a novel DA-based system. In order to overcome the hydrolysis and disproportionation issues related to
amino silicones, the silicone moiety was replaced with alkyl chains; however, these solvents solidified upon standing when
CO2 was loaded. It was hypothesized that two secondary amines were providing too much hydrogen bonding, so tertiary
amine moieties were incorporated to reduce viscosity and solidification. The team started by designing a library for
secondary/tertiary amines. The challenge was to down-select hundreds of molecules to a few candidate derivatives that
would have a low viscosity. PNNL applied its previously developed reduced-order model to a library (Figure 1) to down-
select to final derivatives. Their CO2 uptake capacities were also evaluated. Several other analogues of DAs are in the process
of being synthesized, as shown in Figure 1 (in the pipeline), in order to fully develop the structure activity relationship.
Figure 1: Selected library for non-volatile, low-viscosity secondary/tertiary diamines.
In order to address the volatility issue associated with the second-generation aminopyridine class of CO2 capture solvents,
two low-vapor pressure derivatives were prepared from modeling efforts to synthesize. These third-generation APs were
functionalized with ether and morpholine motifs to promote high internal hydrogen bonding, but to also reduce vapor
pressure. The synthetic approach for these two derivatives involved the condensation of 2-pyridinecarboxaldehyde with
the corresponding amines to in situ generate imines, which were reduced by the treatment with sodium borohydride to
yield 8a 3-methoxy-N- (pyridin-2-ylmethyl)propan-1-amine and 8b 2-morpholino-N-(pyridin-2-ylmethyl)ethan-1-amine
in 70% and 68% yields, respectively (Figure 2).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
109
Post-Combustion Solvent Technologies
Figure 2: Synthetic methodology for the synthesis of third-generation aminopyridine derivatives.
Once the AP and DA screenings were completed, the synthesis team started designing synthesis routes and began
synthesis of the viable derivatives for comprehensive material property testing. For the testing, 50 grams (g) of the
candidate derivatives were synthesized, and their physical and thermodynamic properties were evaluated using the in-
house built pressure-volume-temperature (PVT) cell. Based on the results, PNNL recommends further testing on 8a as the
final candidate AP for larger-scale testing, as it is cheaper, has lower molecular weight while having a lower CO2-rich
viscosity, and has stronger CO2 sorption as compared to other AP derivatives. PNNL recommends 2-EEDEDA as the final
DA candidate, as it has a low molecular weight, comparable CO2 sorption as compared to other DA derivatives, while
having the lowest CO2-rich viscosity of any known water-lean solvent ever developed.
PNNL performed large-scale molecular simulations to assess wetting properties and surface energies of a representative
CO2BOL alkanolguanidine (1-IPADM-2-BOL) adhered to 316 stainless steel and polyethylene interfaces. The goal was to
determine what molecular-level interactions occur on either interface to determine how organics can wet stainless steel
almost as well as plastic. Further, a second goal was to determine any reactions between the solvent molecules and the
interface, to provide a better understanding of solvent durability. The simulations showed negligible interactions between
1-IPADM-2-BOL and a model polyethylene surface, whereas strong interactions were observed on a steel interface. It was
noted that the iron (Fe) atoms appeared to catalyze a reaction between two solvent molecules through mediated proton
transfer, suggesting a potential mechanism of degradation (i.e., hydrolysis) that would occur for water-lean and aqueous
formulations. The solvent at the interface was observed to partially degrade, leaving an organic coating on the steel
interface. These simulations suggest that a steel interface could be catalytic with respect to decomposition reactions of
the solvent, such as hydrolysis. They also shed light as to why organics can wet steel interfaces almost as well as plastic.
This phenomenon was not observed on the polyethylene plastics, suggesting the solvent would not degrade by these
means on a plastic interface, indicating that solvent lifetime would be higher on plastic packings than on stainless as
hypothesized.
PNNL has continued contact angle measurements to determine the wettability of water-lean solvents on different
surfaces. PNNL has continued using ASTM standard (current version: ASTM D7334-08 [2013]), which requires at least six
measurements at 23 ± 2°C on drops with consistent size. The contact angle measurements are especially important when
determining the material composition of the reactors and their interactions with liquid reactants.
In the experimental approach, four surfaces cut in 2-inch by 2-inch pieces were used: Teflon®, Ultra High Molecular
Weight Polyethylene (UHMWPE), polyetheretherketone (PEEK), and 314 stainless steel. The plastics were chosen due to
their chemical and temperature resistance, while the 314 stainless steel is a material currently used in the industrial
installations and serves as a benchmark. The results can be seen in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
110 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
TABLE 1: CONTACT ANGLE MEASUREMENTS OF SOLVENTS ON VARIOUS SURFACES
The current data indicates that the best wettability of the surface is achieved in case of the PEEK surface. The results
obtained for this batch of experiments indicate superiority of the plastic over the commercially used steel. This result is
encouraging, as by removing steel from the system, one can slow down decomposition of the solvents and corrosion of
equipment.
TABLE 2: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 216.3 -
Normal Boiling Point °C 181.0 -
Normal Freezing Point °C <0 -
Vapor Pressure @ 15°C bar 5E-5 -
Manufacturing Cost for Solvent $/kg 13 10
Working Solution
Concentration kg/kg 0.98 (hydrated) -
Specific Gravity (15°C/15°C) - 0.94 -
Specific Heat Capacity @ STP kJ/kg-K 1.95 -
Viscosity @ 15°C cP 11.3 -
Absorption
Pressure bar 1 -
Temperature °C 40 -
Equilibrium CO2 Loading mol/mol 0.29 -
Heat of Absorption kJ/mol CO2 75 -
Solution Viscosity cP 25 -
Desorption
Pressure bar 1.8 -
Temperature °C 117 -
Equilibrium CO2 Loading mol/mol 0.05 -
Heat of Desorption kJ/mol CO2 75 -
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
111
Post-Combustion Solvent Technologies
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2.6E6
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 90
Absorber Pressure Drop bar <0.1
Estimated Absorber/Stripper Cost of __$__
pending
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical.
Solvent Contaminant Resistance – Oxidative degradation and hydrolysis studies indicate solvents are more durable
than 5M MEA under comparable oxidation and hydrolysis testing.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
112 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Solvent Foaming Tendency – Solvent has shown no propensity to foam under operating conditions.
Flue Gas Pretreatment Requirements – Small up-stream cooling is required to reduce water accumulation.
Solvent Makeup Requirements – Not yet available.
Waste Streams Generated – Not yet available.
Process Design Concept – Not yet available.
technology advantages
• Oxidation, foaming, aerosol formation, and corrosion issues are mitigated.
• The solvent volatility is reduced while still maintaining a favorable viscosity.
• The solvent lifetime is increased.
• Adequate wettability of solvents on plastic surfaces enables possible replacement of steel process infrastructure,
reducing CAPEX and eliminating need for corrosion inhibitors.
R&D challenges
• There is potential for the nitration of solvents by NOX potentially making nitrosamines.
• The chemical and physical durability of plastics in presence of solvents and the pressure, temperatures, and stresses of
the system must be proved.
• Manufacturing costs for the solvents must be acceptable.
status
All remaining third-generation DA and AP solvents have been synthesized and tested for vapor liquid equilibrium (VLE),
viscosity, and mass transfer measurements in the PVT cell. There is one derivative that appears to have comparable CO2
bonding strength to that of 1-BEIPADIPA-2-BOL, while also exhibiting the lowest CO2-rich viscosity (29 cP) of any solvent
to come from any of the three solvent classes in the laboratory.
Solvent decomposition findings indicate CO2BOLs such as 1-IPADM-2-BOL (and aqueous amines) are likely to degrade
on steel, suggesting plastics are a better choice for solvent longevity in addition to cost.
The theory team has now started calculations to derive contact angles and surface energies to further shed light on the
wetting behavior of solvents on stainless steel versus plastics. This knowledge will help shed light as to which packing
material will perform best with water-lean solvents as compared to aqueous solvents. Lastly, the experimental team has
nearly completed contact angle measurements for varied water-lean solvents on PEEK plastic using ASTM D7334-08.
available reports/technical papers/presentations
Freeman, C. “Molecular Refinement of Transformational Solvents for CO2 Separations,” presented at the 2019 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-
file/C-Freeman-PNNL-Molecular-Refinement.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 113
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Mixed-Salt-Based technology maturity:
Transformational Solvent
Laboratory-Scale, Simulated
Flue Gas
Technology for CO2 Capture project focus:
Advanced Mixed-Salt
Solvent Process
primary project goals
participant:
SRI International is developing a novel, water-lean, mixed-salt-based SRI International
transformational solvent technology to provide a step-change reduction in the cost
and energy penalties of post-combustion carbon dioxide (CO2) capture.
project number:
FE0031597
technical goals
predecessor projects:
• Demonstrate that the advanced mixed-salt process (A-MSP) can: N/A
o Operate as a solvent-rich system with a very high cyclic CO2-loading
capacity (greater than 0.10 kilogram [kg] CO2/kg of solvent). NETL project manager:
o Regenerate CO2 at greater than 10 bar at temperatures less than 120°C. Andrew Jones
o Operate continuously in an integrated absorber-regenerator using [email protected]
simulated flue gas with 13 to 15% CO2 and balance air.
principal investigator:
• Perform thermodynamic modeling and vapor-liquid equilibrium (VLE)
measurements of multi-component systems. Palitha Jayaweera
SRI International
• Conduct kinetic measurements of CO2 absorption of select compositions.
[email protected]
• Conduct solvent degradation and aerosol formation studies.
• Perform bench-scale testing of integrated absorber-regenerator system. partners:
• Develop a rate-based model and process flowsheet and perform a techno- OLI Systems, Inc., SINTEF,
economic analysis (TEA) to aid identification of development pathways for Technical University of
technology advancement. Denmark, Trimeric
Corporation
technical content start date:
06.01.2018
SRI International, in collaboration with SINTEF, Technical University of Denmark
(DTU), OLI Systems, Inc., and Trimeric Corporation, are utilizing the knowledge
gained during a U.S. Department of Energy (DOE)-funded project (FE0012959) in percent complete:
the design of a mixed-salt process (MSP) that uses a solvent formulation 45%
comprised of ammonium (NH4) and potassium (K) salt solutions to develop a
transformational technology that achieves further improvements in performance.
An analysis conducted by SRI indicates that inclusion of a tertiary amine to the
mixed-salt formulation will yield a high CO2-loading capacity and high-pressure
solvent regeneration at low temperature, thus further reducing the energy penalty
of CO2 capture.
Bench-scale testing of SRI’s first-generation MSP under FE0012959 showed that
the two-component system has significant advantages over single-component
systems. In the MSP chemistry, ammonia (NH3) plays a dual role – the role of
catalyst and the role of the absorbent due to its high mobility and reactivity with
CO2. Ammonia absorbs large amounts of CO2 at low temperature and releases
CO2 at high temperature and pressure, making it a highly useful chemical in CO2
absorption formulations. By blending NH3 with other low-capacity and low-
reactivity components to suppress the undesirable high vapor pressure of NH3,
SRI has identified a next-generation A-MSP formulation that can provide a step-
change reduction in CO2 capture costs. Based on preliminary examinations,
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
114 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
adding methyl diethanolamine (MDEA) into the MSP formulation significantly improves the capture performance, yielding
a regeneration energy of 1.5 to 1.8 megajoules (MJ)/kg-CO2 while operating with less than 50% water. The solvent and
process parameters are provided in Table 1.
The A-MSP concept includes two isothermal absorbers, a selective regenerator, and auxiliary equipment, as shown in
Figure 1. Absorber 1 operates with high NH3/(MDEA+K) solvent composition and absorber 2 operates with low
NH3/(MDEA+K) solvent composition, resulting in efficient absorption and minimum NH3 slip. In the range of 60 to 80% of
the CO2 in the flue gas stream is absorbed in absorber 1 and the remaining CO2 is absorbed in absorber 2. The dual-
stage absorber system reduces NH3 carryover, resulting in less than 10 parts per million (ppm) NH3 in the clean flue gas
stream exiting the water wash. Both absorbers operate with liquid recycle using heat exchangers to remove the heat of
reaction. The bottom stage operates with the highest CO2 loading (up to 0.7 mol/mol). The CO2-rich solutions from the
absorbers are then sent to the regenerator through crossflow heat exchangers, which recover the heat from returning
lean solutions. The A-MSP uses a selective regenerator to produce two CO2-lean salt streams with high and low NH3
content, drawn from the lower-middle and bottom stages of the regenerator. The regenerator is operated under high-
pressure isobaric conditions (10 to 20 bar) and has a temperature gradient in the column (top ~30°C and bottom ~110°C).
At high temperature, the NH3 at the bottom of the regenerator is vaporized along with CO2, making a lean, low-
NH3/(MDEA+K) ratio solution to be used in absorber 2. Vaporized NH3 gets re-absorbed as the vapor moves up the
regenerator column, thereby creating a high-NH3/(MDEA+K) ratio solution in the mid-section of the regenerator for use
in absorber 1. In the A-MSP design, operating the regenerator at relatively low temperature and high pressure eliminates
the water stripping, thus generating an almost-dry CO2 stream (H2Ovap/CO2 < 0.02) at high pressure. Figure 2 shows
equilibrium modeling data comparing MSP and A-MSP systems, illustrating the high-CO2 regeneration pressure
advantage (almost doubled for 0.55 mol/mol CO2 loading) of A-MSP with the inclusion of MDEA to the solvent. This
results in a reduction of regeneration and CO2 compression energy costs (operating cost reduction) and removal of the
expensive first stage of CO2 compression (capital cost reduction). In addition, the lower regeneration temperature and
lower reboiler duty significantly reduce power plant energy loss due to steam extraction, improving the net power output
of the plant (Figure 3).
Figure 1: Conceptual process flow diagram for the A-MSP.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 115
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 2: CO2 loading versus CO2 pressure at 100°C for (i) 10 molal mixed-salt and (ii) 10 molal MDEA-mixed-salt formulations.
Figure 3: Power plant energy loss due to steam extraction.
Following lab-scale and small bench-scale testing, SRI’s large bench-scale integrated CO2 absorber-regenerator system
(Figure 4), originally built for testing the MSP, will be used without any modifications for dynamic and steady-state testing.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
116 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 4: SRI’s large bench-scale integrated absorber-regenerator system (gas flow rates up to 400 standard liters per minute).
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 18 18
Normal Boiling Point °C 100 100
Normal Freezing Point °C 0 0
Vapor Pressure @ 15°C bar 0.17 0.17
Manufacturing Cost for Solvent $/kg -- --
Working Solution
Concentration kg/kg 0.20-0.55 0.30-0.55
Specific Gravity (15°C/15°C) — 1.37 1.37
Specific Heat Capacity @ STP kJ/kg-K 3.2 3.2
Viscosity @ 20°C cP 1.6-35 1.6-35
Surface Tension @ STP dyn/cm 73.4 73.4
Absorption
Pressure bar 1 1
Temperature °C 20-40 20-40
Equilibrium CO2 Loading gmol CO2/kg 1.5-3.5 2.5-3.5
Heat of Absorption kJ/kg CO2 795-1,136 <1,100
Solution Viscosity cP 1.5-3.0 1.5-3.0
Desorption
Pressure bar >10 10-15
Temperature °C 120-180 140-160
Equilibrium CO2 Loading gmol CO2/kg 0.2-1 0.2-0.5
Heat of Desorption kJ/kg CO2 1,500-2,200 <2,000
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 117
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr --
CO2 Recovery, Purity, and Pressure % / % / bar 90% 95% --
Absorber Pressure Drop bar --
Estimated Absorber/Stripper Cost of __$__
Manufacturing and Installation kg/hr
--
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The reaction involves chemical absorption of CO2 through gas/liquid phase
mass transfer followed by chemical reactions in the liquid phase.
These reactions are as follows:
1. CO2 (g) ↔ CO2 (aq)
2. NH3 (aq) + CO2 (aq) + H2O (liq) ↔ (NH4)HCO3 (aq)
3. (NH4)2CO3 + 2CO2 (aq) + H2O (liq) ↔ 2(NH4)HCO3 (aq)
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
118 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
4. 2NH3 (aq) + CO2 (aq) ↔ (NH4)NH2CO2
5. (NH4)NH2CO2 (aq) + CO2 (aq) + 2H2O (liq) ↔ 2(NH4)HCO3 (aq)
6. K2CO3 (aq) + CO2 (aq) + H2O (liq) + catalyst ↔ 2KHCO3 (aq) + catalyst
7. R1R2R3N (aq) + CO2 (aq) + H2O (liq) + catalyst ↔ (R1R2R3NH)HCO3 (aq) + catalyst
where R1=R2=CH2CH2OH and R3=CH3
Solvent Contaminant Resistance – High.
Solvent Foaming Tendency – Low.
Flue Gas Pretreatment Requirements – The process is installed downstream of the FGD unit.
Solvent Makeup Requirements – To be determined.
Waste Streams Generated – To be determined.
Process Design Concept – Flowsheet/block flow diagram shown above in Figure 1.
technology advantages
• Low NH3 emissions.
• High CO2 absorption rate and high CO2 loading capacity.
• Reduced reboiler energy demand.
• Addition of tertiary amine to NH4-based mixed-salt solvent reduces regeneration energy need and water use.
• Lower reboiler duty and regeneration temperature improves net power output, increasing net plant efficiency.
• Low-temperature, high-pressure regeneration of greater than 99% pure dry CO2 reduces compression requirements.
R&D challenges
• Precipitation of solids in the absorber during cold weather conditions.
• Residual amine and/or NH3 in exit gas stream.
• Solvent interaction with acid gases.
• Thermal management of absorber columns and regenerator.
• Volatility and corrosiveness of MDEA.
status
The project team conducted VLE measurements of various CO2 loading levels and compositions for the regenerator side
and is conducting lab-scale absorber tests to investigate reaction kinetics and CO2 absorption capacity. SRI completed
the refurbishment of the existing absorber bench-scale unit and has performed parametric testing in the unit with
simulated flue gas to determine the rate of CO2 absorption in the A-MSP solutions as a function of temperature, gas flow
rate, solution composition, CO2 loading, and liquid/gas ratio. After testing 11 different MSP solvent formulations, it was
determined that a 9 molal (total) formulation comprised of potassium carbonate (K2CO3), NH3, and MDEA exhibited the
highest overall carbon capture efficiency. The existing MSP process model was updated to include MDEA in the solvent
formulation and VLE data will be used to inform model refinements and process design. DTU has assembled a
thermodynamic modeling program for the process to aid with predicting CO2 and NH3 isotherms under various test
conditions and solvent compositions. Oxidative and thermal degradation studies, integrated absorption/desorption
testing, further development of the process flowsheet model, and a TEA will be completed in Budget Period 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 119
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
available reports/technical papers/presentations
Jayaweera, P., “Mixed-Salt Based Transformational Solvent Technology for CO2 Capture,” presented at the 2019
Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting, Pittsburgh, PA, August
2019. https://netl.doe.gov/sites/default/files/netl-file/P-Jayaweera-SRI-Mixed-Salt-Solvent.pdf.
Jayaweera, P., “Mixed-Salt Based Transformational Solvent Technology for CO2 Capture,” Project Kick-Off Meeting,
September 2018. https://www.netl.doe.gov/projects/files/FE0031597-Kickoff-Presentation-090418.pdf.
Jayaweera, P., “Mixed-Salt Based Transformational Solvent Technology for CO2 Capture,” presented at the 2018 NETL
CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/P-Jayaweera-SRI-Mixed-Salt-Based-Transformational-Solvent.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
120 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Initial Engineering, Testing, and technology maturity:
Design of a Commercial-
Commercial-Scale Design
Scale, Post-Combustion CO2
project focus:
KM-CDR™ Process Retrofit
Capture System on an Existing participant:
Coal-Fired Generating Unit University of North Dakota
Energy and Environmental
Research Center (UNDEERC)
primary project goals
project number:
FE0031602
The University of North Dakota (UND) Energy and Environmental Research Center
(EERC), in partnership with the North Dakota Industrial Commission, ALLETE Clean predecessor projects:
Energy, Minnkota Power Cooperative, Mitsubishi Heavy Industries (MHI), and
N/A
Burns & McDonnell, will perform a pre-front-end engineering and design (pre-
FEED) analysis and cost estimate for retrofitting MHI’s Kansai Mitsubishi Carbon NETL project manager:
Dioxide Recovery (KM-CDR™) amine-based post-combustion carbon dioxide
Andrew O’Palko
(CO2) capture process with an existing coal-fired generating unit. [email protected]
technical goals principal investigator:
Jason Laumb
The goal of the project is to determine retrofit costs for a post-combustion CO 2 UNDEERC
[email protected]
capture system on an existing coal-fired electric generating unit. Specific
objectives to support this goal include the following: partners:
Design a fully integrated post-combustion CO2 capture system for Milton R. North Dakota Industrial
Young Unit 2 (MRY2). Commission, ALLETE Clean
Energy, Minnkota Power
Evaluate KS-1™ solvent on lignite coal-derived flue gas to refine critical design Cooperative, Mitsubishi
parameters. Heavy Industries (MHI), and
Complete a techno-economic assessment (TEA) in accordance with the U.S. Burns & McDonnell
Department of Energy’s (DOE) bituminous baseline study (B12B).
start date:
Complete a pre-FEED analysis of the specified post-combustion CO 2 capture
system at MRY2. 06.05.2018
percent complete:
technical content 89%
The commercially available KM-CDR™ process uses an advanced amine solvent,
KS-1™, that exhibits less solvent degradation, a higher working capacity and lower
solvent circulation rate, and reduced steam consumption for regeneration
compared to monoethanolamine (MEA). The solvent technology has shown to be
reliable, routinely achieving 90% CO2 removal, while capturing approximately 1.6
million tonnes of CO2 per year from a 240-megawatt-electric (MWe) sub-
bituminous coal-derived flue gas stream at the W.A. Parish Plant in Thompsons,
Texas, through a DOE-funded project with Petra Nova Parish Holdings, LLC.
Through the development, several improvements to the process have been
implemented, including a novel flue gas quencher and absorber design for lower
capital costs and ease of construction and an amine wash section for minimizing
aerosol emissions from treated flue gas. The team will design a fully integrated
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KM-CDR™ system for installation at MRY2 near Center, North Dakota; perform testing with EERC’s slipstream baghouse
installed at MRY2 to evaluate aerosol emissions; evaluate the KS-1™ solvent on lignite coal-derived flue gas to refine
critical design parameters; complete a TEA in accordance with DOE’s bituminous baseline study; and complete a pre-FEED
analysis and cost estimate of the system at MRY2.
Figure 1: MHI’s KM-CDR TM process.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 proprietary data proprietary data
Normal Boiling Point °C proprietary data proprietary data
Normal Freezing Point °C proprietary data proprietary data
Vapor Pressure @ 15°C Bar proprietary data proprietary data
Manufacturing Cost for Solvent $/kg proprietary data proprietary data
Working Solution
Concentration kg/kg proprietary data proprietary data
Specific Gravity (15°C/15°C) - proprietary data proprietary data
Specific Heat Capacity @ STP kJ/kg-K proprietary data proprietary data
Viscosity @ STP cP proprietary data proprietary data
Absorption
Pressure Bar proprietary data proprietary data
Temperature °C proprietary data proprietary data
Equilibrium CO2 Loading mol/mol proprietary data proprietary data
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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122 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Heat of Absorption kJ/mol CO2 proprietary data proprietary data
Solution Viscosity cP proprietary data proprietary data
Desorption
Pressure Bar proprietary data proprietary data
Temperature °C proprietary data proprietary data
Equilibrium CO2 Loading mol/mol proprietary data proprietary data
Heat of Desorption kJ/mol CO2 proprietary data proprietary data
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,938,700
CO2 Recovery, Purity, and Pressure % / % / bar 95% / 99.9%+ / 158.6
Absorber Pressure Drop Bar proprietary data
Estimated Absorber/Stripper Cost of __$__
proprietary data
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO 2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO 2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
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Composition
Pressure Temperature vol%-wet ppmv
psia °F CO2 H 2O N2 O2 Ar SO2 NOX
13.68 150 10.45 20.5 62.9 5.3 0.79 44 149.7
Chemical/Physical Solvent Mechanism – CO2 is captured by chemical absorption.
Solvent Contaminant Resistance – KS-1™ solvent is highly resistant to contaminant compared to conventional solvent
MEA.
Solvent Foaming Tendency – KS-1™ solvent has low foaming tendency compared to conventional solvent MEA.
Flue Gas Pretreatment Requirements – Flue gas cooling and sulfur oxide (SOX) removal unit may be required depending
on flue gas conditions.
Solvent Makeup Requirements – Solvent makeup rate depends on the impurity levels in the flue gas but is generally
lower than conventional solvent MEA.
Waste Streams Generated – Solvent reclaiming waste is the main waste stream generated.
Process Design Concept – KM-CDR™ process is equipped with a proprietary amine emissions reduction system, energy-
saving system, and amine purification system, which maximize the capture efficiency while minimizing the energy
consumption and environmental impact.
Proposed Module Design –Not applied.
technology advantages
The combination of the state-of-the-art KM-CDR™ technology with refined design criteria and optimized thermal
integration will improve performance of the CO2 capture system and maximize overall system efficiency.
R&D challenges
This project will address challenges associated with a full-scale system, such as the use of lignite coal, effects from cold
climate, treating higher quantities of flue gas, and application of heat integration.
status
Field testing at MRY2 was completed, including long-term stable operation and aerosol mitigation testing. The project
design basis was completed, including utility requirements, flow diagrams, balance of plant, permitting strategy, and
optimization studies. The TEA is underway and the pre-FEED cost estimate is near completion. The project final report
nearing completion will include the pre-FEED cost estimate, system layout, a hazard and operability study (HAZOP),
constructability, the steam integration report, the transportation study, and the technology maturation plan.
available reports/technical papers/presentations
Laumb, J., Initial Engineering, Testing, and Design of a Commercial-Scale Post-Combustion CO 2 Capture System on an
Existing Coal-Fired Generating Unit, Aug 2018, 2018 NETL CO 2 Capture Technology Project Review Meeting, Pittsburgh,
PA, https://www.netl.doe.gov/sites/default/files/netl-file/J-Laumb-UNDEERC-Engineering-Testing-and-Design.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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124 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Laumb, J., Initial Engineering, Testing, and Design of a Commercial-Scale Post-Combustion CO 2 Capture System on an
Existing Coal-Fired Generating Unit, Aug 2019, 2019 NETL CO 2 Capture Technology Project Review Meeting, Pittsburgh,
PA, https://netl.doe.gov/sites/default/files/netl-file/J-Laumb-UND-EERC-Postcombustion-Coal-Plant-Capture.pdf.
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Engineering-Scale technology maturity:
Large Pilot-Scale (~10
Demonstration of the Mixed- Mwe), Actual Flue Gas
Salt Process for CO2 Capture project focus:
Ammonia and Potassium
Carbonate-Based Mixed
primary project goals Salt Solvent
SRI International is developing a novel ammonia (NH3) and potassium carbonate participant:
(K2CO3)-based mixed-salt solvent carbon dioxide (CO2) capture process. Large SRI International
bench-scale and engineering-scale (~10 megawatt-electric [MWe]) testing is being
performed to validate enhanced CO2 capture efficiency, high loading capacity, and
project number:
reduced energy consumption.
FE0031588
technical goals predecessor project:
FE0012959
• Demonstrate the individual absorber and regenerator processes for NH3 and
K2CO3 solvent systems with high efficiency, low NH3 emission, and reduced NETL project manager:
water use compared to the state-of-the-art NH3-based technologies.
Andrew jones
• Establish a rate-based thermodynamic modeling database for the potassium- [email protected]
and NH3-based system heat and mass balance evaluations.
• Demonstrate the completely integrated absorber-regenerator CO2 capture principal investigator:
system at the bench-scale and optimize the system operation. Indira jayaweera
• Test two alternative flowsheets for process optimization, test system at highest SRI International
possible CO2 loadings, and determine steam usage for regeneration. [email protected]
• Test the continuous operation of the process in an integrated absorber-
regenerator system. partners:
• Field test the mixed-salt process (MSP) at engineering scale to determine Technology Center
process operability under both dynamic and steady-state conditions using Mongstad (TCM), Baker
actual flue gas. Hughes (BH), Politechnico di
• Test the process with advanced heat integration for improved process Milano (PoliMi), OLI Systems
efficiency and determine optimal regeneration energy requirement. Inc., Aqueous Solutions Aps
(ASAps)
• Optimize the engineering-scale operation of the MSP to achieve high capture
rate, high cyclic CO2 loading, and high-purity CO2 stream at high pressure.
start date:
• Evaluate solvent and water management strategies.
07.01.2018
• Collect data to perform the detailed techno-economic analysis (TEA) of CO2
capture process integration to a full-scale power plant. percent complete:
50%
technical content
SRI International is developing a novel mixed-salt solvent-based technology for
post-combustion CO2 capture using a non-degradable solvent that combines
readily available, inexpensive potassium and NH3 salt solutions and employs a
novel flow configuration that is optimized to improve absorption kinetics, minimize
NH3 emissions, and reduce water use compared to state-of-the-art NH3-based and
amine technologies. The solvent and process parameters are provided in Table 1.
A singular NH3-based process, such as chilled NH3, has several advantages: very
high CO2 loading capacity, reduced reboiler duty due to high-pressure
regeneration, and fast absorption kinetics. Challenges of this process include the
need for a large water wash to reduce NH3 emissions, requirement to chill the
solvent, and energy usage for solid dissolution. A singular K2CO3-based process
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Post-Combustion Solvent Technologies
offers several advantages: no emissions, long-term industrial use, and simple permitting. However, this process has
lower efficiency and CO2 loading, as well as energy requirements for solid dissolution and vacuum water stripping. By
combining these two solvent technologies, SRI capitalizes on the advantages of each while minimizing the drawbacks.
The MSP maintains the high CO2 loading and enhanced absorption kinetics, delivering high-pressure CO2 in a solids-
free system. The rate of CO2 absorption is enhanced by having NH3 act as a promoter that shuttles the CO2 to the
carbonate ion in the solution across the gas/liquid interface and increases the partial pressure of CO2 in the dissolved
phase. This increases the rate of CO2 collision with carbonate ion and results in an increase in the rate of CO2 absorption.
Furthermore, by combining the salts, the capture system experiences reduced reboiler and auxiliary electricity loads,
reduced NH3 emission, reduced water usage, and a reduced system footprint.
Taking into consideration the key advantages discussed above, the regenerator energy requirement was estimated and
compared to monoethanolamine (MEA)-based and pure K2CO3-based processes. Figure 1 shows a significant reduction
in regenerator heat requirement for the MSP. In the MSP, the sensible heat is lower than that of MEA-based technology
because the MSP is operated with very high CO2 loading and lean regeneration; thus, a lower volume of solvent is
required to carry the CO2. In addition, since the regenerator operates at a higher pressure in the MSP, the reflux ratio is
very low (water [H2O]/CO2 less than 0.01); therefore, the heat of evaporation is insignificant. The heat of reaction is
considerably lower for MSP compared to amine processes, leading to further reduction in reboiler heat duty. Another key
difference in the MSP is that, unlike chilled NH3 or a neat K2CO3-based process, the MSP is designed to operate without
solids in the absorber, eliminating additional heat requirement for solid dissolution in the regenerator or heat exchangers.
Figure 1: Estimated regenerator heat requirement for mixed-salt system with 0.2 to 0.6 cyclic loading of CO2.
The MSP system, shown in Figure 2, comprises two isothermal absorbers, a selective regenerator, and auxiliary
equipment. The absorbers operate with different ammonia to potassium ratio (NH3/K) solutions formulated to maximize
the absorption and minimize the NH3 loss. The absorber system is designed to integrate downstream of a flue-gas
desulfurization (FGD) unit in a pulverized coal power plant. The CO2 in the flue gas stream is absorbed in the absorber
columns, which are operated with liquid recycle and heat exchangers to remove the heat of reaction and keep the solution
at the optimum temperature for efficient absorption and minimum NH3 slip. The CO2-rich solutions from the absorbers
are sent to the regenerator for CO2 stripping and solvent regeneration. The MSP uses a selective regenerator to
regenerate two CO2-lean salt streams with different NH3/K ratios. These streams are drawn from a lower-middle stage
and the bottom stage of the regenerator. The regenerator is operated at high-pressure, isobaric conditions, and has a
temperature gradient along the height of the column. The key advantage of the MSP regenerator design is to capture the
latent heat within the regenerator before the stream exits the vessel, thus generating almost dry CO2 stream (H2Ovap/CO2
less than 0.2) at high pressure, reducing both operational and capital CO2 compression costs. The overall benefit of MSP
is a significant reduction in the cost of the CO2 capture.
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Figure 2: SRI mixed-salt simplified process diagram.
Bench-scale operation of the individual absorber and regenerator units provided optimized process parameters prior to
the design and testing of the large bench-scale integrated absorber-regenerator system. The absorber was operated
near ambient temperature and the regenerator was operated up to 160°C. The absorber system (Figure 3) has two
absorber columns (8-inch diameter) that are designed to operate independently with different absorption solutions, and
the gas stream passes through them in series. The dual absorber system operates with a high NH3/K ratio solution in the
first absorber and low NH3/K ratio solution in the second absorber, which results in a reduction in NH3 loss from the
absorbent solution compared with a single solution approach, as shown in Figure 4. The data from the mixed-salt
absorber system testing also demonstrated that it was possible to reach greater than 90% CO2 capture even using a
solution that has fairly high CO2 loadings (e.g., in the 0.4 to 0.6 range).
Figure 3: Close-up view of two absorber columns.
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Figure 4: Measured NH3 vapor pressure at various CO2 loadings for tests conducted with a single absorber (Runs 4, 5, and 6) and for the
test conducted with the dual absorber (Run 7).
Regenerator tests were performed with 20 and 30 wt.% mixed-salt compositions in a semi-continuous mode. Figure 5
is a photograph of the large bench-scale regenerator showing solution inlets, outlets, and heat exchangers. Figure 6
shows the number of moles of CO2 stripped in a series of runs in the pressure ranges of 6 to 7 and 11 to 12 bar in the
temperature range of 120 to 160°C for 20 wt% mixed-salt solutions with 0.49 CO2 loading.
Figure 5: Large bench-scale regenerator.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Figure 6: CO2 stripping as a function of regeneration temperature and pressure.
The integrated bench-scale CO2 capture and regeneration system, as depicted in Figure 2, was operated for 60 hours.
The rich liquid flow from absorber 1 was split and pumped into the column at two stages with ~20% going to an upper
stage. The rich solution from absorber 2 was cooled to ~15°C and pumped to the top stage of the regenerator column to
reduce the NH3 emission from the regenerator. As a polishing step, the high-pressure water wash was mounted at the
very top of the regenerator such that the emitted CO2 gas has less than 10 parts per million (ppm) NH3 content. The lean
stream with high NH3/K ratio for absorber 1 was drawn from a lower-middle stage of the regenerator column, which was
at ~130°C. The lean solution with low NH3/K ratio for absorber 2 was drawn from the bottom stage of the regenerator
column, and the temperature of this stage was about 160°C. The regenerator was operated under isobaric conditions
with a temperature gradient, ~30 to 50°C at the top and 155 to 160°C at the bottom. Two main heat exchangers recovered
the sensible heat from the regenerated solution to heat the incoming rich solution. The outgoing lean streams from heat
exchangers were ~40°C, and thus they needed to be cooled to about 15 to 20°C before they were fed to the absorber
columns. For the continuous operation of the regenerator, the input rich-solution flows and exit lean-solution flows were
balanced, and the liquid levels of draw stages were carefully controlled to avoid flooding or dry-up of regenerator stages.
The integrated system performed as designed with excellent absorption and regeneration cycles and demonstrated more
than 90% CO2 capture. Two variants of the MSP were tested to further decrease the NH3 loss and water usage. In variant
1, the length of absorber 2 was increased and solvent flow recirculation was slightly modified. A water wash was also
installed, with larger surface area and recirculation than the original MSP design. These changes reduced the NH3 in the
absorber exit from ~3,000 ppm to ~1,000 ppm and the NH3 in the water wash exit to less than 10 ppm. In addition, the
raw water consumption was reduced by a factor of six. In the variant 2 configuration, the CO2-rich solution was introduced
at the exit of the second absorber to reduce the NH3 content in the gas stream leaving the absorbers. In this case, the
system took longer to reach steady-state and needed higher flow rate of water in the water wash to control the NH3
emission; thus, variant 2 was not pursued for more detailed testing.
Using the bench-scale experimental data, a rate-based model for detailed mass-balance and heat-balance calculations
for a flue gas feed equivalent to a 550-MWe flue gas stream was developed and validated in OLI System’s Environmental
Simulation Program. Initially, OLI conducted the mass and heat balance determination for various regenerator options.
The reboiler duty requirement for the best layout with 0.2 to 0.5 cyclic CO2 loading operation was 2.0 (± 0.2) MJ/kg-CO2.
The technology was modeled for the CO2 recovery facility, in which 90% percent of the CO2 from the flue gas was
captured from a supercritical pulverized coal plant with a nominal net output of 550 MWe (U.S. Department of Energy
[DOE] Case 11). The other fixed parameters were regeneration of high-pressure CO2 at 99% purity and an NH3 release
from the absorber that was less than 10 ppm. The study showed the technology offers much lower energy penalty than
Fluor Econamine FG PlusSM technology, which uses a formulation of MEA and a proprietary corrosion inhibitor to recover
CO2 from the flue gas.
A field test of the MSP at engineering-scale is being conducted using the existing Chilled Ammonia Process (CAP)
infrastructure at Technology Center Mongstad (TCM) in Norway. Re-commissioning of the CAP system is required prior
to conducting the field test, followed by a hazard and operability (HAZOP) evaluation. Modeling of the modified flowsheet
is being performed to identify the optimal configuration for MSP implementation at TCM. The process involves modeling
of individual systems blocks (absorber, regenerator, and NH3 recovery block) separately and then integrating them with
the inclusion of flow stream. The absorber block includes three absorbers. In these studies, the NH3 emission from the
water wash tower (less than 10 ppm) and the CO2 capture efficiency (greater than 90%) were set as fixed parameters.
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Figure 7 shows the comparison between the CO2 capture efficiency profiles in each of the absorbers for configurations
A and B as predicted by the model.
Figure 7: CO2 capture efficiency profiles for configurations A and B (total of 90% capture in both cases).
Testing of the integrated system, along with process modeling, provided parametric optimization to update the TEA and
determine costs associated with the use of this system in a 550-MWe power plant. The cost of electricity (COE) found in
the analysis of the mixed-salt technology was 126.1 $/MWh, yielding a reduction of 11.7% compared to the National
Energy Technology Laboratory (NETL) Case 12B COE of 142.8 $/MWh.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 18 18
Normal Boiling Point °C 100 100
Normal Freezing Point °C 0 0
Vapor Pressure @ 15°C bar 0.17 0.17
Manufacturing Cost for Solvent $/kg - -
Working Solution
Concentration kg/kg 0.27-0.35 0.35
Specific Gravity (15°C/15°C) - 1.1-1.3 1.1-1.3
Specific Heat Capacity @ STP kJ/kg-K 3.0-4.0 3.0-4.0
Viscosity @ 15°C cP 1.6 1.6
Absorption
Pressure bar 1 1
Temperature °C 20-40 25-40
Equilibrium CO2 Loading mol/mol 0.6 (rich) 0.6 (rich)
Heat of Absorption kJ/mol CO2 1,000–1,200 <1,200
Solution Viscosity cP 1.5-1.8 <1.9
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Desorption
Pressure bar 10-15 10
Temperature °C 120-170 120-170
Equilibrium CO2 Loading mol/mol 0.2 (lean) <0.2 (lean)
Heat of Desorption kJ/mol CO2 1,000-1,200 <1,200
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr -
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 ~20
Absorber Pressure Drop bar <0.1
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – In the MSP, CO2 is captured by a chemical absorption that involves a series
of ionic chemical reactions among CO2, NH3, K2CO3, and H2O. The mechanism of CO2 capture by chemical absorption
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using various chemical formulations has been studied extensively. The MSP chemistry comprises gas/liquid-phase mass
transfer, followed by a series of chemical reactions in the liquid phase. The overall process chemistry can be summarized
as:
K2CO3 – NH3-xCO2-H2O K2CO3 – NH3-yCO2-H2O
Where y > x
Solvent Contaminant Resistance – The solvent is expected to be resistant to several contaminants, such as sulfur
oxides (SOX) and nitrogen oxides (NOX), nominally present in a flue gas stream. Sulfur dioxide (SO2) reacts with the
solvent, but it can be removed in the direct contact cooler section as sulfates. The resistance of the solvent to trace
metals is not yet known.
Solvent Foaming Tendency – Solvent foaming tendency was not observed in the bench-scale tests.
Flue Gas Pretreatment Requirements – Unlike in an MEA system, a mixed-salt system does not require deep FGD;
200-ppm level SO2 is acceptable.
Solvent Makeup Requirements – Mixed-salt is a mixture of NH3 and K2CO3 and it is inexpensive and readily available.
The loss of the solvent is expected to be less than 0.2 kg/tonne of CO2 captured.
Waste Streams Generated – Water wash with trace ammonium sulfate from the SO2 captured by the direct contact
cooler.
Process Design Concept – See Figure 2.
technology advantages
• Low heat of reaction (35 to 50 kJ/mol) and low reboiler duty (~2 MJ/kg of CO2).
• High temperature (20 to 40°C) absorber operation without solvent chilling.
• High CO2 loading capacity (10 wt%).
• High-pressure regeneration of greater than 99% pure dry CO2, resulting in reduced compression costs.
• Low sensitivity to impurities.
• Non-degradable solvent uses inexpensive, industrially available materials.
• Low NH3 emissions using two-stage absorber approach.
• Low water usage.
• Requires no feed stream polishing.
• No hazardous waste generation.
• Uses known process engineering.
• Operates with no solids in the absorber.
• Reduced energy consumption compared to MEA.
• Reduced auxiliary electricity loads.
R&D challenges
• Residual NH3 in the exit gas stream.
• Reduction of NH3 evaporation at higher reaction rates.
• High-pressure drop in absorber column.
status
SRI has completed bench-scale testing of the integrated two-stage absorber system with the regenerator using simulated
flue gas, indicating cyclic operation with greater than 90% CO2 capture (at ~0.3 ton/day) with cyclic CO2 lean and rich
loading between 0.2 and 0.59 mol/mol (maximum cyclic CO2 loading achieved is ~10 wt%). Lean solutions with two
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
compositions, NH3-rich and potassium-rich, were generated using a two-stage regenerator. The two-stage absorber
approach showed a reduction in NH3 emissions. Overall, long-term operability of the integrated system was shown over
2.5 years. The TEA for the mixed-salt technology showed a reduction in heat duty (compared to the Fluor Econamine FG
PlusSM baseline technology) from 3.56 to 2.0 MJ/kg CO2 and a cost of CO2 captured of approximately $38/tonne CO2. In
preparation for field testing of the MSP at TCM, SRI has completed the HAZOP evaluation of the CAP system and
reconfigured MSP pilot system and has conducted flowsheet modeling to determine the process configuration that is best
suited for MSP implementation at TCM.
available reports/technical papers/presentations
Jayaweera, I., “Engineering-Scale Demonstration of Mixed-Salt Process (MSP) for CO2 Capture,” presented at the
2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting, Pittsburgh, PA,
August 2019. https://netl.doe.gov/sites/default/files/netl-file/I-Jayaweera-SRI-Mixed-Salt-Capture-Process.pdf.
Jayaweera, I., “Engineering-Scale Demonstration of Mixed-Salt Process (MSP) for CO2 Capture,” Project Kick-off and
BP1 Review Meeting, October 2018.
https://netl.doe.gov/projects/files/Engineering%20Scale%20Demonstration%20of%20Mixed-
Salt%20Process%20for%20CO2%20Capture%20Oct%202018.pdf.
Jayaweera, I., “Engineering-Scale Demonstration of Mixed-Salt Process (MSP) for CO2 Capture,” presented at the
2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://netl.doe.gov/projects/files/Engineering%20Scale%20Demonstration%20of%20Mixed-
Salt%20Process%20for%20CO2%20Capture%20Aug%202018.pdf.
Jayaweera, I., “Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants,” Final Report, May
2018. https://www.osti.gov/servlets/purl/1441205.
Jayaweera, I., “Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants,” presented at the
2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://netl.doe.gov/sites/default/files/event-proceedings/2017/co2%20capture/4-Thursday/1I-Jayaweera1-SRI-Mixed-
Salt-Technology.pdf.
Kang, C.A., Brandt, A.R., Durlofsky, L.J., and Jayaweera, I, “Assessment of advanced solvent-based post-
combustionCO2 capture process using bi-objective optimization technique,” Applied Energy, 179 (2016), 1209-1219.
Jayaweera, I., “Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants,” presented at the
2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://netl.doe.gov/sites/default/files/event-proceedings/2016/c02%20cap%20review/4-Thursday/I-Jayaweera-SRI-
Mixed-Salt-Technology-for-CO2-Capture.pdf.
Jayaweera, I., Jayaweera, Palitha, Krishnan, Gopala N., Sanjurjo, Angel, “Rate enhancement of CO2 absorption in
aqueous potassium carbonate solutions by an ammonia-based catalyst,” US Patent 9,339,757, issued May 17, 2016.
Jayaweera, I., Jayaweera, Palitha, Yamasaki, Yuki, and Elmore, R, “Mixed-Salt Solutions for CO2 Capture,” Book
Chapter 8 in Absorption-Based Post-Combustion Capture of Carbon Dioxide; Elsevier, 2016 (pp 167-200).
Jayaweera, I., “Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants,” presented at the
2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015. https://netl.doe.gov/sites/default/files/event-
proceedings/2015/co2captureproceedings/I-Jayaweera-SRI-Mixed-Salt.pdf.
Jayaweera, I., P. Jayaweera, R. Elmore, J. Bao, S. Bhamidi, “Update on mixed-salt technology development for CO2
capture from post-combustion power stations,” Energy Procedia 63, 2014, 640-650.
Jayaweera, I., “Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants,” presented at the
2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014. https://netl.doe.gov/sites/default/files/event-
proceedings/2014/2014%20NETL%20CO2%20Capture/I-Jayaweera-SRI-Development-Of-Mixed-Salt-Technology.pdf.
Jayaweera, I. S., P. Jayaweera, G. Krishnan, and A. Sanjurjo, “The race for developing promising CO2 capture
technologies ready for 2020 deployment: Novel mixed-salt based solvent technology.” Pap.-Am. Chem. Soc., Div.
Energy Fuels 2013, (1):58.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Engineering-Scale Testing of technology maturity:
Large Pilot-Scale (~10
Transformational Non- Mwe), Actual Flue Gas
Aqueous Solvent-Based project focus:
Carbon Dioxide Capture
water-Lean Solvent
Process at Technology Centre participant:
Research Triangle Institute
Mongstad project number:
FE0031590
primary project goals
predecessor projects:
Research Triangle Institute (RTI) is developing and testing at large pilot-scale a FE0026466
non-aqueous solvent (NAS; i.e., water-lean solvent) carbon dioxide (CO2) capture FE0013865
process to confirm the potential to reduce the parasitic energy penalty associated
with the capture of CO2 from flue gas; demonstrate the long-term process NETL project manager:
operational reliability at static and dynamic conditions; and verify the solvent Andrew jones
degradation rate, emissions, solvent loss, and corrosion characteristics of the [email protected]
solvent at engineering scale.
principal investigator:
technical goals Marty Lail
Research Triangle Institute
[email protected]
• Evaluate water-lean solvent degradation and material compatibility.
• Measure water-lean solvent performance over static and dynamic operating partners:
conditions.
Technology Centre
• Design/procure water-lean solvent-specific components for implementation in
Mongstad (TCM), Electric
the host site facility.
Power Research Institute,
• Confirm a reduction in parasitic energy penalty to less than 2.1 gigajoules Inc., Linde, SINTEF
(GJ)/tonne CO2 captured.
• Complete a techno-economic analysis (TEA) to confirm RTI’s NAS process can start date:
reduce CO2 capture costs. 08.08.2018
technical content percent complete:
55%
RTI is advancing the development of a water-lean solvent-based CO2 capture
process that was previously developed and tested at lab- and bench-scale (~10
kilowatts [kW]) with simulated flue gas under the U.S. Department of Energy
(DOE)-funded project FE0013865. Water-lean solvents have the potential to
significantly reduce the cost of CO2 capture from coal-fired flue gas when
compared to aqueous amine-based solvent processes by reducing the energy
required for solvent regeneration. RTI’s water-lean solvent is a hydrophobic,
sterically hindered, carbamate-forming amine with low-water solubility solubilized
in a diluent having low vapor pressure and low viscosity. It is characterized by low
heats of absorption and generation of high CO2 partial pressures at low
temperatures and has the potential to reduce the regeneration energy to less than
2.1 GJ/tonne CO2. The overall reboiler heat duty, or thermal regeneration energy,
is made up of the sensible heat, heat of vaporization of water, and heat of
absorption. The heat of vaporization, due to the lack of water, is significantly less
for water-lean solvents than for aqueous amine-based processes. Also, water-
lean solvents overcome the foaming issues that are often associated with aqueous
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
solvents, as shown in Figure 1. RTI’s CO2-rich water-lean solvent has a viscosity of less than 30 cP and is non-foaming.
Figure 1: Comparison of foaming in aqueous and RTI’s water-lean solvents.
The NAS CO2 capture process includes a solvent regenerator design specifically for water-lean solvents that combines
heat delivery and gas release in a single-step process unit to maintain lower regeneration temperatures. The process, as
shown in Figure 2, is similar to conventional solvent scrubbing systems with key novel design features:
• NAS solvent recovery and wash section—similar to water washing, but water-lean solvents have low water-solubility.
• Solvent regenerator—lack of low-boiling component (conventional reboilers are not applicable).
Figure 2: NAS CO2 capture process diagram.
Under DOE-funded project DE-FE0026466, RTI used the bench-scale test unit (up to 60 kW) at SINTEF’s Tiller plant to
experimentally show that the water-lean solvent is capable of achieving 90% CO2 capture and generating a high-purity
CO2 product (greater than 95% CO2), as well as to evaluate the effectiveness of the developed NAS recovery/wash
section and solvent regenerator design. Bench-scale testing at SINTEF’s Tiller plant was first performed using the
monoethanolamine (MEA) control and the water-lean solvent in an unmodified configuration of the test unit. Baseline
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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testing of the water-lean solvent using propane and coal-fired flue gas was performed over a period of approximately four
months, showing a CO2 capture rate of approximately 90%. Heat stable salts (HSS) and metals analyses were used to
determine the solvent stability and corrosion. The HSS level was relatively constant and low during the test campaign.
The results also indicate that the corrosion rate of NAS is quite low and stable, confirming previous test results that
showed much lower corrosion rate for NAS as compared with MEA.
As the CO2 capture system at Tiller was designed specifically to achieve the optimum performance for an aqueous-based
solvent, it is not an ideal setup to realize the energy reduction benefit by using the water-lean solvent. Based on the
knowledge acquired throughout the testing in RTI’s gas absorption system (BsGAS) with various process configurations,
the following modifications (Figure 3) to the existing absorption system at the Tiller plant were made:
• Addition of two interstage coolers between existing sections of packing in the absorber.
• Replacement of three existing packing sections in the regenerator column with three new sections consisting of an
electric/steam heating portion located at the top-half of the section and a high surface area packing portion located at
the bottom-half of the section.
• Expansion of lean-rich heat exchanger by adding a second crossover plate-and-frame heat exchanger in series.
• Addition of coal-fired burner.
• Rich solvent preheater installed at regenerator inlet.
• Addition of an acid wash/water wash section.
Figure 3: Design improvements for NAS-based process.
The solvent formulation was also refined to increase CO2 loading and working capacity and to reduce the reboiler heat
duty required for solvent regeneration. The improved formulation (NAS-5) results in an increase in CO2 working capacity
from ~0.45 molCO2/molamine to ~0.48 molCO2/molamine, and a decrease in heat of absorption from ~82 kilojoules (kJ)/molCO2
to ~75 kJ/molCO2, and is expected to reduce the reboiler heat duty by decreasing the liquid/gas (L/G) ratios and the heat
of absorption at higher temperatures. Through testing in RTI’s bench-scale BsGAS, it was found to be advantageous to
use two interstage coolers in the absorber column (with one at the bottom and one at the top) to achieve a heat duty near
2 MJ/kg-CO2. The coolers play an essential role in lowering the temperature in the absorber column to maintain a high
CO2 loading in the solvent. A wash column was added to RTI’s BsGAS to allow for testing different conditions to reduce
amine losses for the technology, demonstrating that the wash section could effectively remove 92 to 93% of the amine
emissions from the absorber.
Following the installation of the NAS-specific components into the Tiller plant, including a new particulate filter, updated
coal-burner control software, additional absorber intercoolers, additional water wash section, regenerative “inter-heaters,”
and one additional crossflow heat exchanger, parametric testing was performed with NAS-5 to allow optimal operating
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
conditions to be identified and long-term testing to be completed. Test results showed an average CO2 capture rate of
90% and the lowest reboiler heat duty obtained was 2.3 GJ/tonne CO2 when the rich solvent pre-heater was used.
Additional baseline testing of the new water-lean solvent formulation was performed at the National Carbon Capture
Center (NCCC) to investigate solvent degradation, corrosion, and emissions using the Slipstream Solvent Test Unit
(SSTU) with long-term exposure to coal-derived flue gas from the Gaston Power Plant in Wilsonville, Alabama. The
NCCC system was operated for 580 hours with flue gas with intermittent delays. The effects of flue gas velocity, CO2
capture efficiency, and aerosols on amine emissions were studied during the test campaign. Preliminary testing has
indicated that the water-lean solvent displays minimal corrosion; therefore, the materials of construction for some of the
equipment could be replaced with lower cost options. A TEA and environmental, health, and safety (EH&S) assessment
of the NAS process based on test data obtained from SINTEF’s Tiller plant and from the SSTU at NCCC show that the
NAS technology has the potential to meet DOE’s $40/tonne CO2 capture target when it is fully developed and poses little
EH&S risk.
In RTI’s current DOE-funded project, engineering-scale tests are being performed using the existing large pilot
infrastructure at the Technology Centre Mongstad (TCM) in Norway. The test campaign includes baseline testing with
the water-lean solvent in TCM’s 12-megawatt-electric (MWe) pilot plant in the configuration designed for aqueous-amine
solvents, a hardware revamp of the plant to implement NAS-specific components, and follow-on NAS testing under
optimized conditions. Based on the findings realized during the evaluation of RTI’s BsGAS and SINTEF’s Tiller plant
under various process configurations, the following modifications to the existing system at TCM are being made:
• Addition of one or two interstage coolers between existing sections of packing in the absorber.
• Rich solvent preheater installed between rich outlet of rich/lean heat exchanger and regenerator inlet.
• Expansion of lean-rich heat exchanger by adding a second crossover plate and frame heat exchanger in series.
In addition, strategies for reducing the amine emissions to less than 1 part per million (ppm) are being implemented to
meet TCM’s emissions requirements, including modifying the existing water wash section of the TCM unit, lowering the
gas flow rate, and adding an intercooler to the absorber. Large pilot-scale test results will be used to demonstrate the
applicability of the water-lean solvent as a drop-in replacement solvent in conventional capture systems and the process
scalability and commercial potential of RTI’s transformational NAS CO2 capture process for pulverized coal power plants.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 95–115** 99
Normal Boiling Point °C 185–243** 200
Normal Freezing Point °C (-6 to -24)** -9.15
Vapor Pressure @ 15°C bar 4.47e–4** 4.47e–4
Manufacturing Cost for Solvent $/kg 30 5
Working Solution
Concentration kg/kg 0.5–0.6* 0.55
Specific Gravity (15°C/15°C) - 0.9–1.035* 1.035
Specific Heat Capacity @ STP kJ/kg-K 2.78* 2.78
Viscosity @ STP cP 4.38–4.7* 4.7
Absorption
Pressure bar 0.133* 0.133
Temperature °C 35–45* 38
Equilibrium CO2 Loading mol/mol 2.04–2.22* 2.04
Heat of Absorption kJ/kg CO2 1,700–2,000* 1,931
Solution Viscosity cP 4–30* 28
Desorption
Pressure bar 2–7.8* 2
Temperature °C 90–110* 105
Equilibrium CO2 Loading mol/mol 0.45–1.13* 0.45
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Heat of Desorption kJ/kg CO2 2,100* 2,045
* Experimentally measured data.
** Calculated data for different concentrations and conditions using standard mixing rules from pure components data.
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical.
Solvent Contaminant Resistance – More resistant than MEA to sulfur oxides (SOX) and nitrogen oxides (NOX).
Solvent Foaming Tendency – Less foaming than aqueous amine solvent.
Flue Gas Pretreatment Requirements – Temperature adjustment and SOX control.
Solvent Makeup Requirements – 0.2 to 0.5 kg/tonne CO2.
Waste Streams Generated – None.
Process Design Concept – See Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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139
Post-Combustion Solvent Technologies
technology advantages
• Low water solubility.
• Reduced regeneration energy.
• High solvent regeneration pressure at low regeneration temperatures, such that desorbed CO2 can go directly to
second stage of compression.
• Favorable thermodynamics.
o Low heat of absorption.
o High working capacity based on vapor-liquid equilibrium (VLE).
• Excellent thermal and oxidative stability; no formation of HSS.
• Low vapor pressure (less than 0.3 kPa [40°C], less than 10 ppm emissions in treated flue gas).
• Low conductivity; low corrosion rates.
• Low oxygen solubility.
R&D challenges
• Implementation of NAS-specific components into host site facility.
• Effective control of water content in both the rich and lean water-lean solvent solution to minimize regeneration energy
required.
• Minimizing the rise in absorber temperature.
• Operating TCM plant within emission requirements.
• Obtaining sufficient heat exchange for optimal performance.
• Improving the working capacity of the solvent.
• Solvent emissions control.
status
RTI has tested multiple water-lean solvent formulations and identified an improved formulation (NAS-5). Experimental
testing of NAS-5 in RTI’s BsGAS showed that the lowest regeneration of 2.15 MJ/kg CO2 was achieved when the system
operated at L/G of 4.2. The team performed 405 hours of NAS baseline testing at the SINTEF Tiller plant in an unmodified
configuration, revealing that the energy required for solvent regeneration is 15% lower for NAS than that for MEA, even
though NAS was run under less-than-optimal conditions. Parametric testing and a cumulative 1,200 hours of long-term
testing of NAS-5 in the Tiller plant were conducted following installation of NAS-specific components to determine optimal
operating parameters and validate reduced reboiler duty. The lowest specific reboiler heat duty of 2.3 GJ/tonne CO2,
water balance, and operational stability were maintained during about 1,600 hours of testing using the NAS-5 formulation.
Additional water-lean solvent baseline testing using coal-fired flue gas at NCCC showed that 90% CO2 capture is
consistently observed under varying test conditions. In preparation for large pilot-scale testing, RTI initiated design and
engineering of TCM facility modifications, and a front-end engineering design (FEED) study to determine the cost of
modifications is underway. In addition, solvent qualification testing is underway at SINTEF to demonstrate performance
of the manufactured solvent.
available reports/technical papers/presentations
Lail, M., “Engineering Scale Testing of Transformational Non-Aqueous Solvent-Based CO2 Capture Process at
Technology Centre Mongstad,” presented at the 2019 Carbon Capture, Utilization, Storage, and Oil and Gas
Technologies Integrated Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-
file/M-Lail-RTI-Testing%20at%20TC%20Mongstad.pdf.
Zhou, S. James, et.al. “Pilot Testing of a Non-Aqueous Solvent (NAS) CO2 Capture Process,” 14th International
Conference on Greenhouse Gas Control Technologies, GHGT-14, 21st -25th October 2018, Melbourne, Australia.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
140 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Zhou, S. James, “Engineering Scale Testing of Transformational Non-Aqueous Solvent-Based CO2 Capture Process at
Technology Centre Mongstad,” Project Kickoff Meeting, October 2018.
https://netl.doe.gov/projects/files/Engineering%20Scale%20Testing%20of%20Transformational%20Non-
Aqueous%20Solvent-
Based%20CO2%20Capture%20Process%20at%20Technology%20Centre%20Mongstad%20(Oct%202018).pdf.
Zhou, S. James, “Engineering Scale Testing of Transformational Non-Aqueous Solvent-Based CO2 Capture Process at
Technology Centre Mongstad,” presented at the 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018.
https://netl.doe.gov/projects/files/Engineering%20Scale%20Testing%20of%20Transformational%20Non-
Aqueous%20Solvent-
Based%20CO2%20Capture%20Process%20at%20Technology%20Centre%20Mongstad%20(Aug%202018).pdf.
Tanthana, J., “Large Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power
Plants,” presented at the 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://netl.doe.gov/projects/files/J-Tanthana-RTI-Non-Aqueous-Solvent-Capture-Process.pdf.
Zhou, S., “Large Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power
Plants Utilizing Real Coal Derived Flue Gas,” presented at the 2017 NETL CO2 Capture Technology Project Review
Meeting, Pittsburgh, PA, August 2017. https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-
Tuesday/S-J-Zhou-RTI-Non-Aqueous-Solvent-CO2-Capture.pdf.
Zhou, S. James, et. al., “Large Bench-scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-
fired Power Plants,” 9th Trondheim Conference on CO2 Capture, Transport and Storage, Trondheim, Norway, June 12 -
14, 2017.
Zhou, S., “Large Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power
Plants Utilizing Real Coal Derived Flue Gas,” Budget Period 1 Project Review Meeting, Pittsburgh, PA, April 2017.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0026466-BP1-
Review.pdf.
Lail, M., “Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power Plants,”
Final Scientific/Technical Report, December 2016. https://www.osti.gov/servlets/purl/1389565.
Zhou, S. James, et. al., “Non-Aqueous Solvent CO2 Capture Process,” November 14 - 18, 2016, GHGT 13, Lausanne,
Switzerland.
Lail, M., “Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power Plants,”
2016 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2016.
http://netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/4-Thursday/M-Lail-RTI-Non-Aqueous-Solvent-
CO2-Capture.pdf.
Lail, M., “Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power Plants,”
2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
http://netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/M-Lail-RTI-Nonaqueous-Solvent.pdf.
Coleman, L., “Bench-Scale Development of a Non-Aqueous Solvent CO2 Capture Process for Coal-Fired Power
Plants,” 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/L-Coleman-RTI-Bench-
Scale-Development-Of-A-Nonaqueous-Solvent.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 141
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Alkanolamines for Acid Gas technology maturity:
Removal in Gasification
Laboratory-Scale, Simulated
Syngas
Processes project focus:
CO2-Binding Organic Liquid
Solvents
primary project goals
participant:
Pacific Northwest National Laboratory (PNNL) is performing this project to identify Pacific Northwest National
candidate molecules that have high carbon dioxide (CO2) selectivity compared to Laboratory
other components of syngas (carbon monoxide [CO], hydrogen [H2], and water
[H2O]). This is being done by conducting high-pressure nuclear magnetic project number:
resonance (NMR) measurements using PNNL’s custom high-pressure NMR cells. FWP-72564
Candidate molecules will be identified by conducting vapor-liquid equilibria (VLE)
measurements of anhydrous tertiary alkanolamines with individual components of predecessor projects:
syngas (CO, CO2, H2, and H2O) and simulated syngas. Two-dimensional (2D) NMR N/A
measurements are being used to measure diffusion coefficients for CO2 and the
solvent molecules, which can then be used to calculate the viscosity of the NETL project manager:
solutions. A preliminary techno-economic assessment (TEA) will be made to Sai Gollakota
[email protected]
determine energy savings over activated methyldiethanolamine (aMDEA) for CO2
capture from syngas.
principal investigator:
Phillip Koech
technical goals Pacific Northwest National
Laboratory
• Identify candidate molecules that have high CO2 selectivity compared to other [email protected]
components of syngas (CO, H2, and nitrogen [N2]).
partners:
• Obtain VLE measurements of anhydrous tertiary alkanolamines with individual
Susteon Inc
components of syngas (CO, CO2, H2, and N2).
• Measure diffusion coefficients of CO2 and the solvent molecules using 2D NMR. start date:
• Perform a preliminary TEA. 10.01.2018
• Optimize solvent formulations and measure viscosities using a high-pressure
viscometer.
percent complete:
54%
• Design, construct, and shakedown a high-pressure pressure-volume-
temperature (hp-PVT) cell with validation against known solvent standards,
such as aMDEA or Selexol.
• Perform comprehensive property testing (VLE, viscosity, density, and mass
transfer coefficients) for the best solvent or blend using hp-PVT cell.
• Perform final TEA and process performance projections.
• License intellectual property and transfer it to industrial partner.
technical content
To begin this effort, PNNL performed screening for CO2-binding organic liquid
(CO2BOL) solvents suitable for removal of CO2 from syngas. Three alkanolamine
pressure-swing regeneration solvents were selected for screening: EDEA, DMEA, and
PSA-1 (Figure 1). Additionally, four thermal regeneration solvents were evaluated for
this application: three aminopyridines (2-MAMP, 2-EAMP, and AP) and a diamine
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
142 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
(DA; Figure 1). The specific names and structures of PSA-1, AP, and DA are currently proprietary. EDEA and DMEA solvents
have shown promising CO2 uptake capacity with both chemical and physical absorption, but the performance dropped
significantly in mixed gases. The aminopyridines (2-MAMP, 2-EAMP, and AP) and DA bind CO2 chemically at ambient
pressure with potential additional physical absorption under elevated pressures.
Figure 1: Amine solvents tested for CO2 capture.
In order to improve the CO2 solubility of pressure-swing absorption (PSA) solvents such as EDEA and DMEA, a new solvent
designated as PSA-1 was designed using learnings from past post-combustion CO2 capture work to increase CO2 solubility
while lowering viscosity. VLE measurements for the PSA-1 solvent showed the highest physical solubility (42.22 mol% of
CO2) compared to all CO2BOL solvents. It also showed minimal chemical absorption of 1.38 mol% as carbonate, resulting
into a total uptake capacity 43.6 mol%. PSA-1 exhibited similar drop in CO2 capacity in mixed gases as EDEA and DMEA.
Thermal-swing solvents, DA and AP, exhibited excellent CO2 uptake capacity without significant drop in mixed gases, but
they suffered from increased viscosity under syngas conditions. It was hypothesized that a blend of the best thermal- and
pressure-swing solvents would result in a formulation with high CO2 capture capacity and low viscosity. To evaluate this
concept, controlled blends of DA (the best thermal-swing solvent) and PSA-1 (the best pressure-swing solvent) were made,
and the VLE data of these blends were measured. The gravimetric CO2 uptake capacity of the DA:PSA-1 blends shows a
good uptake capacity under both pure CO2 and mixed gas containing CO2 and H2. These solvent formulations have negligible
H2 uptake under gravimetric conditions.
A blend of the 1:1 mole ratio of DA and PSA-1 was selected for VLE studies using a redesigned high-pressure NMR cell.
Figure 2 shows VLE data for 1:1 DA:PSA-1 for CO2:H2 (1:1) gas mixture at 35 bar. This figure shows high CO2 uptake and VLE
as a function of temperature follows the expected trend of decreasing uptake with increased temperature.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 143
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 2: VLE for 50:50 DA:PSA-1 for CO2:H2 (1:1) gas mixture at 35 bar.
Low viscosity of the CO2-rich solvent is critical for both low capital and operation cost of the plant. To understand the
viscosity of the promising formulation, the viscosity was measured at a CO2 pressure of 500 pounds per square inch (psi).
Figure 4 shows the viscosity of DA:PSA-1 (1:1) as a function of temperature. The highest viscosity measured for this
formulation at 25°C was ~16 cP, which decreased to 4.2 cP when the temperature increased to 45°C, which is comparable
to the viscosity of the aMDEA solvent.
Figure 3: Viscosity versus temperature DA:PSA-1 (1:1) under 500 psi CO2.
Susteon developed a series of process configurations to maximize the CO2 capture efficiency of the solvent, while minimizing
the overall energy requirement and capital cost of the process. This analysis led to a regeneration scheme with a combination
of a flash pressure-reduction and a small reboiler. Preliminary results from this analysis indicated a total energy requirement
between 0.64 to 0.69 gigajoules (GJ)/tonne of CO2 compared to about 1 GJ/tonne of CO2 for the current state-of-the-art
process technologies. These values show that there is a strong potential to achieve up to a 28% improvement in the total
energy for CO2 capture from high-pressure syngas mixtures using the new mixed solvent as a replacement or drop-in solvent
in existing commercial aMDEA plants.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
144 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 TBD -
Normal Boiling Point °C TBD -
Normal Freezing Point °C TBD -
Vapor Pressure @ 15°C bar TBD -
Manufacturing Cost for Solvent $/kg 13 10
Working Solution
Concentration kg/kg TBD -
Specific Gravity (15°C/15°C) - TBD -
Specific Heat Capacity @ STP kJ/kg-K - -
Viscosity @ 15°C cP ~16 ~16
Absorption
Pressure bar - -
Temperature °C 25-45 -
Equilibrium CO2 Loading mol/mol TBD -
Heat of Absorption kJ/mol CO2 TBD -
Solution Viscosity cP -4 -
Desorption
Pressure bar - -
Temperature °C - -
Equilibrium CO2 Loading mol/mol TBD -
Heat of Desorption kJ/mol CO2 TBD -
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr -
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 -
Absorber Pressure Drop bar -
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 145
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Combination of physical and chemical.
Solvent Contaminant Resistance – Currently unknown.
Solvent Foaming Tendency – Currently unknown.
Flue Gas Pretreatment Requirements – Currently unknown.
Solvent Makeup Requirements – Currently unknown.
Waste Streams Generated – Currently unknown.
Process Design Concept – The DA:PSA-1 mixed solvent can be used as a drop-in replacement solvent in a commercial
aMDEA CO2 capture process.
Figure 4: Configuration and operating conditions of the aMDEA process.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
146 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
technology advantages
• Low regeneration energy requirements (less than 0.7 GJ/tonne CO2).
• Lower capital cost from small equipment resulting from higher CO2 capacity and CO2 selectivity.
• Mixed DA:PSA-1 solvent can be used as a drop-in replacement in an aMDEA process.
R&D challenges
• Resource risks, including availability of equipment and staff availability.
• Effect of flue gas contaminants is currently unknown.
• Improving performance in mixed gases versus pure CO2.
status
A new PSA solvent was developed, PSA-1, which was designed to improve CO2 solubility without increasing viscosity. This
new solvent had the highest physically absorbed CO2 of all CO2BOLs (about 44 mol%), but similar to the other PSA
solvents, the CO2 uptake capacity significantly dropped in mixed gases. Thus, it is not able to achieve greater than 90%
CO2 capture from syngas streams.
The TSA solvents, namely 2-MAMP, 2-EAMP, DA, and AP, had high-gravimetric CO2 uptake capacity (up to 129 mol% for
DA), but also had high viscosity in the NMR cell, which prevented further evaluation.
It was found that VLE for blends of DA and PSA-1 showed the best CO2 uptake with a combination of both chemical and
physical absorption of CO2 without significant drop-in uptake in binary and ternary gas mixtures. The viscosity of CO2-
rich DA:PSA-1 (1:1 mole ratio) was measured at 16 cP at 25°C under 500 psi CO2, and decreased to 4.2 cP at 45°C. The
Aspen simulation results showed that the preliminary mixed solvent (DA:PSA-1) process uses lower overall energy.
available reports/technical papers/presentations
Koech, P. “Syngas Purifications Using High-Pressure CO2BOL Derivatives with Pressure Swing Regeneration,” NETL
Carbon Capture Project Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/P-
Koech-PNNL-Syngas%20Purification.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
147
Post-Combustion Solvent Technologies
ROTA-CAP: An Intensified technology maturity:
Bench-Scale, Small-Pilot
Carbon Capture System Using (simulated, natural gas
burner and coal-fired flue
Rotating Packed Beds gases)
project focus:
primary project goals Rotating Packed Bed with
Advanced Solvent
Gas Technology Institute (GTI), with Clean Carbon Solutions Ltd. (CCSL), will
develop and validate a transformational carbon dioxide (CO2) capture technology participant:
(ROTA-CAP) using novel rotating packed-bed (RPB) absorbers and regenerators Gas Technology Institute
combined with an advanced solvent.
project number:
FE0031630
technical goals
predecessor projects:
• Design, construct, and commission the ROTA-CAP equipment at GTI.
N/A
• Develop a preliminary process model and perform an initial fabrication
feasibility study for commercial process. NETL project manager:
• Test the ROTA-CAP system with simulated flue gases and natural gas burner Andrew O’Palko
flue gas at GTI to determine key operating parameters. [email protected]
• Calibrate the process model and measure solvent carryover.
principal investigator:
• Perform long-term reliability and operability testing at the National Carbon Osman Akpolat
Capture Center (NCCC) on coal-fired flue gas. Gas Technology Institute
• Verify the process model. [email protected]
• Determine scale-up challenges, solvent degradation, and aerosol formation. partners:
• Complete a high-level techno-economic analysis (TEA). Clean Carbon Solutions Ltd.
(CCSL), National Carbon
Capture Center
technical content
start date:
The RPB contactor design comprises a rotating disk of packing material that
10.01.2018
generates a high gravity centrifugal force, which distributes solvent radially toward
the outer edge of the disk, providing a high surface area for mass transfer to occur percent complete:
as countercurrent flue gas contacts the solvent droplets. An integrated absorber-
48%
regenerator bench-scale test skid for the ROTA-CAP system will be designed,
constructed, and operated at GTI using simulated flue gas and natural gas burner
flue gas to determine key operating parameters. See Figure 1 for a schematic of
RPBs in gas-liquid contactor operation. CCSL will provide an advanced solvent for
the test, such as its proprietary amine-promoted buffer salt (APBS) solvent. To
compare the performance of ROTA-CAP to the conventional process using
commercial monoethanolamine (MEA) solvent, the team is utilizing the Slip Stream
Test Unit (SSTU) at NCCC. See Figure 2 for a general bench-scale ROTA-CAP skid
process flow diagram. Long-term (1,000-hour) stability testing of the integrated
ROTA-CAP CO2 capture system will be conducted on a coal-fired flue gas
slipstream at NCCC at a scale of 1 tonne CO2 per day, and the collected data will
be used to determine solvent degradation and aerosol formation. A simulation
process model will be developed for integrated RPB carbon capture systems and
will be used to aid in larger-scale deployment of the ROTA-CAP technology, such
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
148 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
as integration with coal-fired power plants. A high-level TEA of the process will be performed based on experimental data
and the capture process model verified with the long-term operation data.
Figure 1: RPB gas liquid contactor.
Captur
Reflux
vent
Reboiler Vapors
Figure 2: ROTA-CAP bench-scale test skid process flow diagram.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
149
Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 57.29 57.29
Normal Boiling Point °C 104-220 104-220
Normal Freezing Point °C N/A N/A
Vapor Pressure @ 15°C bar 18.2 18.2
Manufacturing Cost for Solvent $/kg — —
Working Solution
Concentration kg/kg 0.425 0.425-0.55
Specific Gravity (15°C/15°C) - 1.007 >1.007
Specific Heat Capacity @ STP kJ/kg-K 3.344 >3.344
Viscosity @ STP cP 2.839 >2.839
Absorption
Pressure bar 0.1 0.1
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 3.3 >3.3
Heat of Absorption kJ/mol CO2 75.2 >75.2
Solution Viscosity cP 4.4 >4.4
Desorption
Pressure bar 0.07 0.07
Temperature °C 120 120
Equilibrium CO2 Loading mol/mol 0.7 >0.7
Heat of Desorption kJ/mol CO2 2.7-3.0 2.55-2.85
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
150 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The solvent utilizes a chemical reaction with acid gases to remove them from
the feed gas stream. The reaction is reversed in the stripper unit operation through the application of heat to the solvent.
Solvent Contaminant Resistance – Besides physical contamination (e.g., feed gas solids), the main contaminant expected
in the solvent is heat-stable salts (HSSs). HSSs are a byproduct of heat and solvent reaction with components in the feed
gas (e.g., oxygen [O2], nitrogen oxide [NOX], sulfur oxide [SOX]). In long-term testing by CCSL, the solvent has superior
resistance to HSS generation when compared to other commercial solvents.
Solvent Foaming Tendency – Foaming has not been reported in any test campaign or commercial operation of the
solvent to date.
Flue Gas Pretreatment Requirements – Pretreatment would include:
• Reduction of particulate matter, NOX, and SOX to current U.S. Environmental Protection Agency (EPA) limits.
• Cooling and water saturation of the feed gas to approximately 110°F.
Solvent Makeup Requirements – Solvent makeup is minimal as HSS generation and physical loses should be low. It is
expected that less than 0.35 kg solvent per tonne of CO2 should be added intermittently.
Waste Streams Generated – A water bleed is expected from the regenerator reflux to maintain the solvent concentration
and remove any trapped ammonia salt species. During long-term testing, HSSs could be removed through reclaiming.
The HSS sludge would need to be disposed. However, with only a 1,000-hour target for the long-term testing, reclaiming
is not anticipated during this test campaign.
technology advantages
• The RPB technology provides intense micromixing and internal mass transfer, thereby facilitating significant size
reductions in the absorber and regenerator relative to conventional columns, resulting in lower capital costs.
• The use of a highly concentrated solvent, such as CCSL’s APBS solvent, reduces the regeneration energy and leads to
greater process efficiency.
• Reduced oxidative and thermal degradation.
• Decreased solvent top-up requirements by approximately 77%.
• Reduced waste handling and disposal cost by up to 92%.
• A simulation process model for integrated RPB carbon capture systems will be developed, which can be used in future
larger-scale deployments.
• TEA will evaluate the value of the ROTA-CAP technology in the carbon capture market.
• RPB reactors are non-selective to the solvent used.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
151
Post-Combustion Solvent Technologies
• RPB reactors offer higher efficiencies and are non-selective to the solvent used.
R&D challenges
• The integrated use of RPBs as both absorber and regenerator in a single system.
• The mechanical design parameters of rotating equipment.
• Solvent performance during operation.
• Integrating and achieving required solvent regeneration using an RPB regenerator.
• During testing, GTI will determine the solvent performance and modify it as needed to achieve a 90% CO2 removal
rate. The optimum CO2 removal rate to achieve the lowest cost of removal will be calculated.
• Scale-up limitations exist with rotating equipment. Modular design may be useful to overcome size limitations of RPBs
for larger systems. Capital cost and added complexity of the system will need to be managed.
status
GTI designed and costed the bench-scale ROTA-CAP test skid, a 50-kilowatt-electric (kWe) (1,000-kg/day CO2 removal)
equivalent-scale integrated carbon capture skid. The skid will have a flue gas cooling and filtration section available to be
used when necessary.
The key variables will include:
• RPB rotational speed of 200 to 1,000 RPM.
• Absorber liquid/gas ratio of 0.5 to 5.0 kg/m3.
• Solvent circulation rate of 30 to 150 kg/h.
• Solvent concentration/viscosity of 40 to 80 wt% (5 to 100 cP).
• Regenerator operating pressure/temperature of 0.0 to 1.0 bar(g) (100 to 130°C).
• Flue gas composition (synthetic, natural gas-fired, coal-fired).
The task duration for testing of the bench-scale ROTA-CAP skid at GTI is planned to be five months. This includes three
months for simulated gas testing and one month natural gas burner flue gas testing, with an additional month of testing
that can be used for either. Long-term testing at NCCC is planned to be a cumulative 1,000-hour test.
available reports/technical papers/presentations
Akpolat, O., “ROTA-CAP: An Intensified Carbon Capture System Using Rotating Packed Beds,” 2019 Carbon Capture,
Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting, Pittsburgh, PA. .
https://netl.doe.gov/sites/default/files/netl-file/O-Akpolat-GTI-ROTA-CAP.pdf.
Akpolat, O., “ROTA-CAP: An Intensified Carbon Capture System Using Rotating Packed Beds,” 2018 NETL CO2 Capture
Technology Project Review Meeting, Pittsburgh, PA, August 2019. https://www.netl.doe.gov/sites/default/files/2018-
12/O-Akpolat-GTI-Rotating-Packed-Beds.pdf.
Akpolat, O., “ROTA-CAP: An Intensified Carbon Capture System Using Rotating Packed Beds,” Project Kick-Off Meeting,
Pittsburgh, PA, Dec 2018. https://www.netl.doe.gov/sites/default/files/2019-01/FE0031630-kickoff-presentation-
121418.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
152 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Universal Solvent Viscosity technology maturity:
Laboratory-Scale, Simulated
Reduction Via Hydrogen Flue Gas
Bonding Disruptors project focus:
Novel Additives for water-
Lean Amines
primary project goals
participant:
Liquid Ion Solutions LLC, along with Carnegie Mellon University (CMU) and Carbon Liquid Ion Solutions LLC
Capture Scientific, will develop and evaluate novel additives that lower the
viscosity of water-lean amine solvents for post-combustion carbon dioxide (CO2) project number:
capture. The project will focus on developing a solvent additive that minimizes the FE0031629
formation of long-range hydrogen bonding (HB) networks, in turn decreasing the
solvent viscosity and improving the process economics. Three model solvents will predecessor projects:
be prepared using amines that encompass the characteristics of most amines used N/A
in water-lean solvents, and the solvents will be studied computationally and
experimentally to benchmark the behavior of the solvents’ viscosity in the NETL project manager:
presence of CO2. The project team will then use simulation models to understand Katharina Daniels
the molecular interactions in water-lean solvents and identify additives that disrupt [email protected]
HB networks effectively, measure solvent viscosity reduction with additives at lab-
scale, optimize the combination of additive/solvent and test the optimized system principal investigator:
in synthetic flue gas, and perform a cost-benefit analysis to examine the advantage xu Zhou
of using additives for solvent viscosity reduction. Liquid Ion Solutions LLC
[email protected]
technical goals partners:
Carbon Capture Scientific,
The goal of the project is to evaluate, at lab-scale, the effectiveness of ether and Carnegie Mellon University
ester HB disruptor additives in lowering solvent viscosity without having an
adverse impact on CO2 capture capacity. Objectives include: start date:
10.01.2018
• Computer simulation to understand the molecular interactions in water-lean
CO2 capture solvents. percent complete:
• Synthesis and characterization of HB disrupter molecules with the specific goal 45%
of significantly reducing the viscosity of water-lean carbon capture solvents in
the presence of CO2.
• Proof-of-concept performance testing to demonstrate the effectiveness of HB
disrupters in lowering viscosity.
• Optimization of HB disruptor chemical structure based on insights gained from
computational modeling and experimental proof-of-concept studies.
• Demonstration of the effectiveness of the optimized HB disrupters in the
presence of synthetic flue gas.
technical content
Liquid Ion Solutions, in partnership with CMU and Carbon Capture Scientific, is
developing and evaluating novel additives that minimize the formation of long-
range HB networks and thus decrease the viscosity of water-lean amine solvents
for post-combustion CO2 capture by 50% upon CO2 uptake. Three different
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
153
Post-Combustion Solvent Technologies
amines—2-(methylamino)ethanol (NMAE), 2-methoxyethylamine (MOEA), and bis(2-methoxyethyl)amine (BMOEA) — are
being used for this study.
The project work includes development of computer simulation to understand the molecular interaction in water-lean
CO2 capture solvents; design, synthesis, and performance testing of HB disrupters as additives to reduce solvent viscosity;
optimization of the HB disrupter; and performance testing of the optimized additive in the presence of synthetic flue gas.
The computational study will include a detailed analysis of viscosity and size distribution of HB clusters of three amine
solvents as a function of ammonium/carbamate ion concentration: NMAE, MOEA, and BMOEA. Initial calculations will be
made to determine force field parameters, partial charges of ammonium, and carbamate ions. Molecular dynamics
simulations will allow for study of viscosity, HB structures, and kinetics of HB formation and breaking. Disruptor additives
under consideration to include oxy-dibenzene, pyran, crown-ethers, and dimethyl sulfoxide like moieties. Quantitative
portions of the computational study will investigate the effects of HB disrupting additives, including influence of 3D HB
structures of the absorbents, as well as their HB cluster lifetime; how the additives modulate viscosity; and what key factors
govern the disruption of HB structures.
HB disruptor synthesis and testing will also be conducted, including a proof-of-concept study, additive screening, and
optimization and synthetic flue gas testing. For the proof-on-concept, candidate disruptors will be selected and viscosity
tested at uncharged, CO2-charged, and after desorption states. Then the concentration of the additive will be optimized,
including evaluation of working capacity and viscosity. The optimized additive and solvent will be tested at lab-scale with
synthetic flue gas, evaluating working capacity and viscosity after multiple cycles.
An engineering analysis will also be conducted, examining the impacts of viscosity on momentum, heat and mass transfer
in carbon capture systems, and conducting a preliminary cost-benefit analysis.
Figure 1: Illustration of fully HB network (left) and the breakage of the HB network by addition of HB acceptors (right).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
154 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 80-140 112.4
Normal Boiling Point °C 226.8 226.8
Normal Freezing Point °C 4.4 4.4
Vapor Pressure @ 15°C Bar <0.01 <0.01
Manufacturing Cost for Solvent $/kg N/A 2
Working Solution
Concentration kg/kg 100 50/100
Specific Gravity (15°C/15°C) - 1.02-1.07 1.05
Specific Heat Capacity @ STP kJ/kg-K 3.0-3.5 3.3
Viscosity @ STP cP 2-6 12.5
Absorption
Pressure Bar 1.01 1.01
Temperature °C 40 30
Equilibrium CO2 Loading mol/mol 0.48 0.48
Heat of Absorption kJ/mol CO2 unknown 57
Solution Viscosity cP 2-6 5.3
Desorption
Pressure Bar 1 1
Temperature °C 120 120
Equilibrium CO2 Loading mol/mol 0.10 0.33
Heat of Desorption kJ/mol CO2 Unknown 57.0
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,716,229
CO2 Recovery, Purity, and Pressure % / % / bar 80/10/0.10
Absorber Pressure Drop Bar 0.05
Estimated Absorber/Stripper Cost of __$__
160
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
155
Post-Combustion Solvent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverize coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hour of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – Chemical (Additive).
Solvent Contaminant Resistance – N/A.
Solvent Foaming Tendency – Low.
Flue Gas Pretreatment Requirements – N/A.
Solvent Makeup Requirements – N/A.
Waste Streams Generated – CO2.
Process Design Concept – Standard absorption/desorption column.
technology advantages
The development of an HB disruptor additive capable of significantly reducing the viscosity of any water-lean chemical
solvent will allow for increased heat exchanger and mass transfer efficiency, thus lowering the capital and operating costs
for CO2 capture.
R&D challenges
HB networks in capture solvents result in an increase in viscosity. In order to break down the overall size of the HB network,
additives can be introduced that disrupt the overall network, forming smaller segmented networks.
status
The simulation of relationship between HB and viscosity and quantitative analysis of co-solvent and mixture effects was
completed. The team has completed the proof-of-concept viscosity testing using the rheometer testing system. Initial
additives screening based on viscosity testing has shown up to 50% viscosity reduction in the amine systems upon
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
156 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
addition of up to 10 wt. % additives. The preliminary engineering analysis is still underway. The quantitative assessment
of impact on operating costs has been completed.
available reports/technical papers/presentations
Nulwala, H., “Universal Solvent Viscosity Reduction Via Hydrogen Bonding Disruptors,” Poster at the 2018 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/H-
Nulwala-LIon-Solutions-Solvent-Viscosity-Reduction.pdf.
Zhou, X., Brown, D., Nulwala, H., Liu, J., Li, Y., Kim, H., Chen, S., “Universal Solvent Viscosity Reduction Via Hydrogen
Bonding Disruptors,” Presented at the 2019 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA,
August 2019. https://netl.doe.gov/sites/default/files/netl-file/X-Zhou-LIS-Solvent-Viscosity.pdf.
Nulwala, H., “Universal Solvent Viscosity Reduction Via Hydrogen Bonding Disruptors,” Project Kickoff Meeting.
https://www.netl.doe.gov/projects/files/FE0031629_Kickoff%20meeting_10-12-2018.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
157
Post-Combustion Solvent Technologies
Emissions Mitigation technology maturity:
Bench-Scale (6 kwe), Actual
Technology for Flue Gas
Advanced Water-Lean project focus:
Solvent-Based CO2
water-Lean Solvent
Emissions Mitigation
Capture Processes participant:
Research Triangle Institute
(RTI)
primary project goals
project number:
Research Triangle Institute (RTI) will develop a comprehensive solvent emission
FE0031660
mitigation tool set for reducing the solvent and aerosol emissions from carbon
dioxide (CO2) capture systems using water-lean solvents (WLSs). Due to their low predecessor projects:
energy requirement for solvent regeneration, lower regeneration temperature, low
N/A
corrosivity, and low vapor pressure, WLS systems are rapidly being developed for
CO2 capture. RTI’s tool set is specifically designed for WLS systems, implementing NETL project manager:
an advanced organic solvent wash system in conjunction with water wash, acid Sai Gollakota
wash, and other commercially available, state-of-the-art emission reduction [email protected]
technologies.
principal investigator:
technical goals jak Tanthana
Research Triangle Institute
[email protected]
• Characterize and understand the emission produced by WLSs while capturing
CO2. partners:
• Develop an empirically derived emission model based on the solvent physical Technology Centre
properties and on critical operating parameters from the absorber and wash Mongstad (TCM), Linde
section.
• Evaluate suitable process arrangement for emission-reduction devices.
start date:
10.01.2018
• Demonstrate the effectiveness of these emission mitigation devices on the
bench-scale CO2 capture system optimized for WLSs.
percent complete:
50%
technical content
RTI is advancing development of an effective tool set to reduce amine emissions
for WLSs by means of reducing the vapor loss, liquid entrainment, and aerosol
formation altogether. The project team will characterize the emissions produced
by WLSs while capturing CO2; develop a model that predicts the emissions based
on the solvent’s physical and chemical properties on critical operating parameters
from the absorber and wash section; develop a process tool set for emission
reduction over a range of solvent systems; evaluate the effectiveness of these
emission mitigation devices in a bench-scale (6-kilowatt-electric [kWe])
CO2 capture system by testing with RTI’s current WLS formulation, NAS-5, and a
second selected WLS under actual flue gas conditions; and complete a techno-
economic analysis (TEA) to determine the contribution of the emission control
technologies to the overall CO2 capture cost.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
158 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
The results obtained in this study will assist in process scalability, mitigate the technology’s risk associated with emissions,
improve the economic potential, and aid in the commercial adoption of WLSs.
The project tasks will determine RTI’s Non-Aqueous Solvent (NAS) and selected WLS emissions characteristics from the
absorber column; develop an empirical emission model based on critical operating parameters; screen organic solvents
and amine adsorbents; and determine, implement, and evaluate the effectiveness of the emissions control technologies
(ECTs) at RTI’s Bench-Scale Gas Absorption System (BsGAS). Figure 1 shows the potential ECTs for WLS systems to be
incorporated at a CO2 capture plant. Also, the team will carry out the modifications based on RTI’s findings and evaluate
the amine emissions using NAS-5 and a selected WLS and refine the empirical emission model/determine the impact of
the ECTs to the CO2 capture cost.
Figure 1: Potential emissions control technologies for WLS systems to be incorporated at a CO2 capture plant.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
159
Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 95–115** 99
Normal Boiling Point °C 185–243** 200
Normal Freezing Point °C (-6 to -24)** -9.15
Vapor Pressure @ 15°C bar 4.47e–4** 4.47e–4
Manufacturing Cost for Solvent $/kg 30 5
Working Solution
Concentration kg/kg 0.5–0.6* 0.55
Specific Gravity (15°C/15°C) - 0.9–1.035* 1.035
Specific Heat Capacity @ STP kJ/kg-K 2.78* 2.78
Viscosity @ STP cP 4.38–4.7* 4.7
Absorption
Pressure bar 0.133* 0.133
Temperature °C 35–45* 38
Equilibrium CO2 Loading mol/mol 2.04–2.22* 2.04
Heat of Absorption kJ/mol CO2 1,700–2,000* 1,931
Solution Viscosity cP 4–30* 28
Desorption
Pressure bar 2–7.8* 2
Temperature °C 90–110* 105
Equilibrium CO2 Loading mol/mol 0.45-1.13* 0.45
Heat of Desorption kJ/mol CO2 2,100* 2,045
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure %/%/bar — — —
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
* Experimentally measured data.
** Calculated data for different concentrations and conditions using standard mixing rules from pure components data.
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
160 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical
Solvent Contaminant Resistance – More resistant than MEA to sulfur oxide (SOX) and nitrogen oxide (NOX).
Solvent Foaming Tendency – Less foaming than aqueous amine solvent.
Flue Gas Pretreatment Requirements – Temperature adjustment and SOX control.
Solvent Makeup Requirements – 0.2 to 0.5 kg/tonne CO2.
Waste Streams Generated – None.
Process Design Concept – Absorber with interstage coolers coupling with regenerator with interstage heaters.
technology advantages
• WLS system has a low energy requirement for solvent regeneration and other added benefits, which reduce cost of
CO2 capture.
• Project to provide a model that predicts the amine emissions using the solvent properties, key process parameters,
and the recommended emissions mitigation devices required for solvents specific to the developers.
R&D challenges
• Aerosol particle generation.
• Development of aerosols and particle counts technique for WLSs.
• Quantification and speciation of the emissions from WLSs.
• Emissions model development.
• Solvent screening for organic wash section.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
161
Post-Combustion Solvent Technologies
• Process arrangement for amine extraction.
• Parametric and long-term testing.
• TEA.
status
Under development are various components of the prototype emissions control system for using water-lean solvents for
CO2 capture. Solvent degradation testing systems were constructed to determine the oxidative degradation and chemical
pathways for the formation of nitrosamines (NA) and amine component thermal degradation products. Various solid
adsorbents were tested for their amine absorption capacity and ability to regenerate to identify potential sorbent
candidates to be used for the amine recovery unit.
RTI’s NAS-5 has been tested to evaluate the impact of various process parameters that affect the overall amine emissions
and aerosols formation using BsGAS. The key parameters that may impact the emissions are water wash temperature,
liquid-to-gas ratio, CO2 capture rate, the bulge temperature in the absorber.
Additional water wash, advanced demister, CO2 acidification tanks, and particulate filters were added to BsGAS in late
2019. The effectiveness of these devices in controlling the amine emissions are being evaluated.
RTI has developed a Principle Component Analysis (PCA) framework for an empirical model to predict aerosol-based
emissions utilizing BsGAS. This model correlates the process parameters of a water-lean solvent CO2 capture system that
is based on BsGAS testing of a water-lean solvent.
available reports/technical papers/presentations
Tanthana, J., “Emissions Mitigation Technology for Advanced Water-Lean Solvent Based CO2 Capture Processes,” Project
kickoff meeting presentation, Nov 2018. https://www.netl.doe.gov/projects/files/FE0031660-kickoff.pdf.
Tanthana, J., “Emissions Mitigation Technology for Advanced Water-Lean Solvent Based CO2 Capture Processes,” Poster
presentation by Jak Tanthana, RTI International, 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, https://www.netl.doe.gov/projects/files/J-Tanthana-RTI-Solvent-Emissions-Mitigation.pdf.
Tanthana, J., “ “Emissions Mitigation Technology for Advanced Water-Lean Solvent Based CO2 Capture Processes,”
Presented at the 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting,
Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/J-Tanthana-RTI-Solvent-Emissions-
Mitigtion.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
162 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Fog- and Froth-Based Post technology maturity
Bench-Scale, Simulated and
Combustion CO2 Capture in Actual Flue Gas
Fossil Fuel Power Plants project focus:
Fog and Froth Solvent
Process
primary project goals
participant:
The University of Kentucky Center for Applied Energy Research (UKy-CAER) is University of Kentucky
developing a transformational compact carbon dioxide (CO2) absorber with Center for Applied Energy
internal fog and froth formation, for use in a solvent-based post-combustion CO2 Research
capture process, to surmount the limitations of packed-bed CO2 absorption
columns and to lower the capital cost of carbon capture. project number:
FE0031733
technical goals predecessor projects:
N/A
• Design and fabricate a compact absorber with internal fog and froth sections.
• Develop and finalize the atomizing nozzle and froth generating screens and NETL project manager:
operation conditions for fog and froth formation and destruction. Andrew jones
• Evaluate the fog and froth sections performance in a cold test unit. [email protected]
• Complete a bench-scale parametric testing campaign followed by a long-term
principal investigator:
campaign to assess performance and investigate the effects of solvent
Heather Nikolic
degradation on fog and froth formation.
University of Kentucky
• Prepare a techno-economic analysis (TEA) and environmental, health, and [email protected]
safety (EH&S) assessment.
partners:
Industrial Climate Solutions,
technical content
Inc., Nexant, Smith
Management Group
UKy-CAER is developing an open-tower compact absorber with internal fog and
froth for enhanced solvent-based CO2 capture, as shown in Figure 1. In the process, start date:
the flue gas enters the bottom of the absorber and contacts the solvent in a 05.01.2019
counter-current flow through a section containing structured packing, capturing
approximately 30% of the total CO2 before passing through a riser to the top of percent complete:
the fog/froth capture section. In this section, the gas first contacts a lean amine 15%
mist in a co-current flow in a temperature-controlled environment, with up to five
times the liquid/gas contact area. Both the gas and liquid exiting from the fog
section are forced through froth generating and propagating screens in the froth
section. Here, also a temperature-controlled environment, the mass transfer is
increased because a thin (target of ~10 μm) liquid film virtually eliminates the CO2-
amine diffusion resistance that typically impedes mass transfer in the conventional
capture technologies. By greatly increasing the liquid/gas contact area and
minimizing the diffusion resistance, the absorber column size can be reduced by
up to 70% compared to a standard absorber design. Combining this fog-froth
process with other UKy-CAER CO2 capture technologies could potentially reduce
the CO2 capture capital cost by 57%.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
163
Post-Combustion Solvent Technologies
Figure 1: Schematic of University of Kentucky’s compact absorber.
The project is designing and fabricating the complete compact absorber including the atomizing nozzle, froth generating
and propagating screens, and in-situ heat removal. The frothing screens, as shown in Figure 2, are optimized for froth
generation and propagation. They are designed and supplied by Industrial Climate Solutions. Fog generation includes
spray nozzle selection and optimization of the nozzle arrangement, as well as mist size distribution in the column, via
liquid supply parameters and solvent properties. Individual testing of the fog section and froth section will be followed
by parametric and long-term testing of the compact absorber integrated in UKy-CAER bench-scale post-combustion
capture facilities using simulated and actual flue gas. Data from testing supports development of a TEA and EH&S
assessment for the process.
Figure 2: Froth generating and propagation screens.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
164 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
The solvent and process parameters are provided in Table 1.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight g/mol Amine Amine
Normal Boiling Point °C 155-170 155-170
Normal Freezing Point °C -2 -2
Vapor Pressure @ 20°C bar 0.0007 0.0007
Manufacturing Cost for Solvent $/kg (pure chemical, small batch) 14.74 14.74
Working Solution
Concentration kg/kg 0.35 to 0.45 0.35 to 0.45
Specific Gravity (15°C/15°C) - ~1.0 ~1.0
Specific Heat Capacity @ 40°C kJ/kg-K 2.7-3.3 2.7-3.3
Viscosity @ STP cP 5-7 5-7
Absorption
Pressure bar 1.01 1.01
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.5 0.45
Heat of Absorption kJ/mol CO2 ~-65 ~-70
Solution Viscosity cP 3-5 3-5
Desorption
Pressure bara 3-5 3-5
Temperature °C 110-130 110-130
Equilibrium CO2 Loading mol/mol 0.20 0.20
Heat of Desorption kJ/mol CO2 ~85 ~85
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 24
CO2 Recovery, Purity, and Pressure % / % / bara 90 >95% 1.65
Absorber Pressure Drop bar <20”WC
Estimated Absorber/Stripper Cost of
$ $36K
Manufacturing and Installation
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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Post-Combustion Solvent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – The solvent is an aqueous solution of a hindered primary amine. A carbamate
species is formed upon CO2 absorption. In a CO2 capture absorber, the absorption rate, R, as a function of temperature,
T, and carbon loading, C/N, can be expressed as: R(T, C/N) = kG·a·(PCO2 – P*CO2) where kG is mass transfer coefficient, a
is effective wetted surface area, and (PCO2 – P*CO2) is the driving force, the difference in the concentration of CO2 in liquid
from the gas. Significant increase in R, via kG and a, and corresponding reduction of capital cost comes from the mass
transfer enhancement of the proposed aqueous system compared to any 2nd-gen technology because there is an order
of magnitude greater effective wetted surface area n in the top of the absorber.
Solvent Contaminant Resistance – UKy-CAER analysis show the solvent is more resistant to degradation, 40 to 50%
improvement than 30 wt% MEA. Accumulation of metals within the solvent is expected to be equivalent to that within 30
wt% MEA.
Solvent Foaming Tendency – Unstable froth formation (not persistent foaming) is a key aspect to the proposed compact
absorber. Surfactant is added to reduce the surface tension and therefore control the frothing behavior. Initial CO2 capture
experiments on solvent physical properties were performed in a packed column (2-inch internal diameter [ID] mini-
scrubber). Adding surfactant to change the solvent surface tension led to a CO2 capture efficiency increase of 15 to 20%
throughout the carbon loading range. The key reason for this enhancement is the presence of fine froth (bubbles) that
increase surface area with the addition of surfactant. It was also found that as carbon loading increases, the tendency to
form bubbles decreases due to increased viscosity and surface tension. For an unstable froth, the dispersion rate is also
important. A surfactant was chosen with the faster dispersion rate compared to others considered.
Flue Gas Pretreatment Requirements – The flue gas pretreatment requirement is sulfur dioxide (SO2) removal to less
than 5 ppm to minimize heat stable salt formation. This can be done with a standard counter-current pretreatment column
with a circulating solution of either of soda ash (Na2CO3) or sodium hydroxide (NaOH). The solvent used is a hindered
primary amine and does not form stable nitrosamine species, therefore no additional NOX removal is required. No
additional moisture removal required, as it is for ionic liquids.
Solvent Makeup Requirements – Two factors contributing to solvent makeup rate are degradation and emission. UKy-
CAER analysis show the solvent has degradation rates less than 30 wt% MEA and when the UKy-CAER developed solvent
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
166 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
recovery technology is applied, the solvent emission will be about 0.5 ppm. The anticipated solvent makeup rate is less
than 0.5 kg/tonne CO2 captured.
Waste Streams Generated – The waste streams of the post-combustion CO2 capture process using the proposed
compact absorber are the same as any other post-combustion CO2 capture process. There will be a blowdown stream
from the SO2 pretreatment column and a reclaimer waste stream from the solvent loop.
Process Design Concept – The proposed concept is shown in Figure 3. A 3-inch column is used for the fogging and
frothing section where the flue gas and solvent flow in a co-current fashion. The bottom section contains typical structured
packing with the flue gas and solvent moving in a counter-current fashion.
Figure 3: Compact absorber design concept.
Proposed Module Design – The proposed absorber would be modular with a natural divide between the bottom packed
section and the top fog and froth section.
technology advantages
• Up to five times increase in liquid/gas contact area over structured packing.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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167
Post-Combustion Solvent Technologies
• Up to four times increase in mass transfer over conventional columns due to a thin (target of ~10 μm) liquid film,
eliminating the CO2-amine diffusion resistance that can impede the overall mass transfer of a capture technology.
• Up to 70% reduction in absorber height.
• Up to 50% reduced pump power requirement.
• Maintain carbon loading as close as achieved with conventional column containing structured packing.
• Potential, when combined with other University of Kentucky CO2 capture features, for a 57% reduction in capital cost
for carbon capture.
R&D challenges
• Demonstration at the bench scale due to wall effects in the small column.
• Controlling the froth size.
status
The University of Kentucky has compared and selected options for the atomizing nozzle and frothing screens for their
system. The initial design and construction of the fog and froth sections has been completed.
available reports/technical papers/presentations
Nikolic, H. “Fog+Froth-based Post-Combustion CO2 Capture in Fossil-Fuel Power Plants,” Presented at 2019 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/H-Nikolic-
UKY-CAER-Fog-Froth-Capture.pdf.
Nikolic, H. “Fog+Froth-based Post-Combustion CO2 Capture in Fossil-Fuel Power Plants,” Presented at the Project
Kickoff Meeting, Pittsburgh, PA, May 2018. https://www.netl.doe.gov/projects/files/Fog%20Froth-
Based%20CO2%20Capture%20Kickoff_May%202019.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
168 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Validation of Transformational technology maturity:
Pilot-Scale (0.6 Mwe),
CO2 Capture Solvent Actual Flue Gas
Technology with Revolutionary project focus:
Stability
water-Lean Amine-Based
Solvent for CO2 Capture
participant:
primary project goals ION Clean Energy, Inc.
ION Clean Energy, Inc. (ION) is developing a novel amine-based solvent (ICE-31) project number:
with transformational stability and excellent carbon dioxide (CO2) capture
performance. The project, designated by ION as “Apollo,” aims to scale-up the FE0031727
solvent technology from bench-scale to pilot-scale (0.6 megawatt-electric [MWe]).
predecessor projects:
N/A
technical goals
NETL project manager:
• Develop an understanding of breakdown pathways and confirm the
Katharina Daniels
revolutionary stability of the new solvent using various laboratory techniques. [email protected]
• Develop and validate a ProTreat® process simulation model for design at a
commercial scale. principal investigator:
• Determine values for key performance indicators through testing on coal-fired
Erik Meuleman
or natural gas-fired flue gas: minimum energy consumption, emissions profile,
ION Clean Energy, Inc.
solvent degradation rates, and washing section efficiency. [email protected]
• Perform parametric tests to understand the impact of dynamic operations and
operational upsets beyond design parameters, followed by long-term, steady- partners:
state (at least 1,500 hours) testing for solvent stability assessment. Commonwealth Scientific &
• Develop a techno-economic assessment (TEA) to compare against commercial Industrial Research
technologies. Organisation (CSIRO),
Optimized Gas Treating,
technical content National Carbon Capture
Center, Sargent & Lundy
After conducting an extensive screening of both commercially available amines
start date:
and designer amines, ION has identified a transformational water-lean amine-
based solvent (ICE-31). ICE-31 exhibits exceptional regeneration energy, working 06.01.2019
capacity, kinetics, material compatibility, stability under both oxidative and
thermally challenging environments, and a minimal environmental impact. percent complete:
ION’s current solvent technology, ICE-21, has demonstrated significant reductions 40%
in the cost of CO2 capture by reducing the parasitic load resulting from the CO2-
stripping process, enhancing reaction kinetics, expanding solvent carrying
capacity, lowering the corrosion rate, and lowering emissions relative to the base
case 30 wt% monoethanolamine (MEA) solvent. The novel ICE-31 solvent
properties are superior to traditional MEA and even ICE-21 regarding energy
consumption, emissions, and thermal and oxidative degradation.
ICE-31’s revolutionary stability reduces the solvent makeup rate and associated
costs, such as pre-treatment and reclaimer operations. The fast capture kinetics
of the solvent, coupled with low water content, further enhance the carrying
capacity and drive down the regeneration energy. A 2017 TEA of ICE-21
performed by Sargent & Lundy, using the U.S. Department of Energy’s (DOE)
Bituminous Baseline Case 12, based on incorporating ICE-21 in the process
simulation model ProTreat for a greenfield net-550 MW coal-fired power plant with
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 169
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
CO2 capture, reported that the capture cost for ICE-21 is in the range of $39 to $45/tonne of CO2.
In this project, the project team is conducting comprehensive lab-scale research to understand the chemical properties
of the solvent ICE-31. Optimized Gas Treating (OGT) is using lab-scale results to develop a rate-based model of the
solvent in ProTreat that can simulate operations at a commercial scale for conducting the TEA. The empirical data
includes the operation of the Commonwealth Scientific & Industrial Research Organisation’s (CSIRO) 0.01-MWe Process
Development Facility (PDF) on simulated flue gas for initial performance studies. Other empirical data for the model will
come from the operation of CSIRO’s Solvent Degradation Rig (SDR) to forecast long-term solvent stability through
accelerated degradation under harsh conditions. ION is also further validating the performance of the solvent through
testing with actual flue gas at the National Carbon Capture Center’s (NCCC) pilot-scale (0.6-MWe) pilot solvent test unit
(PSTU) in Wilsonville, Alabama. The test campaign includes parametric studies to determine optimal operating conditions
and validate the new ProTreat simulation model; dynamic operations studies to evaluate the impact of variations in flue
gas flow rates due to load fluctuations from the power station and other process upsets; emissions studies under steady-
state and dynamic conditions; and long-term, steady-state testing to evaluate solvent stability. The results from the trials
at the PSTU provide additional data to validate the new ProTreat module and produce a stronger TEA at the end of the
project for a large-scale capture facility.
The objectives in the test plan at NCCC include:
• Validating the instrumentation and equipment performance.
• Conducting parametric testing to develop a dataset for identifying the optimum performance, operating window, and
validation of the ProTreat model for ICE-31.
• Conducting accelerated oxidative and thermal degradation experiments in the PSTU.
• Evaluating dynamic operation conditions, including the determination of maximum safe ramp rates and optimal ramp
rates.
• Simulating potential system upsets, including flue gas desulfurization (FGD) and direct contact cooler (DCC) outages
(hot/dry flue gas, sulfur dioxide [SO2] concentration spikes) that mimic real conditions found in a commercial system.
• Demonstrating the viability of continuous operation on aging solvent.
The combination of the ICE-31 solvent’s performance and lower solvent replacement results in a significant improvement
from DOE’s Bituminous Baseline Case 12B ($58/tonne of CO2 captured) and estimated values for ION’s solvent
technology, ICE-21 ($39/tonne of CO2 captured [2017]). Since 2017, further reduction in the cost of capture has been
realized through incorporating heat recovery from the compression system. ION intends to follow a similar development
path for ICE-31 to the accelerated scale-up of ION’s ICE-21 solvent, consisting of testing at Technology Centre Mongstad
(TCM; 12 MWe), followed by front-end engineering design (FEED), and then demonstration at commercial scale.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 80 – 150 100 – 150
Normal Boiling Point °C 220 – 250 220 – 250
Normal Freezing Point °C <-15 <-20
Vapor Pressure @ 15°C bar <0.0001 <0.0001
Manufacturing Cost for Solvent $/kg - -
Working Solution
Concentration kg/kg 650 – 800 650 – 800
Specific Gravity (15°C/15°C) - 0.8 – 1.1 0.8 – 1.1
Specific Heat Capacity @ STP kJ/kg-K ~1.5 – 2.5 1.3 – 2.0
Viscosity @ STP cP <10 <10
Surface Tension @ STP dyn/cm <50 <50
Absorption
Pressure bar 1.0 1.0
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.5 – 1.0 0.5 – 1.0
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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170 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Heat of Absorption kJ/mol CO2 -1,600 to -1,750 -1,600 to -1,750
Solution Viscosity cP <20 <20
Desorption
Pressure bar 1.5 – 2.0 1.5 – 4.5
Temperature °C 110 – 125 110 – 140
Equilibrium CO2 Loading mol/mol 0.05 – 0.20 0.05 – 0.20
Heat of Desorption kJ/mol CO2 <1,800 <1,800
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD unit (wet
basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical absorption/desorption of CO2 to/from working solution.
Solvent Contaminant Resistance – Sulfur oxide (SOX) and nitrogen oxide (NOX) are manageable. Extremely stable
towards oxygen (O2).
Solvent Foaming Tendency – No issues (more than 3,000 hours experience).
Flue Gas Pretreatment Requirements – As for any stable amine-based solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 171
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Post-Combustion Solvent Technologies
Solvent Makeup Requirements – Aimed at less than 0.010 kg/tCO2.
Waste Streams Generated – Similar profile, but estimated to be less than other stable amine-based solvents.
Process Design Concept – Similar to stable amine-based solvents, just a smaller footprint.
Proposed Module Design – N/A.
technology advantages
• Fast kinetics, coupled with low water content, enhances the carrying capacity and reduces regeneration energy.
• Environmentally benign (i.e., low parasitic load, near-zero emissions, and negligible solvent makeup).
• Low thermal and oxidative degradation rates result in revolutionary solvent stability, reducing solvent makeup rates
and associated operating costs (OPEX).
• Low Specific Reboiler Duty (SRD) and solvent stability result in smaller capture plant equipment, reducing capital
expenditure (CAPEX).
• Field-testing with coal-derived and natural gas-derived flue gas at NCCC will expand the critical knowledge base for
ICE-31.
• The output from the field test campaign, supporting laboratory work, and process modeling will facilitate continued
scale-up of the technology.
• The ICE-31 solvent is currently available from commercial chemical manufacturers.
R&D challenges
• Implementation of heat-integration strategies.
• Verification of long-term solvent performance in coal- or natural gas-fired flue gas environment.
status
Initial testing using CSIRO’s 0.01-MWe PDF test rig and simulated flue gas is underway to evaluate the ICE-31 solvent’s
performance. The data collected will feed forward into the test plan development by ION for small-scale pilot testing using
real flue gas at NCCC’s PSTU, a 0.6-MWe scale. The collected data from the PSTU serves to indicate the exactness of
the process model being developed by OGT for a new module in the ProTreat simulation software. Collaborating with
OGT and refining the internal parameters and calculations of the process model, the compilation of the data from the
PSTU will support the creation of a TEA for a large-scale facility using ICE-31.
available reports/technical papers/presentations
Meuleman, E., Fine, N., Silverman, T., “Validation of Transformational CO2 Capture Solvent Technology with
Revolutionary Stability (Apollo),” Project kickoff meeting presentation, Pittsburgh, PA, December 2019.
https://netl.doe.gov/projects/files/DE-FE-0031727-Apollo-Kickoff%20Public.pdf.
Meuleman, E., Fine, N., Silverman, T., “Validation of Transformational CO2 Capture Solvent Technology with
Revolutionary Stability (Apollo),” presented at the 2019 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/E-Meuleman-ION-Transformational-
Solvent.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
172 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Full-Scale FEED Study for technology maturity:
Front-End Engineering
Retrofitting the Prairie State Design (FEED)
Generating Station with an project focus:
816-MWe Capture Plant Using
Advanced KM CDR Process
Retrofit
Mitsubishi Heavy Industries participant:
America Post-Combustion CO2 University of Illinois at
Urbana-Champaign
Capture Technology project number:
FE0031841
primary project goals
NETL project manager:
The University of Illinois and its partners will perform a front-end engineering Andrew jones
design (FEED) study for the retrofit of the Prairie State Generation Company’s [email protected]
(PSGC) coal-fired power station with post-combustion carbon capture. The
University of Illinois and the team will produce a FEED study that uses Mitsubishi principal investigator:
Heavy Industries’ (MHI) Advanced Kansai Mitsubishi Carbon Dioxide Kevin O’Brien
Recovery (KM CDR) Process™ carbon dioxide (CO2) capture technology to University of Illinois at
retrofit one of PSGC’s two generating units (approximately 816 megawatt-electric Urbana-Champaign
[MWe]) in Marissa, Illinois, to become the largest post-combustion capture plant [email protected]
in the world.
partners:
technical goals Mitsubishi Heavy Industries,
Ltd., Prairie State
• The purpose of the FEED study is to complete preliminary engineering and Generating Company,
design work to support developing a detailed cost estimate for the cost of Kiewit Corporation, Sargent
retrofitting CO2 capture at PSGC. & Lundy
• The team will perform multiple feasibility and design studies based on project-
start date:
specific details in preparation for developing engineering deliverables. These
studies will help define the scope of the retrofit project, based on project-specific 10.01.2019
decisions, technology-specific performance, site-specific requirements, and
client-specific needs. percent complete:
• Once the scope has been defined, detailed design will commence for the CO2 10%
capture system and its integration with the existing facility. Various design and
engineering deliverables will be developed that will help define commodity
quantities, equipment specifications, and labor effort required to execute the
project.
technical content
The overall project goal is a full FEED study on a carbon capture system for Unit
#2 (816 MWe) at the PSGC Energy Campus in Marissa, Illinois, based upon on
the KM CDR Process CO2 capture technology from MHI. This capture technology
represents the current state-of-the-art and employs an improved solvent from that
used at the 240-MWe Petra Nova capture plant in Thompsons, Texas. The capture
technology will be scaled-up to 816 MWe.
Work on this FEED study will produce detailed engineering designs, costing, and
timelines for the construction. It will also designate permitting agencies and
timelines in order to execute the follow-on build and operate project. Lessons
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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173
Post-Combustion Solvent Technologies
learned during the FEED study will be documented to assist in future large-scale capture retrofit projects at coal-fired
power plants.
TREATED FLUE GAS
CO2 LEAN
(1) (2) SOLUTION (3) (4) CO2
Existing Flue Gas CO2 Solvent CO2 PRODUCT
Boiler FLUE Pretreatment Recovery Regeneration Compression
GAS ABSORBER REGENERATOR Dehydration
CO2 RICH
SOLUTION
Figure 1: Block flow diagram of the CO2 recovery plant.
The KM CDR Process is an improvement upon MHI’s original KM CDR Process and is an amine-based CO2 capture
process that uses a newly developed solvent known as KS-21. The CO2 capture system will recover 95% of the CO2 from
the flue gas and compress and treat the CO2 to adequate pipeline conditions.
The CO2 recovery facility consists of four main sections, as shown in Figure 1: (1) flue gas pretreatment, (2) CO2 recovery,
(3) solvent regeneration, and (4) CO2 compression and dehydration. In flue gas pretreatment, the flue gas temperature
is cooled in the flue gas quencher by direct contact with circulation water. The circulation water is injected with caustic
soda to reduce the amount of sulfur dioxide (SO2) in the flue gas entering the amine system. A flue gas blower is installed
downstream of the flue gas quencher to overcome the pressure drop across the flue gas quencher and the CO2 absorber.
Figure 2 shows the process flow diagram for the CO2 recovery and solvent regeneration steps. In CO2 recovery, the
cooled flue gas from the flue gas quencher is introduced at the bottom of the CO2 absorber. The flue gas moves upward
through the packing while the CO2-lean solvent is supplied at the top of the absorption section where it flows down onto
the packing. The flue gas contacts with the solvent on the surface of the packing, where 95% of the CO2 in the flue gas
is absorbed by the solvent. The CO2-rich solvent from the bottom of the CO2 absorber is sent to the regenerator. The
CO2-lean flue gas exits the absorption section of the CO2 absorber and enters the flue gas washing section of the CO2
absorber. The flue gas contacts with circulating water to reduce the carryover amine that is emitted from the top of the
CO2 absorber.
In solvent regeneration, cool rich solvent is heated by the hot lean solvent extracted from the bottom of the regenerator
in a heat exchanger. The pre-heated rich solvent is then introduced at the top of the regenerator column and flows down
over the packing, where it contacts with stripping steam. As it flows down the column, the rich solvent releases captured
CO2 and is regenerated back into lean solvent. The steam in the regenerator is produced by the reboiler, where low-
pressure steam is used to heat the lean solvent. The lean solvent is then cooled to the optimum absorption temperature
before being recycled back to the CO2 absorber.
The overhead vapor leaving the regenerator is cooled, and the condensed liquid from this unit is then returned to the
system. In CO2 compression and dehydration, CO2 is compressed through a multi-stage gas compressor. Treatment
such as oxygen (O2) removal or dehydration may be necessary to meet pipeline and storage guidelines.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
174 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
Figure 2: Carbon capture basic process flow diagram.
technology advantages
• Uses an improved, newly developed proprietary solvent known as KS-21. This solvent’s properties translate into
reduced capital costs.
o Has less volatility, which reduced the height of the water wash section of the CO2 absorber, lowering capital cost.
o Has improved thermal stability, allowing the regenerator to be operated at a higher pressure and temperature,
thereby reducing the equipment size and the power consumption for CO2 compression, resulting in lowering
operating and capital costs.
o More resistance to oxidative degeneration, which reduces solvent loss.
o Has lower heat of absorption, which allows higher circulation rate and therefore slightly less steam consumption.
• Will recover 95% of the CO2 from the flue gas and compress and treat the CO2 to adequate pipeline conditions.
• The capture system will be scaled-up using multiple trains so that it can standardized, modularized, and overall project
cost can be reduced.
R&D challenges
• To deploy the post-combustion amine technology on coal-fired gas while adequately managing accumulation of
impurities in the exhaust without excessive cost.
• Ensuring reliable operation over a long period at large-scale (19,000 to 25,000 short tons per day).
status
This project has commenced.
available reports/technical papers/presentations
None.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
175
Post-Combustion Solvent Technologies
Commercial Carbon Capture technology maturity:
Front-End Engineering Design
Design and Costing: Part Two (FEED)
(C3DC2) project focus:
water-Lean Solvent
Technology Retrofit
primary project goals
participant:
ION Clean Energy, Inc. (ION), Nebraska Public Power District (NPPD), and their ION Clean Energy, Inc.
partners are conducting a front-end engineering design (FEED) study for a carbon
capture system designed for retrofit onto Unit 2 of NPPD’s Gerald Gentleman
project number:
Station (GGS2), a 700-megawatt (MW) coal-fired power station located in Western
Nebraska. For the proposed project, a 700-MW-equivalent (two parallel 350 FE0031840
megawatt-electric [MWe] capture units) commercial-scale carbon dioxide (CO2)
capture plant will be designed and costed for GGS2. The team is leveraging work predecessor project:
performed during a previously awarded commercial carbon capture design and FE0031595
costing project (FE0031595).
NETL project manager:
technical goals Katharina Daniels
[email protected]
The overall objective of the proposed project is to conduct a FEED study for a
principal investigator:
commercial-scale CO2 capture system retrofitted onto an existing coal-fueled
power station. With this approach, the team strives to decarbonize as much of Unit Erik Meuleman
2 as possible utilizing ION’s ICE-21 solvent technology. This project will leverage ION Clean Energy, Inc.
[email protected]
prior U.S. Department of Energy (DOE) project award FE0031595, which
conducted a design and costing study for a 300-MW slipstream carbon capture
partners:
system for GGS2.
Nebraska Public Power
District, Sargent & Lundy,
technical content Koch Modular Process
Systems, Siemens
The project team will design the capture system and produce a capital cost
estimate that will cover both engineering design for the carbon capture process start date:
and the balance of plant. The engineering design will be performed at a level 10.01.2019
consistent with an Association for the Advancement of Cost Engineering (AACE)
Class 2 estimate, which would result in accuracy ranges of -15 to +20% for the percent complete:
capital cost estimate. The FEED study development will include process flow
10%
diagrams, utility flow diagrams, piping and instrument diagrams, heat and material
balances, a 3D model, plot plans, final layout drawings, complete engineered
process and utility equipment lists, one-line diagrams for electrical, electrical
equipment and motor schedules, vendor quotations, detailed project execution
plans, and resourcing and workforce plans developed by the project team.
Balance of plant engineering design will include specifications for utilities, such as
compression, cooling water, and waste treatment, as well as the sources of
energy, electricity, and/or steam necessary to power the capture process. Civil
and structural engineering tasks will also be incorporated throughout the design
to include the proper stormwater runoff and spill containment, as well as geological
assessments to support foundation design.
Additionally, the team will conduct a series of studies and investigations to aid in
the design of the carbon capture facility, including steam sourcing, cooling water
system, solvent materials compatibility, wastewater treatment, permitting and
regulatory review, reagent handling, constructability review, overpressure relief,
and project execution and operations management planning.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
176 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
The final report will summarize project results from the FEED study, including a systems and benefits analysis, summarize
the results from the technical and economic feasibility analysis of scale-up, and make recommendations for future
research and development.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Design value
Molecular Weight mol-1 75–95
Normal Boiling Point °C 150–210
Normal Freezing Point °C -15–2
Vapor Pressure @ 15°C bar 1-2 x 104
Manufacturing Cost for Solvent $/kg Proprietary
Working Solution
Concentration kg/kg 0.6–0.85
Specific Gravity (15°C/15°C) - 0.9–1.2
Specific Heat Capacity @ STP kJ/kg-K 2–3
Viscosity @ STP cP <5
Absorption
Pressure bar 1.0–1.15
Temperature °C 20–50
Equilibrium CO2 Loading mol/mol 0.4–1.0
Heat of Absorption kJ/mol CO2 50–100
Solution Viscosity cP <20
Desorption
Pressure bar 1.1–1.8
Temperature °C 80–150
Equilibrium CO2 Loading mol/mol 0.01–0.40
Heat of Desorption kJ/mol CO2 50–100
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – Estimated manufacturing cost for new solvents, or the estimated cost of bulk
manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
177
Post-Combustion Solvent Technologies
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 150 10.5 20.5 66.4 5.3 0.80 44 150
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The physico-chemical properties of ION’s solvent system allow for a unique
mechanism that combines fast kinetics with low energy consumption.
Solvent Contaminant Resistance – Sulfur oxides (SOX) and nitrogen oxides (NOX), other than nitric oxide (NO), are
absorbed into the solvent and lower the carrying capacity of CO2. Oxidative and thermal degradation are manageable.
To date, ION’s solvent system has not been limited by contaminant concentration.
Solvent Foaming Tendency – No foaming issues have been seen during either of ION’s solvent pilot test campaigns.
Flue Gas Pretreatment Requirements – It is preferred that the flue gas be saturated with water vapor and can include
any concentration of CO2. Pretreatment to levels of SOX less than 10 to 30 parts per million (ppm) (spikes are
manageable) and NOX less than 100 to 200 ppm is also favored.
Solvent Makeup Requirements – Proprietary.
Waste Streams Generated – Proprietary.
Process Design Concept – ION’s solvent-based process steps include pre-scrubbing to remove SOX, several other
gases, and most of the particles; a direct contact cooling unit to control the inlet flue gas temperature and humidity; an
absorber consisting of a packed column with counter-flow for removal of CO2 into the proprietary solvent; and water wash
to remove solvent droplets and vapors from the exhaust gas. Following the absorption step, the final unit operation is a
regenerator to produce the CO2, recover the solvent, and recycle the solvent back to the absorber.
technology advantages
As part of the FEED study, the proprietary ION ICE-21 solvent technology will be utilized. Relative to aqueous MEA
technology and other commercial capture systems, ION’s ICE-21 solvent technology offers the following benefits to lower
operating and capital costs for CO2 capture:
• Reduction in regeneration energy requirements.
• Higher CO2 loading capacities.
• Reduced corrosion and solvent losses.
• Faster absorption kinetics.
• Less water used by the process.
The carbon capture plant will be designed to take full advantage of these benefits, which will result in a smaller physical
plant, reduced energy requirements, less solvent degradation, lower emissions, and lower capital costs relative to
systems built with DOE Bituminous Baseline Study (BBS) case benchmark solvents.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
178 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
R&D challenges
In the project, ION will look to optimize the operating costs versus the capital costs, which will be defined by some design
basis decisions such as sparing philosophy, process robustness, and maintenance.
status
The project has commenced.
available reports/technical papers/presentations
Meuleman, E., Awtry, A., Atcheson, J., “Commercial Carbon Capture Design & Costing: Part Two,” Project Kick-off
Meeting, December 5, 2019. https://netl.doe.gov/projects/files/DE-FE0031840%20-
%20C3DC2%20DOE%20Kickoff%20Meeting%20-%20PUBLICUSE.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
179
Post-Combustion Solvent Technologies
Front-End Engineering Design technology maturity:
Front-End Engineering
Study for Retrofit Post- Design (FEED)
Combustion Carbon Capture project focus:
on a Natural Gas Combined
Econamine FG PlusSM (EFG+)
Retrofit to NGCC
Cycle Power Plant participant:
Electric Power Research
Institute, Inc.
primary project goals
project number:
Electric Power Research Institute (EPRI) and its partners Fluor Corporation and
FE0031842
California Resources Corporation (CRC) are conducting a front-end engineering
design (FEED) study to determine the technical and economic feasibility of a NETL project manager:
retrofit, post-combustion, carbon capture technology on a commercially
Sai Gollakota
operating, natural gas-fired combined cycle (NGCC) power plant. [email protected]
technical goals principal investigator:
Abhoyjit Bhown
EPRI
Conduct a FEED study for 75% overall capture (90% capture on 83% slipstream) at
[email protected]
CRC’s 550-megawatt-electric (MWe) NGCC Elk Hills Power Plant (EHPP) using
Fluor’s proprietary Econamine FG PlusSM (EFG+) aqueous amine technology. The partners:
captured 4,000 tonnes of carbon dioxide (CO2) per day will be used by CRC for Fluor Corporation, California
enhanced oil recovery (EOR) in fields adjacent to the power plant. Resources Corporation
technical content start date:
10.01.2019
The FEED study will examine the cost and engineering requirements for installing
percent complete:
a plant to capture CO2 produced by the 550-MWe NGCC unit located in the Elk
Hills Oil Field in Kern County, California. Fluor is the design engineering contractor 10%
and Fluor’s EFG+ technology will be used for the carbon capture system design.
CRC is the owner and operator of the host site, EHPP. Fluor’s EFG+ technology is
a post-combustion CO2 capture technology with proven process for removal of
CO2 from flue gases, with the CO2 product used for EOR and other applications.
The FEED study deliverables are to include a design basis, process flow diagrams,
piping and instrument diagrams, equipment datasheets, a plot plan, bulk material
takeoffs, and a capital cost estimate. For the design basis of the FEED study, the
completed and ongoing details include: consolidated historic performance and
run history of the power plant, evaluating various operating scenarios and
conditions; results from flue gas testing review and validation of solvent
performance through FEED; historic construction details from surrounding
facilities to incorporate site requirements; ongoing review and optimization of
energy use and waste streams; and ongoing evaluation of construction practices
and contracting strategies to optimize cost, schedule, and risk.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
180 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 1: Simplified schematic of Fluor Corporation’s Econamine FG PlusTM CO2 capture process.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the NGCC unit (wet
basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.5 205 4.54 9.30 72.95 12.34 0.88 0.7 1.7
Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The absorption of CO2 is by chemical reaction.
Solvent Contaminant Resistance – The solvent has high resistance to contaminants in the flue gas due to the solvent
maintenance system’s ability to maintain the solvent in pristine condition.
Solvent Foaming Tendency – None.
Flue Gas Pretreatment Requirements – None.
Solvent Makeup Requirements – 0.42 kg/tonne CO2.
Waste Streams Generated – Solvent maintenance system waste.
Process Design Concept – Flowsheet/block flow diagram shown above in Figure 1.
Proposed Module Design – To be prepared after logistics/route study.
technology advantages
• FEED studies for carbon capture systems at actual sites such as this will provide the U.S. Department of Energy (DOE)
with a more detailed understanding of carbon capture costs in a commercial application, thereby enabling DOE to
better design its research and development (R&D) program to reduce those costs for similar carbon capture
technologies being developed in its R&D portfolio.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
181
Post-Combustion Solvent Technologies
• This FEED study could lead to the world’s first commercial deployment of carbon capture on a natural gas-fired power
plant, and could be duplicated at other power plants across the world.
• Fluor’s latest version of its EFG+ technology has several key features, including enhanced solvent formulation that has
a high resistance to degradation, reduced amine circulation rate, a solvent maintenance system that keeps the solvent
in pristine condition, low waste production, very low absorber vent emissions, and load-following capability. These
features are proven on both gas turbine exhaust and coal flue gas. The enhanced dual-cell column and absorber design
enables a large flue gas throughput, which reduces capital costs.
R&D challenges
• Targeting not just operating expenses, but also capital expenses in this FEED study to minimize the overall cost of CO2
capture, via utilization of various technology and process synergies.
• Optimizing cooling water usage as California and the Bakersfield area’s ongoing challenge of water availability for
power production.
status
The project has commenced.
available reports/technical papers/presentations
“Front-End Engineering Design Study for Retrofit Post-Combustion Carbon Capture on a Natural Gas Combined Cycle
Power Plant,” DOE Project Kick-off Meeting, October 30, 2019.
https://www.netl.doe.gov/projects/files/FE0031842%20Kickoff%20Meeting.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
182 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Piperazine Advanced Stripper technology maturity:
Front-End Engineering
Front-End Engineering Design Design (FEED)
project focus:
primary project goals Piperazine Solvent with
Advanced Stripper Retrofit
The University of Texas at Austin (UT-Austin) is performing a front-end engineering to NGCC
design (FEED) study of the piperazine advanced stripper (PZAS) process for carbon
dioxide (CO2) capture from the natural gas combined cycle (NGCC) power plant at participant:
Golden Spread Electric Cooperative’s (GSEC) Mustang Station in Denver City, University of Texas at Austin
Texas.
project number:
FE0031844
technical goals
NETL project manager:
• To develop a comprehensive estimate for the total installed cost of PZAS with
Isaac Aurelio
CO2 compression on an NGCC power plant. [email protected]
• To provide cost details to be used in the economic optimization of the process
features of PZAS and other second-generation amine scrubbing processes. principal investigator:
• To provide the host site and cost-share partners with the information necessary Gary T. Rochelle
The University of Texas at
to determine whether a commercial project to capture and use CO2 for
Austin
enhanced oil recovery (EOR) can be justified. [email protected]
• To provide the U.S. Department of Energy (DOE) with a more detailed
understanding of carbon capture costs in a commercial application. partners:
Trimeric Corporation
technical content
start date:
10.01.2019
The PZAS process is a second-generation amine scrubbing process with advanced
solvent regeneration for post-combustion CO2 capture. Figure 1 shows the flow
percent complete:
and operating conditions for PZAS as tested at the National Carbon Capture
10%
Center (NCCC) pilot plant and reflects the planned design for Mustang Station.
The NGCC at Mustang Station is comprised of a combined cycle facility, which
consists of two gas turbines with two heat recovery steam generators (HRSGs) and
a steam turbine with a total rating of 464 megawatt-electric (MWe).
The system uses 5 molal piperazine (PZ) solvent that absorbs CO2 two and half
times faster than 30 wt% monoethanolamine (MEA), requiring only 30 feet of
absorber packing height to achieve 90% CO2 removal. Flue gas from the NGCC is
contacted with PZ solvent at a lean loading of 0.24 mol CO2/gram-equivalent PZ
to remove 90% of the CO2. The hot flue gas leaving the HRSG is cooled in the
bottom section of the absorber by recirculation of rich solvent through an
exchanger using cooling water at the heat sink, mostly eliminating the temperature
bulge of the absorber. Gas leaving the middle section of the absorber is contacted
with cooled wash water in the top section of structured packing.
Rich PZ solvent is pumped through the cold cross-exchanger, the hot cross-
exchanger, and the steam heater to the sump of the stripper. A fraction of the rich
solvent (5 to 10%) is heated in the cold bypass exchanger. A fraction of the warm
rich solvent (10 to 30%) is bypassed at its bubble point after the cold cross-
exchanger. The two bypass streams are combined and fed to the top of the
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
183
Post-Combustion Solvent Technologies
stripper. The flows of the bypassed streams are optimized to minimize the steam duty. Heat is recovered from the hot
lean solvent as it is returned through the hot cross-exchanger and the cold cross-exchanger and then further cooled in
the trim cooler. The stripper sump is maintained at 150°C and 6.3 bar(a). Vapor from the stripper sump flows through two
sections of random packing. Heat is recovered from the vapor leaving the stripper in the cold bypass exchanger. The CO2
product is further cooled in a condenser and the water is separated and returned to the absorber water wash. The
advanced stripper configuration results in a heat duty less than 2.1 gigajoules (GJ)/tonne CO2, compared to values of 2.4
to 2.7 GJ/tonne CO2 for six other solvents tested at NCCC with the simple stripper under coal and NGCC operations. The
improvement in energy performance is achieved through use of the cold rich bypass and warm rich bypass streams in
the advanced stripper configuration.
Figure 1: PZAS process flowsheet.
The PZAS process has evolved from bench-scale experiments to pilot-scale test campaigns, including testing at UT-
Austin’s Separations Research Program (SRP) pilot plant using simulated coal and natural gas flue gas and testing at
NCCC using flue gas derived from fossil fuels at both coal and NGCC conditions. Previous testing has confirmed that PZ
with a 5 molal concentration is a superior solvent to PZ with an 8 molal concentration. The reduced viscosity of 5 molal
PZ results in an enhanced CO2 absorption rate in the absorber and improved heat transfer performance in the cross-
exchanger, reducing the heat duty in the advanced flash stripper (AFS) steam heater. Combining the 5 molal PZ solvent
with the AFS decreases the cost of CO2 capture to less than $40/tonne.
The details of the techno-economic analysis (TEA) that was prepared for the PZAS process in the previous DOE-funded
project DE-FE0005654 are being utilized to determine equipment sizes and to develop an approximate capital cost
estimate for installing PZAS at Mustang Station. The PZAS process is estimated to require a capital investment roughly
two-thirds that of other second-generation amine scrubbing processes, which is largely attributable to a significant
decrease in absorber column size and modest decrease in stripper column size.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
184 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
The FEED study will allow the project team to develop detailed estimates for these direct capital cost components and
provide a more accurate estimate of total plant costs for a PZAS installation at Mustang Station. The resulting estimates
can be used to arrive at a more accurate Lang factor for developing future cost estimates for carbon capture on NGCC
plants. The project team will interface directly with vendors to obtain detailed design and cost estimates for individual
pieces of equipment for a full-scale capture facility. Operating costs can be estimated based on PZAS experience at the
NCCC pilot plant and the resulting TEA. Parasitic loads are calculated based on developed thermodynamic properties of
PZAS and the design of heat exchangers and other equipment requiring either electricity or steam energy. An appropriate
source of steam will be identified that results in maximum efficiency. The FEED will also examine the benefits and
economics of integrating CO2 captured from a power station directly into an existing CO2 pipeline network and possibly
direct use by local CO2-EOR end-users in the area.
Definitions:
Bar(a) – Unit used to indicate absolute pressure, where the reference pressure is absolute zero (i.e., not taking into
account atmospheric pressure).
Molal Concentration (Molality) – The amount (in moles) of solute, divided by the mass (in kilograms) of the solvent.
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The reaction of PZ with CO2 involves formation of the following four PZ
species:
Figure 2: Molecular structure of piperazine species.
These reactions are as follows:
1. PZH+ + H2O ↔ PZ + H3O+
2. PZ + CO2 + H2O ↔ PZCOO- + H3O+
3. H2O + H+PZCOO- ↔ H3O+ + PZCOO-
4. PZCOO- + CO2 + H2O ↔ PZ(COO-)2 + H3O+
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
185
Post-Combustion Solvent Technologies
TABLE 1: EQUILIBRIUM CONSTANTS FOR ABOVE REACTIONS
ln K = A + B/T + C lnT
Eq. No Equilibrium Constant
A B C
1
-11.91 -4,351 ─
2
-29.31 5,615 ─
3
-8.21 -5,286 ─
4
-30.78 5,615 ─
This speciation and solubility model has been used to predict the partial pressure of CO2 and mole fraction of species in
solution as a function of PZ loading; the results show a good match between the model and the experimental data.
Solvent Contaminant Resistance – 5 molal PZ is thermally stable at 150°C with negligible oxidative (Freeman, 2011)
degradation. The total amine loss is estimated to be 0.5% per week when stripping at 150°C. At 135°C, the estimated total
amine loss of PZ is 0.3%, as compared to 3.0% in the case of an MEA solvent. PZ forms nitrosamines and other nitro
products with nitrogen dioxide (NO2). Both pilot-scale flue gas testing and bench-scale testing have confirmed that
nitrosamines decompose at temperatures of 150°C and greater. The main degradation products of PZ are formate (0.04
mM/hr) and ammonia (0.09 mM/hr) (Freeman, 2011).
Solvent Foaming Tendency – Pilot plant tests of PZ with two different sources of coal-fired flue gas and with air/CO2
have experienced no persistent problems with foaming. However, bench-scale experiments have shown the possibility
for PZ to foam under certain conditions (e.g., after undergoing oxidation degradation). In the bench-scale tests, foaming
of PZ was greatly reduced with use of an oxidation inhibitor or with use of 1 part per million (ppm) of silicone antifoam
(Chen, 2011).
Solvent Makeup Requirements – Including an estimate for additional amine lost in the reclaiming process, the required
makeup rate is estimated to be 0.76 kg of 30 wt% PZ per metric ton of CO2 captured for PZ regenerated at 150°C. The
estimated makeup rate for 30 wt% MEA at 120°C is approximately 2.0 kg/MT CO2.
Waste Streams Generated – The major amine solid/liquid waste streams come from reclaimer waste. There could be
fugitive liquid amine emissions, which can be controlled by incorporating seamless valves, rupture disks, closed-loop
ventilation systems, pumps with dual mechanical seals, minimum welds, and correct gasket material selection. Due to the
low fly ash concentration of natural gas combustion gas, the heavy metal concentration in the solvent is not expected to
trigger a hazardous waste classification with this technology. Gas-phase amine emissions from the absorber can be
minimized by controlling aerosol formation and aerosol emissions from the absorber. Although amine aerosol emissions,
which require sulfur trioxide (SO3) or other sources of aerosol nuclei, are not expected to be problematic with natural gas
combustion, careful measurement of PZ emissions from the NCCC pilot plant with NGCC conditions have established that
the PZAS process will produce less than 1 ppm PZ in the clean flue gas.
Process Design Concept – Flowsheet/block flow diagram shown above in Figure 1.
technology advantages
As compared to conventional amine solvents, the advantages of PZ are:
• Faster CO2 absorption rate, higher working capacity, higher thermal stability, and less oxidative degradation—all of
which point toward 10 to 20% less energy use.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
186 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
• Advanced stripper configuration minimizes steam heater heat duty required for regeneration, limiting equipment sizes
for major process equipment.
• Elevated regeneration pressure allows for elimination of lean solvent pump and elimination of two initial stages of CO2
compression, resulting in capital cost savings.
• High absorption rate leads to smaller absorber size, reducing capital cost.
• PZ is resistant to oxidative degradation in the absorber.
• Five molal PZ is less corrosive than MEA at typical absorber temperatures, allowing less expensive and more readily
available materials of construction to be used.
• No direct contact cooler or inlet booster fan are required.
R&D challenges
• Like other amines, PZ may absorb on aerosols in flue gas, leading to high amine emissions. Aerosol formation needs
to be managed.
• PZ reacts with dissolved or entrained oxygen (O2) at temperatures exceeding 150°C, potentially leading to greater than
expected solvent makeup, but still less than MEA.
• PZ forms as a solid phase with water (PZ • 6H2O) and also with CO2 (H+PZCOO- • H2O). Process robustness to
excursions in CO2 loading, temperature, and water balance is being demonstrated by quantifying their effects on solids
precipitation and plant operation.
status
The project team has begun establishing the project design basis for the FEED, taking into account site-specific
characteristics and design specification, potential permitting requirements, and process targets for CO2 capture and CO2
product purity. Process modeling efforts have been initiated; process simulations will be used to arrive at a baseline heat
and mass balance.
available reports/technical papers/presentations
Chen, E., et al. “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” Final Report, Rev. 0,
March 2019. https://www.osti.gov/servlets/purl/1512446.
Rochelle, G., “Piperazine with Advanced Flash Stripper (AFS): NCCC Pilot Plant Results,” presented at the 2018 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018. https://netl.doe.gov/projects/files/G-Rochelle-
UTA-Piperazine-Flash-Regeneration.pdf.
Rochelle, G., “Pilot Plant Testing of Piperazine with Advanced Flash Regeneration,” presented at the 2017 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-Thursday/G-Rochelle-UTA-Evaluation-of-
Piperazine.pdf.
Rochelle, G., “Pilot Plant Testing of Piperazine with Advanced Flash Regeneration,” presented at the 2016 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/G-Rochelle-UTAustin-
Piperazine-with-Flash-Regeneration.pdf.
Dombrowski, K., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2015 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/K-Dombrowski-AECOM-Concentrated-
Piperazine.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
187
Post-Combustion Solvent Technologies
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2014 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/G-Rochelle-UTAustin-
Evaluation-Of-Concentrated-Piperazine.pdf.
Nielsen, P. T.; Li, L.; Rochelle, G. T., “Piperazine Degradation in Pilot Plants.” GHGT-11; Energy Proc. 2013.
Fulk, S. M.; Rochelle, G. T., “Modeling Aerosols in Amine-Based CO2 Capture,” GHGT-11, Energy Proc. 2013.
Fine, N. A.; Goldman, M. J.; Nielsen, P. T.; Rochelle, G. T., “Managing N-nitrosopiperazine and Dinitrosopiperazine,”
presented at GHGT-11 Kyoto, Japan. November 18–22, 2012. Energy Procedia, 2013.
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2013 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/G-Rochelle-UTA-Concentrated-Piperazine-for-
CO2-Capture.pdf.
Madan, T.; “Stripper Configurations and Modeling for CO2 Capture Using Piperazine.” M. S. Thesis. The University of
Texas at Austin, May 2013.
Rochelle, G., “Pilot Plant Testing of Piperazine with High T Regeneration,” presented at the 2012 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, July 2012.
https://www.netl.doe.gov/File%20Library/Events/2012/CO2%20Capture%20Meeting/G-Rochelle-UT-Austin-Piperazine.pdf.
Sexton, A., “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” presented at the 2011
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2011.
https://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/23Aug11-Sexton-Trimeric-Concentrated-
Piperazine-for-CO2-Capt.pdf.
Freeman, S.A., “Thermal Degradation and Oxidation of Aqueous Piperazine for Carbon Dioxide Capture,” Ph.D. Thesis,
University of Texas at Austin, May 2011.
Dombrowski, K., “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” presented at the
2010 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, September 2010.
https://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/Katherine-Dombrowski---URS-
Corporation.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
188 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Front-End Engineering and technology maturity:
Design: Project Tundra Carbon
Front-End Engineering
Design (FEED)
Capture System project focus:
Econamine FG PlusSM (EFG+)
Retrofit to Coal Plant
primary project goals
participant:
Minnkota Power Cooperative is performing a front-end engineering and design Minnkota Power
(FEED) study to install a post-combustion carbon dioxide (CO2) capture system at Cooperative, Inc.
Square Butte Electric Cooperative’s Milton R. Young Station, Unit 2 (MRY2), located
near Center, North Dakota. Based on the results of pre-FEED studies of two leading project number:
commercial-ready carbon capture technologies, Fluor’s Econamine FG PlusSM FE0031845
(EFG+) technology has been selected for installation.
NETL project manager:
Andrew O’Palko
technical goals [email protected]
• Complete a FEED study for constructing the carbon capture system at MRY2, principal investigator:
including balance of plant (BOP). Gerry Pfau
• Address final challenges to implementing CO2 capture with studies to optimize Minnkota Power
plant efficiency. Cooperative, Inc.
[email protected]
• Finalize a permitting strategy for the overall project.
• Evaluate environmental, health, and safety (EH&S) concerns and mitigation partners:
approaches. Fluor Enterprises, Inc., Burns
• Conduct a hazard and operability (HAZOP) review. & McDonnell, David
Greeson Consulting, Hunt
• Complete a FEED-level cost estimate and construction schedule.
International Energy
Services, North Dakota
technical content Industrial Commission,
Energy & Environmental
Research Center, Golder
Minnkota is executing a FEED study on the addition of Fluor’s EFG+ technology to
Associates, AECOM, Square
an existing power plant fueled by North Dakota lignite to deliver the engineering
Butte Electric Cooperative
and design work needed to demonstrate the feasibility of a next-generation
carbon capture system technology at world-scale. The FEED comprises a broader start date:
effort led by Minnkota, titled Project Tundra, which is an initiative to build the 10.01.2019
world’s largest carbon capture facility in North Dakota and to implement carbon
capture, utilization, and storage (CCUS) to preserve the use of lignite, support the percent complete:
CO2 enhanced oil recovery (EOR) industry, and revitalize legacy oil fields. 10%
The project team aims to substantiate the economics and engineering supporting
the business case for construction and operation of Fluor’s EFG+ technology to
capture 90% (11,000 tonnes/day) of the CO2 from the flue gas of the 477-
megawatt-electric (MWe) MRY2, producing near “zero carbon” power with limited
or no impact on the price of electricity.
Fluor’s EFG+ technology is an advanced amine-based process tailored for removal
of CO2 from low-pressure, high-oxygen-containing flue gas (up to 15 vol%) and is
used in more than 30 commercial plants worldwide to process flue gases derived
from a variety of fuels. The basic plant configuration consists of a two-stage direct
contact cooler (DCC) for flue gas cooling and sulfur dioxide (SO2) removal, an
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 189
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
absorber, a regenerator, and a compression and dehydration system to generate pipeline-ready CO2, as shown in Figure
1. As the conditioned flue gas flows up the absorber, CO2 is chemically absorbed into a circulating solvent stream flowing
down the column. The CO2-loaded solvent is then pumped from the bottom of the absorber, through a heat recovery
exchanger where it is heated against hot CO2-lean solvent, and into the top of the regenerator. As the solvent flows down
the regenerator, it is contacted by steam, which strips the CO2 from the solvent, producing an overhead mixture of steam
and CO2. The steam/CO2 product is cooled, and the steam is condensed and separated from the CO2 product. Hot CO2-
lean solvent from the bottom of the regenerator is pumped back through the heat recovery exchanger where it is cooled
against the cold CO2-loaded solvent before being returned to the top of the absorber.
Figure 1: Schematic of Fluor’s EFG+ CO2 capture technology.
Advancements to progress the technology beyond the current state-of-the-art include steam cycle integration with
advanced heat recovery to improve energy efficiency; methods for removing aerosols and a unique solvent maintenance
system to minimize solvent degradation, thereby improving the environmental and cost profile; design of the world’s
largest capture facility (3.6 million tonnes/year, a twofold increase over any other facility) to capture greater economies
of scale; optimization for cold climate performance; and establishment of the lowest levelized cost of capture attempted
at world-scale.
Experience gained from Fluor’s EFG+ demonstration plant in Wilhelmshaven, Germany, that captures 70 tonnes of CO2
per day from a coal-fired power plant has enabled Fluor to make significant improvements to the process. Some of the
unique features of the process design include:
• The EFG+ solvent is a proprietary formulation of primary amines with a regeneration steam requirement 30% lower
than monoethanolamine (MEA).
• Fluor’s patented two-stage DCC treats the flue gas in two sections, cooling the flue gas to harvest quality combustion
knock-out water and removing SO2 to single-digit part per million (ppm) levels.
• Fluor’s patented absorber intercooling technology removes heat of absorption to increase the CO2 carrying capacity
of the solvent, reducing the net steam demand of the EFG+ process by 3 to 5%.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
190 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
• A lean solvent flash/vapor compression configuration, in which the lean vapor compressor (LVC) recycles residual heat
from the hot-lean solvent leaving the regenerator and transfers it back to the regenerator, resulting in a lower steam
demand for the reboiler and reducing the total solvent regeneration energy requirement by ~10 to 15%.
• Minimized pressure drop in absorber due to advanced design of internals and packing in the DCC and absorber,
thereby reducing the blower power by approximately 65% compared to conventional carbon capture plants.
• A solvent maintenance system (SMS) to remove heat-stable salts (HSSs) and other non-volatile degradation products
in order to maintain solvent hygiene and performance.
Prior successful installations of the EFG+ process at a variety of facilities worldwide has prepared the project team for
addressing new challenges, including processing a higher flue gas volume, effects from cold climate, and aerosols/solvent
degradation concerns with using lignite coal-based flue gas.
The project team previously conducted a pre-FEED study to determine constructability, tie-in locations, preliminary pipe
routings and interfaces, electrical interconnections, equipment specifications, capture system power requirements,
geotechnical details, and control design. These components form the basis of the full FEED study, which will result in the
following multidisciplinary design package:
• A FEED study report along with an electronic 3D model in SmartPlant® 3D.
• Material takeoffs (MTOs) exported from the 3D model for large-bore pipe lengths, fittings, flanges, valves, raceway,
cables, and instrumentation; structural steel and concrete takeoffs developed from structural design software and
sketches.
• An optimized general arrangement drawing.
• A tie-in list and location plan, with input from construction specialists during the detailed design phase; updates to
process and instrumentation diagrams (P&IDs) with tie-in information.
• Detailed specifications for the major equipment packages.
• A Level 2 Process Hazard Analysis (i.e., HAZOP) report utilizing the overall P&IDs.
• A steam supply design.
• A fire protection study in accordance with National Fire Protection Agency codes and standards.
• An instrument control list with inputs and outputs and distributed control system (DCS) points, including cost
specifications for all major instrument and control packages.
• Exploratory excavation plans and specifications to verify that proposed foundation and subsurface facilities are clear
of obstructions.
• Preliminary foundation sketches to support equipment and ancillaries required for FEED cost estimates.
• Preliminary architectural drawings and sketches to support a cost specification for pre-engineered buildings and
heating, ventilation, and air conditioning (HVAC), and obtaining budgetary quotes to support the FEED cost estimate.
Based on the pre-FEED study, a $50/tonne 45Q tax credit for CO2 storage or a $35/tonne 45Q tax credit for EOR, plus
projected CO2 sales to oil companies for EOR operations, provides enough revenue to cover the capital, return on capital,
and plant’s operating costs, while yielding a near 10% return to tax equity. In addition, the cost of capture is expected to
be $49/tonne CO2, which is a 20% reduction from the cost of CO2 capture at the Petra Nova facility, the U.S.’s first
commercial post-combustion carbon capture system at a coal-fired power plant. The FEED study is the next step in
verifying and optimizing these costs and projections to reflect the higher level of engineering and design and cost-
estimating certainty.
For the BOP items, operating cost estimates will be developed through detailed studies involving Fluor, owner’s engineer
Burns & McDonnell, and Minnkota. Both the operating and capital costs for an EFG+ plant are dependent on a number
of variables, including, but not limited to, plant location, site conditions, plant capacity, final configuration, modularization
versus field erected, flue gas conditions, air versus water cooling, and cost of utilities such as steam and electricity.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 191
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Although the EFG+ technology and the chemistry of the process are the same regardless of scale, the process equipment
in the EFG+ process must be designed to ensure that the EFG+ chemistry occurs efficiently. Specifically, the scale-up
challenge is construction of large-diameter columns and achieving good gas/liquid distribution in the packing.
As part of the pre-FEED, the team evaluated natural gas-fired auxiliary boiler and steam turbine extraction scenarios. Early
stages of the FEED study will choose which steam source will be utilized.
In addition to removing ~3.6 million tonnes per year of CO2, the carbon capture facility installed at MRY2 will also be
designed to remove ~2,200 tonnes of SO2 annually. However, significant concentrations of alkali-derived aerosols have
been measured at MRY2 during previous studies, which can impact both amine solvent emissions and degradation rates.
Also, solvent emissions from the absorber may include ppm levels of amine and degradation byproducts in the form of
ammonia and aldehydes. The combination of the aldehydes/amine may constitute a new major source of VOCs, which
requires a Title V permit under the Clean Air Act. In the FEED, Fluor will evaluate the cost-effectiveness of solutions for
removal of aerosols upstream of the absorber, thereby eliminating/mitigating the challenge of aerosol-exacerbated
emissions of amine from the absorber. Preliminary air dispersion modeling was performed in the pre-FEED study to
determine appropriate stack height, parameters, and location. In order to confirm that the site will not exceed National
Ambient Air Quality Standards (NAAQS), an additional air dispersion model will be required using the final FEED study
parameters, emissions, and layout.
An SMS will also be included in the EFG+ plant design for MRY2 to maintain favorable solvent purity and produce a small
waste effluent stream that is collected and periodically hauled offsite for disposal. Furthermore, by maintaining low
impurity levels in the solvent, undesired VOC emissions are reduced dramatically.
Wastewater produced by the EFG+ plant includes blowdown from the DCC (knock-out water and SO2 scrubbing solution).
The condensed water vapor from cooled flue gas is of high quality and can be used as cooling water makeup at MRY2
after minor treatment. After investigating the compatibility of existing MRY Station wastewater treatment, Minnkota
concluded that disposal via a Class I injection well is the likely method of disposal for some of the effluents. The FEED
study will include design and costing of a Class I well. The proposed changes will require the MRY2 plant to modify its
National Pollutant Discharge Elimination System (NPDES) permit for industrial wastewater discharges.
Any plant constructed in North Dakota requires a winterization plan, as temperatures can reach to -40°C or less. Through
the pre-FEED effort, the project team identified best practices for ensuring the plant remains efficient and operational
during the winter months, including specifications for building foundation depth, insulation and material specifications,
cold process startup/shutdown, and buried fluid lines.
Modularization is a key component of the construction strategy for Project Tundra, which includes a transportation study
to determine module size and onsite fabrication requirements. A construction-driven strategy is key to schedule certainty,
risk reduction, and cost-effective execution and delivery of the project.
Flue Gas Assumptions – Unless noted, average flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
13.5 141 10.2 20.5 65.1 6.9 0.80 42.7 148.3
Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The absorption of CO2 is a chemical reaction.
Solvent Contaminant Resistance – The solvent has very good resistance to contaminants in the flue gas aided by the
solvent maintenance system.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
192 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Solvent Foaming Tendency – None.
Flue Gas Pretreatment Requirements – SO2 removal and temperature control is required prior to the absorber.
Solvent Makeup Requirements – Estimated at 0.25 kg/tonne.
Waste Streams Generated – Solvent maintenance system waste, water treatment waste, and cooling tower blowdown.
Process Design Concept – Flowsheet/block flow diagram shown above in Figure 1.
Proposed Module Design – Will be determined based on results of a logistics/route study.
technology advantages
• Advanced solvent formulation with high CO2 capacity and high absorption rate.
• Low pressure-drop packing in DCC and absorber has the potential to lower the power consumption for the blower by
65%.
• Large diameter column design for absorber and DCC reduces the number of absorption trains required, thereby
lowering capital costs.
• Novel absorber intercooler configuration increases solvent loading and lowers the overall solvent circulation rate,
further reducing power consumption and solvent loss.
• An LVC unit reduces the steam demand for solvent regeneration by 10 to 15%.
• Fluor’s proprietary SMS lowers overall solvent loss and makeup.
• Advanced reclaiming technology significantly reduces reclaimer waste.
R&D challenges
• Lignite coal-based flue gases, such as that produced at MRY2, contain alkali-derived aerosols and particulate matter
that can have a detrimental impact on both amine solvent emissions and degradation rates.
• Integration into an existing facility poses many operating and plant layout challenges.
• Maintaining a proper water balance for the facility becomes a challenge.
status
The project team has developed a formal optimized design manual that establishes the common design basis for the
project. The design of the carbon capture system, along with an analysis of integrating the carbon capture system with
the plant’s steam cycle or utilizing natural gas-fired auxiliary boilers, are underway. A preliminary meeting with the North
Dakota Department of Environmental Quality (NDDEQ) was held to discuss the requirements for air emissions and water
discharge permitting.
available reports/technical papers/presentations
“Front-End Engineering & Design: Project Tundra Carbon Capture System,” DOE Kick-off Meeting, November 12, 2019.
https://netl.doe.gov/projects/files/Slides%20Minnkota%20FE0031845%20Kickoff%20Mtg%202019-11-12%20Non-
Confidential.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
193
Post-Combustion Solvent Technologies
Front-End Engineering Design technology maturity:
Front-End Engineering
Study for a Carbon Capture Design (FEED)
Plant Retrofit to a Natural Gas- project focus:
Fired Gas Turbine Combined
Amine-Based Solvent
Technology Retrofit to
Cycle Power Plant
NGCC
participant:
Bechtel National, Inc.
primary project goals
project number:
Bechtel National, Inc. is performing a comprehensive front-end engineering design
FE0031848
(FEED) study for a carbon capture and compression plant retrofit to an existing
natural gas-fired combined cycle (NGCC) power plant located in Texas. The
capture plant is based on conventional technology comprising a non-proprietary NETL project manager:
aqueous solvent, monoethanolamine (MEA), an absorber-stripper cycle, and Naomi O’Neil
multi-stage centrifugal compressors. [email protected]
principal investigator:
technical goals
william Elliott
Bechtel National, Inc.
• Develop a project design basis to provide general project requirements that [email protected]
apply to the specific plant site, ambient conditions, fuel feedstock and flue gas
characteristics, environmental requirements, and modularization design partners:
requirements.
Electric Power Research
• Develop process engineering documents for constructing the carbon capture
Institute, Inc., Nexant
system, including block flow diagrams, heat and mass balance diagrams,
process flow diagrams for major components, and a water balance diagram.
start date:
• Conduct a preliminary hazard and operability (HAZOP) study and produce a
report to document the results. 10.01.2019
• Develop civil, structural, mechanical, electrical, and control systems percent complete:
engineering design packages.
10%
• Develop a layout and design package that includes process plant arrangement
drawings and piping and instrumentation diagrams.
• Summarize expected emissions and waste streams.
• Review various contracting and purchasing options for procuring a new process
system and perform a constructability review to identify construction access,
lay-down areas, and sequencing of construction work.
• Develop an overall project capital cost estimate within a ±15% accuracy.
• Prepare a final FEED study package.
technical content
Bechtel is executing a FEED study on retrofitting an existing NGCC power plant
with an amine-based post-combustion carbon capture plant. The prospective end
use for the captured carbon dioxide (CO2) is enhanced oil recovery (EOR). Bechtel
is aiming to develop a technology readiness level (TRL) 9 carbon capture,
utilization, and storage (CCUS) concept for retrofitting an existing NGCC with
mature and field-proven technology and equipment. Figure 1 illustrates a
simplified process flow diagram of a conventional absorber-stripper scrubbing
system with a non-proprietary solvent such as MEA.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
194 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Figure 1: Generic simplified flowsheet for amine-based CO2 capture from flue gas.
Bechtel is applying an “open access” and “open technology” methodology to the process and physical design of the
facilities and the solvent used in the technology. An “open access” technology approach denotes that the owner/operators
of a post-combustion carbon capture plant are in full control of the technology used in the plant. The post-combustion
carbon capture hardware can be procured by competitive tendering against a non-proprietary specification, similar to
conventional power plants. This allows the owner/operators to specify the post-combustion carbon capture plant
hardware and solvent selection based on the latest published technology and operating experience. “Open access”
technology utilizes a generic, non-proprietary solvent that is readily purchased on the open market from chemical
manufacturers at a relatively low cost. These features facilitate lower capital and operating expenses and avoid royalty
payments and technical restrictions associated with use of proprietary system designs and solvent selection.
The host site selected for the FEED study is the Sherman Generating Station, a 2x2x1 NGCC located in Sherman, Texas.
The 758-megawatt-electric (MWe) power plant built by Bechtel is powered by two Siemens F class gas turbines. The
selection of the site has several advantages, including:
• The NGCC plant was built by Bechtel; therefore, key project personnel have access to all design documents and are
familiar with the facility.
• The plant includes F class gas turbines, a state-of-the-art technology.
• The location of the host plant is near oil-bearing formations favorable for EOR operation.
Lessons learned and experience gained from earlier FEED and FEED verification studies performed by Bechtel are being
used as a basis for this FEED study. Bechtel prepared a FEED verification in 2015 under the direction of Shell for a proposed
carbon capture retrofit to gas turbine Unit 13 at the Peterhead Power Station in Scotland. In 2009, Bechtel performed a
FEED study for a CO2 capture and compression facility designed to capture 85% of the CO2 emissions from a 420-MWe
gas-fired power plant in Norway. Both a proprietary solvent and MEA were used as bases of design. The plants involved
in both FEED studies employ Siemens gas turbines, similar to the gas turbines in the Sherman facility; thus, much of the
engineering work has already been completed by Bechtel for flue gas conditions very similar to the host site in Texas.
Bechtel’s FEED report will be based on these past design reports.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
195
Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Design value
Molecular Weight mol-1 61.08
Normal Boiling Point °C 170
Normal Freezing Point °C 10.3
Vapor Pressure @ 15°C bar <1
Manufacturing Cost for Solvent $/kg 1–2
Working Solution
Concentration kg/kg 35
Specific Gravity (15°C/15°C) - 1.02
Specific Heat Capacity @ STP kJ/kg-K 3.6
Viscosity @ STP cP 4
Absorption
Pressure bar 1.089
Temperature °C 53.5
Equilibrium CO2 Loading mol/mol 0.4 – 0.49
Heat of Absorption kJ/mol CO2 TBD
Solution Viscosity cP 2.56
Desorption
Pressure bar 2.31
Temperature °C 130.8
Equilibrium CO2 Loading mol/mol 0.22 – 0.25
Heat of Desorption kJ/mol CO2 TBD
Module Design
Flue Gas Flowrate kg/hr 2.53 x 106
CO2 Recovery, Purity, and Pressure % / % / bar 80-90 / 99.0+ / 200
Absorber Pressure Drop bar 0.076
Estimated Absorber/Stripper Cost of __$__ TBD
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
196 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.5 194 3.82 7.74 74.78 12.81 0.85 10 370
Flue Gas Pretreatment Requirements – Flue gas is cooled to approximately 50°C before entering absorber towers
through a fogging system that reduces temperature and saturates flue gas with water.
Solvent Makeup Requirements – To be detailed in the FEED report.
Chemical/Physical Solvent Mechanism – The chemical/physical solvent mechanism is primarily controlled by the
solubility and alkalinity characteristics of the amine. MEA is fully water soluble and exhibits high alkalinity. MEA’s low
molecular weight permits higher solution capacity and its low boiling point allows higher recovery during reclamation of
contaminated solution. Carbon dioxide solubility in MEA solutions is relatively high. Regeneration of MEA solutions is
accomplished at reasonable temperatures with moderate heat input. Further discussion will be included in the FEED
report.
Solvent Contaminant Resistance – To be detailed in the FEED report.
Solvent Foaming Tendency – To be detailed in the FEED report.
Waste Streams Generated – MEA and ammonia emissions from the absorber are reasonable and will be defined in the
FEED report. Liquid and solid wastes from solvent maintenance and reclaiming will be defined in the FEED report.
Process Design Concept – The process overview under normal operation consists of the following systems:
• Flue gas diversion—The flue gas is directed from the existing stack to the plant.
• Flue gas cooling—The flue gas as supplied is too hot to process efficiently in the absorber and is cooled to its saturation
temperature before entering the absorber.
• CO2 absorption—Parallel absorbers use an amine solution to remove the CO2 from the flue gas.
• Heat integration—Heat is recovered from internal streams to enhance plant energy efficiency.
• CO2 stripping—The amine is regenerated for reuse by liberating the CO2 from the amine solution.
• CO2 compression and drying—The CO2 is compressed, dried, further compressed, and liquefied to meet the CO2
specifications.
• Amine reclamation—Heat stable salts (HSS) and degradation/oxidation products are removed from the amine solution.
• Amine storage—Fresh amine and lean amine are stored and injected into the absorption system to maintain the amine
solution concentration.
Proposed Module Design – To be detailed in the FEED report.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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197
Post-Combustion Solvent Technologies
technology advantages
• Use of generic solvent avoids restrictions and costs associated with proprietary solvents.
• An “open access” and “open technology” approach can accelerate CCUS deployment and reduce the costs of CCUS
by facilitating efficient know-how exchange and competition within the fleet of plants that may be built over the next
five to 10 years.
• “Open access” and “open technology” full-scale plants can facilitate the progression of post-combustion capture
systems currently at TRL 9 to achieve a commercial readiness index of 6 within 10 years or less.
• Bechtel has extensive experience in carbon capture studies, plus detailed design, construction, and operation of
NGCC power plants and CO2 capture plants, including involvement in several previous FEED studies on CO2 capture
retrofits to NGCC plants.
R&D challenges
• Steam extraction complexity.
• Confirmation of carbon capture simulation software accuracy for generic amine solutions at high solvent strengths.
status
The project team is developing final engineering documents to include block flow diagrams, process flow diagrams, heat
and mass balances, water balance diagrams, piping and instrument diagrams, and summary equipment specifications.
Engineering design packages will be prepared for civil, structural, mechanical, electrical, automation, and environmental
systems.
available reports/technical papers/presentations
“Front-End Engineering Design (FEED) Study for a Carbon Capture Plant Retrofit to a Natural Gas-Fired Turbine
Combined Cycle Power Plant (2x2x1 Duct-Fired 758-MWe Facility with F Class Turbines),” DOE Kick-off Meeting,
November 15, 2019. https://netl.doe.gov/projects/files/Bechtel%20Kickoff%20DE-FE0031848%20r3%20PUBLIC.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
198 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Front-End Engineering Design technology maturity:
Front-End Engineering
of Linde-BASF Advanced Post- Design (FEED)
Combustion CO2 Capture project focus:
Technology at a Southern
Linde-BASF Amine Solvent-
Based Technology Retrofit
Company Natural Gas-Fired
to NGCC
Power Plant
participant:
Southern Company
Services, Inc.
primary project goals project number:
FE0031847
Southern Company Services, Inc. is conducting a front-end engineering design
(FEED) study for a carbon dioxide (CO2) capture system based on Linde-BASF’s predecessor projects:
aqueous amine solvent-based technology installed at an existing Southern
N/A
Company natural gas-fired combined cycle (NGCC) power plant. The CO2 capture
plant will be of commercial scale (at least ~375 megawatt-electric [MWe]) and NETL project manager:
designed to achieve a high removal of CO2 from the flue gas feed stream.
Andrew O’Palko
[email protected]
technical goals
principal investigator:
• Select an NGCC generating plant as the host site for the FEED study based on a Landon Lunsford
Southern Company
set of defined criteria (performance of the gas turbines, availability of space to
[email protected]
house a carbon capture system, availability of utilities to support the system,
suitability of the surrounding geology for enhanced oil recovery [EOR] or storage). partners:
• Produce a design basis for the carbon capture system based on the specific site Linde Gas North America
requirements, including flue gas composition, environmental requirements, and LLC, BASF, Linde Engineering
requirements for modularization. Dresden
• Complete a conceptual design package for the process area of the post-
combustion capture plant and assess the logistics for solvent delivery required
start date:
for a commercial-scale carbon capture plant. 01.29.2020
• Complete design packages for mechanical, electrical, structural, instrumentation percent complete:
and control, and facilities engineering and assess the cost and logistics for
10%
constructability and site security.
• Utilize the cost and schedule estimates of equipment vendors and contractors to
derive a total project cost and schedule estimate within ±15% error.
technical content
Linde and BASF have been jointly developing, optimizing, and testing an advanced
post-combustion CO2 capture technology since 2007. The Linde-BASF technology
for capturing CO2 from flue gas using the BASF OASE® blue solvent is a mature
technology that has been tested in two pilot plants with different flue gas sources
covering a wide variety of flue gas compositions and impurities. The Linde-BASF
aqueous amine solvent-based post-combustion CO2 capture technology provides
a solution for key challenges encountered by solvent-based carbon capture
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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199
Post-Combustion Solvent Technologies
technologies, which include relatively high capital costs, significant parasitic energy requirements, and solvent stability
and degradation issues.
The technology is based on a typical lean-rich solvent absorption/regeneration cycle for CO2 capture, but leverages
several key innovative features for both solvent and process optimization to reduce the cost of CO2 capture from NGCC
plants. The optimized properties of the OASE blue solvent lead to capital and operating cost reduction due to efficient
CO2 capture from low pressure sources through favorable reaction kinetics and reduced reboiler steam energy
consumption; better stability than monoethanolamine (MEA); and a lower solvent circulation rate. In addition to advances
in solvent design, Linde has achieved significant improvements in process design, as outlined in Figure 1.
A. Flue gas blower provides sufficient pressure to overcome pressure drop across the direct contact cooler (DCC)/pre-scrubber and absorber.
The blower location can be adjusted to minimize cost based on arrangement of equipment and piping at the NGCC site.
B. Integrated DCC/pre-scrubber to reduce sulfur oxides (SOX) content below 5 parts per million (ppm) and simultaneously cool the flue gas
stream to ~35 to 40°C.
C. Innovative and patented water wash section at the top of the column to reduce amine losses, even in the presence of aerosols. Dry bed
configuration helps mitigate aerosol-driven amine losses.
D. A gravity-driven inter-stage cooler for the absorber that eliminates the need for a pump and related controls.
E. High-capacity structured packing reduces the absorber diameter, thereby enabling a larger single-train plant construction and greatly
reduced capital costs.
F. Solvent-based heat exchanger designed to operate over a wide range of temperature approaches, which provides the opportunity to
optimize the performance and capital cost trade-off.
G. Regenerator designed for operation at pressures up to 3.4 bara significantly reduces CO2 compression energy and eliminates the bulky first
stage of the CO2 compressor, resulting in capital cost savings.
H. Innovative plate and frame design of the reboiler minimizes thermal degradation of solvent and provides for a lower solvent inventory and
faster dynamics to respond to flue gas load and composition changes.
I. Stripper Inter-Stage Heater (SIH) enhances energy-efficient CO2 stripping from the solvent by recovering heat from the lean solvent to
provide intermediate reboil, thereby reducing energy consumption of solvent regeneration.
J. Variations of the stripper-reboiler flashing configuration, which are being evaluated to further minimize solvent regeneration energy.
Figure 1. Process flow diagram of Linde-BASF OASE® blue post-combustion CO2 capture technology.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
200 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Solvent Technologies
A development timeline of the Linde-BASF technology is shown in Figure 2. Previous testing of a 0.45-MWe dry lignite-
fired pilot plant incorporating the Linde-BASF technology has shown that the OASE blue solvent is more stable than MEA
after 2,500 hours of testing. The process was also previously tested at 1.5-MWe-scale at the National Carbon Capture
Center (NCCC) under the U.S. Department of Energy (DOE)-funded project DE-FE0007453, validating solvent stability and
revealing a cyclic capacity 20% higher than MEA and regenerator steam consumption 25% lower than MEA. These results
confirmed the ability of this technology to be cost-effective, energy efficient, and compact.
Figure 2. Linde-BASF post-combustion CO2 capture technology development.
Milestones achieved thus far for the Linde-BASF post-combustion CO2 capture technology applied to NGCC flue gas
conditions are outlined in Figure 3. These include testing on an NGCC flue gas composition at the 0.45-MWe pilot-scale
in Niederaussem, Germany; completion of a detailed FEED study on CO2 capture from a 510-MWe NGCC power plant in
2011; and completion of a pre-FEED study for CO2 capture at a 480-MWe NGCC power plant in 2018.
Figure 3. Milestones achieved by Linde-BASF post-combustion CO2 capture technology.
The capital and operating costs determined from the previous pre-FEED and FEED studies are shown in Table 1. The
studies were based on commercial Linde-BASF post-combustion CO2 capture plants recovering 85 to 90% of the CO2 in
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
201
Post-Combustion Solvent Technologies
the flue gas supplied to the process from an NGCC power plant. All major process components were included in each
study and the CO2 product purity was specified at greater than 99 mol% (dry) with less than 100 parts per million (ppm)
oxygen (O2) content. Capital costs were estimated using Linde’s proprietary cost estimation methodology for new
commercial plants and were derived from databases of actual equipment quotes from vendors collected from recent
projects. Capital costs for CO2 capture plants integrated with NGCC plants are significantly higher compared to those
integrated with coal-fired power plants due to the reduced flue gas CO2 concentration in natural gas-derived flue gas (~4
mol% versus ~12% mol% CO2 for coal-fired plants). This reduced flue gas CO2 concentration necessitates a taller and
larger diameter absorber column to achieve 90% CO2 capture at low or ambient pressures. The optimum CO2 capture
rate at the host site will be defined in the FEED study to achieve an attractive cost option.
TABLE 1: ESTIMATED CAPEX, OPEX, AND COST OF CO2 CAPTURED FOR LARGE-SCALE LINDE-
BASF CO2 CAPTURE AND COMPRESSION PLANT (550+ MWE) FOR NGCC BASED ON PAST
LINDE STUDIES (COST YEAR=2019) (WITHOUT TRANSPORTATION AND STORAGE)
The general approach for the FEED follows the methodology described in Figure 4.
Figure 4. FEED approach.
Process designs that reduce the energy required for solvent regeneration through heat recovery integration are being
optimized as part of the FEED study. Waste heat sources at the NGCC-fired host site can be leveraged to reduce the
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
202 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
parasitic steam consumption of the CO2 capture system and reduce the negative impact of the capture plant on power
plant steam cycle efficiency or net electrical power generation. Sources include: (1) supplemental low- to medium-
pressure steam from the power plant steam cycle in the range of 5 to 6 bara not currently used for electricity production
can be redirected for use in the post-combustion CO2 capture plant reboiler; (2) waste heat recovered from the hot flue
gas upstream of the CO2 capture plant after the heat recovery steam generator (HRSG) can be used to pre-heat CO2-rich
solvent entering the stripper column; or (3) external steam generation can reduce the steam input from the power plant.
In addition, process optimization within the post-combustion CO2 capture plant itself, including lean vapor compression
(LVC) involving flashing of the CO2-lean solution at the bottom of the stripper and redirecting the vapor after compression
back to the bottom of the stripper, is an option that can substantially reduce the reboiler steam consumption for NGCC-
fired CO2 capture down to 2.4 gigajoules (GJ)/tonne CO2 based on past FEED studies conducted for large Linde-BASF
post-combustion CO2 capture plants.
Linde has conducted extensive research on the management of flue gas aerosol particles that contribute to amine losses
through the treated gas exiting the absorber, including literature studies and aerosol measurements taken during testing
of the Linde-BASF post-combustion CO2 capture technology at NCCC. Experimentally, Linde has determined that if aerosol
concentrations are less than 107 particles/cm3 for particles ranging from 70 to 200 nanometer (nm) in diameter, there is
no need for pre-treatment beyond a direct contact cooler (DCC)/pre-scrubber and dry bed wash section in the absorber
to manage the aerosols. Aerosol concentrations are expected to be much lower for NGCC-derived flue gas than for coal-
fired flue gas; therefore, typical emission control measures have been integrated into the Linde-BASF CO2 capture plant
design.
Two Southern Company host sites are being evaluated in the first phase of the FEED study: Alabama Power Company’s
Plant Barry (Units 6 and 7), located in Bucks, Alabama, and Mississippi Power Company’s Plant Daniel (Units 3 and 4),
located in Moss Point, Mississippi. Each of the gas-fired combined cycle units (Units 6 and 7 at Plant Barry and Units 3
and 4 at Plant Daniel) produce a nominal 525 MWe (net). For either host site, equipment and operating modifications in
the combined cycle to increase CO2 concentration in the flue gas is a primary focus of the FEED study to minimize carbon
capture costs. Cooling water capacity at both combined cycle plants is limited; therefore, evaluations of new cooling tower
capacity versus air cooling are being performed in the FEED. For each site, steam supply to the carbon capture process
may be available via extraction from the steam turbine, but the overall impact on the HRSG, steam cycle, and steam
turbine is being evaluated during the FEED to determine the cost impact of extraction versus alternate steam production
from a package boiler or cogeneration unit.
The FEED will provide a financial indicator of the costs of installation at an actual domestic NGCC power plant site and
potentially illustrates that this capture system can be employed at operating commercial coal-fired power plants. The
commercial FEED will provide a realistic framework for NGCC power plants to be built CO2 capture-ready or to retrofit
existing NGCC plants with an economical CO2 capture system.
TABLE 2: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Design value
Molecular Weight mol-1 proprietary
Normal Boiling Point °C proprietary
Normal Freezing Point °C -5 to 25
Vapor Pressure @ 15°C bar(a) proprietary
Manufacturing Cost for Solvent $/kg proprietary
Working Solution
Concentration kg/kg proprietary
Specific Gravity (15°C/15°C) - 1.0 – 1.2
Specific Heat Capacity @ STP kJ/kg-K proprietary
Viscosity @ STP cP 1.5 – 7.0
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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203
Post-Combustion Solvent Technologies
Absorption
Pressure bar(a) 0.9 – 1.1
Temperature °C 30 – 60
Equilibrium CO2 Loading mol/mol proprietary
Heat of Absorption kJ/mol CO2 proprietary
Solution Viscosity cP 1.5 – 7
Desorption
Pressure bar(a) 1.6 – 3.4
Temperature °C 125 – 140
Equilibrium CO2 Loading mol/mol proprietary
Heat of Desorption kJ/mol CO2 proprietary
Module Design
Flue Gas Flowrate kg/hr Designed for >375 MWe
slipstream
CO2 Recovery, Purity, and Pressure % / % / bar 90%, >99.9% (dry), 3.4
bar(a)
Absorber Pressure Drop bar proprietary
Estimated Absorber/Stripper Cost of __$__ proprietary
Manufacturing and Installation kg/hr
Definitions:
Bar(a) – Unit used to indicate absolute pressure, where the reference pressure is absolute zero (i.e., not taking into
account atmospheric pressure).
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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204 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the HRSG unit (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.8 231 4 9 74 12 1 0.08 2
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Carbon dioxide in the flue gas chemically binds to the OASE blue aqueous
amine-based solvent via an exothermic absorption step and this chemical bond is broken in the endothermic desorption
step via heat provided by steam in the reboiler of the regenerator column, generating pure CO2.
Solvent Contaminant Resistance – The OASE blue solvent is highly resistant against many contaminants in the flue gas,
as shown in both parametric and long-term continuous tests (see Electric Power Research Institute [EPRI] report1 for
additional information).
Solvent Foaming Tendency – During the pilot plant operations, although anti-foaming injection was included in the
design, its use was not found necessary.
Flue Gas Pretreatment Requirements – The pretreatment requirement includes reducing sulfur oxide (SOX) in the flue
gas to 2 to 5 ppm in order to limit solvent degradation and is implemented in a DCC in conjunction with flue gas cooling,
typically by adding appropriate amount of sodium hydroxide corresponding to the SOX present in the flue gas.
Solvent Makeup Requirements – The OASE blue solvent makeup rate is determined by the sum of the amine losses in
the treated gas leaving the absorber column and the rate of solvent degradation during operation over time. Low makeup
rates were observed during long-term testing well below an operationally manageable threshold. Low solvent makeup is
expected at scale when processing flue gas from power plants with a baghouse filter for particulate removal or with
upstream flue gas pretreatment for aerosol mitigation.
Waste Streams Generated – The main waste liquid stream is from the DCC where SOX and nitrogen oxide (NOX) are
removed; this stream is typically handled in the power plant wastewater treatment facility. A small amount of solid waste
is removed using an activated carbon filter and mechanical cartridge filter that are replaced at regular intervals. Since the
solvent degradation observed in the pilot testing is small, no solvent reclamation unit is envisioned in the large scale.
Process Design Concept – Flowsheet/process flow diagram shown in Figure 1.
Proposed Module Design – Free standing absorber and stripper columns will be tied into a modularized process skid.
There will be associated containers for electrical equipment, analytical equipment, and process control.
technology advantages
• Exhibits a lower solvent circulation rate, reduced reboiler steam energy consumption compared to process using MEA
solvent, reduced absorber diameter due to high efficiency packing, and lower downstream CO2 compression cost due
to the ability to operate at higher desorber pressures.
• BASF is the producer of the OASE blue solvent and the owner of the solvent technology. A major global player in the
chemical industry, BASF has the capabilities to reliably produce and supply the OASE blue solvent in sufficient volumes
needed for commercialization, thereby enabling application at scale by avoiding issues related to solvent
manufacturing for large-scale commercial plants.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
205
Post-Combustion Solvent Technologies
• The Southern Company-Linde-BASF partnership combines the necessary capabilities and experience to deliver the
complete CO2 capture technology value chain from solvent production to full-scale CO2 capture plant engineering,
procurement, and construction (EPC); commercial deployment; and long-term, continuous operations.
R&D challenges
• Carryover and emissions of amines and amine degradation products.
• Handling large volumes of process condensate from DCC.
• Disposal of spent activated carbon and filters can generate solid waste management.
• Designing for low liquid/gas ratios caused by lower CO2 concentration in natural gas flue gas may result in below-
target CO2 capture rate or vapor and liquid maldistribution.
• Equipment scale-up associated with large vapor flows due to low CO2 concentration.
• Engineering the liquid hydraulics and gas distribution in large manifolds needed for multiple absorbers.
• Integration of post-combustion CO2 capture plant with host site.
status
The project team is evaluating the two potential host sites, Plant Barry in Alabama and Plant Daniel in Mississippi, for
installation of the Linde-BASF CO2 capture technology.
available reports/technical papers/presentations
Lundsford, Landon, “Front End Engineering Design of Linde-BASF Advanced Post-Combustion CO2 Capture Technology
at a Southern Company Natural Gas-Fired Power Plant,” DOE Kick-off Meeting, November 2019.
https://netl.doe.gov/projects/files/Slides%20SCS%20FE0031847%20Kickoff%20Mtg%202019-11-22%20public%20copy.pdf.
Bostick, D., Krishnamurthy, K., “Final Testing Report to NCCC,” January 27, 2017. NCCC Technology Developer Reports,
National Carbon Capture Center,
https://static1.squarespace.com/static/566b0ac3df40f3a731712cf4/t/58f53329bebafb77565eda81/1492464428545/Linde-
BASF+-+Slipstream+Pilot-Scale+Demonstration+of+a+Novel+Amine-Based+Post-
Combustion+Technology+for+Carbon+Dioxide+Capture+from+Coal-Fired+Power+Plant+Flue+Gas.pdf.
Bostick, D., Stoffregen, T., Rigby, S., “Final Techno-Economic Analysis of 550 MWe Supercritical PC Power Plant with CO2
Capture using the Linde-BASF Advanced PCC Technology,” January 9, 2017. https://www.osti.gov/servlets/purl/1338328.
O’Brien, K., “Large Pilot Testing of Linde-BASF Advanced Post-Combustion CO2 Capture Technology at a Coal-Fired
Power Plant,” presented at 2018 NETL CO2 Capture Technology Project Review Meeting, August 2018.
https://netl.doe.gov/sites/default/files/netl-file/K-OBrien-ISTC-Linde-BASF-Post-Combustion-CO2-Capture.pdf.
Moser, P., Schmidt, S., Stahl, K., Vorberg, G., Lozano, G., Stoffregen, T., Rösler, F., “Demonstrating Emission Reduction –
Results from the Post-combustion Capture Pilot Plant at Niederaussem,” GHGT-12. Energy Procedia 2014; 63: Pages 902-
910. https://www.sciencedirect.com/science/article/pii/S1876610214019158.
Moser, P., Schmidt, S., Wallus, S., Ginsberg, T., Sieder, G., Clausen, I., Garcia Palacios, J., Stoffregen, T., Mihailowitsch, D.,
“Enhancement and Long-Term Testing of Optimised Post-Combustion Capture Technology – Results of the Second Phase
of the Testing Programme at the Niederaussem Pilot Plant,” GHGT-11. Energy Procedia 2013; 37: Pages 2377–2388.
https://www.sciencedirect.com/science/article/pii/S1876610213003627.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
206 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
references
1
BASF-Linde Post Combustion Carbon Capture Pilot Plant at the National Carbon Capture Center, 2016 Test Campaign
Results, EPRI, February 2017.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
207
Post-Combustion Solvent Technologies
Large-Scale Commercial technology maturity:
Carbon Capture Retrofit of the
Front-End Engineering
Design (FEED)
San Juan Generating Station project focus:
KM CDR Process™ Retrofit
primary project goals participant:
Enchant Energy, LLC
The overall goal of this project is to perform a front-end engineering design (FEED)
study for the retrofit of the San Juan Generating Station (SJGS) with post- project number:
combustion carbon capture. The FEED study will document the initial engineering
and cost estimates for the retrofit project, including the levelized cost of carbon FE0031843
capture on an existing plant, and provide estimates of the technical and economic
viability of extending the life of the existing SJGS coal-fired power plant through NETL project manager:
the installation of Mitsubishi Heavy Industries’ (MHI) Kansai Mitsubishi Carbon Andrew Jones
Dioxide Recovery (KM CDR) Process™ carbon dioxide (CO2) capture [email protected]
technology. The FEED study will enable SJGS to move forward into detailed
engineering, procurement, installation, and operation in future work. principal investigator:
Jason Selch
technical goals Enchant Energy, LLC
[email protected]
The purpose of the FEED study is to complete preliminary engineering and
design work to support developing a detailed cost estimate for the cost of
partners:
retrofitting CO2 capture at SJGS. City of Farmington,
The team will perform multiple feasibility and design studies based on project- Mitsubishi Heavy Industries
specific details in preparation for developing engineering deliverables. These America, Inc., Mitsubishi
studies will help define the scope of the retrofit project, based on project-specific Heavy Industries
decisions, technology-specific performance, site-specific requirements, and Engineering, Ltd., Sargent
client-specific needs. and Lundy, LLC, Navigant
Consulting, EJM Associates,
Once the scope has been defined, detailed design will commence for the CO 2
LLC, Baker Tilly Virchow
capture system and its integration with the existing facility. Various design and
Krause, LLP
engineering deliverables will be developed that will help define commodity
quantities, equipment specifications, and labor effort required to execute the
project. start date:
10.15.2019
technical content percent complete:
N/A
Enchant and its partners will perform a FEED study for retrofitting the host site
with an advanced amine-based carbon capture technology. The FEED study will
be performed for 847 megawatts-electric (MWe; Units 1 and 4 at SJGS in
Waterflow, New Mexico). The coal is supplied by the adjacent mine, San Juan
Coal Company, owned by Westmoreland Holdings. The current contract expires
on June 30, 2022; however, San Juan Coal has offered SJGS a new contract for
3.2 million tons of coal per year from 2022 to 2033. Both operating units are
equipped with state-of-the-art environmental controls that meet or exceed
government-permitted levels of emissions for nitrogen oxide (NOX), sulfur dioxide
(SO2), particulate matter (PM), and mercury (Hg), making the unit carbon capture-
ready from an emissions perspective.
SJGS is currently owned by a group of public utilities and municipal power entities
and is operated by Public Service of New Mexico (PNM), pursuant to the Amended
San Juan Participation Agreement (ASJPA). The City of Farmington (Farmington),
currently a part-owner and also sub-recipient under this award, has the right under
the ASJPA to acquire the 95% interest in SJGS held by all the other owners
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
208 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Solvent Technologies
effective at the termination of the existing coal contract on June 30, 2022. Prior to taking over ownership from the exiting
owners on June 30, 2022, Enchant, who acquired Farmington’s acquisition rights in August 2019, will manage the CO 2
capture retrofit process by virtue of the Agency Agreement with the City of Farmington. The ASJPA also provides
Farmington and its agent, Enchant, the right to access the site immediately for purposes of completing this FEED study.
Work on this FEED study will produce detailed engineering designs, costing, and timelines for the construction. It will
also designate permitting agencies and timelines in order to execute the follow-on build and operate project. Lessons
learned during the FEED study will be documented to assist in future large-scale capture retrofit projects at coal-fired
power plants.
Figure 1: Block flow diagram of the CO2 recovery plant.
The KM CDR Process has the following key features: (1) demonstrated performance on a large-scale (240 MWe); (2)
high-performing amine solvent KS-1™ (high absorption capacity, low steam consumption, high resistance to oxidation
and thermal degradation); and (3) key process technologies, such as an amine emission reduction system, solvent
degradation reduction, automatic load adjustment control system, and amine purification system.
The CO2 recovery facility consists of four main sections, as shown in Figure 1: (1) flue gas pretreatment, (2) CO2 recovery,
(3) solvent regeneration, and (4) CO2 compression and dehydration. In flue gas pretreatment, the flue gas temperature
is cooled in the flue gas quencher by direct contact with circulation water. The circulation water is injected with caustic
soda to reduce the amount of SO2 in the flue gas entering the amine system. A flue gas blower is installed downstream
of the flue gas quencher to overcome the pressure drop across the flue gas quencher and the CO 2 absorber.
Figure 2 shows the process flow diagram for the CO2 recovery and solvent regeneration steps. In CO2 recovery, the
cooled flue gas from the flue gas quencher is introduced at the bottom of the CO 2 absorber. The flue gas moves upward
through the packing while the CO2-lean solvent is supplied at the top of the absorption section where it flows down onto
the packing. The flue gas contacts with the solvent on the surface of the packing, where 95% of the CO 2 in the flue gas
is absorbed by the solvent. The CO2-rich solvent from the bottom of the CO2 absorber is sent to the regenerator. The
CO2-lean flue gas exits the absorption section of the CO2 absorber and enters the flue gas washing section of the CO 2
absorber. The flue gas contacts with circulating water to reduce the carryover amine that is emitted from the top of the
CO2 absorber.
In solvent regeneration, cool-rich solvent is heated by the hot-lean solvent extracted from the bottom of the regenerator
in a heat exchanger. The pre-heated rich solvent is then introduced at the top of the regenerator column and flows down
over the packing, where it contacts with stripping steam. As it flows down the column, the rich solvent releases captured
CO2 and is regenerated back into lean solvent. The steam in the regenerator is produced by the reboiler, where low-
pressure steam is used to heat the lean solvent. The lean solvent is then cooled to the optimum absorption temperature
before being recycled back to the CO2 absorber.
The overhead vapor leaving the regenerator is cooled, and the condensed liquid from this unit is then returned to the
system. In CO2 compression and dehydration, CO2 is compressed through a multi-stage gas compressor. Treatment such
as oxygen (O2) removal or dehydration may be necessary to meet pipeline and storage guidelines.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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209
Post-Combustion Solvent Technologies
Figure 2: Carbon capture basic process flow diagram.
technology advantages
FEED studies for carbon capture systems at this site will provide the U.S. Department of Energy (DOE) with a more
detailed understanding of carbon capture costs in a commercial application, thereby enabling DOE to better design its
research and development (R&D) program to reduce those costs for similar carbon capture technologies being developed
in its R&D portfolio.
R&D challenges
To deploy the post-combustion amine technology on coal-fired gas while adequately managing accumulation of
impurities in the exhaust without excessive cost.
Ensuring reliable operation over a long period at large-scale.
status
Project has commenced.
available reports/technical papers/presentations
“Preliminary Assessment of Post-Combustion Capture of Carbon Dioxide at the San Juan Generating Station: An
Independent Assessment of a Pre-feasibility Study Conducted by Sargent & Lundy for Enchant Energy,”12 December
2019, Los Alamos National Laboratory. https://www.lanl.gov/science-innovation/science-programs/applied-energy-
programs/_assets/docs/preliminary-technical-assessment-december2019.pdf.
“Enchant Energy, San Juan Generating Station – Units 1 & 4, CO 2 Capture Pre-Feasibility Study, FINAL,” July 8, 2019,
Project No. 13891-001, Prepared by Sargent & Lundy. https://www.enchantenergy.com/wp-
content/uploads/2019/07/Enchant-Energy_SJGS-CO2-Pre-feasibility-Study_FINAL-Rev-0-7-8.pdf .
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
210 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
POST-COMBUSTION
SORBENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
211
Post-Combustion Sorbent Technologies
Sorbent-Based Post- technology maturity
Pilot-Scale, Actual Flue Gas
Combustion CO2 Slipstream Slipstream (0.5 Mwe)
Testing project focus:
Alkalized Alumina Sorbent
primary project goals participant:
TDA Research, Inc.
TDA Research, Inc. is designing, constructing, and operating a slipstream 0.5-
megawatt-electric (MWe) pilot-scale process for post-combustion carbon dioxide project number:
(CO2) capture using their low-cost alkalized alumina sorbent to conduct parametric
and long-term steady-state testing to demonstrate the effectiveness of the FE0012870
technology to reduce the cost of CO2 capture and to develop scale-up conditions
for the process. predecessor projects:
NT0005497
technical goals
NETL project manager:
Andrew O’Palko
• Modify bench-scale unit to mimic proposed pilot plant configuration and conduct
[email protected]
testing in bench unit to optimize process and collect data for pilot plant design.
• Characterize breakthrough performance and pressure drop for different sorbent principal investigator:
pellet sizes.
jeannine Elliott
• Design pilot plant unit based on developed low-cost alkalized alumina sorbent TDA Research, Inc.
technology. [email protected]
• Scale-up production of sorbent.
• Fabricate and install pilot plant unit at the National Carbon Capture Center partners:
(NCCC). University of California at
• Perform parametric and steady-state testing on pilot plant using actual flue gas. Irvine, Porocel, Babcock
and wilcox, Louisiana State
• Update environment, health, and safety (EH&S) study and techno-economic
University, western Research
analysis (TEA) based on pilot plant testing results.
Institute
technical content start date:
02.03.2014
TDA Research, Inc. is designing, constructing, and operating a slipstream 0.5-
MWe pilot-scale process for post-combustion CO2 capture. This technology is percent complete:
based on their novel dry alkalized alumina sorbent developed previously in a U.S.
95%
Department of Energy (DOE)-funded project (DE-NT0005497). The regenerable
sorbent acts as a physical adsorbent for CO2. The CO2 capture process runs near
isothermally at around 140 to 150°C in both adsorption and regeneration, requiring
no heating or cooling between adsorption and regeneration steps. The sorbent is
regenerated with low pressure (15.5 pounds per square inch absolute [psia])
steam. The sorbent shows excellent tolerance to contaminants, including sulfur
dioxide (SO2) and nitrogen oxides (NOX).
An overall schematic of TDA’s system is shown in Figure 1, consisting of two
primary components: (1) the adsorber/regenerator unit and (2) the CO2
compression and purification unit. The process is designed for the sorbent to
remove the CO2 from the flue gas at intermediate temperature and near-ambient
pressure, and then be regenerated with low-pressure superheated steam. A
multiple fixed-bed design is used, providing counter-flow contact between solids
and gases, where the beds cycle between adsorption and desorption. The flue
gas flows in parallel through the adsorption beds and in series across regeneration
beds. This setup has several advantages over moving beds, including a simple-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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212 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Sorbent Technologies
bed design, basic ductwork, low construction cost, and the elimination of parasitic power required to move the sorbent,
all of which result in a lower overall cost than moving beds.
Figure 1: Block flow diagram of TDA’s CO2 capture system.
The slipstream pilot plant is a 0.5-MWe skid-mounted system (shown in Figure 2) installed at the NCCC. The
adsorber/regeneration system is made up of multiple fixed beds containing the alumina sorbent that switch between
adsorption, regeneration, and purge operations. The complete slipstream pilot unit includes adsorber/regeneration beds,
heat exchangers, blowers, valving, and instrumentation.
Figure 2: TDA’s 0.5-MWe test skid.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
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213
Post-Combustion Sorbent Technologies
Slipstream pilot unit testing under both parametric and steady-state conditions using actual coal-fired flue gas provides
data and recommended operating conditions to update the TEA and EH&S assessment, as well as for definition of
recommended scale-up conditions. The project aims to demonstrate the novel system for reduction in carbon capture
cost.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 750 750
Bulk Density kg/m3 520 520
Average Particle Diameter mm 1.5 3.175
Particle Void Fraction m3/m3 0.55 0.55
Packing Density m2/m3 9.4E+07 9.4E+07
Solid Heat Capacity @ STP kJ/kg-K 0.72 0.72
Crush Strength kgf 8 8
Manufacturing Cost for Sorbent $/kg 6.5 3
Adsorption
Pressure bar 1.12 1.12
Temperature °C 140 140
Equilibrium Loading g mol CO2/kg 1.0 1.5
Heat of Adsorption kJ/mol CO2 -12.5 to -41.9 -12.5 to -41.9
Desorption
Pressure bar 1.17 1.17
Temperature °C 150 150
Equilibrium CO2 Loading g mol CO2/kg 0.93 1.0
Heat of Desorption kJ/mol CO2 12.5 to 41.9 12.5 to 41.9
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — Multiple fixed bed
Flue Gas Flowrate kg/hr 2,273
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 1.013
Adsorber Pressure Drop bar 0.02
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The sorbent is an adsorbent and is regenerated with steam.
Sorbent Contaminant Resistance – Based on extended cycling 1,500 hours with simulated flue gas with 13.8% CO2,
104 parts per million (ppm) SO2, 3% oxygen (O2), and 9% water (H2O), sorbent life was calculated to be one year with 5
ppm of SO2. No effect of NOX on capacity was seen after 200 cycles with 739 ppm nitric oxide (NO) and 84 ppm nitrogen
dioxide (NO2).
Sorbent Attrition and Thermal/Hydrothermal Stability – None provided.
Flue Gas Pretreatment Requirements – Flue gas should have <5 ppm sulfur oxides (SOX).
Sorbent Makeup Requirements – 15% per year.
Waste Streams Generated – None known.
Process Design Concept – See Figure 1 above.
Proposed Module Design – Note the module location, as well as the pressure, temperature, and composition of the gas
entering the module. TDA’s CO2 capture system is located downstream of the FGD unit. The adsorbent removes dilute
CO2 from the flue gas (10 to 14% CO2, 8 to 10% H2O, <5 ppm SO2) at intermediate temperature (140°C) and near-
ambient pressure.
technology advantages
• Inexpensive, durable sorbent.
• Low-pressure (17 psi) steam for sorbent regeneration, low regeneration energy.
• Near isothermal operation.
• No heat recovery from solids required.
• Rapid adsorption/regeneration kinetics due to surface-only adsorption.
• Low heat of adsorption.
• Counter-current operation maximizes capture efficiency and sorbent loading.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
215
Post-Combustion Sorbent Technologies
R&D challenges
• Minimize the parasitic demands from the sorbent system.
• Effectively produce a sorbent from low-cost raw materials with extensive regenerative life.
status
TDA Research, Inc. has designed and constructed the 0.5-MWe-scale pilot plant test unit and produced the sorbent
needed for testing. The skid has been installed at the NCCC, to be followed by 1.5 months of parametric testing and two
months of steady-state testing using an actual flue gas slipstream.
available reports/technical papers/presentations
Elliott, J. and Yi, F. “Update on Pilot Unit of Sorbent Based Post-Combustion CO2 Capture,” Presented at 2019 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/J-Elliott-
TDA-Sorbent-CO2-Capture.pdf.
Elliott, J. and Yi, F. “Update on Pilot Unit of Sorbent Based Post-Combustion CO2 Capture,” Presented at 2018 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/J-Elliott-TDAR-
Pilot-Unit-Sorbent-Based-Capture.pdf.
Elliott, J. and Yi, F. “Sorbent Based Post-Combustion CO2 Slipstream Testing,” Presented at 2017 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2017. https://netl.doe.gov/sites/default/files/event-
proceedings/2017/co2%20capture/2-Tuesday/J-Elliott-TDA-Post-Combustion-CO2-Slipstream-Testing.pdf.
Elliott, J., “Post-Combustion CO2 Capture with Low Cost Solid Sorbent Slipstream Testing,” Presented at 2016 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2016. https://www.netl.doe.gov/projects/files/J-Elliott-TDA-
Slipstream-Test-of-Sorbent-Based-Capture.pdf.
Elliott, J. and Copeland, B. “Sorbent Based Post-Combustion CO2 Slipstream Testing,” Presented at 2015 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, June 2015. https://netl.doe.gov/sites/default/files/event-
proceedings/2015/co2captureproceedings/J-Elliot-TDA-Sorbent-Slipstream-Testing.pdf.
Elliott, J., et al. “Sorbent Based Post-Combustion CO2 Slipstream Testing,” Presented at 2014 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, July 2014. https://www.netl.doe.gov/projects/files/J-Elliot-TDA-Sorbent-Based-
Post-Combustion-CO2-Slip-Stream.pdf.
Elliott, J., et al. “Sorbent Based Post-Combustion CO2 Slipstream Testing,” Project Kick-Off Meeting Presentation,
Pittsburgh, PA, May 20, 2014. https://www.netl.doe.gov/projects/files/FE0012870-Kickoff-Mtg-05-2014.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
216 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Sorbent Technologies
Lab- and Bench-Scale technology maturity:
Laboratory-Scale, Simulated
Applications for Research and Flue Gas
Development of project focus:
Transformational Carbon
Fluidizable Solid Sorbents
Dioxide Capture
participant:
Research Triangle Institute
project number:
primary project goals
FE0026432
Research Triangle Institute (RTI) is developing novel third-generation fluidizable solid
sorbents for their sorbent-based carbon dioxide (CO2) capture process. Two different types predecessor projects:
of sorbents are being developed, based on hybrid metal organic frameworks (MOFs) and N/A
hybrid phosphorus dendrimers (P-dendrimers), with long-term performance testing of the
most promising sorbents in a fluidized-bed reactor. NETL project manager:
Steven Mascaro
[email protected]
technical goals
principal investigator:
• Design, synthesize, and optimize two novel fluidizable CO2 adsorbents based on hybrid
MOFs and hybrid P-dendrimers. Mustapha Soukri
RTI
• Demonstrate superior performance of these solid sorbents at lab-scale in a packed-bed [email protected]
reactor (PBR).
• Evaluate impact of flue gas contaminants such as sulfur oxides (SOX), nitrogen oxides partners:
(NOX), oxygen (O2), and water (H2O).
N/A
• Scale-up production of selected sorbents in fluidizable form.
• Complete performance testing in lab-scale fluidized-bed reactor. start date:
• Conduct a high-level techno-economic analysis (TEA). 10.01.2015
percent complete:
technical content
100%
RTI is developing novel hybrid fluidizable sorbents for CO2 capture based on hybrid
MOFs and hybrid P-dendrimers. The hybrid MOF-based sorbents are based on
impregnating polyethylenimine (PEI) on an MOF-silica support. For this sorbent, the silica
provides attrition resistance, fluidizability, low cost, and acceptable density. The MOF has
very high surface area and tunable pore sizes. The PEI is a polymer with a repeating amine
unit, providing high amine content, high CO2 affinity, and a relatively low cost. RTI has
developed a new general approach to selectively grow well-dispersed MOF nanocrystals
within mesoporous silica via novel “solid-state” synthesis, which will be used for
preparing the novel MOF hybrid CO2 sorbents. The ability to control and direct the growth
of MOFs on confined surfaces (pores) paves the way for new prospective applications of
such hybrid systems (i.e., CO2 adsorption). As confirmed by a combination of different
characterization techniques, an outstanding high loading of mesoporous cavities (up to 50
wt%) by the smallest MOF crystals yet reported (4.5±1 nm) leads to several improved
properties, including diffusion, attrition resistance, handling, and, particularly for this
project, fluidizability, which can approach, for the first time, MOFs to applications in a
fluidized-bed reactor, in which MOFs have never been proposed.
Figure 1 shows the high MOF loading in the silica using a confocal microscope. Figure 2
shows the full characterization of the resulting hybrid material. Figure 2(a) shows the N2
sorption isotherms at 77K (closed symbols correspond to adsorption branches while open
symbols correspond to desorption branches, 20%MOF: green line, 40%MOF: blue line).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
X-ray diffractograms (Cu Kα radiation) are shown in Figure 2(b). Figure 2(c) shows the pore-size distribution calculated from Barrett-
Joyner-Halenda (BJH) adsorption pore volume versus pore diameter (dV/dD) plot (inset figure: pore diameter [nm] at X-axis and
pore volume [cm3 g-1 nm-1] at Y-axis). Figure 2(d) shows the Fourier transform infrared spectroscopy (FTIR) spectra measured in
attenuated total reflectance (ATR) mode [Reference lines: Pure MOF (black line, the FTIR intensity was divided by 3 for better
comparison), Silica(A) (grey line) and MOF precursors loaded on Silica(A) (dark yellow line)].
Figure 1: MOF loading in silica: (a) transparent amorphous silica; (b) 20% MOF; (c) 40% MOF.
Figure 2: Characterization of the hybrid material: (a) N2 sorption isotherms at 77K; (b) X-ray diffractograms; (c) pore-size distribution; (d) FTIR
spectra measured in ATR mode.
In order to evaluate the utilization of these novel MOF hybrid materials prepared via solid-state synthesis for CO2 capture from post-
combustion flue gas, fluidized MOF/silicon dioxide (SiO2) hybrid sorbents containing different polyamines and selected MOF
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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nanocrystals have been systematically studied. Hybrid sorbents containing a moderate loading of (Zn)ZIF-8 are the most promising
sorbents in terms of CO2 capacity and long-term stability (250 cycles) and were successfully prepared at the kilogram scale. Two
sorbents exhibited excellent stability for 250 cycles under simulated flue gas conditions, as shown in Figure 3.
These hybrid sorbents demonstrated excellent fluidizability and performance under the relevant process conditions in a visible
fluidized-bed reactor.
Dendrimers are repeatedly branched, large spherical molecules. P-dendrimers provide a rigid scaffold, hydrophobic interior, and
well-defined spatial location of the functional groups, along with high thermal stability. An example of a dendrimer structure is shown
in Figure 4. RTI is developing an approach to produce sorbents by covalently grafting amine-functionalized P-dendrimers on solid
supports, such as silica, to improve stability and fluidizability.
Extensive cyclic adsorption/desorption testing was conducted with the best performing P-dendrimer sorbent (1-G0/600PEI) produced
in this study, revealing an average CO2 capacity of 13.1 wt% from simulated flue gas over 350 cycles running for 700 contiguous
hours. A heat of adsorption value of 103 kJ mol-1 was determined from CO2 isotherms, providing evidence for chemisorption binding.
The effect of common contaminants of flue gas (sulfur dioxide [SO2], nitric oxide [NO], and nitrogen dioxide [NO2]) were
investigated with 1-G0/600PEI. The sorbent was significantly impacted by SO2 exposure at low concentrations (50 parts per million
[ppm]), binding the SO2 irreversibly and blocking active amine sites. Like many solid amine sorbents, for 1-G0/600PEI to be utilized
on a practical scale for post-combustion CO2 capture, a desulfurization step would be required. The impact of NOX contaminants,
NO and NO2, was less influential – with only a small decrease over 100 cycles presumably from the binding of NO2 as a nitrite
species. Extensive efforts were made to fluidize the 1-G0/600PEI sorbent so that it could be utilized in a fluidized-bed reactor.
Unfortunately, this material was unable to reach high capacities and attain packed-densities greater than 0.6 g/mL required for
fluidization. Alongside the poor physical properties for fluidization, the material also had much higher costs when projected for
commercial-scale production in comparison to the MOF-based hybrid sorbents.
A PBR is used to screen the novel hybrid sorbents with multi-cycle adsorption-regeneration, measuring CO2 loading and rate along
with contaminant effects. A visual fluidized-bed reactor, shown in Figure 5, is utilized to verify the fluidizability of the sorbents
under realistic process conditions and to test optimal fluidization conditions.
Figure 3: Long-term CO2 adsorption performance stability for
PEI/(Zn)ZIF-8/SiO2 (green) and PEI/(Zn)ZIF-7/SiO2 (dark red)
under simulated flue gas conditions.
Figure 4: Dendrimer structure.
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Post-Combustion Sorbent Technologies
Figure 5: RTI visual fluidized-bed reactor.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 — —
Bulk Density kg/m3 650-750 —
Average Particle Diameter mm 165 —
Particle Void Fraction m3/m3 — —
Packing Density m2/m3 — —
Solid Heat Capacity @ STP kJ/kg-K 1.5 —
Crush Strength kgf 10% —
Manufacturing Cost for Sorbent $/kg 15 —
Adsorption
Pressure bar 1-1.2 —
Temperature °C 60-70 —
Equilibrium Loading g mol CO2/kg 12.5 —
Heat of Adsorption kJ/mol CO2 85-90 —
Desorption
Pressure bar 1.3-1.4 —
Temperature °C 110-120 —
Equilibrium CO2 Loading g mol CO2/kg 0.5-1 —
Heat of Desorption kJ/mol CO2 75-90 —
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost for
new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs at
the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated data.
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Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent. Measured
data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total pressure of the flue
gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of CO2 is roughly 0.132 atm or 0.130
bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization (FGD)
unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – To provide insight regarding the influence that the presence of MOF nanocrystals causes
on the CO2 dynamics of impregnated PEI, the adsorption-desorption profiles for 35 wt% of PEI confined on 4.6 wt% of (Zn)ZIF-
8/SiO2 and bare SiO2 at the tenth cycle are compared in Figure 6. The adsorption breakthrough profile for the MOF-containing solid
sorbent shows a superior CO2 adsorption compared with PEI/SiO2. The characteristic adsorption-regeneration profiles for the PBR
filled with inert silicon carbide SiC4 are represented by the red line, which determines the dead volume of the PBR. However, the
regeneration profile shows an interesting difference in terms of CO2 desorption for the composite incorporating MOF nanocrystals.
Larger concentrations of early release adsorbate are measured for the MOF/SiO2 hybrid sorbent, which is attributed to weakly
adsorbed CO2 via physisorption because the temperature required to release them is lower than 80°C.
PEI/SiO2 also exhibited an early release, but it is mainly attributed to CO2 trapped in the dead volume of the PBR, as suggested by
comparison with the profile for the inert SiC4. In addition, PEI/MOF/SiO2 exhibited higher CO2 desorption between 80 and 100°C,
which suggests slightly better use of the PEI amines for CO2 chemisorption as well. This result highlights the unusual dual adsorption
performance of our hybrid sorbents containing MOF nanocrystals compared with the pure silica counterpart.
Figure 6: Adsorption (left) and regeneration (right) profiles for 35 wt% of PEI/4.6 wt% of (Zn)ZIF-8/SiO2 and 35 wt% of PEI/SiO2.
Sorbent Contaminant Resistance – Fluidized MOF/SiO2 hybrid sorbents have demonstrated good CO2 adsorption capacity under
simulated flue gas conditions, since they exhibit 140% higher CO2 capacity and similar deactivation (ca 10% after 250 cycles) than
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the reference PEI impregnated on bare mesoporous silica. As flue gas from coal-fired power plants typically contains other acid gas
impurities, such as SO2 and NOX, that can dramatically influence the CO2 capture efficiency. The results show a clear deactivation
of the CO2 adsorption capacity of the sorbents under the presence of SO2. This deactivation is due to the irreversible reaction occurring
during the adsorption step between SO2 and PEI amines, which are not further active for the CO2 capture. On the other hand, excellent
stability has been observed under elevated concentration of NOX. Therefore, the presence of MOF nanocrystals within the hybrid
solid sorbent does not reduce the tendency of PEI amines to be deactivated by irreversible binding with SO2, as similar deactivation
has been measured for PEI/SiO2.
Sorbent Attrition and Thermal/Hydrothermal Stability – This work is the first example of CO2 capture from simulated flue gas in a
fluidized-bed configuration using an MOF-based CO2 solid sorbent. The application of MOFs on this configuration have never been
proposed due to the poor attrition, handling, and lack of fluidizability of bulk MOFs. By engineering MOFs within mesoporous silica,
the final sorbent is demonstrating excellent fluidizability, handling, and improved attrition resistance (up to two to three times
compared to SiO2, and six to seven times compared to MOF). Very aggressive regeneration conditions (stream containing 80
volume/volume % H2O balanced with nitrogen [N2] at 100°C for one hour) were used to check the stability of this sorbent; the CO2
adsorption capacity was practically maintained for PEI/MOF/SiO2, whereas a significant drop was observed for the MOF-free
sorbent.
Flue Gas Pretreatment Requirements – An additional unit should be included up-stream for scrubbing the SO2 levels in the flue gas
down to a single-digit ppm level prior to reaching the fluidized-bed reactor to elongate the life of the hybrid solid sorbents and reduce
the makeup rate.
Sorbent Makeup Requirements – Fluidized MOF/SiO2 hybrid sorbents demonstrate an excellent attrition resistance and therefore
significantly reduced the makeup rate.
Waste Streams Generated – Two waste streams could be generated:
• Sorbent attrition fines could be reprocessed and used as sulfur guard-bed.
• Steam condensate from regenerator CO2 capture steam usually has leached PEI. However, water-wash experiments of the sorbent
showed no PEI leaching. This suggests that the condensed water will be easily processed and reused.
Process Design Concept – RTI proposes the use of a multi-stage, fluidized-bed, absorber-regenerator process for the capture and
recovery of CO2. By employing fluidized-bed reactors with heat transfer internals, the process temperature in each stage will be
controlled precisely by removing heat during adsorption and adding heat in the regenerator. Multi-stage reactors are essential in
maximizing sorbent-rich loading in the absorber and lean-loading in the regenerator, thereby maximizing working capacity.
technology advantages
• High theoretical CO2 loading for P-dendrimers.
• MOF/silica fluidized hybrid materials offer several advantages:
o High MOF loading (up to 50%).
o Excellent MOF dispersion and homogeneity.
o Good water and air stability.
o Good chemical and thermal stability.
o Tunable pore size distribution.
o Elevated surface area (up to 900 m2/g) and density (0.65 g/cm3).
o Enhanced attrition resistance.
o Good fluidizability.
• High CO2 capacity (≥12 wt%) and good stability of hybrid MOF-based adsorbents.
R&D challenges
• Reducing sorbent production costs, particularly for the P-dendrimer-based adsorbents.
• Transforming the P-dendrimer-based adsorbents to fluidizable form.
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status
The project was completed on June 30, 2018. RTI has developed a novel technique to grow MOF inside the pores of silica supports.
Testing of the three most promising PEI-impregnated silica-MOF sorbents has shown high (greater than 12%) CO2 capacity with
good MOF dispersion and homogeneity, good water and air stability, good chemical and thermal stability, enhanced attrition
resistance, and excellent fluidizability. The sorbents exhibit better performance and long-term stability in a fluidized configuration.
Production of the hybrid MOF-based sorbent has been scaled from 20-mg to 5-kg scale. Three P-dendrimer sorbents were evaluated
and showed high (greater than 12.0 wt%) CO2 capacities over at least 250 cycles. The project team has down-selected a PEI-
impregnated silica-MOF sorbent, based on performance characteristics and the successful scale-up in a fluidized form to kilogram
quantities, which was then tested in RTI’s lab-scale fluidized moving-bed reactor prototype. This hybrid MOF sorbent was capable
of achieving 90% CO2 capture.
available reports/technical papers/presentations
Soukri, M., et al. “Lab-Scale Development of a Solid Sorbent for CO2 Capture Process for Coal-Fired Power Plants,” presented at
the 2017 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-Thursday/M-Soukri-RTI-Solid-Sorbent.pdf.
Soukri, M., et al. “Lab-Scale Development of a Solid Sorbent for CO2 Capture Process for Coal-Fired Power Plants,” presented at
the 2016 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2016. https://netl.doe.gov/sites/default/files/event-
proceedings/2016/c02%20cap%20review/4-Thursday/M-Soukri-RTI-Lab-scale-Sorbent.pdf.
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Novel Process that Achieves technology maturity:
Laboratory-Scale, Simulated
10 mol/kg Sorbent Swing Flue Gas
Capacity in a Rapidly Cycled project focus:
Pressure Swing Adsorption
Pressure Swing Adsorption
Process with Novel Sorbent
Process participant:
Georgia Tech Research
Corporation
primary project goals
project number:
The Georgia Institute of Technology is developing prototype fiber sorbent modules
FE0026433
containing polymeric fibers embedded with metal organic framework (MOF) for
use in a sub-ambient rapid-cycle pressure swing adsorption (RCPSA) post-
combustion carbon capture process. predecessor projects:
N/A
technical goals NETL project manager:
Sai Gollakota
• Scale-up the MOF sorbent. [email protected]
• Experimentally determine sub-ambient sorption isotherms.
• Spin fibers containing the MOF. principal investigator:
• Construct the RCPSA system and complete testing of fiber sorbent modules Ryan Lively
and fiber sorbent modules with phase-change materials. Georgia Tech Research
• Model and optimize fiber module operation, as well as flue gas conditioning Corporation
[email protected]
optimization.
• Prepare an overall system techno-economic analysis (TEA). partners:
Inmondo Tech, Inc.
technical content
start date:
Georgia Tech Research Corporation is developing a process to achieve 10 10.01.2015
mole/kg sorbent swing capacity using an RCPSA process. The sorbent system
includes novel polymeric fibers embedded at high loadings with MOF materials. percent complete:
An example of the fibers is shown in Figure 1. MOFs are known to have good
100%
carbon dioxide (CO 2 ) capacity and rapid adsorption/desorption kinetics if kept
isothermal. The team is developing a scalable, modular contactor for the sorbents
with high surface area, low pressure drop, and low mass transfer resistance. An
encapsulated, stationary phase-change material is incorporated in the hollow fiber
sorbents (Figure 2) to maintain isothermal adsorption/desorption. This material
has a melting/freezing point equivalent to the system operating temperature. It will
melt as heat is released upon CO 2 adsorption and freeze as CO 2 is desorbed;
therefore, steam and cooling water are not necessary. The system consists of
modules containing the hollow fibers.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Figure 1: MIL-101(Cr)/cellulose acetate fiber sorbents: ~50 wt% MIL-101(Cr); (a) low magnification fiber, (b) Zoomed in sub-structure.
Figure 2: Phase-change material in hollow fiber sorbents.
A simplified schematic of the overall CO 2 capture process is shown in Figure 3. The conditioned flue gas is passed
through a sub-ambient heat exchanger before entering the PSA unit containing the hollow fiber sorbent modules. The
steps of the RCPSA process (pressurization, adsorption, depressurization, desorption) are shown in Figure 4. Sub-
ambient conditions increase adsorption selectivity and working capacity.
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Figure 3: Process flow diagram.
Charging Blow-
Feed Evacuation
down
N2 Product CO2 Product
Recovery Recovery
Figure 4: Pressure swing adsorption process.
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The sorbent and process parameters are shown in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 — —
Bulk Density kg/m3 1,200 1,200
Average Particle Diameter (diameter of fiber) mm 0.8 0.8
Particle Void Fraction (void fraction of the fiber bed) m3/m3 0.4 0.35
Packing Density m2/m3 1,000 2,000
Solid Heat Capacity @ STP kJ/kg-K 1,600 1,600
Crush Strength kg f unknown not specified
Manufacturing Cost for Sorbent $/kg unknown 30
Adsorption
Pressure bar 2 2
Temperature °C -30 -30
Equilibrium Loading
g mol CO 2 /kg 10.2 delta (ads-des) =10
Heat of Desorption kJ/mol CO 2 21.5 < 35
Desorption
Pressure bar 0.3 0.3
Temperature °C -30 -30
Equilibrium CO 2 Loading g mol CO 2 /kg 1.2 Delta (ads-des) =10
Heat of Adsorption kJ/mol CO 2 21.5 < 35
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — fixed fiber/parallel flow/cyclic
Flue Gas Flowrate kg/hr —
PSA CO 2 Recovery, Purity, and Pressure [from PSA]
(from total process) %/%/bar [92/80/1] (90/99.5/60) [92/95/1] (90/99.9/60)
Adsorber Pressure Drop bar 0.1
Estimated Adsorber/Stripper Cost of Manufacturing __$__
and Installation 390-480 (process)
kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO 2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO 2 . Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2%. Therefore, the partial pressure of
CO 2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Physisorption.
Sorbent Contaminant Resistance – High, resistant to humid sulfur dioxide (SO 2 ) at 50 parts per million (ppm).
Sorbent Attrition and Thermal/Hydrothermal Stability – Irreversible sorption of SO 2 and nitrogen dioxide (NO 2 ) with
little effect on CO 2 capacity
Flue Gas Pretreatment Requirements – Pressurization, dehydration, cooling.
Sorbent Makeup Requirements – None.
Waste Streams Generated – Clean (100% RH) nitrogen (N 2 ).
Process Design Concept – Discussed above.
technology advantages
• High working capacity of MOF sorbents.
• High contact area, low pressure drop, and low mass transfer resistance for the modules.
• Sub-ambient conditions increase adsorption selectivity and working capacity.
• The efficiency of the pressure swing cycle is boosted by installing a stationary phase-change material in the fiber
sorbents that will isothermally melt upon release of sorption enthalpy and conversely isothermally freeze upon CO 2
desorption, requiring no steam or cooling water.
• Improved performance in the presence of flue gas contaminants due to physisorption separation mechanism (as
opposed to a chemisorption mechanism).
• Carbon dioxide liquefaction and pumping can be used instead of CO 2 compression.
• Sub-ambient heat exchange and CO 2 liquefaction are commercially demonstrated.
R&D challenges
• Scale up of MOFs.
• Integrating MOF into the fiber to maintain CO 2 capacity.
• Integration of phase-change material into MOF-loaded fibers to maintain near isothermal operation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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• Effective operation of tightly heat- and work-integrated system.
• Monitoring and management of sorbent lifetime over extended operating periods.
status
The project was completed on September 30, 2019. Two MOFs were manufactured in large quantities and subsequently
converted into adsorbent-loaded fiber materials. These were shown to have more than order-of-magnitude reductions in
flue gas pressure drop compared to traditional adsorbent structures. The MOF materials could be composited with glycol-
loaded capsules that would freeze and melt during each sorption-desorption cycle, enabling nearly isothermal operation
of the RCPSA. The sub-ambient RCPSA process was estimated to have competitive operating and capital costs via a
preliminary TEA based on the experimental data and computational modeling at molecular and process levels.
available reports/technical papers/presentations
Lively, R., et al. “Novel Process That Achieves 10 mol/kg Sorbent Swing Capacity in a Rapidly Cycled Pressure Swing
Adsorption Process,” Presented at the Final Project Meeting, Pittsburgh, PA, September 2019.
https://www.netl.doe.gov/projects/files/Final%20project%20presentation%20(FE0026433).pdf.
Lively, R., et al. “Enabling 10 mol/kg Swing Capacity via Heat Integrated Sub-ambient Pressure Swing Adsorption,”
presented at the 2018 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/K-Walton-GIT-10-MOL-per-KG-Swing-Capacity.pdf.
Lively, R., et al. “Enabling 10 mol/kg Swing Capacity via Heat Integrated Sub-ambient Pressure Swing Adsorption,”
presented at the 2017 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/projects/files/R-Lively-GIT-10-MOLKG-Sorbent-Swing-Capacity.pdf.
Lively, R., et al. “Enabling 10 mol/kg Swing Capacity via Heat Integrated Sub-ambient Pressure Swing Adsorption,”
presented at the 2016 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/projects/files/R-Lively-GeorgiaIT-Sub-ambient-Pressure-Swing-Adsorption.pdf.
Lively, R., et al. “Enabling 10 mol/kg Swing Capacity via Heat Integrated Sub-ambient Pressure Swing Adsorption,”
Presented at the Project Kickoff Meeting, Pittsburgh, PA, December 2015.
https://www.netl.doe.gov/projects/files/FE0026433-Kickoff-Meeting.pdf.
Park, J,. et al. “Establishing upper bounds on CO 2 swing capacity in sub-ambient pressure swing adsorption via
molecular simulation of metal–organic frameworks” J. Mater. Chem. A, 2017, 5, 12258-12265
http://pubs.rsc.org/-/content/articlehtml/2017/ta/c7ta02916k.
Park, J., et al. “How Reproducible Are Isotherm Measurements in Metal–Organic Frameworks?” Chem. Mater., 2017,
29, 24, 10487–10495.
DeWitt, SJA, et al. “Development of Phase-Change-Based Thermally Modulated Fiber Sorbents” Ind. Eng. Chem. Res.
2019, 58, 155, 768-5776.
DeWitt, SJA, et al. “Critical Comparison of Structured Contactors for Adsorption-Based Gas Separations” Annu. Rev.
Chem. Biomol. Eng. 2018 Jun 7;9:129-152.
DeWitt, SJA et al. “Incorporation of microencapsulated phase change materials into wet-spin dry jet polymer fibers.”
PCT US18/48110; WO 2019/099086.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Evaluation of Amine- technology maturity:
Laboratory-Scale, Simulated
Incorporated Porous Polymer Flue Gas
Networks as Sorbents for Post- project focus:
Combustion CO2 Capture
Porous Polymer Networks
participant:
Texas A&M University
primary project goals
project number:
Texas A&M University is developing amine-incorporated porous polymer networks
(aPPNs) for use as sorbents for post-combustion carbon dioxide (CO2) capture, FE0026472
including lab-scale, fixed-bed testing of sorbent performance and the scale-up of
sorbent synthesis. predecessor projects:
N/A
technical goals NETL project manager:
Andrew jones
• Complete initial CO2 adsorption testing with multiple aPPN formulations. [email protected]
• Identify synthesis conditions that result in optimal sorbent performance and
cost. principal investigator:
• Produce approximately 200 grams of at least the two top-performing sorbent Hong Cai “joe” Zhou
formulations. Texas A&M
• Determine CO2 working capacity of top-performing sorbent formulation after 30 [email protected]
cycles in automated fixed-bed testing.
• Scale-up to synthesis of at least 1 kilogram (kg) of top-performing aPPN. partners:
• Complete fixed-bed cycling tests with top-performing aPPN in simulated flue framergyTM, Inc.
gas in the presence of moisture and sulfur dioxide (SO2).
start date:
• Perform initial technical and economic feasibility study.
10.01.2015
technical content percent complete:
100%
Porous polymer networks are crosslinked polymers with high surface area, low
density, and high thermal and chemical stability. These properties can be
advantageous for CO2 capture sorbents. The incorporation of amine groups also
provides the capability to fine-tune CO2 selectivity. Texas A&M is developing novel
aPPNs with high CO2 uptake capacities and working capacities. Multiple aPPN
formulations, specifically the PPN-150 and PPN-151 series sorbents, are being
synthesized and tested. Sorbent synthesis parameters, including reaction time,
reaction headspace, solvent systems, and amine loading times and conditions,
are being optimized. The PPN-150 series molecule is shown in Figure 1. The
optimal sorbent, PPN-151 modified with diethylenetriamine (DETA), identified as
PPN-151-DETA, is being scaled-up and CO2 capture performance is being tested
in fixed-bed cycling tests. The chemistry of the PPN-151-DETA synthesis is shown
in Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Figure 1: PPN-150 series.
Figure 2: PPN-151-DETA synthesis chemistry.
technology advantages
• aPPNs have high surface area, extremely low density, and high thermal and chemical stability.
• aPPNs show large increases in CO2 uptake capacities at low pressures and high CO2/nitrogen (N2) selectivity.
R&D challenges
• Reducing the cost of sorbent production.
• Scaling-up sorbent production while maintaining sorbent performance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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status
The project was completed on March 31, 2019. Texas A&M has synthesized and screened multiple aPPN candidates and
demonstrated that their PPN-151-DETA aPPN sorbent can achieve up to 0.2 gram CO2/gram sorbent (g/g) CO2 loading at
the laboratory scale. Sorbent synthesis parameters, including reaction time, reactor headspace, solvent systems, and amine
loading times and conditions, have been optimized. Synthesis of PPN-151-DETA sorbent has been successfully scaled to
a 1-kg batch size. Fixed-bed testing of the sorbent from the 1-kg batch showed greater than 0.12 g/g CO2 loading. The
material performed optimally in the presence of moisture, but SO2 results in material degradation. An initial techno-economic
assessment (TEA) shows a cost of CO2 capture of $47/tonne, based on 3.5% loading from 1 part per million (ppm) SO2
tests.
available reports/technical papers/presentations
Day, G. S.; Drake, H. F.; Joseph, E. A.; Bosch, M.; Tan, K.; Willman, J. A.; Carretier, V.; Perry, Z.; Burtner, W.;
Banerjee, S.; Ozdemir, O. K.; Zhou, H. C., Improving Alkylamine Incorporation in Porous Polymer Networks through
Dopant Incorporation. Advanced Sustainable Systems 2019, 3 (12), 1900051.
Zhou, H. “Evaluation of Amine-Incorporated Porous Polymer Networks (aPPNs) as Sorbents for Post-Combustion CO2
Capture,” presented at the 2018 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/HC-Zhou-TAMU-Amine-Incorporated-Porous-Polymer-Networks.pdf.
Zhou, H. “Evaluation of Amine-Incorporated Porous Polymer Networks (aPPNs) as Sorbents for Post-Combustion CO2
Capture,” presented at the 2017 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/projects/files/H-C-J-Zhou-Texas-A-M-Porous-Polymer-Networks.pdf.
Zhou, H. “Evaluation of Amine-Incorporated Porous Polymer Networks (aPPNs) as Sorbents for Post-Combustion CO2
Capture,” presented at the Budget Period 2 Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/projects/files/FE0026472-BP2-Review-Presentation-08-15-17.pdf.
Zhou, H. and Perry, Z. “Evaluation of Amine-Incorporated Porous Polymer Networks (aPPNs) as Sorbents for Post-
Combustion CO2 Capture,” presented at the 2016 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/projects/files/J-Zhou-TAMU-Amine-Incorporated-Porous-Polymer-Networks.pdf.
Zhou, H. “Evaluation of Amine-Incorporated Porous Polymer Networks (aPPNs) as Sorbents for Post-Combustion CO2
Capture,” presented at the Project Kickoff Meeting, Pittsburgh, PA, December 2015.
https://www.netl.doe.gov/projects/files/FE0026472-Kick-off-Presentation.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
232 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Process for CO2 Capture from technology maturity:
Laboratory-Scale, Simulated
Low-Concentration Sources Flue Gas
project focus:
primary project goals Structured Sorbent-Based
Process for Low-
InnoSepra, LLC is developing a low-cost capture process using structured sorbents Concentration Sources
to remove carbon dioxide (CO2) from low-concentration feed streams. This project
is based on utilizing physical sorbents in structured form for concentrating CO2 participant:
from low-concentration coal-based sources. The process utilizes a moisture- InnoSepra, LLC
removal stage (if needed) and a CO2-enrichment stage. The enriched CO2 stream
can then be combined with the feed stream of a post-combustion capture process, project number:
ultimately allowing cost-effective capture of 98 to 99% CO2 from a coal-based SC0015114
power plant.
predecessor projects:
N/A
technical goals
NETL project manager:
• Fabricate adsorption test modules for CO2 and moisture adsorption. David Lang
• Complete semi-bench-scale testing for moisture removal. [email protected]
• Complete lab- and semi-bench-scale testing for CO2 adsorption.
principal investigator:
• Perform an engineering design for CO2 enrichment of the residue stream for a
Ravi jain
550-megawatt-electric (MWe) power plant.
InnoSepra, LLC
• Prepare a techno-economic analysis (TEA) for a 1 million standard cubic feet [email protected]
per minute (scfm) feed plant.
partners:
N/A
technical content
start date:
InnoSepra developed a process, as shown in the schematic in Figure 1, using
02.22.2016
structured sorbents to capture CO2 from low-concentration sources, which
minimizes the pressure drop for the very high flows associated with the low- percent complete:
concentration sources. For a dry residue stream, a single-stage process is utilized
100%
to remove CO2 with the structured sorbents. To treat a wet residue stream, a two-
stage process is employed. Moisture is removed in the first stage in a rapid cycle
adsorption process. The CO2 adsorption occurs in the second stage, using the
structured sorbents in an adsorption process. This stage produces a CO2-enriched
stream containing 10 to 15% CO2 after regeneration, which can be fed to a new or
an existing post-combustion CO2 capture system. The structured sorbents used in
this process have very high capacities at low-CO2 concentrations and can be
regenerated to produce the CO2-enriched stream, achieving a CO2 enrichment by
a factor of five to 10.
Phase I focused on lab-scale evaluation of prototype adsorbents using low-CO2
concentration simulated feed gas. Phase II included fabrication of test modules
and evaluation of the structured sorbents for moisture removal and CO2
adsorption capacity. Test unit modules were evaluated in two different
configurations: a rotating-bed configuration and a fixed-bed configuration.
Testing results inform parameters needed for an engineering design of a full-scale
plant and for a TEA.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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233
Post-Combustion Sorbent Technologies
Figure 1: InnoSepra capture process.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,500 1,500
Bulk Density kg/m3 500 500
Average Particle Diameter mm N/A N/A
Particle Void Fraction m3/m3 0.45-0.50 0.45-0.50
Packing Density m2/m3 1.3 e8 1.3e8
Solid Heat Capacity @ STP kJ/kg-K 0.90 0.90
Crush Strength kgf N/A N/A
Manufacturing Cost for Sorbent $/kg 8.0 6.0-8.0
Adsorption
Pressure bar 1.05 1.02-1.03
Temperature °C 25-35 25-35
Equilibrium Loading g mol CO2/kg 2.5 2.5
Heat of Adsorption kJ/mol CO2 35 35
Desorption
Pressure bar 0.97 0.98
Temperature °C 100 100
Equilibrium CO2 Loading g mol CO2/kg 1.0 1.0
Heat of Desorption kJ/mol CO2 42 40
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — —
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure % / % / bar 90 10-15% 1.0
Adsorber Pressure Drop bar 0.03
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
234 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Estimated Adsorber/Stripper Cost of __$__
300
Manufacturing and Installation kg/hr
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The adsorption is physical sorption based on weak van der Waals forces. This
leads to low heats of adsorption.
Sorbent Contaminant Resistance – Under normal operation, the sorbent is not irreversibly damaged by any contaminant
in the flue gas. The residue gas is likely to have little or no contaminants.
Sorbent Attrition and Thermal/Hydrothermal Stability – In the structured form, the sorbent attrition is minimal. If
moisture should break through onto the CO2 sorbent, the sorbent can be regenerated completely. The adsorbent is
thermally stable at temperatures of more than 300°C.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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235
Post-Combustion Sorbent Technologies
Flue Gas Pretreatment Requirements – No special flue gas pretreatment is required. A conventional FGD and a direct
contact cooler (DCC) are sufficient for normal process operation.
Sorbent Makeup Requirements – Based on prior experience with similar sorbents in similar operating environments, the
adsorbent life would be between five and 10 years. An adsorbent life of five years has been assumed to estimate the
makeup requirements.
Waste Streams Generated – N/A.
Process Design Concept – Flowsheet/block flow diagram, if not included above.
Proposed Module Design – Except for the sorbents loaded with flue gas components, no other waste streams are
generated in the process. These can be disposed of as per current power plant practices for materials loaded with sulfur
oxide (SOX) and mercury (Hg).
technology advantages
The structured sorbents have:
• A very high surface area-to-volume ratio and a lower heat requirement for regeneration compared to amine-based
absorption using structured packing.
• Are not subject to fluidization constraints or attrition concerns.
• Very low pressure drops, typically 1/5 to 1/10th of particulate adsorbents.
• Very small effective particle size (less than 80 μm) that provides very short mass transfer zones.
• Ability to process significantly higher flows for a given bed volume compared to particulate adsorbents, which is
particularly beneficial for low-concentration source CO2 capture where flow rates can be much higher.
• Able to be fabricated using virtually any commercially available adsorbent.
R&D challenges
• Assuring sufficient moisture removal to enable significantly higher CO2 capacity for the sorbent in the CO2 adsorption
stage.
• Validating the process model with test results.
status
This project was completed on April 9, 2019. InnoSepra completed sorption isotherms at low-CO2 concentrations (0.5 to
2.0 wt% CO2). Breakthrough capacities of 5.0 to 8.5 wt% at 25°C and 4.0 to 7.0 wt% at 35°C, along with cyclic CO2 capacities
of greater than 90% of the breakthrough capacities, were achieved. Carbon dioxide enrichment by a factor five to 10 was
achieved depending on the feed CO2 concentration, regeneration temperature, and cycle time. Moisture-removal testing
was completed in both fixed-bed and rotating-bed test units, with better performance and more process flexibility noted
in the fixed-bed units. The CO2 enrichment cost depends on the moisture content of the residue stream. If the residue
stream is moisture-saturated (such as that from an amine-based capture process), the enrichment cost is about $55/ton.
If the residue stream is nearly dry (such as that from InnoSepra’s adsorption-based post-combustion CO2 capture process),
the enrichment cost is about $37/ton. The original project milestones, both in terms of process performance and the CO2
capture cost, were exceeded during the execution of this project. The current CO2 enrichment costs of $37 to $55/ton are
significantly better than a cost of $350/ton for the amine-based process for low-concentration streams. If the enriched
CO2 stream is mixed with the feed to a post-combustion CO2 capture process, cost-effective capture of 98 to 99% of CO2
is possible.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
236 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
available reports/technical papers/presentations
Jain, R. “Process for CO2 Capture from Low Concentration Streams,” Presented at the 2018 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/R-Jain-InnoSepra-Low-
Concentration-Capture.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
237
Post-Combustion Sorbent Technologies
High-Efficiency Post technology maturity
Bench-Scale, Actual Flue
Combustion Carbon Capture Gas
System project focus:
Metal Organic Framework
Nanosorbent
primary project goals
participant:
Precision Combustion, Inc. (PCI) is developing a compact, modular post- Precision Combustion, Inc.
combustion carbon capture system using high-capacity metal organic framework
(MOF) nanosorbents supported on a tailorable mesh substrate. This system project number:
enables low-pressure drop, high volumetric utilization, and high mass transfer SC0017221
rates, and is suitable for the rapid heat transfer and low temperature regeneration
operating modes needed for cost-effective carbon capture predecessor projects:
N/A
technical goals
NETL project manager:
Andrew O’Palko
• Optimize the sorbent to higher capacities with good selectivity towards carbon
[email protected]
dioxide (CO2), as well as resistance to humidity and contaminants.
• Optimize mesh geometry and coating process to achieve higher loadings principal investigator:
without affecting sorbent structure at increased production capacity. Codruta Loebick
• Simulate a scaled-up plant design with steady and dynamic process and Precision Combustion, Inc.
computational fluid dynamics (CFD) modeling of the system. cloebick@precision-
combustion.com
• Assemble small-scale module and test with actual coal-derived flue gas to show
the efficacy of the system and further refine the operating conditions. partners:
• Integrate with U.S. Department of Energy (DOE) Carbon Capture Simulation Boston University, BASF
Initiative (CCSI) software.
• Perform full-scale techno-economic modelling of CO2 capture with sensitivity start date:
analysis. 02.21.2017
percent complete:
technical content 70%
PCI is developing a post-combustion carbon capture system using high-capacity
MOF nanosorbents coated on PCI’s patented Microlith® mesh sorbent substrate.
MOF materials are crystalline organic-inorganic compounds formed by
coordination of metal clusters or ions with organic linkers – usually bivalent or
trivalent aromatic carboxylic acids or nitrogen-containing aromatics. They have
extremely high surface area, high pore volume, uniform size pores, and high metal
content, making them excellent candidates for selective CO2 capture. The modular
cartridge form factor enables low-cost retrofit to existing systems. For the high
space velocity sorbent structure, PCI has developed and patented a short contact
time mesh-based substrate, trademarked Microlith® coated with the densified
nanostructured sorbent. The combination enables higher surface area per unit
volume and decreased bed volume with equivalent effectiveness to other types of
monolithic or loose packing, without pressure drop penalty. Additionally, up to 20
times higher mass and heat transfer coefficients are obtainable as compared to
other sorbent systems such as monoliths and pellets, due primarily to boundary
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
238 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
layer minimization and break-up, boosting CO2 removal rates with greater sorbent bed utilization and less bypass inherent
to packed beds or monoliths. This sorbent manufacturing technology allows for adherent and durable MOF coatings (as
well as alternative future high surface area sorbents) on the Microlith® substrate. Sorbent coated on Microlith® mesh is
shown in Figure 1.
The process as shown in Figure 2 includes a modular capture system containing the MOF nanosorbents coated on
Microlith®, with adsorption at 30°C and desorption at 80°C. This capture system configuration enables low-pressure drop,
high volumetric utilization, and high mass transfer, and also has a low energy of regeneration.
During Phase II PCI:
• Selected the currently best capacity commercial large-scale intent MOF and further tested it under realistic conditions
and developed means for improving its stability.
• Developed means for deploying the MOF at large scale by coating it on PCI’s low-pressure drop Microlith® support
and matured the operational map of the post-combustion carbon capture system unit in thermal swing adsorption (at
30ºC) and desorption (at 80ºC) to bring energy expense to 255 kWh/tonne of CO2 recovered at the end of the Phase
and utilization of materials with lower heat capacity. In comparison, a monoethanolamine (MEA) system requires more
than 1,100 kWh/tonne due to steam injection.
• Developed a techno-economic analysis (TEA) showing that the system can achieve the $30/tonne of CO2 captured
target (including compression), with $35.8/tonne projected at Phase II performance and further cost savings expected
from reduction of balance of plant components and increased efficiency to under the $30/tonne target (Phase II A
target – $26/tonne – including compression).
• Developed CFD models of pilot-scale units – to be integrated with CFD package of the CCSI software.
• Assembled a small-scale MOF – Microlith® unit to be deployed at the National Carbon Capture Center (NCCC) for
initial testing with live flue gas for model and economics validation.
Figure 1: Microlith® mesh coated with sorbent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
239
Post-Combustion Sorbent Technologies
Figure 2: Process block diagram.
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Physical Sorption with selectivity for CO2 over 95%.
Sorbent Contaminant Resistance – 200-hour test with 200 parts per million (ppm) sulfur dioxide (SO2) showed no major
effects
Sorbent Attrition and Thermal/Hydrothermal Stability – Excellent attrition resistance because the sorbent is
immobilized on mesh, good thermal resistance up to 200 to250ºC, tolerant to some humidity (still under development).
Flue Gas Pretreatment Requirements – Condensation of some of the water with heat recovery.
Sorbent Makeup Requirements – None. Cartridge replacement of the mesh coated with sorbent to be performed at
sorbent lifetime end.
Waste Streams Generated – None.
Process Design Concept – Flowsheet/block flow diagram, if not included above – see above.
Proposed Module Design – Sorbent bed consists of coiled layers of Microlith® meshes coated with sorbents; ability to
coat different sections of mesh with different sorbents for one-step removal of CO2 and other contaminants.
Figure 3: Sorbent bed.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
240 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 4: CFD model of post-combustion carbon capture system unit (Microlith® media), GHSV – 160,000 h-1.
Pressure drop as a function of flue gas flow velocity
0.04
0.03
DP, psi
0.02
0.01
0
0 50000 100000 150000
Gas Hourly Space Velocity, h-1
Figure 5: Pressure drop versus gas flow velocity.
technology advantages
• The MOF materials have a lower regeneration energy and a lower degradation rate due to their physical adsorption
capture mechanism as opposed to chemical reaction.
o Greatly reduces boundary layer formation, with reduced pressure drop for similarly performing post-combustion
carbon capture systems (pellets or monoliths based), resulting in process intensification with corresponding
reduction in post-combustion carbon capture system volume.
o Increased mass and heat transfer coefficients and enhanced diffusion of gas in the sorbent.
o Immobilizing the sorbent increases its lifetime by reducing attrition.
o Modular design flexibility (e.g., planar, radial); easily scalable.
• PCI’s Microlith® mesh substrate supporting the MOF material has higher surface area per unit volume and much
higher mass and heat transfer coefficients, as well as low-pressure drop compared to other monolith substrates or
pellets, resulting in increased CO2 capture rate and reduced regeneration energy.
R&D challenges
• Maintaining higher CO2 loadings without affecting sorbent structure at increased production capacity.
• Identifying optimal sorbent to maximize capacity and selectivity.
• Achieving acceptable sorbent cost at large-scale production.
• Optimizing the material for long-term (thousands of cycles) operation in flue gas environment.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
241
Post-Combustion Sorbent Technologies
status
In Phase II, PCI demonstrated the Microlith®-based approach to carbon capture via adsorption on MOF materials. The
sorbent was stable over multiple thermal cycles and showed stability to contaminants and some humidity, as well as high
selectivity for CO2 over other components of the flue gas. The system was demonstrated to have energy-saving
performance due to enhanced sorption properties, heat and mass transfer and low-pressure drop. A TEA shows potential
for achieving the DOE goal of $30/tonne of CO2 captured.
available reports/technical papers/presentations
Loebick, C., et al., “High-Efficiency Post Combustion Carbon Capture System,” Presented at the Phase II Project Review
Meeting, Pittsburgh, PA, November 2018. https://www.netl.doe.gov/projects/files/High-
Efficiency%20Post%20Combustion%20Carbon%20Capture%20System%20Nov%202018.pdf.
Loebick, C. and Weisman, J., “High-Efficiency Post Combustion Carbon Capture System,” Presented at the Phase I
Project Review Meeting, Pittsburgh, PA, December 2017. https://www.netl.doe.gov/projects/files/High-
Efficiency%20Post%20Combustion%20Carbon%20Capture%20System%20Dec%202017.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
242 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Amine-Appended Metal- technology maturity
Bench-Scale, Simulated and
Organic Frameworks as Actual Flue Gas
Switch-Like Adsorbents for project focus:
Energy-Efficient Carbon
Amine-Appended Metal-
Organic Framework Sorbent
Capture participant:
Lawrence Berkeley National
Laboratory
primary project goals
project number:
Lawrence Berkeley National Laboratory (LBNL), as part of the Discovery of
FwP-FP00006194
Carbon Capture Substances and Systems (DOCCSS) Initiative, is developing
amine-appended metal-organic framework (MOF) sorbents having step-change
adsorption isotherms with larger sorbent working capacities with minor predecessor projects:
temperature swings for low-energy post-combustion carbon dioxide (CO2) N/A
capture.
NETL project manager:
technical goals Andrew jones
[email protected]
• Identify, synthesize, and characterize amine-MOF pairs using existing and new
principal investigator:
computationally designed MOF and amine structures.
jeffrey Neaton
• Test the synthesized sorbent materials using simulated flue gas to determine
LBNL
CO2 adsorption and desorption kinetics, tolerance to impurities, and cycling
[email protected]
performance.
• Identify the most promising sorbents with realistic potential for implementation partners:
in carbon capture.
Mosaic Materials, Svante,
• Field test the MOF sorbent using actual coal-derived flue gas. Electricore
technical content start date:
08.31.2017
LBNL is combining computational and experimental programs to synthesize and
characterize amine-appended MOF sorbents for energy-efficient carbon capture. percent complete:
An example of the structure of an MOF with appended amines is shown in Figure 55%
1. These MOF materials show switch-like CO2 adsorption behavior and can be
tuned to optimize working capacities under mild regeneration conditions. They
exhibit step-change isotherms enabled by a cooperative CO2 adsorption
mechanism, as shown in Figure 2. This step-change isotherm allows for larger
sorbent working capacities with minor temperature swings, as opposed to the
large temperature swings required by traditional amine-based sorbents. The step-
change isotherm shows very little hysteresis upon desorption of CO2, and the step
shifts rapidly to higher pressure with increasing temperature. Balancing CO2
capture performance and cost is done through vigorous optimization efforts of the
amine molecules and pore geometries, combining computational modeling,
characterization of molecules, and experiments to evaluate CO2 capture
performance.
Diamine-appended MOFs are being identified and synthesized, targeting
materials showing step-change or switch-like reversible CO2 adsorption
isotherms. Computational modeling is used to identify promising amine-MOF
pairs. The computational analysis and measurements of CO2 adsorption behavior
provide insight to identify second-generation materials with desired properties.
The research team will identify, synthesize, and characterize amine-MOF pairs
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
243
Post-Combustion Sorbent Technologies
using existing and new computationally designed MOF and amine structures. The synthesized sorbent materials will be
tested using simulated flue gas to determine CO2 adsorption and desorption kinetics, tolerance to flue gas impurities, and
cycling performance, as well as to identify the most promising sorbents with realistic potential for industrial implementation
in carbon capture.
Figure 1: Example of an MOF with appended amines.
Figure 2: Cooperative CO2 adsorption.
The project is part of DOCCSS, a partnership coupling unique skillsets of national laboratories, industry, and academic
institutions to work collaboratively to facilitate discovery, synthesis, performance assessment, and functionalization of
new carbon capture materials, and to accelerate the rate at which transformational processes for carbon capture are
commercialized. This project includes a combined effort among several entities. LBNL is responsible for materials
discovery, synthesis, and characterization. Mosaic Materials is developing materials production protocols and scale-up
research and development. Sorbent production scale-up and optimization efforts include evaluating four distinct steps:
synthesis of the MOF, purification of the MOF to remove impurities, amination where the purified MOF is impregnated
with amines, and activation where the solvent is removed. Svante and Electricore are integrating the diamine-appended
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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244 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
MOFs in a cost-effective CO2 capture system through system development efforts. Svante will perform testing of the
sorbent in powder form and in a structured-bed form in their capture test units to confirm performance.
The overall effort will test first-generation (Gen1) materials, continue to develop and synthesize improved diamine-
appended MOF (Gen2) materials, and evaluate long-term stability, impurity effects, and alternate regeneration strategies
to recover greater CO2 capacity, culminating in field testing using actual coal-derived flue gas.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,560 1,560
Bulk Density kg/m3 300 300
Average Particle Diameter mm N/A N/A
Particle Void Fraction m3/m3 N/A N/A
Packing Density m2/m3 N/A N/A
Solid Heat Capacity @ STP kJ/kg-K 1.46 1.46
Crush Strength kgf N/A N/A
Manufacturing Cost for Sorbent $/kg 4,586 3,033
Adsorption
Pressure bar 0.13 0.13
Temperature °C 50 50
Equilibrium Loading g mol CO2/kg 2.5 2.5
Heat of Adsorption kJ/mol CO2 74 74
Desorption
Pressure bar 1 1
Temperature °C 110 110
Equilibrium CO2 Loading g mol CO2/kg 0.1 0.1
Heat of Desorption kJ/mol CO2 74 74
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — Fixed structured beds with rapid cycling
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure % / % / bar 90 90 1
Adsorber Pressure Drop bar 0.08
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – See above.
Sorbent Contaminant Resistance – Flue gas pre-conditioning required in some applications to limit sulfur oxide (SOX)
and nitrogen oxide (NOX) in contact with adsorbent material.
Sorbent Attrition and Thermal/Hydrothermal Stability – Thermal stability of the sorbent has been demonstrated for
the operating temperature range of the process. Hydrothermal stability for the Gen1 material is insufficient due to water-
amine-MOF interactions. Gen2 material development or a change in Gen1 material formulation are being evaluated to
minimize the impact of steam on the composite material.
Flue Gas Pretreatment Requirements – To be determined. Initial pilot test on simulated flue gas without SOX and NOX
supplemented by lab-scale tests and modeling of SOX/NOX interaction with the sorbent.
Sorbent Makeup Requirements – No makeup, structured sorbent modules do not allow for in-process addition of
adsorbent material.
Waste Streams Generated – Condensate water from flue gas pre-conditioning unit with flue gas particulates, solid waste
from discarded sorbent modules every two to five years. No makeup liquid amine solution to discard greatly reduces
waste streams for solid sorbents compared to liquid amine sorbent technology.
Process Design Concept – Multi-bed structured solid sorbent assembled on rotary contactor for rapid adsorption-
desorption cycle. Cycle times are between one to two minutes using rapid thermal swing.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
246 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 3: Rotary adsorbent machine.
Proposed Module Design – Modules are built to define parallel passageways, enabling large contact area between the
solid and the gas while minimizing flow resistance and maximizing volumetric loading of adsorbing material. Modules are
typically meter-scale in flow direction, with channels in the millimeter scale.
technology advantages
• Amine-appended framework materials are highly tunable.
• Sorbent has large working capacity due to step-shaped CO2 adsorption.
• Sorbent has high CO2 selectivity over nitrogen, oxygen, and water.
R&D challenges
• Large-scale and economic production of materials.
• Durability and chemical stability of these MOFs under actual flue gas.
• Reducing the regeneration cost in temperature swing.
status
LBNL has identified and synthesized a Gen1 material with a 2.4 mmol CO2/gram working capacity with a 60°C
temperature swing. Mosaic Materials successfully synthesized 1 kilogram of Gen1 material that met CO2 performance
metrics and was delivered for testing at the Svante test unit.
A screening database has been established to discover new MOFs with similar open metal site distance distributions to
the Gen1 material, with three candidate materials of interest identified with potential for greater than 3.0 mmol/gram CO2
uptake. One of these Gen2 materials showed a 3.6 mmol/gram working capacity with a 45°C temperature swing and an
approximate regeneration energy of 2.2 MJ/kg CO2. This Gen2 material was stable over 1,000 humid
adsorption/desorption cycles under simulated coal flue gas conditions.
available reports/technical papers/presentations
Long, J., Neaton, J., and Haranczyk, M. “Amine-Appended Metal-Organic Frameworks as Switch-Like Adsorbents for
Energy-Efficient Carbon Capture,” Presented at 2019 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August
2019. https://netl.doe.gov/sites/default/files/netl-file/J-Long-LBNL-Amine-Appended-MOF.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
247
Post-Combustion Sorbent Technologies
Long, J., Neaton, J., and Haranczyk, M. “Amine-Appended Metal-Organic Frameworks as Switch-Like Adsorbents for
Energy-Efficient Carbon Capture,” Presented at the Project Review Meeting, Pittsburgh, PA, August 2019.
https://www.netl.doe.gov/projects/files/2019%20LBL%20DOCCSS%20Project%20Review%20Meeting_08-01-19.pdf.
Long, J., Neaton, J., and Haranczyk, M. “Amine-Appended Metal-Organic Frameworks as Switch-Like Adsorbents for
Energy-Efficient Carbon Capture,” Presented at 2018 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August
2018. https://www.netl.doe.gov/projects/files/J-Long-LBNL-Amine-Appended-MOFs.pdf.
Long, J., Neaton, J., and Haranczyk, M. “Amine-Appended Metal-Organic Frameworks as Switch-Like Adsorbents for
Energy-Efficient Carbon Capture,” Presented at 2017 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August
2017. https://www.netl.doe.gov/projects/files/J-Long-LBNL-Metal-Organic-Frameworks.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
248 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
A New Sorbent Process for technology maturity
Bench-Scale, Simulated Flue
Transformational Carbon Gas
Capture Process project focus:
Amine-Functionalized Resin
Sorbent
primary project goals
participant:
TDA Research (TDA) is developing amine-functionalized resin sorbents to TDA Research, Inc.
selectively remove carbon dioxide (CO2) from flue gas using a vacuum swing
adsorption (VSA) cycle. Activities include identification of polymers that can be
project number:
formed with amine functionalities tuned for CO2 uptake, scaling-up sorbent
production, and testing performance at the bench-scale. SC0018682
predecessor projects:
technical goals N/A
• Optimize the sorbent formulations to achieve higher CO2 capacity and uptake NETL project manager:
rates and evaluate use of co-polymers to increase the processability of the
David Lang
materials into structures easily integrated into modules.
[email protected]
• Screen polymers and structures in bench-scale testing and prepare test
modules using the best identified polymers. principal investigator:
• Test the modules in the TDA test apparatus using the VSA cycle and optimize Gökhan Alptekin
operating conditions and cycle sequence. TDA Research, Inc.
• Complete a minimum of 20,000 adsorption/desorption cycles in presence of [email protected]
flue gas contaminants.
• Design a CO2 capture process around this new material. partners:
• Assess the techno-economic viability of the process. Membrane Technology and
Research, Inc.
technical content start date:
07.02.2018
TDA is developing a sorbent based on amine-functionalized resin structures for
the capture of CO2 from coal-fired power plants. In Phase I, TDA modified percent complete:
commercial polymeric resins with amines and tuned them for CO2 uptake. In-
house polymers were also prepared with amine functionalities and showed 30%
higher CO2 loading than the commercial resins, along with high selectivity and
kinetics. The presence of moisture enhanced the CO2 loading. Furthermore, the
TDA resins provide the flexibility to be used as coatings on engineered
structures, which can reduce pressure drop and allow for the treatment of high
volumes of flue gas. The sorbent regeneration occurs using a VSA cycle, and
the mild vacuum conditions required results in lower regeneration energy.
In Phase II, TDA is optimizing the sorbent formulations for improved CO2
capacity and processability to form engineered structures capable of integration
into modules. Polymer scale-up will occur in a 50-gallon reactor system.
Polymers will be shaped into various forms, including pellets, extruded
honeycomb structures, and polymer films via spin coating. Working with partner
Membrane Technology and Research (MTR), polymer beads will be processed
into thin sheets, which will then be made into spiral-wound and planar modules.
Examples are shown in Figure 1.
Sorbent will be evaluated as loose granules and as modules in TDA’s existing
VSA prototype test system (shown in Figure 2), which can treat 5 standard cubic
feet per minute (scfm) of flue gas and remove up to 2.5 kilogram (kg)/hour of
CO2. Testing includes optimization of the process and the VSA cycle sequence,
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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249
Post-Combustion Sorbent Technologies
as well as long-term tests in the presence of contaminants. Testing results will inform the design of a CO2 capture
process around this new polymer-based adsorbent material.
Figure 1: Example of preparation of spiral-wound modules (left) and of MTR’s polymer membrane modules (right).
Figure 2: TDA’s four-bed VSA system.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 600 600
Bulk Density kg/m3 300 300
Average Particle Diameter mm N/A N/A
Particle Void Fraction m3/m3 <0.1 <0.1
Packing Density m2/m3 500 500
Solid Heat Capacity @ STP kJ/kg-K 2.0 2.0
Crush Strength kgf N/A N/A
Manufacturing Cost for Sorbent $/kg <20 <5
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
250 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Adsorption
Pressure bar 1.1 1.1
Temperature °C 60 60
Equilibrium Loading g mol CO2/kg 0.72 0.8
Heat of Adsorption kJ/mol CO2 <50 <50
Desorption
Pressure bar 0.2 0.2
Temperature °C 60 60
Equilibrium CO2 Loading g mol CO2/kg 0.04 0.04
Heat of Desorption kJ/mol CO2 <50 <50
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — Countercurrent
Flue Gas Flowrate kg/hr TBD
CO2 Recovery, Purity, and Pressure % / % / bar 90% 95% 150
Adsorber Pressure Drop bar 0.15
Estimated Adsorber/Stripper Cost of __$__
TBD
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which
typically occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure
(corresponding to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are
preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which
typically occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper
are process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total
pressure; if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power
plant, the total pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the
partial pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in
either continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
251
Post-Combustion Sorbent Technologies
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Amine-functionalized proprietary polymer.
Sorbent Contaminant Resistance – Sulfur oxide (SOX) and nitrogen oxide (NOX) tolerant up to 100 parts per million
(ppm).
Sorbent Attrition and Thermal/Hydrothermal Stability – N/A.
Flue Gas Pretreatment Requirements – None.
Sorbent Makeup Requirements – Five-year replacements.
Waste Streams Generated – None.
Proposed Module Design – Plate and frame or spiral-wound.
technology advantages
• Structured sorbents have potential for high CO2 uptake with low pressure drop while treating high volumes of gas.
• Use of sorbents in a structured form instead of pellets favors use of a modular design.
• Reduced regeneration energy through a regeneration process using mild vacuum.
R&D challenges
• Preparation of the functionalized resin sorbent in engineered structures.
• Life cycle of sorbents in operational conditions with flue gas contaminants.
• Economic viability in large power plant applications due to the volume of sorbent required and cost of ancillary
equipment (ductwork distribution system, vacuum pumps, etc.).
status
In Phase I, TDA Research has identified new polymers that can be formed into desirable structures (monoliths or
planar contactors) with amine functionalities tuned for high CO2 uptake and selectivity. Carbon dioxide capture cost was
estimated to be $29.7/tonne, excluding transportation, storage, and monitoring (T&SM).
available reports/technical papers/presentations
Alptekin, G. and Jayaraman, A., “A New Sorbent Process for Transformational Carbon Capture Process,” Presented at
the Phase I Final Briefing/Phase II Kickoff Meeting, Pittsburgh, PA, August 2019.
https://www.netl.doe.gov/projects/files/Phase%20II_Project_Kickoff_DE-SC0018682_082119_NonConfidential.pdf.
Alptekin, G, et al., “A New Sorbent Process for Transformational Carbon Capture Process,” Presented at the Phase I
Project Kickoff Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/A%20New%20Sorbent%20Process%20for%20Transformational%20Carbon%20
Capture%20Process.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
252 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Membrane-Sorbent Hybrid technology maturity
System for Post-Combustion
Pilot-Scale, Actual Flue Gas
Slipstream (1.0 MWe)
Carbon Capture project focus:
Membrane-Sorbent Hybrid
System
primary project goals
participant:
TDA Research, Inc. (TDA) is designing and constructing a 1.0 megawatt-electric TDA Research, Inc.
(MWe)-scale membrane-sorbent hybrid post-combustion carbon capture system
and evaluating its operation in a long-duration field test using industrial flue gas
project number:
that closely resembles coal-fired flue gas. Their hybrid process consists of a
polymeric membrane and low-temperature physical adsorbent to remove carbon FE0031603
dioxide (CO2) from flue gas.
predecessor projects:
SC0011885
technical goals
NETL project manager:
• Design the 1-MWe-scale test unit.
Andrew O’Palko
• Fabricate the test unit. [email protected]
• Install the test unit at the Technology Centre Mongstad (TCM).
• Complete a 9- to 12-month-long field test campaign at TCM using actual flue principal investigator:
gas. Gokhan Alptekin
• Complete an updated techno-economic analysis (TEA) based on the field test TDA Research, Inc.
data. [email protected]
partners:
technical content Membrane Technology and
Research, Technology
TDA Research is designing, constructing, and operating a slipstream 1.0-MWe Centre Mongstad, Gas
pilot-scale process for post-combustion CO2 capture using actual flue gas. The Technology Institute,
hybrid process consists of a polymeric membrane and a low-temperature University of California Irvine
physical adsorbent. This technology is based on TDA’s previously developed
sorbent and a membrane developed by Membrane Technology and Research start date:
(MTR). TDA’s sorbent uses a mesoporous carbon modified with surface
functional groups to remove CO2 via physical adsorption. Carbon dioxide-surface 08.15.2018
interaction is strong enough to allow low partial pressure operation and
regeneration energy is low because the CO2 is not bonded to the sorbent. The percent complete:
feasibility of the hybrid sorbent-membrane system was initially proven in a prior 40%
U.S. Department of Energy (DOE)-funded project (DE-SC0011885) using coal-
derived flue gas at 4-kilowatt-electric (kWe) scale, showing greater than 90%
CO2 capture and high purity.
An overall schematic of TDA Research’s system is shown in Figure 1, consisting
of two primary components: (1) the membrane unit and (2) the CO2 adsorption
unit. The membrane operates at approximately 50°C under mild vacuum,
removing approximately 50% of the CO2 and nearly all of the water. The reduced
vacuum pump requirements reduce power consumption and system cost. The
sorbent removes the remaining CO2 from the membrane effluent to ensure 90%
carbon capture. Sorbent regeneration is facilitated using boiler feed air as a
sweep gas and the CO2-laden air after sorbent regeneration is fed to the boiler to
generate a CO2-rich flue gas stream to increase the driving force across the
membrane. The overall energy intake of the CO2 capture process is reduced by
using a hybrid membrane-sorbent configuration, while the capture efficiency is
not degraded.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 253
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 1: Flow diagram of the TDA Research hybrid membrane-sorbent CO2 capture system.
TDA is developing its modular sorbent bed concept known as the radial outflow reactor, shown in Figure 2. Two
modules would be used, one operating in adsorption and one in desorption, to provide continuous transfer of CO2 into
the boiler air. For the 1-MWe-scale tests at TCM, three modules are to be used, as shown in Figure 3, with two of the
modules operating in series to show the modular design concept works.
Figure 2: TDA Research’s modular radial outflow reactor concept.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
254 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 3: TDA Research 1-MWe modules.
The 1.0-MWe membrane-sorbent hybrid pilot test unit is being designed and built to be installed for testing at TCM in
Norway. A 9- to 12-month test campaign using industrial flue gas that closely resembles coal-fired flue gas is planned
to evaluate the operating performance of the capture system at various conditions and to complete at least 6,000 hours
of continuous operation. This testing under both parametric and steady-state conditions provides data and
recommended operating conditions to update the membrane performance data and the TEA and environment, health,
and safety (EH&S) analysis. The project aims to demonstrate the novel hybrid system for reduction in carbon capture
cost.
The sorbent and process parameters are provided in Table 1 and the membrane and process parameters are provided
in Table 2.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D Value Target R&D Value
True Density @ STP kg/m3 1300 1300
Bulk Density kg/m3 589 589
Average Particle Diameter mm 0.4-1.7 0.8-2.4a
Particle Void Fraction m3/m3 0.37 0.37
Packing Density m2/m3 240 240
Solid Heat Capacity @ STP kJ/kg-K 0.93b 0.93b
Crush Strength kgf — —
Manufacturing Cost for Sorbent $/kg 3.75 3.75
Adsorption
Pressure bar 1.0 1.0
Temperature °C 30 30
Equilibrium Loading g mol CO2/kg 0.5 0.5
Heat of Adsorption kJ/mol CO2 20-30 20-30
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 255
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Desorption
Pressure bar 1.0 1.0
Temperature °C 30 30
Equilibrium CO2 Loading g mol CO2/kg 0.05 0.05
Heat of Desorption kJ/mol CO2 20-30 20-30
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — Radial flow fixed beds
Flue Gas Flowrate kg/hr TBD
CO2 Recovery, Purity, and Pressure+ % / % / bar N/A NA N/A
Adsorber Pressure Drop bar <100 mbar
Estimated Adsorber/Stripper Cost of __$__
TBD
Manufacturing and Installation kg/hr
+ Sorbent subsystem does only recirculation of CO2 and is the secondary separation system in the hybrid configuration.
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which
typically occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure
(corresponding to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are
preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which
typically occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper
are process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total
pressure; if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power
plant, the total pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the
partial pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in
either continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
256 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – U.S. Patent No. 9,120,079 B1.
Sorbent Contaminant Resistance – Sulfur oxide (SOX) and nitrogen oxide (NOX) tolerant up to 100 parts per million
(ppm).
Sorbent Attrition and Thermal/Hydrothermal Stability – Less than 0.1% over one year.
Flue Gas Pretreatment Requirements – None.
Sorbent Makeup Requirements – Five-year replacements.
Waste Streams Generated – None.
Process Design Concept – Flowsheet/block flow diagram, included above.
Proposed Module Design – Radial flow fixed beds.
TABLE 2: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — Proprietary Polymer
Materials of Fabrication for Support Layer — Proprietary Polymer
Nominal Thickness of Selective Layer m <1 <1
Membrane Geometry — Thin film composite Thin film composite
Max Trans-Membrane Pressure bar 1.0 1.0
Hours Tested without Significant Degradation — 11,000 3 years
Manufacturing Cost for Membrane Material $/m2 — —
Membrane Performance
Temperature °C 30 30
CO2 Pressure Normalized Flux GPU or equivalent 1,000 to 3,000 3,000
CO2/H2O Selectivity — 0.25 0.25
CO2/N2 Selectivity — 25-30 30
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — mixed mixed
Proposed Module Design (for equipment developers)
Flow Arrangement — Partial countercurrent
Packing Density m2/m3 500 to 1,000
Shell-Side Fluid — N/A
Flue Gas Flowrate kg/hr TBD
CO2 Recovery, Purity, and Pressure+ %/%/bar 90% 95% 150
Pressure Drops Shell/Tube Side bar 0.15
Estimated Module Cost of Manufacturing and __$__
TBD
Installation kg/hr
+ CO2 recovery, purity, and pressure downstream of the cryogenic purification and pumping system.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 257
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Post-Combustion Sorbent Technologies
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear
materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures
measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
14.7 psia 135°F CO2 H2O N2 O2 Ar SOX NOX
13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Membrane Permeation Mechanism – proprietary polymeric membrane
Contaminant Resistance – SOX and NOX tolerant up to 100 ppm.
Flue Gas Pretreatment Requirements – None.
Membrane Replacement Requirements – TBD.
Waste Streams Generated – None.
Process Design Concept – Flowsheet/block flow diagram, if not included above.
Proposed Module Design – Plate and frame module design for full-scale unit, spiral wound modules used in field test.
technology advantages
• Low pressure drop and high performance at the low CO2 partial pressure in the adsorption stage.
• Efficient membrane operation due to high driving force and low cost due to mild vacuum requirements.
• Reduced capture cost while maintaining CO2 capture performance due to the hybridization of the process.
• A preliminary TEA showed a substantial improvement in net plant efficiency (~3.5% increase on higher heating value
[HHV] basis) compared with the state-of-the-art amine-based CO2 capture system.
R&D challenges
• Scaling-up the hybrid system from bench-scale to the 1-MWe system size for testing in this project.
• Assuring high membrane selectivity to get to greater than 95% purity CO2.
• Maintaining uniform flow distribution in sorbent reactor.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
status
TDA Research has completed the design of the 1-MWe-scale test unit and completed their initial design review.
available reports/technical papers/presentations
Alptekin, G., et al. “Membrane-Sorbent Hybrid System for Post-Combustion CO2 Capture,” Presented at 2019 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/G-
Alptekin-TDA-Membrane-Sorbent-Hybrid.pdf
Alptekin, G., et al. “Membrane-Sorbent Hybrid System for Post-Combustion CO2 Capture,” Presented at the Project
Kickoff Meeting, Pittsburgh, PA, October 2018. https://www.netl.doe.gov/projects/files/Membrane-
Sorbent%20Hybrid%20System%20for%20Post-Combustion%20CO2%20Capture%20Oct%202018.pdf
Alptekin, G., et al. “Membrane-Sorbent Hybrid System for Post-Combustion CO2 Capture,” Presented at 2018 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/Membrane-
Sorbent%20Hybrid%20System%20for%20Post-Combustion%20CO2%20Capture%20Aug%202018.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
259
Post-Combustion Sorbent Technologies
Advanced Structured technology maturity
Bench-Scale, Simulated
Adsorbent Architectures for Coal-Fired Flue Gas and
Actual Flue Gas from a Gas-
Transformational Carbon Fired Boiler
Dioxide Capture Performance project focus:
Advanced Structured
Adsorbent Architectures
primary project goals
participant:
Electricore, Inc. is evaluating Svante Mark-II VeloxoTherm™ technology via Electricore, Inc.
development and optimization of novel bi-layer laminated structured sorbents for post-
combustion carbon dioxide (CO2) capture, including bench-scale testing on simulated project number:
coal-fired flue gas and on actual flue gas from a gas-fired boiler.
FE0031732
technical goals predecessor projects:
N/A
• Select, synthesize, and characterize tailored solid adsorbents.
• Optimize the post-combustion CO2 adsorption technology architecture, including the NETL project manager:
bi-layer, laminated adsorbent structure design, integrated rapid cycle temperature swing Andrew jones
adsorption (RC-TSA) cycle, flow path architecture, and bi-layer adsorbent bed [email protected]
construction.
• Conduct bench-scale testing using an existing single-bed variable test station (VTS) principal investigator:
and multi-bed process validation unit (PVU) with flue gas from a natural gas-fired Deborah jelen
boiler and simulated coal flue gas. Electricore, Inc.
• Assess the techno-economic performance of the technology integrated into a 550- [email protected]
megawatt-electric (MWe) coal-fired power plant.
partners:
technical content Svante Inc., Susteon, DNv
GL USA, Inc.
Electricore is developing a bi-layer structured sorbent-based process for post-combustion
start date:
CO2 capture and evaluating Svante’s Mark II VeloxoTherm technology. The bi-layer
configuration contains two separate sorbents, the layer A sorbent and the layer B sorbent, 05.01.2019
in a laminate structure form. An example of the bi-layer cycle design is shown in Figure
1. Layer A is steam-compatible with a high heat of adsorption (greater than 70 kilojoule percent complete:
[kJ]/mole). Water promotes CO2 adsorption on this sorbent. Layer B has a low CO2 heat 20%
of desorption (less than 40 kJ/mole), air-stable up to 120°C, and is stable to the feed
moisture content. Both layer A and layer B sorbents have fast kinetics.
The bi-layer process cycle is approximately 60 seconds in duration and includes two
different regenerative environments. Sorbent A uses steam-assisted desorption. Sorbent B
has the lower heat of desorption and is regenerated using the heat generated during Sorbent
A adsorption, eliminating the need for steam as a carrier gas in that step.
The process is optimized for thermal management in the thermal swing adsorption to allow
synergistic design to reduce the amount of steam injected in the system. The combination
of structured sorbents with a thermally conductive matrix enable a RC-TSA process that
is faster than a conventional thermal swing process. Overall, this process has potential for
increased sorbent CO2 capacity with fast regeneration and reduced steam demands.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
260 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 1: Typical example of the bi-layer cycle design.
Single-bed sorbent testing using simulated coal-fired flue gas is done in the Svante VTS shown in Figure 2, at a scale of approximately
1 to 10 kilograms (kg) of CO2/day captured. The multi-bed process utilizes the Svante rotating adsorption machine in the PVU that
is coupled with a natural gas-fired boiler for testing at a maximum of 10 kg of CO2 captured/day scale.
Figure 2: The variable test station at Svante.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 N/A (laminate) N/A
Bulk Density kg/m3 100-300 (structured) 100-300 (structured)
Average Particle Diameter Mm N/A (laminate) N/A (laminate)
Particle Void Fraction m3/m3 40-60% 40-60%
Packing Density m2/m3 N/A N/A
Solid Heat Capacity @ STP kJ/kg-K 1.4-2.2 1.4-2.2
Crush Strength kgf N/A N/A
Manufacturing Cost for Sorbent $/kg 100-200 50-100
Adsorption
Pressure bar 1-1.1 1-1.1
Temperature °C 40-50 40-50
Equilibrium Loading g mol CO2/kg 1.5-2.5 1.5-2.5
Heat of Adsorption kJ/mol CO2 35-100 35-100
Desorption
Pressure bar 0.9-1 0.9-1
Temperature °C 100-120 100-120
Equilibrium CO2 Loading g mol CO2/kg 0-0.3 0-0.3
Heat of Desorption kJ/mol CO2 35-100 35-100
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation Fixed structured bed Rotary Adsorption Machine
Flue Gas Flowrate kg/hr Pilot scale
CO2 Recovery, Purity, and Pressure% / % / bar 80%, 80%, 0.9-1 90%, 90%, 0.9-1
Adsorber Pressure Drop bar 0.1 0.1
Estimated Adsorber/Stripper Cost of
N/A TBD
Manufacturing and Installation ($/kg/hr)
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs at
the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent. Measured
data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total pressure of the flue
gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of CO2 is roughly 0.132 atm or 0.130
bar.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization (FGD)
unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Using a combination of physisorption and chemisorption for CO2 capture to have large
difference in heat of CO2 adsorption between the two adsorption sub-units.
Sorbent Contaminant Resistance – System requires sulfur oxide (SOX) and nitrogen oxide (NOX) abatement down to about 1 part
per million (ppm) for sulfur dioxide (SO2) and nitrogen dioxide (NO2) in order to maximize sorbent lifetime.
Sorbent Attrition and Thermal/Hydrothermal Stability – Sorbent developed for this rapid cycle system has excellent attrition
resistance as it is embedded in sheets. Hydrothermal stability is also excellent, as the process used pure steam during regeneration
steps.
Flue Gas Pretreatment Requirements – Removal of particulates, cooling of the flue gas to 40 to 50ºC, and condensate removal and
control of NO2 and SO2 levels through the use of a solid sorbent guard bed.
Sorbent Makeup Requirements – N/A; solid sorbent in solid fix bed – estimated replacement frequency between two to five years.
Waste Streams Generated – Condensate water, SOX and NOX guard beds.
Process Design Concept – See above.
Proposed Module Design – Module of about 1 meter long; other dimensions scaled for flow. For pilot total adsorbent module of 0.6
to 1 liter.
technology advantages
• Using of the bi-layer made up of two sorbents working synergistically, has multiple advantages:
o The second sorbent can have lower heat of desorption and use the heat generated by the first adsorbent, reducing the
steam/energy requirement.
o The second sorbent does not need to be steam resistant, therefore a metal-organic framework (MOF) can be used, for example.
o MOFs can provide higher CO2 capacity, highly tunable adsorption, and better oxygen resistance.
R&D challenges
• Tuning the two sorbents, materials and coatings, to work in synergy in the process.
• Designing sorbents for resistance to the water, oxygen, and contaminants in the feed.
• Maintaining defect-free barrier that is resistant to moisture with good transverse heat transfer.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
263
Post-Combustion Sorbent Technologies
status
Electricore has begun material down-selection and scale-up for candidate sorbent materials.
available reports/technical papers/presentations
Jelen, D. “Advanced Structured Adsorbent Architectures for Transformative CO2 Capture Performance,” presented at 2019 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/D-Jelen-
Electricore-Adsorbent-Architectures.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
264 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Transformational Sorbent- technology maturity:
Laboratory-Scale, Simulated
Based Process for a Substantial Flue Gas; Bench-Scale,
Actual Flue Gas
Reduction in the Cost of CO2 project focus:
Capture Microporous Sorbent
participant:
primary project goals InnoSepra, LLC
InnoSepra, LLC is developing a sorbent-based process using novel microporous project number:
materials to reduce the cost of carbon dioxide (CO2) capture. The project includes FE0031722
identification of sorbent materials, process development, and lab-scale testing
with simulated flue gas, culminating in bench-scale testing with actual flue gas at predecessor projects:
Technology Centre Mongstad (TCM). FE0007948
SC0010208
technical goals
NETL project manager:
• Identify suitable materials through literature search and Monte Carlo Andrew jones
[email protected]
simulations and produce/procure suitable materials for lab-scale testing.
• Complete lab-scale testing of multiple materials in simulated flue gas to principal investigator:
determine CO2 capture performance and down-select best materials. Ravi jain
• Simulate process to obtain heat and mass transfer parameters. InnoSepra, LLC
[email protected]
• Design and build the bench-scale test unit.
• Test the best identified materials on the bench-scale unit using actual flue gas partners:
at TCM. Main Line Engineering, Plant
• Perform engineering design and complete a techno-economic analysis (TEA) on Process Equipment, Arizona
the process for installation of the technology at a commercial 550-megawatt State University
(MW) power plant to estimate CO2 capture cost.
start date:
05.01.2019
technical content
percent complete:
InnoSepra is developing a sorbent-based CO2 capture process, utilizing physical 15%
sorbents based on microporous materials. These sorbents have low heats of
adsorption (26 to 44 kJ/mole CO2), high net CO2 capacity (greater than 9 wt%), and
high surface area-to-volume ratio (greater than 10 x 106 m2/m3). The combination
of the process and sorbent materials provides capture performance similar to or
better than amines, although needing much lower regeneration energy. The
process schematic of the CO2 capture process is shown in Figure 1. After the
removal of moisture and sulfur oxides (SOX) in a pretreatment system, the CO2 is
captured in an adsorber at 25 to 40°C. A high-purity CO2 is produced during
sorbent regeneration at 90 to 100°C. Some of the heat of adsorption is removed
during the adsorption process; the remaining heat is removed during the cooling
steps. Regeneration heat is supplied via low-pressure steam, as well as by utilizing
other process waste heat in the system.
The first-generation of the InnoSepra process using the physical sorbents was
developed and tested at the bench-scale in a previous U.S. Department of Energy
(DOE)-funded project (DE-FE0007948). Testing occurred at NRG Energy’s Indian
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
River Plant using actual flue gas, taken off the process after the dry flue gas desulfurization (FGD) unit, containing about
50 parts per million (ppm) sulfur dioxide (SO2) and 10 to 12% CO2, with 80 to 100 standard cubic feet per minute (scfm)
flow rate. The adsorption test skid used at the testing at NRG is shown in Figure 2. Eight weeks of testing was completed
showing 8 to 10.5 wt% net CO2 capacity, greater than 94% CO2 recovery, and greater than 98% purity.
Figure 1: InnoSepra capture process schematic.
Figure 2: InnoSepra test skid used for testing at NRG Energy.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
266 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Sorbent Technologies
Projections based on detailed engineering evaluations show that at commercial scale, the first-generation process can
reduce the power consumption for CO2 capture by more than 40%, including CO2 compression. There is about a 70%
lower power loss due to steam extraction for the InnoSepra process compared to the amine process and approximately
48% reduction in capture cost compared to monoethanolamine (MEA).
In this current project, InnoSepra is developing the second-generation process, which is simpler, with capital savings,
compared to the first-generation process. In testing of the second-generation process at the lab scale, an absolute energy
requirement of 1.5 gigajoule (GJ)/metric ton (MT) of CO2 was obtained, which is 57% lower than MEA, and lower than the
2.1 GJ/MT obtained for the first-generation process in field testing. The lower absolute amount of regeneration energy
coupled with lower regeneration temperature leads to a 78% lower power loss due to steam extraction compared to MEA.
The key feature of the second-generation process is a significant reduction in the heating requirement (from 1.3 GJ/MT
to 0.7 GJ/MT) through a combination of the sorbent selection and regeneration method. The project team is
demonstrating the effectiveness of the InnoSepra sorbent-based post-combustion capture technology to achieve at least
90% CO2 removal with greater than 95% purity. Lab-scale testing and process simulation will support sorbent and
regenerant identification and optimization of the process. The test unit will be designed, built, and installed for testing at
TCM at greater than 100 scfm scale.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,990 1,990
Bulk Density kg/m3 690 690
Average Particle Diameter mm 1.5-3.0 0.5-1.5
Particle Void Fraction m3/m3 0.45 0.45
Packing Density m2/m3 1.79e8 1.79e8
Solid Heat Capacity @ STP kJ/kg-K 0.96 0.96
Crush Strength kgf 2.9 2.9
Manufacturing Cost for Sorbent $/kg 4.0 3.0-4.0
Adsorption
Pressure bar 1.15 1.1
Temperature °C 25-32 25-32
Equilibrium Loading g mol CO2/kg 3.25 3.5-4.0
Heat of Adsorption kJ/mol CO2 38 38
Desorption
Pressure bar 0.3-1.0 0.3-1.0
Temperature °C 100 90-110
Equilibrium CO2 Loading g mol CO2/kg 1.5 1.5-2.0
Heat of Desorption kJ/mol CO2 38 38
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — fixed/cyclic
Flue Gas Flowrate kg/hr 2,320,000
CO2 Recovery, Purity, and Pressure % / % / bar 90 99 1.0
Adsorber Pressure Drop bar 0.14 0.10
Estimated Adsorber/Stripper Cost of __$__
336
Manufacturing and Installation kg/hr
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
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Post-Combustion Sorbent Technologies
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The adsorption is physical sorption based on weak van der Waals forces. This
leads to low heats of adsorption.
Sorbent Contaminant Resistance – Under normal operation, the sorbent is not irreversibly damaged by any contaminant
in the flue gas. If substantial quantities of SO2 are present in the feed to the CO2 adsorption section, the sorbent may
require higher than normal regeneration temperature to restore performance.
Sorbent Attrition and Thermal/Hydrothermal Stability – The process design protects the adsorbent from moisture
and potential hydrothermal degradation. If moisture should break through onto the adsorbent, the adsorbent can be
regenerated completely. The adsorbent is thermally stable at temperatures of more than 300°C.
Flue Gas Pretreatment Requirements – No special flue gas pretreatment is required. A conventional FGD and a direct
contact cooler (DCC) are sufficient for normal process operation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
Sorbent Makeup Requirements – Based on prior experience with similar sorbents in similar operating environments, the
adsorbent life would be between five and 10 years. An adsorbent life of five years has been assumed to estimate the
makeup requirements.
Waste Streams Generated – Except for the sorbents loaded with flue gas components, SOX and mercury (Hg), no other
waste streams are generated in the process. These can be disposed of as per current power plant practices for materials
loaded with SOX and Hg.
Process Design Concept – The commercial process configuration is shown in Figure 3. The adsorption equipment is
modular in nature and five adsorption skids are needed for a 550-MW power plant. The rest of the process equipment,
such as the feed blower, DCC, and the CO2 compressor, is very similar to the amine process.
Figure 3: Commercial process configuration.
Proposed Module Design – The CO2 capture modules will be designed to capture CO2 from a 550-MW pulverized coal
power plant. Multiple modules will be used to minimize field fabrication and maximize offsite fabrication. The separation
skid will consist of a feed preparation section (flue gas compression and cooling), the CO2 adsorption section (removal of
impurities, CO2 adsorption, and desorption), and the CO2 compression section.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Post-Combustion Sorbent Technologies
technology advantages
• The physical sorbents have a low heat of adsorption (approximately 0.8 GJ/MT).
• Combination of lower absolute amount of heat needed and lower steam extraction temperature leads to a 78% lower
power loss compared to MEA.
• The process can produce high-purity CO2 (greater than 98%) and recovery (greater than 90%).
• The estimated absolute energy required for the process, excluding compression, is 1.5 GJ/MT of CO2, about 57% lower
than for MEA.
• The process has a projected capture cost of $31/MT CO2, excluding transportation, storage, and monitoring (TS&M)
costs.
R&D challenges
• Heat management during both adsorption and regeneration.
• Maintaining heat transfer rate upon scale-up.
• Assuring effective moisture and contaminant removal from the flue gas prior to adsorption to prevent decrease in
sorbent performance.
status
The project has commenced.
available reports/technical papers/presentations
Jain, R. “Transformational Sorbent-Based Processes for a Substantial Reduction in the Cost of CO2 Capture,” Presented
at the Project Kickoff Meeting, Pittsburgh, PA, September 2019.
https://www.netl.doe.gov/projects/files/FE0031722_InnoSepra%20Kickoff_09-30-19.pdf.
Jain, R. “Transformational Sorbent-Based Processes for a Substantial Reduction in the Cost of CO2 Capture,” Presented
at the 2019 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/R-Jain-InnoSepra-Cost-Reduction-Capture.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
270 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Transformational Sorbent technology maturity
Laboratory-Scale, Simulated
System for Post-Combustion Flue Gas; Bench-Scale,
Actual Flue Gas (2-3 kwe)
Carbon Capture project focus:
Metal-Organic Framework
primary project goals (MOF)-Based Sorbent
TDA Research, Inc. is developing a highly stable high-capacity metal-organic participant:
framework (MOF)-based physical adsorbent to remove carbon dioxide (CO2) from TDA Research, Inc.
the flue gas using a vacuum/concentration swing adsorption (VCSA) cycle scheme
that will culminate in field testing in a prototype test unit using 3 to 5 cubic feet project number:
per minute (cfm) of actual coal-derived flue gas. FE0031734
predecessor projects:
technical goals
N/A
• Optimize the sorbent formulation.
NETL project manager:
• Assess impact of flue gas contaminants (sulfur dioxide [SO2], nitrogen oxide Andrew O’Palko
[NOX], hydrogen chloride [HCl]). [email protected]
• Scale-up sorbent production.
principal investigator:
• Complete long-term sorbent cycling experiments at bench scale using
simulated flue gas. Gökhan Alptekin
TDA Research, Inc.
• Design and construct a prototype system with fixed-bed radial flow reactors. [email protected]
• Design the VCSA cycle sequence.
partners:
• Perform field testing in a prototype test unit using actual flue gas for a minimum
of 4,000 hours. University of California Irvine,
University of Alberta,
• Prepare a high-fidelity techno-economic analysis (TEA) and environmental, wyoming Integrated Test
health, and safety (EH&S) assessment. Center
start date:
technical content
06.01.2019
TDA Research is developing a high-capacity sorbent for CO2 capture in a system
percent complete:
that uses a novel adsorption cycle scheme. TDA’s MOF sorbent has very high CO2
15%
uptake, high CO2 selectivity over nitrogen (N2), and a relatively low energy
requirement for regeneration. The process, shown in Figure 1, includes sorbent
that operates at approximately 50°C during adsorption under mild vacuum (~0.2
to 0.3 atmosphere [atm]). The regeneration occurs in a two-step process, using
vacuum to recover the CO2 and a purge using the boiler intake air, which then
feeds the CO2-laden air back to the boiler. This approach generates a flue gas that
is rich in CO2, thereby benefiting the adsorption of the CO2 on the sorbent while
allowing use of a practical, single-stage vacuum pump with a low auxiliary load.
The project team is designing a fixed-bed radial flow reactor-based test unit for
field testing at a project partner host site with actual coal-derived flue gas to show
the performance of their CO2 capture system. TDA’s radial flow contactor increases
the viability of using sorbents in fixed beds for post-combustion capture by
reducing the pressure drop through the beds and allowing for rapid regeneration
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
271
Post-Combustion Sorbent Technologies
of the sorbent. The radial flow reactor configuration allows for use of multiple modular beds for ease of scale-up to large-
scale processes.
Figure 1: Schematic of TDA’s CO2 capture system.
TDA Research is optimizing sorbent performance through lab-scale experiments and using computational modeling to
show the technical merit of both the sorbent and the capture process. The impacts of flue gas contaminants, including
SO2, NOX, and HCl, on sorbent performance are being evaluated. The project team will also design and construct the
prototype system, design the VCSA cycle, optimize the process design, and complete a detailed cost analysis to compare
this process technology against amines. Evaluations using the prototype test unit will be completed first with simulated
flue gas in the lab and then at the Wyoming Integrated Test Center (ITC) with actual coal-based flue gas, followed by
optimization of the cycle design, finalization of the process design, and completion of an engineering analysis to fully
assess the techno-economic viability of the process.
The sorbent and process parameters are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 650-1,000 650-1,000
Bulk Density kg/m3 540 550
Average Particle Diameter mm 3 3
Particle Void Fraction m3/m3 0.2-0.5 0.2-0.5
Packing Density m2/m3 1.6x108 2.7x108
Solid Heat Capacity @ STP kJ/kg-K — 700
Crush Strength kgf 1.5-3 3
Manufacturing Cost for Sorbent $/kg — 30
Adsorption
Pressure bar 1.0 1.0
Temperature °C 30 3.0
Equilibrium Loading g mol CO2/kg 2.3 2.3
Heat of Adsorption kJ/mol CO2 30-40 30-40
Desorption
Pressure bar 0.05 0.05
Temperature °C 30 30
Equilibrium CO2 Loading g mol CO2/kg 0.7 0.7
Heat of Desorption kJ/mol CO2 30-40 30-40
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
272 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — Radial flow fixed beds
Flue Gas Flowrate kg/hr TBD
CO2 Recovery, Purity, and Pressure % / % / bar 90% 95% 150
Adsorber Pressure Drop bar < 100 mbar
Estimated Adsorber/Stripper Cost of __$__
TBD
Manufacturing and Installation kg/hr
Definitions:
STP – Standard Temperature and Pressure (15°C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Physical adsorption
Sorbent Contaminant Resistance – TBD
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
273
Post-Combustion Sorbent Technologies
Sorbent Attrition and Thermal/Hydrothermal Stability –TBD.
Flue Gas Pretreatment Requirements – TBD.
Sorbent Makeup Requirements – Five-year replacements.
Waste Streams Generated – None.
Process Design Concept – Flowsheet/block flow diagram, included above.
Proposed Module Design – Radial flow fixed beds.
technology advantages
• Very high CO2 uptake (2 to 3 mmol/g) at 0.15 to 0.20 bar CO2 partial pressure.
• High CO2 selectivity over N2.
• Relatively low energy input requirement for sorbent regeneration.
R&D challenges
• Minimizing the loss in adsorption capacity due to the sorbent pelletization process.
• Designing the sorbent to maintain stability and life in the presence of moisture.
• Maintaining the low vacuum and purge requirements for the process upon scale-up.
status
TDA Research has begun work to optimize the MOF sorbent formulations.
available reports/technical papers/presentations
Alptekin, G., et al. “Transformational Sorbent System for Post Combustion Carbon Capture,” Presented at 2019 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/G-
Alptekin-TDA-Next-Gen-Sorbent.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
274 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Transformational Molecular technology maturity
Bench-Scale, Actual Flue
Layer Deposition Tailor-Made Gas Slipstream
Size-Sieving Sorbents for Post- project focus:
Combustion CO2 Capture
Size-Sieving Sorbent
Integrated with Pressure
Swing Adsorption
primary project goals participant:
Rensselaer Polytechnic
Rensselaer Polytechnic Institute (RPI) is developing a transformational molecular Institute
layer deposition (MLD)-modified, size-sieving sorbent/pressure swing adsorption
(PSA) process for post-combustion carbon dioxide (CO2) capture from coal-fired project number:
and natural gas-fired power plant flue gas. The integrated technology provides
step-change reductions in CO2 capture cost and energy penalties. FE0031730
predecessor projects:
technical goals N/A
• Generate tailor-made, size-sieving sorbents by using MLD to coat sorbents. NETL project manager:
• Identify promising sorbent materials through computational screening. Sai Gollakota
• Optimize MLD process to develop sorbents with high CO2 adsorption capacity [email protected]
and stability in the presence of water vapor.
• Perform single-bed testing and simulation with the developed sorbents. principal investigator:
• Identify allowable contaminant levels for sorbents by further single-bed testing Miao Yu
and simulation. Rensselaer Polytechnic
Institute
• Design PSA cycle schedule tailored to best MLD-modified sorbent. [email protected]
• Design and construct MLD-modified sorbent/PSA skid system.
• Test skid system under simulated flue gas and actual flue gas conditions. partners:
• Perform a techno-economic analysis (TEA) of process integrated with a 550- University of South Carolina,
megawatt-electric (MWe) power plant. Gas Technology Institute,
Trimeric Corporation
technical content start date:
10.01.2019
RPI, in collaboration with the University of South Carolina (USC) and Gas
Technology Institute (GTI), is developing a process that integrates
percent complete:
transformational, tailor-made, MLD-modified sorbents with a novel PSA process
concept to achieve U.S. Department of Energy (DOE) CO2 capture performance 10%
and cost goals. RPI has developed sorbents with CO2/nitrogen (N2) selectivity as
high as 130, much higher than state-of-the-art commercial sorbents, such as 13X
zeolite, with similar CO2 capacity under similar adsorption conditions, enabling
achievement of 95% CO2 purity in one stage of PSA for CO2 capture from flue gas.
The sorbents are coated with an inorganic material to achieve pore misalignment,
which allows for fine-tuning the pore mouth size on the surface of sorbents (Figure
1). Using MLD, a vapor phase deposition technique utilizing self-limiting surface
reactions, the external surface of the base sorbent is uniformly coated by ultrathin
(less than 20 nanometers [nm]) microporous coatings. A wide range of porous
materials (zeolites, activated carbon, and metal-organic frameworks) in different
forms (powder or pellets) can be used directly as the base material for MLD
coating, and the pore mouth size can be precisely designed by controlling the
coating layer composition and thickness, as well as the thermal treatment
conditions. The MLD-modified sorbents provide precise pore mouth size control in
the range of 0.01 nm, which is crucial for achieving highly selective separation of
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
275
Post-Combustion Sorbent Technologies
CO2 from N2, as illustrated in Figure 2. MLD treatment results in minimal loss to the CO2 adsorption capacity of the base
sorbent.
Figure 1: Schematic of pore misalignment for fine-tuning pore mouth size of sorbents.
Figure 2: High CO2/N2 selectivity achieved by size-sieving for the MLD tailor-made sorbent.
Early studies on the pore misalignment concept show that 5A zeolite with and without MLD coatings have almost identical
surface areas (343.5 ± 8.3 m2/g) and micropore volume, suggesting that the coatings are only on the external surface
and the internal cavity of the zeolite is maintained (Figure 3). Furthermore, the effective pore size of the treated 5A zeolite
can be precisely controlled by the number of MLD cycles. Preliminary experiments on MLD-coated 13X zeolite show that
almost no N2 is adsorbed, suggesting a molecular sieving mechanism, and indicate a reduction in the heat of adsorption
of CO2. The sorbent and process parameters are provided in Table 1. In addition to 5A and 13X zeolites, other
microporous sorbents have the potential to achieve high CO2 adsorption capacity and CO2/N2 selectivity with MLD
modification.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
276 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
Figure 3: Characterization of MLD-modified 5A zeolite: (A) transmission electron microscopy (TEM) image of 5A zeolite with 60 cycles of
aluminum oxide coating; (B) BET surface area of 5A zeolite with different cycles of MLD.
USC has recently developed a proprietary PSA cycle schedule concept for CO2 capture from flue gas that involves the
use of fewer number of beds than employed in their previously DOE-supported project DE-FE0007639, thereby reducing
the CO2 capture cost significantly. The number of required beds is reduced from 240 to 48 (i.e., six, eight-bed PSA
systems operating in parallel) for the MLD-coated sorbent/PSA process integrated into a 550-MWe power plant. Figure
4 shows a diagram of the process, including identification of the numbered streams. The flow sheet incorporates desiccant
wheels for water vapor removal upstream of the PSA process that are regenerated by a simple concentration swing with
the light product from the PSA system and ambient air without the use of any heating. The dry light product (~2.4 mol%
CO2) produced by the PSA system is used to regenerate Dryer 2, and slightly compressed ambient air is used to
regenerated Dryer 1. A reflux compressor produces a concentrated recycle stream containing ~83 mol% CO2, facilitating
the production of greater than 95 mol% CO2 in the final CO2 product. The system is uniquely designed with six adsorption
beds being fed simultaneously, while two beds are being regenerated. This ensures low pressure drop during the feed
step with a beaded adsorbent for large flow rate feed streams, allowing for the use of fewer number of adsorption beds
in the PSA system since the adsorption bed height can be increased without a pressure drop penalty.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
277
Post-Combustion Sorbent Technologies
Figure 4: USC’s PSA process flow diagram integrated with the MLD sorbent/PSA system.
USC’s dynamic adsorption process simulator (DAPS) has been used to design a hypothetical MLD-treated sorbent/PSA
system, showing a 6% reduction in separation energy when using MLD-coated 13X zeolite compared to commercial 13X.
Preliminary TEA results compared to the DOE/National Energy Technology Laboratory (NETL) Base Case 9 (subcritical
pulverized coal plant without CO2 capture) and Base Case 10 (subcritical pulverized coal plant with amine scrubbing) are
shown in Figure 5, indicating that the MLD-treated sorbent/PSA system can achieve 90% CO2 capture rate with 95% CO2
purity with a cost of $28/tonne CO2.
Figure 5: Comparison of the cost of CO2 capture between DOE/NETL Base Case 9 (subcritical pulverized coal plant without CO2 capture),
Base Case 10 (subcritical pulverized coal plant with amine scrubbing), and the MLD-coated sorbent/PSA process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
278 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,800 1,800
Bulk Density kg/m3 1,130 1,130
Average Particle Diameter mm 0.003-0.005 0.003-0.005
Particle Void Fraction m3/m3 0.374 >0.3
Packing Density* m2/m3 3.96x108–5.82x108 3.96x108–6.33x108
Solid Heat Capacity @ STP kJ/kg-K 0.96 <1
Crush Strength kgf 3.6 3.6
Attrition Index - <0.1 <0.1
Manufacturing Cost for Sorbent $/kg TBD 3.6
Adsorption
Pressure bar 0.15 0.15
Temperature °C 20 20-60
Equilibrium Loading g mol CO2/kg 0.965-1.2 >1.5
Heat of Adsorption kJ/gmol CO2 43 <35
Desorption
Pressure bar 0.05 >0.05
Temperature °C 20 40-80
Equilibrium CO2 Loading g mol CO2/kg 0.32 <0.3
Heat of Desorption kJ/gmol CO2 32 <35
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — TBD
Flue Gas Flowrate kg/hr 1.5
CO2 Recovery, Purity, and Pressure+ % / % / bar 90% 95% TBD
Adsorber Pressure Drop bar 0.07
Estimated Adsorber/Stripper Cost of __$__
TBD
Manufacturing and Installation kg/hr
*Sorbent BET surface area used for packing density (m2/m3) calculation.
Definitions:
BET surface area – Surface area calculated using the Brunauer-Emmett-Teller (BET) equation, relating to the total
surface area (reactive surface) based on gas adsorption.
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated bulk
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
279
Post-Combustion Sorbent Technologies
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – See Figure 1 and Figure 2
Sorbent Contaminant Resistance – TBD
Sorbent Attrition and Thermal/Hydrothermal Stability – TBD
Flue Gas Pretreatment Requirements – TBD
Sorbent Makeup Requirements – TBD
Waste Streams Generated – TBD
Process Design Concept – See Figure 4.
Proposed Module Design – TBD
technology advantages
• High CO2/N2 selectivity (greater than 130), enabling a 95 vol% CO2 purity to be achieved in a single stage for a typical
coal flue gas containing 12 to 15 vol% CO2.
• Uses low-cost commercial sorbents as base material.
• Metal and organic precursors required to form the coating materials are low cost.
• MLD is comparable to commercially available atomic layer deposition technology and suitable for roll-to-roll
manufacturing.
• MLD tailor-made sorbent technology allows for reduced vacuum level and reduced light reflux flow during regeneration,
thereby reducing the size and energy required by the product and reflux vacuum pump.
• Advanced sorbent fabrication procedure reduces manufacturing cost.
• Low pressure drop during feed step leads to use of fewer adsorption beds in PSA cycle, reducing capital costs.
• Compact, stand-alone, and modularized system design, reducing upfront installation costs and footprint.
• Serves as a platform for CO2 capture from both coal-fired and natural gas-fired power plants.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
280 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Sorbent Technologies
R&D challenges
• Design of PSA process to achieve greater than 95% CO2 purity.
• Improve manufacturing process to lower MLD sorbent costs.
• Sorbent performance in presence of flue gas contaminants.
status
The project team is using MLD to apply microporous coatings of less than 30 nm thickness on base sorbent material.
Computational screening of various sorbent materials is underway to identify three promising sorbents for further
development. The DAPS is being used to design the PSA system based on commercial 13X zeolite to establish baseline
performance.
available reports/technical papers/presentations
Yu, M., et al. “Transformational Molecular Layer Deposition Tailor-Made Size-Sieving Sorbents for Post-Combustion
CO2 Capture,” presented at the 2019 NETL Carbon Capture, Utilization, Storage, and Oil and Gas Technologies
Integrated Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/M-Yu-RPI-
Tailor-Made-Sorbents.pdf.
Ritter, J., et.al. “Bench-Scale Development and Testing of Rapid PSA for CO2 Capture,” presented at the 2015 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015. https://netl.doe.gov/sites/default/files/event-
proceedings/2015/co2captureproceedings/J-Ritter-USCarolina-Rapid-PSA.pdf.
Ritter, J., et.al. “Bench-Scale Development and Testing of Rapid PSA for CO2 Capture,” presented at the 2014 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014. https://netl.doe.gov/sites/default/files/event-
proceedings/2014/2014%20NETL%20CO2%20Capture/J-Ritter-USCarolina-Rapid-Pressure-Swing-Adsorption.pdf.
Ritter, J., et.al. “Bench-Scale Development and Testing of Rapid PSA for CO2 Capture,” presented at the 2013 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, July 2013. https://netl.doe.gov/sites/default/files/event-
proceedings/2013/co2%20capture/J-Ritter-USC-Rapid-Pressure-Swing-Adsorption.pdf.
Ritter, J., “Bench-Scale Development and Testing of Rapid PSA for CO2 Capture,” presented at the 2012 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2012. https://netl.doe.gov/sites/default/files/event-
proceedings/2012/co2%20capture%20meeting/J-Ritter-USC-RPSA.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 281
Post-Combustion Sorbent Technologies
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NATIONAL ENERGY TECHNOLOGY LABORATORY
282 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
POST-COMBUSTION
MEMBRANE TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
283
Post-Combustion Membrane Technologies
Bench-Scale Testing of Next- technology maturity:
Bench-Scale, Simulated Flue
Generation Hollow-Fiber Gas (0.1 Mwe) and Actual
Flue Gas (0.3 Mwe)
Membrane Modules project focus:
Sub-Ambient Temperature
primary project goals Membrane
Air Liquide is developing a novel polyimide-based membrane material, PI-2, for participant:
application in their hybrid process that combines cold membrane operation with American Air Liquide, Inc.
cryogenic separation to reduce the overall cost of capturing carbon dioxide (CO2)
from flue gas. The focus of the project is to advance the high CO2 permeance PI-2 project number:
material to commercial-scale, 6-inch bundles for testing with actual flue gas in a FE0026422
0.3-megawatt-electric (MWe) test unit at the National Carbon Capture Center
(NCCC). predecessor projects:
FE0013163
FE0004278
technical goals
NETL project manager:
• Design and manufacture 4-inch PI-2 bundles reaching greater than 90 normal
Andrew O’Palko
meters cubed per hour (Nm3/hr) feed at 90% CO2 recovery and greater than [email protected]
58% CO2 purity.
• Identify other hybrid processes with possibility of economic feasibility. principal investigator:
• Design and manufacture 6-inch PI-2 bundles reaching greater than 400 Nm3/hr Shilu Fu
feed at 90% CO2 recovery and greater than 58% CO2 purity. American Air Liquide
[email protected]
• Field-test 6-inch bundles at 0.3-MWe scale with real flue gas at NCCC.
• Complete a techno-economic analysis (TEA) to evaluate potential to meet partners:
greater than 90% carbon capture at a cost of electricity (COE) of 30% less than Air Liquide Engineering, Air
U.S. Department of Energy (DOE) baseline. Liquide – ALAS, Parsons
Corporation
technical content start date:
10.01.2015
Air Liquide is developing a next-generation membrane material, PI-2, for
application with their novel, sub-ambient temperature, membrane-based CO2 percent complete:
capture technology. The process combines the use of commercial polyimide (PI) 98%
hollow-fiber membrane bundles with cryogenic operation to selectively remove
the CO2 from flue gas.
Figure 1 presents a simplified block diagram of the cold membrane process. A
highly selective membrane provides pre-concentration of CO2 prior to CO2 partial
condensation in a liquefaction unit. The membrane is operated at sub-ambient
temperature, approximately -30°C, for enhanced CO2/nitrogen (N2) selectivity. The
cryogenic heat exchanger system provides energy integration between the
membrane and the CO2 liquefaction system.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
284 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 1: Block diagram of the cold membrane process.
Figure 2 shows a schematic diagram of the hybrid cold membrane process. The process lines in Figure 2 are color-coded
(black for ambient temperature, dark blue for approximately -30°C, and light blue for approximately -50°C). The pre-
treated flue gas is compressed to approximately 230 pounds per square inch (psi; 16 bar). The heat of compression is
captured in boiler feed water, raising its temperature to approximately 147°C. The compressed flue gas is then dried in a
dehydration unit to prevent water condensation when the stream is cooled in the brazed aluminum heat exchanger to
approximately -40°C. The cooled, dried, compressed flue gas is then fed to the membrane to produce a residue stream
with approximately 1.8% CO2 at approximately 215 psi (15 bar) and a permeate stream with 60 to 70% CO2 at
approximately 17 psi (1.1 bar). After the residue is sent through the heat exchanger, further cooling and energy recovery
is done via a series of turbo-expanders with the resulting stream at -57°C. The cold stream is again sent through the heat
exchanger to provide cold for the overall process. Finally, the excess pressure energy remaining in the warmed residue is
partly recovered in a warm turbo-expander before venting. A fraction of the vent gas is used to regenerate the drier. The
permeate stream is recompressed, cooled in the heat exchanger, and undergoes phase separation in the cryo-phase
separator. Liquid CO2 is pumped from the separator to provide a storage-ready product CO2 at approximately 870 psi
(60 bar), or greater, and 20°C. The overhead from the cryo-phase separator is warmed through the heat exchanger and
then undergoes energy recovery in a turbo-expander. This stream is mixed with the incoming dried flue gas, which raises
the mixed feed concentration entering the membrane to 18% CO2. The higher CO2 content improves system recovery
and efficiency of the membrane separation.
Figure 2: Schematic diagram of cold membrane process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
285
Post-Combustion Membrane Technologies
For most membrane materials, permeability decreases and selectivity increases with a decrease in operating temperature.
However, laboratory measurements of Air Liquide’s commercial PI hollow-fiber membranes operated at temperatures
below -20°C show two- to four-times higher CO2/N2 selectivity with minimal loss of CO2 permeance compared to ambient
temperature values. Closed-loop, bench-scale (0.1 MWe) testing of Air Liquide’s existing low-cost commercial membranes
(PI-1) was conducted at sub-ambient temperatures in project FE0004278 using synthetic flue gas (CO2 and N2). The 6-
inch bundles exhibited stable performance over eight months of operation and 12-inch bundles showed excellent
mechanical integrity for two months. Preliminary data indicated that 12-inch bundle performance was lower compared
to the 6-inch bundles due to non-ideal flow conditions. By modifying bundle fabrication methods and incorporating a
membrane sweep stream in the process, productivity of the 12-inch bundles was improved by approximately 30%. A
novel membrane material (PI-2) has shown the potential to have similar high selectivity and greater than five times the
fiber permeance of PI-1 in initial laboratory testing with simulated flue gas. PI-2 has the potential for a significant
reduction in membrane system cost. Productivity increases as the membrane is scaled to 4-inch and 6-inch bundles.
Testing of the PI-2 membranes at 0.1- to 0.3-MWe scale with actual flue gas allows for a direct comparison with the PI-1
material based on identical test equipment and conditions.
Fabrication and installation of the 0.3-MWe field-test unit (Figure 3) at the NCCC allows for parametric testing and long-
term continuous runs on the optimized PI-1 membrane modules, as well as the advanced high-permeance PI-2 membrane
modules. Dynamic tests to quantify the performance of the carbon capture system provide data for a final TEA for a 550-
MWe power plant with optimized membrane bundles to assess the system’s ability to reach the targets of greater than
90% CO2 capture and greater than 95% purity at a capture cost approaching $40/tonne.
Figure 3: 0.3-MWe test unit at the NCCC, Pilot Bay 3.
Hybrid process configurations, such as membrane/absorption or membrane/sorbent processes, have also been proposed
incorporating PI-2 membrane material to reduce the compression energy penalty.
The membrane and process parameters identified to date are provided in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
286 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — polyimide polyimide
Materials of Fabrication for Support Layer — polyimide polyimide
Nominal Thickness of Selective Layer µm <0.1 µm <0.1 µm
Membrane Geometry — hollow fiber hollow fiber
Maximum Trans-Membrane Pressure bar 20 20
PI-2: 4-inch bundle 340 hrs
(synthetic flue gas) 500+ hours
Hours Tested without Significant Degradation —
PI-2: 6-inch bundle 3,800+ (actual flue gas)
hrs (actual flue gas)
Manufacturing Cost for Membrane Material $/m2 - -
Membrane Performance
Temperature °C -30°C to -45°C -30°C to -45°C
PI-2 6-inch bundle: 657
CO2 Pressure Normalized Flux GPU or equivalent 400 Nm3/h
Nm3/hr of bundle productivity
CO2/H2O Selectivity — <0.2 (dry gas) <0.2 (dry gas)
CO2/N2 Selectivity — >50 >70
CO2/SO2 Selectivity — 0.3 0.3
6” bundle parametric and 6” bundle parametric and
Type of Measurement — long-term testing with actual long-term testing with actual
flue gas flue gas
Proposed Module Design (for equipment developers)
Flow Arrangement — hollow fiber
Packing Density m2/m3 approximately 1,500 m2/m3
Shell-Side Fluid — CO2-rich permeate
Flue Gas Flowrate kg/hr >400 Nm3/hr / 6-inch bundle
CO2 Recovery, Purity, and Pressure %/%/bar 80-90%, >95% purity in hybrid process (>58% CO2 purity
from membrane), 16 bar
Pressure Drops Shell/Tube Side bar 0.1 bar shell side/1 bar tube side
Estimated Module Cost of Manufacturing and __$__
kg/hr 100
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units). Bundle productivity in terms of
feed flow rate in Nm3/hr is reported.
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in de-sulfurized flue gas.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
287
Post-Combustion Membrane Technologies
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Membrane Permeation Mechanism – Nominally based on solution-diffusion.
Contaminant Resistance – Expected to be resistant to acidic components based on experience to date.
Flue Gas Pretreatment Requirements – Particulate removal and acid component removal to meet compressor
specifications, dehydration to meet cold box specifications, Hg removal to meet heat exchanger specification.
Membrane Replacement Requirements – Membrane productivity decline was too small to be quantified in bench-scale
test with synthetic gases.
Waste Streams Generated – Acidic water.
Process Design Concept – See Figure 2.
technology advantages
• Novel high flux PI-2 material enables a significant reduction in membrane area and corresponding capital cost.
• Sub-ambient operation improves membrane performance.
• Process design provides partial recovery of the flue gas compression energy.
• Process design provides an economic method of cooling the flue gas feed to the required sub-ambient temperature
for optimal membrane operation without external refrigeration.
• The process design can be combined with a novel scheme for contaminant (sulfur dioxide [SO2], nitrogen oxide [NOX])
removal.
R&D challenges
• Sub-ambient membrane operation requires development of suitable membrane module materials with adequate
permeance and selectivity in a commercial membrane module.
• Long-term membrane module performance stability.
• Integration of sub-ambient membrane process, including energy integration with the CPU, as well as energy integration
with the power plant, such as compression and turbo-expansion schemes, heat economizers, and energy conservation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
288 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
• Flue gas contaminant-specific challenges, including acid gas (SO2, NOX) separation, compressor materials of
construction, particulate removal, Hg removal, and water management.
• Novel PI-2 material development must achieve tolerance to operating pressure/temperature, effective epoxy seals,
long-term stability, and manufacturing reproducibility.
status
The 1-inch PI-2 permeators and PI-1 commercial-scale bundles completed more than 500 hours of steady-state testing
on the 0.3-MWe test unit at the NCCC showing stable performance. Multiple 4-inch prototype PI-2 membrane modules
have achieved greater than 90 Nm3/hr productivity at 90% capture and greater than 58% CO2 purity through testing on
the 0.1-MWe bench-scale skid with synthetic flue gas. Multiple 6-inch PI-2 bundles have achieved greater than 400
Nm3/hr productivity at 90% capture and 58% CO2 purity through testing on the 0.3-MWe field-test unit with real flue gas.
The 6-inch PI-2 bundle long-term stability test was concluded successfully, showing 500-hour stable performance that
exceeds the target. Air Liquide cold membrane process design and cost estimation have been validated by third-party
Parsons Government Service.
available reports/technical papers/presentations
Fu, Shilu, “Bench Scale Testing of Next Generation Hollow Fiber Membrane Modules (FE0026422),” presented at the
2019 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/S-Fu-Air%20Liquide-Next-Gen-Hollow-Fiber.pdf.
Augustine, A., “Bench Scale Testing of Next Generation Hollow Fiber Membrane Modules (FE0026422),” presented at the
2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/A-Augustine-AAL-Next-Generation-Hollow-Fiber-Modules.pdf.
Augustine, A., “Bench Scale Testing of Next Generation Hollow Fiber Membrane Modules (FE0026422)/CO2 Capture by
Cold Membrane Operation with Actual Power Plant Flue Gas (FE0013163),” presented at the 2017 NETL CO2 Capture
Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-Tuesday/A-Augustine-Air-Liquide-Hollow-Fiber-
Modules.pdf.
Augustine, A., “Project Review: Bench Scale Testing of Next Generation Hollow Fiber Membrane Modules,” presented at
the 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/4-Thursday/A-Augustine-AirLiquide-Hollow-
Fiber-Membrane-Modules.pdf.
Chaubey, T., “CO2 Capture by Cold Membrane Operation with Actual Power Plant Flue Gas,” presented at the 2016 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/T-Chaubey-AirLiquide-Cold-
Membrane-Operation.pdf.
Augustine, A., “Project Kick-off: Bench Scale Testing of Next Generation Hollow Fiber Membrane Modules,” Project
kickoff meeting presentation, November 2015. https://www.netl.doe.gov/projects/files/FE0026422-Next-Gen-Polyimide-
Kick-off.pdf.
Chaubey, T., CO2 Capture by Cold Membrane Operation with Actual Power Plant Flue Gas,” presented at the 2015 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/T-Chaubey-Air-Liquide-Cold-Membrane-
Operation.pdf.
Chaubey, T., “CO2 Capture by Cold Membrane Operation with Actual Power Plant Flue Gas,” Project Continuation
Request Meeting, March 2015.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
289
Post-Combustion Membrane Technologies
Hasse, D., et al., “CO2 Capture by Cold Membrane Operation,” presented at the International Conference on Greenhouse
Gas Technologies, October 2014.
Chaubey, T., “CO2 Capture by Cold Membrane Operation with Actual Coal-Fired Power Plant Flue Gas,” presented at the
2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/T-Chaubey-AL-CO2-Capture-
by-Cold-Membrane-Operation.pdf.
“CO2 Capture by Cold Membrane Operation,” GHGT-12, Energy Procedia, 2013.
“CO2 Capture by Subambient Membrane Operation,” Final Report, January 2013.
Kulkarni, S., “CO2 Capture by Sub-Ambient Membrane Operation,” presented at the 2012 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2012. https://www.netl.doe.gov/sites/default/files/event-
proceedings/2012/co2%20capture%20meeting/S-Kulkarni-AAL-Sub-ambient-Membrane.pdf.
Sanders, E., “CO2 Capture by Sub-Ambient Membrane Operation,” presented at the 2011 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, August 2011.
Kulkarni, S.S., et al., “CO2 Capture by Sub-Ambient Membrane Operation,” presented at the 2010 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, September 2010.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
290 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Novel Carbon Dioxide- technology maturity:
Pilot-Scale, Simulated Flue
Selective Membranes for CO2 Gas
Capture from Less than 1% project focus:
CO2 Sources
Selective Membranes for
<1% CO2 Sources
participant:
primary project goals Ohio State University
Ohio State University (OSU) is developing a cost-effective design and project number:
manufacturing process for new membranes and membrane modules that capture
carbon dioxide (CO2) from sources with less than 1% CO2. Synthesis of novel FE0026919
CO2-selective membranes using a nanoporous polyethersulfone (PES) polymer
support and coating a top layer of thin, highly selective, yet permeable amine- predecessor projects:
containing polymer membrane will be performed. Pilot-size membranes will be N/A
used to fabricate at least three membrane modules for testing with the simulated
gas mixture. NETL project manager:
David Lang
technical goals [email protected]
principal investigator:
• Synthesize and characterize membranes to obtain a CO2 permeance of 1,800
gas permeation units (GPU) and a CO2/nitrogen (N2) selectivity of greater than w.S. winston Ho
140. Ohio State University
[email protected]
• Fabricate a membrane prototype at least 14 inches in width and greater than
50 feet in length using the continuous membrane fabrication machine at OSU.
partners:
• Use prototype to fabricate at least three membrane modules and conduct pilot
testing using a simulated gas mixture containing less than 1% CO2. TriSep Corporation;
American Electric Power
• Perform an economic feasibility study.
start date:
technical content 03.01.2016
OSU is continuing their work on developing novel CO2-selective membranes that percent complete:
capture CO2 from less than 1% CO2 concentration sources. The membrane is 100%
inexpensive, consisting of a cost-effective nanoporous polymer support and a top
layer coating of thin, highly selective, yet permeable amine-containing polymer
membrane, as shown in Figure 1. The membrane modules are incorporated in a
two-stage membrane process that would be implemented after the primary CO2
capture system in a power plant, which has already captured greater than 90%
CO2 from flue gas. In the first membrane module, CO2 is removed from the feed
gas by using vacuum and the permeate stream is used as the feed for the second
membrane module, where additional CO2 is removed by vacuum such that the
90% capture and 95% purity targets are met.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
291
Post-Combustion Membrane Technologies
Figure 1: Selective amine polymer layer/polymer support.
Carbon dioxide permeates through the membrane via a facilitated transport mechanism where CO2 reacts with amines
reversibly to facilitate CO2 transport, whereas N2 cannot react with amines, resulting in very high CO2/N2 selectivity. The
amine polymer layer contains mobile carriers that react with CO2 to facilitate transport (Figure 2). The CO2 flux increases
as pressure increases until it reaches a saturation point in which CO2 reacts with all carriers in the membrane. At low
pressure (or low CO2 concentration), more free carriers are available; therefore, the CO2 permeance is higher due to
greater CO2 facilitation. Since sulfur dioxide (SO2) permeates through the membrane, OSU proposes to add an SO2
polishing step before the membrane process to remove SO2 to less than 1 to 3 parts per million (ppm). A CO2 permeance
of 1,800 GPU and a CO2/N2 selectivity of greater than 140 using a simulated gas mixture containing less than 1% CO2
are the target performance criteria for these membranes. New and improved membranes are synthesized, in which the
polyamine layer is modified to achieve a higher CO2 permeance and a hydrophilic agent is incorporated into the polymer
support to improve its porosity, permeance, and adhesion. Membranes containing unhindered polyamine but with a
thinner selective layer yielded a high CO2 permeance of 2,299 GPU with a CO2/N2 selectivity of 179 at 67°C with 1%
CO2, which was the most permeable membrane developed during the project.
Figure 2: Facilitated transport on amine polymer layer.
The fabrication of the representative spiral-wound membrane modules for the performance testing at OSU was performed
by using a multiple-leaf configuration for the membrane element (Figure 3). The number of membrane leaves was increased
from six to seven pieces, while the length of each leaf was increased from 30 to 36 inches. Hence, the total membrane area
was raised from 2 m2 to 2.94 m2. The spiral-wound membrane element was loaded in the stainless-steel housing to become
the stainless-steel membrane module as shown in Figure 4.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
292 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 3: Images of a spiral-wound membrane element from (a) the side and (b) the end of the element.
Figure 4: Image of an assembled stainless-steel spiral-wound membrane module.
A pneumatic unwinder was integrated into the existing module rolling machine. The new unwinder delivered the stack of
membrane leaves to the central tube with better tension control. A schematic of the modified rolling machine is shown in
Figure 5. Compared to the manual tension control, the modified machine ensured an even and steady rolling. This improved
the membrane packing density and uniformity and minimized any feed gas channeling. In addition, the modified machine is
capable of fabricating full-size commercial spiral-wound modules (8-inch diameter by 40-inch length).
Figure 5: Schematic of spiral-wound membrane element rolling machine with tension control.
The two-stage membrane process is shown in Figure 6. The feed gas, containing less than 1% CO2, is pressurized by
Blower 1 to 4 atmosphere (atm) and passed to Membrane Stage 1. This stage produces a CO2-depeleted retentate, with
90% CO2 from the feed removed, and a CO2-rich permeate, containing 15 to 20% CO2 on dry basis. A vacuum of 0.2 to
0.3 atm is pulled on the permeate side of this stage to increase the transmembrane driving force. The permeate is re-
compressed by Blower 2 to 4 atm and passed to Membrane Stage 2. This stage further enriches the CO2 to greater than
95% purity in the permeate; the remaining CO2 in the retentate is recycled back to the feed of Membrane Stage 1. A
vacuum of 0.2 to 0.3 atm is also pulled on the permeate side. The vacuum discharge is eventually compressed to 150
atm for transport and storage.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
293
Post-Combustion Membrane Technologies
Figure 6: Schematic of the two-stage membrane process.
The techno-economic analysis (TEA) was updated. The membrane synthesized recently resulted in an estimated capture
cost of $246/tonne (which takes into consideration the varying CO2 permeance), and a cost of electricity (COE) increase
of 17.9%.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — Fixed and mobile amine carriers as the membrane matrix
Materials of Fabrication for Support Layer — Nanoporous polyethersulfone
Nominal Thickness of Selective Layer nm 100–200 100–170
Membrane Geometry — Flat sheet Flat sheet
Max Trans-Membrane Pressure bar 10 10
Hours Tested without Significant Degradation — 1,900 1,200
Manufacturing Cost for Membrane Material $/m2 10 <10
Membrane Performance
Temperature °C 57–67 57–87
CO2 Pressure Normalized Flux GPU or equivalent 2,299 2,200
CO2/H2O Selectivity — About 1 About 1
CO2/N2 Selectivity — 140–200 150–225
CO2/SO2 Selectivity — About 1 About 1
CO2/H2 Selectivity — About 100 About 100
Type of Measurement — Simulated gas mixture Simulated gas mixture
Proposed Module Design (for equipment developers)
Flow Arrangement — Countercurrent spiral wound
Packing Density m2/m3 1,800
Shell-Side Fluid — Permeate containing CO2 (vacuum is used on the
permeate side)
Flue Gas Flowrate kg/hr 4.346
CO2 Recovery, Purity, and Pressure %/%/bar 90%, >95%, 152 bar
Pressure Drops Shell/Tube Side bar 0 bar/m permeate/0.07 bar/m feed
Estimated Module Cost of Manufacturing and __$__ $500/(kg/hr), $32/m2 or
Installation kg/hr $246/tonne CO2 capture cost
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
294 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm 3 (1 atm, 0°C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.35 × 10-10 mol/(m2-s-Pa) (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (hydrogen [H2]-rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD; wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
14.7 psia 135°F CO2 H2O N2 O2 Ar SOX NOX
0.99 17.25 78.62 2.34 0.80 42 74
Other Parameter Descriptions:
Membrane Permeation Mechanism – Facilitated transport using chemical reaction to enhance separation.
Contaminant Resistance – 3 ppm SO2 and 3 to 7% oxygen (O2).
Flue Gas Pretreatment Requirements – SO2 polishing step (with 5% sodium hydroxide [NaOH]) to have 1 to 3 ppm
SO2.
Membrane Replacement Requirements – About once every four years.
Waste Streams Generated – No additional waste streams generated.
technology advantages
• Energy-efficient technology.
• Low-cost membrane (less than $2.00/ft2).
• High CO2/N2 selectivity due to amine polymer layer.
• Facilitated transport mechanism allows for increase in CO2 permeance at low CO2 concentrations.
• Membrane stability.
• Hydrophilic additives in polymer support improve membrane performance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
295
Post-Combustion Membrane Technologies
R&D challenges
• Achieving very high membrane performance (CO2 permeance of 1,800 GPU and CO2/N2 selectivity of greater than
140).
• Membrane stability in presence of contaminants.
• Requires two membrane stages.
status
Spiral-wound prototype membrane module with an active membrane area of 2.94 m2 was tested with a simulated residual
flue gas at 4 atm and 67°C. The membrane module showed a CO2 permeance of 1,921 GPU and a CO2/N2 selectivity of
209 with 1% CO2. The module showed good stability with 3 ppm SO2. The TEA showed a CO2 capture cost of $246/tonne,
which is a 17.9% increase in COE. The project has concluded.
available reports/technical papers/presentations
Ho, W., Han, Y., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” Final project review
meeting presentation, Pittsburgh, PA, October 2019. https://www.netl.doe.gov/projects/plp-
download.aspx?id=17279&filename=DE-FE0026919_Project%20Final%20Review%20Meeting%2010-28-19.pdf.
Ho, W., Han, Y., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” presented at the 2019
NETL CCUS Integrated Project Review Meeting, Pittsburgh, PA, August 2019. https://www.netl.doe.gov/projects/plp-
download.aspx?id=17322&filename=FE0026919_OSU_2019%20NETL%20CCUS%20project%20review%20meeting.p
df.
Ho, W., Han, Y., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” presented at the 2018
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13108&filename=Y-Han-OSU-Membrane-Capture-from-less-
than-1--CO2-Sources.pdf.
Ho, W., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” presented at the 2018 NETL
continuation application status meeting, Pittsburgh, PA, February 2018. https://www.netl.doe.gov/projects/plp-
download.aspx?id=13105&filename=FE0026919-Mtg-021918.pdf.
Ho, W., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” presented at the 2017 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-Tuesday/W-Ho-OSU-Capture-from-less-than-
1--CO2-Sources.pdf.
Ho, W., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” Continuation Application Status
Meeting, Pittsburgh, PA, February 2017. https://www.netl.doe.gov/projects/plp-
download.aspx?id=13107&filename=DE-FE0026919-Continuation-Application-Status-Mtg-2-27-17.pdf.
Ho, W. “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” presented at the 2016 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016. https://www.netl.doe.gov/projects/plp-
download.aspx?id=13109&filename=W-Ho-OSU-CO2-Selective-Membranes.pdf.
Ho, W., “Novel CO2-Selective Membranes for CO2 Capture from <1% CO2 Sources,” Project Kickoff Meeting
presentation, April 2016. https://www.netl.doe.gov/projects/plp-download.aspx?id=13106&filename=DE-FE0026919-
Project-Kick-off-Meeting.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
296 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Solid Phase Supports for Flue technology maturity:
Bench-Scale, Simulated Flue
Gas CO2 Separation with Gas
Molten Electrolytes project focus:
Membrane Support
Materials
primary project goals
participant:
Luna Innovations will take a systems-level approach to demonstrating dual phase Luna Innovations
carbon dioxide (CO2) separation membrane solid support technology. Luna will
evaluate yttria-stabilized zirconia (YSZ) and its derivatives as standalone solid project number:
phase supports and in the presence of a single molten carbonate electrolyte. SC0017124
Through modification of current YSZ supports, development of structure-property
relationships, and prototype modeling of scaled-up technology form factors, predecessor projects:
Luna’s solid phase supports will have the unique potential to provide the N/A
performance and scalability to separate CO2 from flue gas in the heat recovery
steam generators (HRSGs). Successful demonstration of this dual phase carbon NETL project manager:
capture and storage (CCS) technology will pave the way for retrofit in high- David Lang
temperature exhausts found in power plant HRSGs. [email protected]
principal investigator:
technical goals
Matthew Merrill
Luna Innovations
• Establish performance and design requirements for the dual phase membrane [email protected]
technology, including the system, safety, and operating parameters for HRSG
integration. Expand multitube module test capabilities. partners:
• Design and fabricate a scalable CO2 separation module prototype. Lawrence Livermore
National Laboratory,
• Perform relevant testing on single and multitube membrane assemblies.
Nooter/Eriksen, University of
Evaluate performance under relevant conditions in long-term (~months) tests Illinois at Chicago
to establish membrane durability and stability.
• Conduct a systems-level analysis and evaluate techno-economic viability. start date:
• Evaluate membrane module performance results and create a module design 02.21.2017
for pilot-scale testing. Develop Phase III plan.
percent complete:
85%
technical content
Luna Innovations, in partnership with the Lawrence Livermore National Laboratory
(LLNL), the University of Illinois, Chicago (UIC), and Nooter/Eriksen, is leading the
scale-up and demonstration of a new type of dual phase membrane technology.
The dual phase membrane consists of a thin wall of nanoporous ceramic solid
phase that retains a non-volatile molten phase within the pores with capillary
action. The molten liquid phase selectively sorbs CO2 with high concentrations and
transport rates. This results in superior separation performance with an unrivaled
combination of CO2 permeability and selectivity of CO2 over nitrogen (N2). This
Small Business Innovation Research (SBIR) program is focusing on developing YSZ
nanoporous solid phase materials to achieve the mechanical performance and
form factors required for integration and operation inside an HRSG or boiler for
operation at 250 to 500°C.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
297
Post-Combustion Membrane Technologies
Currently, there is an unmet need for commercialized membrane systems that can efficiently separate CO2 from power
plant flue gas exhausts at thermally favorable conditions with reduced costs. The proposed solution is to develop a
membrane that uses the difference in water vapor concentration between low-pressure steam and the flue gas to drive
CO2 separation through the membrane. This approach has a theoretical minimum separation energy 10 to 15 times
smaller (0.2 gigajoules [GJ]/ton CO2 at 300°C) than the conventional amine solvents. These high-temperature membranes
have greater potential for large-scale, energy-efficient separation by being directly integrated within power plant HRSGs,
as shown in Figure 1. Luna’s dual phase membrane technology shows potential for meeting the power generation
industry’s needs by separating CO2 from power plant flue gas under operational conditions (250 to 500°C) and with
drastically reduced costs.
Figure 1: Luna’s dual phase membrane technology introduces a unique ability to implement carbon capture technologies into power
plant HRSGs (250 to 500°C).
In the dual phase membrane technology, a porous, solid material supports a non-volatile liquid electrolyte. Carbon
dioxide actively absorbs into the molten electrolyte at the flue gas side, diffuses through the membrane as the carbonate
ion (CO32-) from high to low concentration, and desorbs from the membrane into a steam sweep gas (Figure 2). The steam
sweep serves to both chemically desorb CO2 and minimizes the concentration of permeated CO2.
Figure 2: Luna’s dual phase membrane technology for highly efficient and scalable CCS.
The unique operational conditions and performance capabilities of Luna’s membrane enables a new opportunity to
achieve more energy-efficient and less-expensive carbon capture. This membrane is not limited by the same physics
governing Robeson’s upper bound as conventional, polymer-based membranes and enables unrivaled combinations of
permeability and selectivity (Figure 3). Such a novel system has never before been scaled-up to demonstrate the technical
feasibility at the membrane module scale.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
298 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 3: In a Robeson plot comparison, the Luna team’s membrane (star) outperforms other CO2 separation membrane technologies
funded by the National Energy Technology Laboratory (NETL).
In Phase I of this project, the Luna Innovations team targeted solid phase support materials with high strength, increased
CO2 separation capabilities, and stability in the presence of the new molten electrolyte formulations. It was critical that
these materials were evaluated in context of the HRSG operational conditions to demonstrate their mechanical, thermal,
and chemical stability, as well as their scale-up to larger membrane systems. Luna developed the capability to manufacture
membranes using nanoporous YSZ tubes procured from CoorsTek Ceramics. The nanoporous (~100 nm) ceramic
materials from CoorsTek are 4 mol% YSZ tubes with 1/4-inch outside diameter (OD) and 3/16-inch inside diameter (ID).
These tubes are initially extruded to 120 centimeters (cm) and then cut into smaller segments for this stage of testing by
Luna. The mechanical properties of this high-strength ceramic material were characterized and determined to be scalable
for the operational conditions expected for the membrane. The solid phase materials, fabrication methods, and design
features were successfully developed in Phase I to manufacture and test multitube membrane modules in Phase II.
Luna has extensive experience operating the thermochemical membrane test setup constructed in the early stages of this
Phase II project, which is now being referred to as the Scale I membrane reactor. Modifications to the Scale I reactor
include: (1) automating the application of sequential steps of gas composition and flow rates; (2) complimenting the gas
chromatograph (10-minute resolution) with nondispersive infrared (NDIR) CO2 sensors (one-second resolution) to better
evaluate permeation in real time; (3) modifying membrane holder design; and (4) upgrading to more robust heating
tapes. This Scale 1 reactor presently enables testing of flue gas simulants based on 0 to 500 standard cubic centimeters
per minute (SCCM) of N2, CO2, and oxygen (O2) gases, as well as steam sweep simulants of argon (Ar), water (H2O; up to
30 mol%), and CO2. The concentration of H2O in the steam simulant is limited in the Scale 1 reactor because of the
technical challenges of generating steam with analytical control over flow rate and pressure for scales less than 500 SCCM.
A Scale II membrane reactor is presently under construction that represents a 20-times scale-up for large membrane
modules. The Scale II reactor will be used to test larger CO2 separation membrane modules with advanced features, such
as analytically controlled steam generation for greater than 500 SCCM at 1 to 6 atmospheres (atm).
While Luna has focused on developing low-temperature electrolyte formulations, parametric testing in conditions relevant
to operation, and module scale-up and integration efforts, Luna’s partner, UIC, has transitioned to focusing on
complimentary membrane testing efforts on their smaller test setup. Upon completing the construction of UIC’s two-path
test setup, one path will be dedicated to achieving 1,000 hours of continuous membrane testing. The previous record of
400 hours of continuous membrane testing ended prematurely due to a tube furnace programming error. The other path
will be modified to evaluate the effects, if any, of nitric oxide (NO) and/or nitrogen dioxide (NO2) on membrane
performance and stability.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
299
Post-Combustion Membrane Technologies
Luna has reviewed the options for designing the CO2 separation membrane module. Tube-based form factor designs
remain the most reliable option for further developing and scaling-up the membrane technology primarily based upon
the maturity of possible ceramic material manufacturing methods, as well as the supporting technical capabilities required
to develop a complete, functional membrane module. The current tube module design is based upon a Swagelok flange
and custom interface to multiple short tube samples (Figure 4). This design minimizes module development costs by
using commercially available off-the-shelf (COTS) parts whenever possible, while also supporting flexibility and
adaptability. The goal is to develop and demonstrate the construction and operation of a small module of five short (8
cm) single tubes. Once the basic design and construction approach is established, it is expected to be relatively easy to
scale-up by using larger numbers of longer tubes. Larger Swagelok flange sizes will enable scale-up to 19 single-channel
tubes or eight of the multichannel tubes. CoorsTek tube lengths can be extended to 120 cm. The initial multitube module
has been manufactured and demonstrated to enable scaled-up test and evaluation.
Figure 4: The multitube membrane module with five tubes has been revised to reduce the manufacturing time and costs, while also
enabling easier and more flexible modifications for evolution and scale-up.
Luna has continued to achieve both faster CO2 permeation rates and lower operational temperatures (Figure 5). The
transition to lower operational temperatures is important to enable installation of the membrane system into the HRSG
after the selective catalyst reduction (SCR), where the flue gas has reached temperatures below 400°C. Capturing the CO2
at lower temperatures lowers separation energy costs and avoids the use of higher-temperature steam, which has a higher
value use by generating electricity by the steam turbine. The present low-temperature electrolyte was selected for high
CO2 permeation rates, as well as a relatively wide operational temperature range of 300 to 450°C. The low-temperature
limit of the membrane is generally governed by the freezing of the molten electrolyte phase. Additional molten phase
development efforts may be able to extend the operational temperature down to 250°C; however, the present operational
range is sufficient to demonstrate technical feasibility and the team will move forward to addressing other critical efforts
of the Phase II program.
Figure 5: Progress in both improving the CO2 permeability and decreasing the membrane operational temperatures for more efficient
integration into new and retrofitted HRSGs of NGCC power plants.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
300 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
UIC is presently preparing their two-line test setup for long-term stability testing, as well as stability with regards to NO
and NO2 exposure. The NO and NO2 at 250 parts per million (ppm) will be included in the flue gas simulant, along with
10 mol% O2, which is also present in significant concentrations in flue gases. In combination with oxidation by O2, the NO
and NO2 gases could be incorporated into the molten electrolyte as nitrates. While a thermodynamic evaluation indicates
that only a small concentration of nitrate could form in the molten phase, it is not yet clear whether the nitrogen oxide
(NOX) gases would become captured along with the CO2 by permeation through the membrane or just reach a small,
saturation concentration that would have little effect beyond slightly lowering the electrolyte melting temperature.
Nooter/Eriksen has begun modeling the integration of the CO2 capture membranes into a 370-megawatt (MW) HRSG. If
the target membrane performance metrics are achieved, there is enough space already available in the HRSG to
incorporate the membrane system. The membranes could therefore be incorporated into new HRSGs with relatively little
design modification or retrofit existing HRSGs for carbon capture. Retrofits of HRSGs of existing natural gas combined
cycle (NGCC) power plants is expected to be the largest and most valuable market to target for commercialization. The
membranes would be positioned downstream of the SCR, where flue gas temperature has decreased to about 350°C and
has lower-value heat.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — Molten hydroxide dual phase
Materials of Fabrication for Support Layer — Metal oxide
Nominal Thickness of Selective Layer µm 950 <100
Membrane Geometry — tubes tubes
Max Trans-Membrane Pressure bar 30 30
Hours Tested without Significant Degradation — 400 1,000
Manufacturing Cost for Membrane Material $/m2 300 50
Membrane Performance
Temperature °C 300 300
CO2 Pressure Normalized Flux GPU or equivalent 800 >6,000
CO2/H2O Selectivity — undetermined 0.3
CO2/N2 Selectivity — 999 999
CO2/SO2 Selectivity — undetermined 0.5
Type of Measurement — mixed gas mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — crossflow and countercurrent
Packing Density m2/m3 200
Shell-Side Fluid — steam
Flue Gas Flowrate kg/hr 2,200
CO2 Recovery, Purity, and Pressure %/%/bar 99%, >96%, 140 bar
Pressure Drops Shell/Tube Side bar feed: 1/sweep: 0.3
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
301
Post-Combustion Membrane Technologies
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation through the membrane occurs by the high concentration of H2O in
the steam sweep, selective gas sorption reactions (bicarbonate and carbonate mechanisms).
Contaminant Resistance – Significant quantities of ash in coal power plants represents a contaminant hazard for the
membranes. NGCC power plants have therefore been identified as the target application.
Flue Gas Pretreatment Requirements – The temperature must be less than 450°C.
Membrane Replacement Requirements – The membrane lifetime is currently unknown.
Waste Streams Generated – The membrane process will generate a zirconia-based composite that may be recyclable.
technology advantages
• High thermal, mechanical, and chemical stability.
• Rapidly separates CO2 from flue gas in a temperature range of 250 to 500°C, resulting in improved overall energy
efficiency.
• Uses inexpensive materials.
• The combination of high selectivity and permeability exceeds those of competitive technologies.
• Modular design allows for easy integration with existing power plants.
R&D challenges
• Performance of materials under operational conditions.
• Possibility of degradation due to contaminants.
• Integration with HRSG systems.
• Design and modification of YSZ solid phase supports to prevent material degradation.
status
Multitube module testing is underway.
Nooter/Eriksen is focusing on further developing the systems-level analysis of how the membrane technology can be
integrated into the HRSG and the resulting impact on HRGS performance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
302 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
available reports/technical papers/presentations
Ceron, M., Lai, L., Amiri, A., Monte, M., Katta, S., Kelly, J., Worsley, M., Merrill, M., Kim, S., Campbell, P. “Surpassing the
conventional limitations of CO2 separation membranes with hydroxide/ceramic dual-phase membranes,” Journal of
Membrane Science, 2018, Issue 567, pages 191-198.
https://www.sciencedirect.com/science/article/pii/S0376738818318209.
Merrill, M. “Passive CO2 Separation Membranes for Hot Flue Gases,” presented at the 2018 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/sites/default/files/2018-12/M-Merrill-Luna-
Passive-Separation-Membranes_Aug%202018.pdf.
Merrill, M. “Solid Phase Supports for Flue Gas CO2 Separation with Molten Electrolytes,” Phase I Final Review Meeting,
Pittsburgh, PA, November 2017. https://www.netl.doe.gov/sites/default/files/2018-12/DE-
SC0017142%20Solid%20Membrane%20Materials%20Final%20Review%20NETL%2020171129.pdf.
Merrill, M. “Passive CO2 Separation Membranes for Hot Flue Gases,” presented at the 2017 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2017. https://www.netl.doe.gov/sites/default/files/2018-12/M-Merrill-Luna-
Passive-CO2Separation_Aug%202017.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
303
Post-Combustion Membrane Technologies
Large Pilot Testing of the MTR technology maturity:
Large Pilot-Scale, Actual
Membrane Post-Combustion Flue Gas (140 TPD)
CO2 Capture Process project focus:
Large Pilot Polymer
Membrane System
primary project goals
participant:
The overall goal of this project is to bring Membrane Technology and Research, Membrane Technology and
Inc.’s (MTR) innovative membrane-based post-combustion carbon dioxide (CO2) Research, Inc.
capture process to the final pre-commercial stage of development. The recipient’s
plan in this three-phase project is to design, build, and operate a 140 tonne-per- project number:
day (TPD) large pilot capture system at the host site for the project, the Wyoming FE0031587
Integrated Test Center (WITC) in Gillette, Wyoming. The membrane large pilot will
be designed to achieve ∼70% CO2 capture from a 10 megawatt electricity (MWe) predecessor projects:
equivalent slipstream of flue gas. This range of partial capture using membranes FE0005795
offers the lowest cost of capture ($/tonne CO2). Completion of all phases of this FE0026414
project will signify that the MTR membrane capture process is ready to proceed to FE0007553
the demonstration scale.
NETL project manager:
Sai Gollakota
technical goals [email protected]
• Phase I (completed in year 1) included selection of the host power plant, principal investigators:
securing financial commitments, conducting an environmental review, updating Richard Baker/Brice Freeman
design and budget, and finalizing team commitments and organization for Membrane Technology and
subsequent phases. Research, Inc.
[email protected]
• Phase II (year 2) focuses on the detailed design portion of the program, [email protected]
including a complete front-end engineering and design (FEED) study, National
Environmental Policy Act (NEPA) review, and finalized project cost projections. partners:
• Phase III (years 3 to 6 if chosen from down-select) includes construction, The wyoming Integrated
installation, and operation of the large pilot system. Test Center, Sargent &
Lundy, Trimeric Corporation,
Electric Power Research
technical content Institute
MTR has developed a new class of membranes, called Polaris™, that have 10 times start date:
the CO2 permeance of conventional gas separation membranes. A tenfold increase 04.01.2018
in permeance leads to a tenfold decrease in the required membrane area, which
substantially reduces the capital cost and footprint of the capture system. These percent complete:
membranes, along with innovative process modifications, address challenges for 55%
post-combustion carbon capture.
Over the past decade, MTR has worked with the U.S. Department of Energy (DOE)
to develop these innovations into a cost-effective CO2 capture process. As a result
of these successes, the technology was scaled-up to a 20-TPD (1-MWe) small pilot
system that was operated in slipstream tests at the National Carbon Capture
Center (NCCC). These activities have brought the MTR technology to the point
where it is ready for large pilot evaluation. The large pilot system to be built in this
project will be based on the fully validated Gen-1 Polaris™ membranes. This
membrane has been scaled-up to commercial production quantities. In addition
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
304 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
to successful use for CO2 capture in field tests at NCCC and Babcock & Wilcox Enterprises Inc. (B&W), the Polaris™ Gen-
1 membrane has been used in commercial natural gas and refinery membrane applications.
A simplified version of the process to be used in the pilot plant is shown in the block diagram in Figure 1.
Figure 1: Simplified block diagram of the MTR large pilot CO2 capture plant to be built.
The large pilot unit will capture ∼70% of the CO2 content (140 TPD) from a 10-MWe slipstream of flue gas provided by
WITC. The flue gas to be delivered to the unit is at 85°C and contains 12.7% CO2 and 18% water on average. A blower is
used to increase the flue gas pressure to 1.2 bar absolute. The flue gas is then cooled in a direct contact cooler (DCC). A
dedicated evaporative cooling tower will produce the cooling water required for the DCC and the various vacuum and
compression intercoolers and aftercoolers. The DCC reduces the water content of the gas to 1.5% and increases the CO2
content to ~15%.
The gas leaving the DCC then enters the first-stage membrane modules. The membranes partition the gas into a CO2-
enriched permeate (~50% CO2) and a CO2-depleted vent gas (~4% CO2). The CO2-depleted flue gas is vented to the
atmosphere via a dedicated stack.
The driving force for CO2 permeation is provided by a vacuum pump, which pulls to about 0.1 bar absolute pressure on
the permeate-side of the membrane. From the discharge of the vacuum pump, the CO2-enriched permeate is compressed
to about 1.1 bar and sent to a second-stage membrane, which further enriches the gas to ~85% CO2. The second-stage
membrane unit is much smaller than the first one, and also uses a vacuum pump to provide driving force.
The twice-enriched permeate gas from the second membrane stage is compressed to 25 bar. Some of the water in the
gas is removed in the inter-stage cooler of the compressor. Most of the water that remains is removed from the
compressed gas by cooling to 5°C. A molecular sieve drier is then used to produce bone dry gas. The dry gas is passed
to a low-temperature distillation unit to provide high-purity CO2. The liquid CO2 is then pumped to 153 bar as required
for enhanced oil recovery (EOR) or storage.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
305
Post-Combustion Membrane Technologies
A model of the 140-TPD large pilot membrane skid is shown in Figure 2. The membranes are housed in low-pressure-drop
modules, which reduce cost and increase packing density. There are eight modules per stack and six stacks per container
skid. The skids are stacked two high. This will be the final form factor for this membrane CO2 capture technology. The
membrane portion of the capture plant has a compact footprint, processing 10 MWe of flue gas in an area of approximately
100 by 100 feet, with a maximum height of 30 feet.
Figure 2: Preliminary general arrangement drawing of the 140-TPD large pilot system to be installed at WITC.
WITC will provide the test site and a significant cost-share contribution for the Phase II and Phase III programs. WITC is
located in Gillette, Wyoming, adjacent to the Basin Electric Dry Fork 420-MWe coal power plant. Basin Electric will supply
the project with the equivalent of 10 MWe of flue gas. Duct work and fans to deliver flue gas to the test site are in place.
Power and water necessary for the project have also been installed. The membrane unit will recover ∼70% of the CO2 content
of this gas, or ∼140 TPD. At full-scale, a 70% reduction in CO2 emissions would bring the remaining CO2 emissions of a coal
power plant to below that of an equivalent-sized natural gas power plant.
All of the objectives of the Phase I feasibility study were met. Preliminary engineering drawings for the 140-TPD plant have
been prepared. Budget estimates have been obtained for the major equipment items and initial cost estimates for the Phase
III construction and operation work have been prepared. A preliminary cost analysis indicates that at the end of the Phase
III program, the technology will be ready for scale-up to large demonstrations and CO2 capture costs in the $40/tonne CO2
range will be possible.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer µm <1 <1
Membrane Geometry — flat sheet flat sheet
Max Trans-Membrane Pressure bar 1.1 1.1
Hours Tested without Significant Degradation — 11,000 h 11,000 h
Manufacturing Cost for Membrane Material $/m2 50-100 50-100
(Module and Skid)
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
306 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Membrane Performance
Temperature °C 30 30
CO2 Pressure Normalized Flux GPU or equivalent 1,000 2,000
CO2/H2O Selectivity — 0.3 0.3
CO2/N2 Selectivity — 50 50
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — flue gas flue gas
Proposed Module Design (for equipment developers)
Flow Arrangement — plate-and-frame
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flowrate tons/hr 70.31
CO2 Recovery, Purity, and Pressure %/%/bar 70-75%, 99%, 153 bar
Pressure Drops Shell/Tube Side bar feed: 0.05/sweep: 0.025
Definitions:
Membrane Geometry – Flat discs or sheets, hollow-fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure-gas measurements; target permeance and selectivities should be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation occurs by a passive, solution-diffusion process. Permeation driving
force through the first-stage membrane module is provided by a vacuum pump, which pulls to about 0.1 bar absolute
pressure on the permeate-side of the membrane. The second-stage membrane unit is much smaller than the first one,
and also uses a vacuum pump to provide driving force.
Contaminant Resistance – The membranes are known to be unaffected by water (H2O), oxygen (O2), and sulfur dioxide
(SO2). The effect of trace contaminants, such as Hg, etc., is unknown.
Flue Gas Pretreatment Requirements – Testing at NCCC showed no additional pretreatment was required downstream
of a wet flue gas desulfurization (FGD).
Membrane Replacement Requirements – Greater than three-year membrane lifetime.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
307
Post-Combustion Membrane Technologies
Waste Streams Generated – The membrane process will recover greater than 95% of the H2O in flue gas as liquid. The
quality of this H2O and its potential to be reused in the plant will be studied in future work.
technology advantages
• The process does not use any hazardous chemicals. No new emission streams are produced.
• The membranes developed are 10 times more permeable to CO2 than conventional membranes, which reduce the
required membrane area and capital costs.
• A membrane system does not contain any chemical reactions or moving parts, making it simple to operate and
maintain.
• The system is compact and modular.
• The two-stage membrane design allows for high-purity CO2 combined with high capture rates.
• The low-pressure-drop modules reduce parasitic energy.
• The system is very efficient at partial capture (50 to ∼70%).
R&D challenges
• There is a risk that the membranes may be less stable at large scale than anticipated.
status
The overall design of the 140-TPD large pilot plant was finalized. Preliminary layout drawings for the system at the WITC
site were prepared. Based on the final design, a table listing the expected cost of all the major equipment items was
prepared. This information formed the basis of a preliminary estimate of the Phase III schedule and budget. The Phase II
project team was assembled and a division of responsibilities for the Phase II and Phase III programs was completed.
Finally, WorleyParsons finalized the preliminary environmental information volume (EIV) for the pilot system at WITC.
available reports/technical papers/presentations
Baker, R.W., et al. “Large pilot Testing of the MTR Membrane Post-Combustion CO2 Capture Process,” Phase II kickoff
meeting presentation, Pittsburgh, PA, October 2019. https://www.netl.doe.gov/projects/plp-
download.aspx?id=17214&filename=MTR%20Ph2%20DOE%20Kickoff%20Mtg%20100119.pdf.
Baker, R.W., et al. “Large pilot Testing of the MTR Membrane Post-Combustion CO2 Capture Process,” presented at the
2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13129&filename=R-Baker-MTR-Membrane-Large-Pilot-
Testing.pdf.
Baker, R.W., et al. “Large pilot Testing of the MTR Membrane Post-Combustion CO2 Capture Process,” Phase I kickoff
meeting presentation, Pittsburgh, PA, May 2018. https://www.netl.doe.gov/projects/plp-
download.aspx?id=13128&filename=MTR-Kickoff-Presentation-Public-FE0031587-FOA1788.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
308 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Initial Engineering Design of a technology maturity:
Commercial-Scale Design
Post-Combustion CO2 Capture project focus:
System for Duke Energy's East Polymeric Membrane-Based
Bend Station Using
Process Retrofit
Membrane-Based Technology participant:
Electric Power Research
Institute, Inc.
primary project goals project number:
FE0031589
The Electric Power Research Institute, Inc. (EPRI) will produce an initial
engineering design and cost estimate of a first-of-a-kind, full-scale, membrane-
based post-combustion carbon dioxide (CO2) capture system retrofit to an existing predecessor projects:
U.S. coal power plant. The capture technology is provided by Membrane N/A
Technology and Research (MTR), and the power plant is Duke Energy’s East
Bend Station (EBS) located on the Ohio River in Kentucky. The primary objective NETL project manager:
is to develop a design that will minimize the impact on the power plant by disrupting
Sai Gollakota
as little of the existing facilities as possible, minimizing the cost of each tonne of [email protected]
captured CO2 while also maintaining the net 600 megawatt (MW) output of EBS.
This will be done by optimizing the percentage of CO2 captured from the coal-fired
principal investigator:
power plant (expected to be somewhere between 45 and 75% of the total CO2 in
the flue gas). The initial phase will also examine options for integrating waste heat Desmond Dillon
from the new combustion turbine (CT) with the existing coal plant in order to EPRI
improve the thermal efficiency of the coal-fired unit. Once an optimal configuration [email protected]
is selected, an engineering design, sufficient in detail to support a +/-30% capital
cost estimate, will be generated, along with a techno-economic analysis (TEA). partners:
Membrane Technology and
Research, Inc., Duke Energy,
technical goals
Nexant Inc., Bechtel Inc.,
Trimeric Corporation
• Develop, review, and approve a design basis document for EBS.
• Develop a steam cycle model of an existing power plant and benchmark start date:
existing performance. 04.06.2018
• Optimize the configuration of the membrane CO2 capture system, including a
decision on the level (percentage) of capture for the design that offers the percent complete:
lowest cost on a $/tonne of CO2 captured basis.
80%
• Evaluate options for supplying auxiliary power to the CO2 capture system.
• Develop a complete process design package of the membrane-based CO2
capture system.
• Define retrofit modifications required to integrate the membrane-based process
into EBS and conduct a hazard and operability (HAZOP)/constructability review
of a retrofitted capture facility.
• Complete a TEA for the retrofitted power plant.
technical content
For this retrofit design project, second-generation Polaris™ membranes from MTR
and an optimized level of CO2 capture will be used to reduce capture costs, toward
a goal of $30/tonne CO2. These second-generation Polaris™ membranes have
double the CO2 removal capacity of the original membrane and will be packaged
in low-pressure-drop modules optimized for high-volume flue gas treatment.
Prototypes of these modules have been validated in prior field trials that confirm
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
309
Post-Combustion Membrane Technologies
large energy and cost savings. Targeting a lower degree of capture for this proposed project will obtain a post-combustion
CO2 capture system that provides the lowest cost on a $/tonne CO2 captured basis. Membrane-based post-combustion
CO2 capture systems achieve an optimal cost in the range of 45 to 75% capture.
Duke Energy’s EBS will be the host site for the retrofit study (Figure 1). EBS is a 600-MW-net coal-fired power plant
located on a 1,600-acre site along the Ohio River in Boone County, Kentucky. Duke originally envisioned having multiple
600 megawatt-electric (MWe) units at this site, but only one unit was built. As a result, there is an abundance of space
around the existing facility, which will facilitate the addition of the CO2 capture plant.
Figure 1: Duke Energy’s East Bend Station 600-MWe coal-fired power plant.
The preliminary design case for the EBS post-combustion CO2 capture system is shown in Figure 2. It will be a two-
stage membrane system that aims for 45 to 75% CO2 capture with no boiler recycle.
Figure 2: Preliminary design case for the East Bend unit.
Unlike solvent post-combustion CO2 capture systems, there is no steam requirement for the membrane system. However,
power is required to drive the membrane system’s fans, blowers, vacuum compressors, pumps, and CO2 compression.
To make up for the increased auxiliary load imposed by the post-combustion CO2 capture system, and to minimize the
disruption to the existing power plant, the addition of a natural gas-fired CT power plant to the EBS site was investigated.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
310 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Four integration options were considered to provide power to the optimized membrane system retrofit:
1. New natural gas-fired simple cycle (maintain original net output).
2. New combined cycle (maintain original net output).
3. New simple cycle with additional waste heat recovery unit sized to supplying steam to power plant feedwater heaters.
4. Auxiliary power supplied from existing station (decrease net output).
Option 1 with the MTR post-combustion CO2 capture plant supported by a single gas turbine simple cycle (GTSC) power
island was determined to be the best arrangement for this project. It was found to provide:
• The lowest upfront cost of all the external power options considered.
• A phased implementation of feedwater pre-heat if required later (phase in Option 3 if required).
• Enough temperature and heat available for future EBS high-pressure feedwater preheating, if desired.
• Potential for future retrofit with full-size heat recovery steam generator (HRSG) for additional power export if New
Source Review (NSR) regulations are relaxed.
• A well-established commercial operation history.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer µm <1 <1
Membrane Geometry — flat sheet flat sheet
Max Trans-Membrane Pressure bar 1.1 1.1
Hours Tested without Significant Degradation — 11,000 (coal) 11,000 (coal)
Manufacturing Cost for Membrane Material $/m2 50-100 50-100
Membrane Performance
Temperature °C 30 30
CO2 Pressure Normalized Flux GPU or equivalent 1,600 1,600
CO2/H2O Selectivity — 0.3 0.3
CO2/N2 Selectivity — 50 50
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — Actual flue gas Actual flue gas
Proposed Module Design (for equipment developers)
Flow Arrangement — plate-and-frame
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flowrate kg/hr 2,661,428
CO2 Recovery, Purity, and Pressure %/%/bar 50-70%, >99%, 153 bar
Pressure Drops Shell/Tube Side bar feed: <0.05/sweep: 0.025
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
311
Post-Combustion Membrane Technologies
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation occurs by a passive, solution-diffusion process. Permeation driving
force through the first-stage membrane module is provided by a vacuum pump, which pulls to about 0.1 bar absolute
pressure on the permeate-side of the membrane. The second-stage membrane unit is much smaller than the first one,
and also uses a vacuum pump to provide driving force.
Contaminant Resistance – Very fine particulates flow through the membrane channels and are discharged to the stack.
Nitrogen oxides (NOX) will not harm the membranes. The sulfur oxides (SOX) that reach the membrane will not harm it.
Some trace elements may reach the membrane. Their effect on the post-combustion CO2 capture system is unknown.
Flue Gas Pretreatment Requirements –The flue gas desulfurization (FGD) system at EBS will remove SOX, hydrogen
chloride, soluble salts, and particulate matter (PM). EBS is also equipped with an electrostatic precipitator that will remove
PM.
Membrane Replacement Requirements – Membrane modules will nominally be replaced every three years.
Waste Streams Generated – The post-combustion CO2 capture system will generate liquid waste streams in the form
of water condensate streams. Experience from test campaigns show that these streams are acidic and will either need
to be pH-corrected prior to discharge or be combined and managed with other liquid waste streams present at the host
power plant. Disposition and possible re-use of the condensates at EBS (e.g., as FGD makeup water) will be investigated
as part of this design study. The current industry practice for membrane plants is to landfill the spent membrane elements.
As part of the environment, health, and safety (EH&S) evaluation, the project team will review federal and state
regulations regarding solid waste steams to determine if any flue gas contaminates entrained in the spent modules may
require special handling or disposal. MTR’s current understanding is that no special disposal measures are needed.
technology advantages
• The process does not use any hazardous chemicals. No new emission streams are produced.
• Reduces coal plant CO2 emissions to those of a natural gas-fired plant.
• Utilizes MTR’s second-generation Polaris™ membranes with CO2 permeance two times that of their first-generation
membrane technology.
• No modifications to existing plant steam cycle; potential to avoid NSR.
• Simple passive operation; no degradation caused by flue gas SOX and NOX.
• Compact modular system design.
R&D challenges
• Minimizing the cost of each tonne of CO2 captured while maintaining current net output of the 600-MWe station.
• Efficiently supplying auxiliary power to the capture system at low cost.
status
The general arrangement of the membrane capture process has now been established, with the number and position of
membranes, flow streams, membrane areas, expected utility requirement, and capture rate all calculated. Various
sensitivities, such as the impact of air in-leakage and ambient temperature effects on the membrane system, have also
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
312 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
now been examined and quantified. An option for auxiliary power has been chosen. The final overall design for the post-
combustion CO2 capture system retrofit is complete with major equipment specified and capital cost being finalized.
available reports/technical papers/presentations
Dillon, D.,” Initial Engineering Design of a Post-Combustion CO2 Capture System for Duke Energy’s East Bend Station
Using Membrane-Based Technology,” presented at the 2019 NETL Carbon Capture, Utilization, Storage and Oil and
Gas Technologies Integrated Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-
file/D-Dillon-EPRI-East-Bend-Membrane.pdf.
Bhown, A., “Initial Engineering Design of a Post-Combustion CO2 Capture System for Duke Energy’s East Bend Station
using Membrane-Based Technology,” presented at the 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/plp-download.aspx?id=13091&filename=A-Bhown-
EPRI-Duke-Energys-East-Bend-Station.pdf.
Dillon, D., “Initial Engineering Design of a Post-Combustion CO2 Capture System for Duke Energy’s East Bend Station
using Membrane-Based Technology,” Kick-off meeting presentation, Pittsburgh, PA, June 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13090&filename=EPRI-KickOff-Meeting-FE0031589-
FOA1791.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
313
Post-Combustion Membrane Technologies
Development of Self-Assembly technology maturity:
Bench-Scale, Actual Flue
Isoporous Supports Enabling Gas
Transformational Membrane project focus:
Performance for Cost-Effective
Polymeric Membranes
Carbon Capture participant:
Membrane Technology and
Research, Inc.
primary project goals project number:
FE0031596
Membrane Technology and Research, Inc. (MTR) is developing composite
membranes with superior carbon capture performance using a novel
transformational approach. Two membrane targets have been identified: (1) predecessor projects:
carbon dioxide (CO2) permeance of 4,000 gas permeation units (GPU) with mixed- N/A
gas CO2/nitrogen (N2) selectivity of 25, and (2) CO2 permeance of 3,000 GPU with
mixed-gas selectivity of 50. The first type will be used in the CO2 removal step and NETL project manager:
the second type will be used in the CO2 sweep step, both of which are parts of
Isaac Aurelio
MTR’s innovative post-combustion CO2 capture process. [email protected]
technical goals principal investigator:
Hans wijmans
• Develop methods to produce isoporous supports, first manufacturing single- Membrane Technology and
layer supports (14 inches wide) using the laboratory’s continuous casting Research, Inc.
system and then manufacturing dual-layer supports (40 inches wide) using [email protected]
MTR’s commercial-scale casting equipment.
• Synthesize and characterize polymers containing high ether-oxygen content for
partners:
CO2/N2 separation, and down-select polymers with most promising CO2/N2 State University of New York
separation properties for scale-up and production of composite membranes. at Buffalo, University of Texas
• Prepare composite membranes by coating selective layers onto isoporous at Austin
support, first using a laboratory-scale coating machine (12 inches wide) and
then using MTR’s commercial-scale coater (40 inches wide). start date:
• Fabricate and test laboratory-scale spiral-wound and plate-and-frame modules, 06.01.2018
optimize the design to minimize pressure drop, and produce prototype modules
of both types for testing at the National Carbon Capture Center (NCCC). percent complete:
• Design a bench-scale test skid for testing prototype membrane modules. 33%
• Install and operate a test skid at NCCC for at least three months with actual
coal-fired flue gas.
• Perform a techno-economic analysis (TEA) and sensitivity analysis of the
process.
technical content
MTR will develop composite membranes with superior CO2 capture performance
using a novel transformational approach. Composite membranes consist of a
selective polymer layer coated on a support that, ideally, does not hinder transport
in the selective layer. MTR has conclusively demonstrated that this objective is not
met for current supports when coated with very thin selective layers, leading to a
reduction in permeance by a factor of two or larger. The proposed three-year
project consists of two parallel technology developments that address the support
issue, as well as the development of more selective materials.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
314 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
The first development is to replace the conventional porous supports used to fabricate composite membranes with novel
isoporous supports. The remarkable pore structure of isoporous supports is created through self-assembly of block
copolymers and is the ideal surface to support the nonporous layers that perform the separation in composite membranes.
Work at MTR has shown that the surface pore structure of conventional supports restricts diffusion in the adjacent
selective layers, and this geometrical effect significantly reduces the permeance of layers thinner than 1 micron. The high
surface porosity and uniformity in pore size and pore location of the isoporous supports (Figure 1) eliminates this
restriction and allows fabrication of Polaris™ composite membranes with significantly increased CO2 permeances as high
as 4,000 GPU. Building on extensive work on isoporous membranes reported in the open literature, the isoporous support
preparation methods will be adapted to MTR’s commercial membrane casting equipment.
Figure 1: Surface pore structure of (a) a conventional porous support, and (b) an isoporous support.
The probability of successfully producing isoporous supports at commercial scale is high. The method to be used is very
similar to existing methods for the manufacture of conventional supports. Moreover, the isoporous support, while of great
importance, does not perform the actual separation, which means the occasional pore defects or misalignments are able
to be tolerated. This is unlike the ultrafiltration and nanofiltration applications that are the traditional focus of isoporous
membrane development.
The project team has prepared many support membranes using the Polystyrene-b-Poly-4-vinylpyridine (BCP1) polymer
and has used scanning electron microscopes (SEMs) to evaluate the structures obtained. It is not easy to create the very
perfect isoporous surfaces that are reported in the literature for these block copolymers. These surfaces likely represent
a few out of many attempts, with the unsuccessful attempts not being reported. However, in the current work, perfect
isoporous surfaces are not required; only surfaces that are an improvement over the conventional support membranes
are needed. Figure 2 shows the top surface of a BCP1 support that by no means is perfectly isoporous, but is expected
to be a better support membrane than the conventional support made by MTR, of which a surface SEM is shown in the
inset.
Figure 2: Top surface of a BCP1 support membrane. The inset is a conventional polyethylenimine (PEI) support.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
315
Post-Combustion Membrane Technologies
The second development within this project is to build on materials research carried out at the University of New York at
Buffalo (NYUB), where materials have been identified that, in the form of films, have shown the potential to double the
mixed-gas selectivity of the Polaris™ membrane, albeit at the expense of permeability. Variations of the materials will be
synthesized at NYUB, and MTR will produce and test composite membranes using both conventional porous supports
and the novel isoporous supports. It is expected that by using the isoporous supports, composite membranes can be
produced that are significantly more selective than the current Polaris™ membrane without increasing the membrane
area required.
Recently, the research group at NYUB has developed a new series of copolymers based on poly(1,3 dioxolane), which
has the highest ether-oxygen (O)/carbon (C) ratio of any known chemical structure and significantly higher than
polyethylene oxide (PEO) (O/C ratio of 0.67 versus 0.5 for PEO). Initial work has confirmed that the higher ether-oxygen
content leads to superior CO2/N2 separation properties. In the proposed project, a series of PDXLA-co-PDXLEA materials
will be thoroughly evaluated with simulated flue gas at various temperatures, pressures, and compositions.
Some of the new materials developed at NYUB are 25 to 50% less permeable than the Polaris™ polymer, but have
shown mixed-gas selectivities for CO2 over N2 as high as 50 at temperatures between 50 and 60ºC. This mixture
selectivity is nearly double what Polaris™ would give at this temperature. Figure 3 compares the predicted performance
of these materials coated directly on an isoporous support with Polaris™ performance. The data point on the PPDXLA
curves represents the target performance for the new Polaris™ high selectivity (HS). This type of performance is well-
suited for the sweep step in MTR’s patented process design.
Figure 3: (a) Mixed-gas CO2 permeance and (b) CO2/N2 selectivity as a function of selective layer thickness for Polaris™ and PPDXLA on an
isoporous support.
The research group at NYUB will focus on the synthesis of polymers containing high ether-oxygen content for CO2/N2
separation. The production of polymers will be optimized and scaled-up gradually. The polymers with the most promising
properties will be delivered to MTR for the production of thin-film composite membranes and then bench-scale membrane
modules.
Composite membranes will be prepared by coating selective layers onto the isoporous support produced. The selective
materials used will be (1) MTR’s Polaris™ formulation and (2) the selective materials to be developed by NYUB.
Composite membranes will be characterized first in pure-gas permeation experiments with CO2 and N2. Promising
membranes will be tested more extensively, including pure-gas permeation at different pressures and temperatures, and
experiments with CO2/N2/O2 mixtures representative of coal-derived flue gas. It is expected that the coating step with
Polaris™ will be straightforward, as MTR has considerable experience with this material. More development and
optimization work will be required for the newly developed materials.
The very high permeance membranes under development will require a redesign of the feed and permeate channels in
the MTR planar membrane module. A few options to reduce pressure-drop in those channels are starting to be developed.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
316 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer µm <1 <1
Membrane Geometry — planar planar
Max Trans-Membrane Pressure bar 70 70
Hours Tested without Significant Degradation — 10,000+ hrs (coal) 10,000+ hrs (coal)
Manufacturing Cost for Membrane Material $/m2 50 10
Membrane Performance
Temperature °C 30 30
Type 1: 4,000
CO2 Pressure Normalized Flux GPU or equivalent 1,700
Type 2: 3,000
CO2/H2O Selectivity — 0.3 0.3
Type 1: 25
CO2/N2 Selectivity — 60
Type 2: 50
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — pure gas mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — crossflow and countercurrent
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flowrate kg/hr 500
CO2 Recovery, Purity, and Pressure %/%/bar 90%, >96%, 140 bar
Pressure Drops Shell/Tube Side bar feed: <0.05/sweep: 0.05
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation of individual components through the Polaris™ membrane is driven
by partial pressure differences across the membrane generated by a permeate vacuum.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
317
Post-Combustion Membrane Technologies
Contaminant Resistance – The membranes are known to be unaffected by water (H2O), oxygen (O2), and sulfur dioxide
(SO2). The effect of trace contaminants, such as Hg, arsenic, etc., is unknown.
Flue Gas Pretreatment Requirements – Currently, pretreatment requirements are unknown.
Membrane Replacement Requirements – Membrane lifetime is estimated at three years.
Waste Streams Generated – The membrane process will recover greater than 95% of the H2O in flue gas as liquid.
technology advantages
• The novel isoporous supports increases the CO2 permeance (up to 4,000 GPU).
• The novel membrane selective layer material nearly doubles the CO2/N2 selectivity compared to membranes that use
Polaris™ selective material.
• The two-stage capture process allows for high CO2 capture rates and a high-purity product.
• The selective recycle of CO2 to the boiler using the air sweep stream increases the CO2 concentration in flue gas,
reducing capital and operating expenditures.
R&D challenges
• Producing dual-layer isoporous supports.
• Scale-up of polymer synthesis of improved selective layer materials.
• Coating of novel selective layer on isoporous support.
status
MTR continued to vary casting formulations and conditions to identify promising support membrane structures. Although
a truly isoporous surface structure has not been produced yet, some of the support membranes exhibit promising surface
porosity that may be superior to conventional supports used commercially. Membranes prepared from new selective layer
materials synthesized by NYUB show pure-gas CO2/N2 selectivity up to 89, which is considerably higher than
conventional Polaris™ membranes (CO2/N2 selectivity = 50) and demonstrates the potential of this approach.
available reports/technical papers/presentations
Wijmans, H., et al. “Development of Self-Assembly Isoporous Supports Enabling Transformational Membrane
Performance for Cost Effective Carbon Capture,” Kickoff meeting presentation, Pittsburgh, PA, September 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=12056&filename=Development%20of%20Self-
Assembly%20Isoporous%20Supports%20Enabling%20Transformational%20Membrane%20Performance%20for%20C
ost%20Effective%20Carbon%20Capture%20Sept%202018.pdf.
Wijmans, H., et al. “Development of Self-Assembly Isoporous Supports Enabling Transformational Membrane
Performance for Cost Effective Carbon Capture,” presented at the 2018 NETL CO2 Capture Technology Project Review
Meeting, Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/plp-
download.aspx?id=12057&filename=Development%20of%20Self-
Assembly%20Isoporous%20Supports%20Enabling%20Transformational%20Membrane%20Performance%20for%20C
ost%20Effective%20Carbon%20Capture%20Aug%202018.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
318 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Bench-Scale Development of technology maturity:
a Transformational Graphene
Bench-Scale, Actual Flue
Gas
Oxide-Based Membrane project focus:
Process for Post-Combustion
Graphene Oxide
Membranes
CO2 Capture participant:
Gas Technology Institute
primary project goals
project number:
FE0031598
Gas Technology Institute (GTI) is developing a transformational graphene oxide
(GO)-based membrane process that can be installed in a new or retrofitted into an predecessor project:
existing pulverized coal or natural gas power plant for carbon dioxide (CO2) FE0026383
capture ready for demonstration by 2030. The expected product from this project
will be a compact, GO-based membrane prototype system capable of achieving at NETL project manager:
least 70% CO2 removal with a single-stage process and 90% CO2 removal with a Andrew O’Palko
two-stage process. The system will be tested over an extended duration on actual [email protected]
flue gas at GTI and the National Carbon Capture Center (NCCC).
principal investigator:
Shiguang Li
technical goals
Gas Technology Institute
[email protected]
• Scale-up the GO-based membranes to 50 to 100 cm2 area and demonstrate
that the scaled membranes show CO2/nitrogen (N2) selectivity ≥200 and CO2 partners:
permeance ≥1,000 gas permeation units (GPU) for the high-selectivity Rensselaer Polytechnic
membranes (designated as GO-1 membranes), and CO2/N2 selectivity ≥20 and Institute, The Ohio State
CO2 permeance ≥2,500 GPU for the high-flux membranes (designated as GO-2 University, Trimeric
membranes). Corporation
• Perform 100 hours of stability testing to demonstrate the CO2 permeance and
start date:
CO2/N2 selectivity decrease by less than 10% in the presence of flue gas
contaminants (oxygen [O2], sulfur oxide [SOX], nitrogen oxide [NOX]). 06.01.2018
• Scale-up the GO-based membranes to 500 to 1,000 cm2 area and demonstrate percent complete:
that the scaled membranes show CO2/N2 selectivity ≥200 and CO2 permeance
30%
≥1,000 GPU for the GO-1, and CO2/N2 selectivity ≥20 and CO2 permeance
≥2,500 GPU for the GO-2.
• Achieve 95% CO2 purity by integrating the GO-1 and GO-2 membranes in a skid
(designated as GO2) for both natural gas and coal-derived flue gases.
• Perform a techno-economic analysis (TEA) to validate that the cost of electricity
(COE) is 30% less than the U.S. Department of Energy (DOE) baseline CO2
capture approach.
technical content
GTI is developing GO-based membranes for CO2 capture from flue gases. The
high-selectivity membranes (GO-1) show CO2 permeances as high as 1,020 GPU
with a CO2/N2 selectivity of 680, which is much higher than state-of-the-art
membranes. In addition, GTI is also developing high-flux membranes (GO-2) with
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 319
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
CO2 permeance as high as 2,500 GPU using GO quantum dots (GOQD) as a membrane building block. The proposed
transformational GO-based membrane process integrates the GO-1 and GO-2 membranes (GO2), offering a new
opportunity to explore further reductions in the cost of CO2 capture.
Graphene-based materials, such as graphene and GO (Figure 1), have been considered as next-generation membrane
materials. They are only sub-nanometer thick and thus may form ultrathin separation membranes to minimize transport
resistance and maximize flux. The feasibility of using a vacuum filtration process to fabricate ultrathin GO membranes
(thickness of ~1.8 nm) has been demonstrated. It was observed that the molecular-sized pores of structural defects on
GO flakes could serve as a transport pathway for selective gas separations.
Figure 1: Chemical structural model of GO.
Because of the different morphologies of GO and GOQDs, ultrathin membranes (less than 20 nm) composed of these two
different building blocks are expected to have different nanostructures. Figure 2 shows different membrane
nanostructures of GO-1 and GO-2 membranes and the proposed transport pathways.
Figure 2: Membrane nanostructures of GO-1 and GO-2 membranes and proposed CO2 separation mechanisms.
Large GO flakes (greater than 100 nm) with high aspect ratio of lateral size to the flake thickness typically lead to regular
and uniform lamellar structure (GO-1, left in Figure 2) with a negligible quantity of defects after hydration of surface
functional amine groups with water in the flue gas. As a result, CO2 molecules can quickly transport through the membrane
by a facilitated transport mechanism via reaction with amine (CO2 + R-NH2 ↔ R-NH3+ + HCO3-) and block the permeation
of N2 molecules. Therefore, GO-1 membranes have moderate CO2 permeance but high CO2/N2 selectivity. In contrast, in
GO-2 membranes, the small GOQDs may form a randomly packed nanostructure (right in Figure 2) containing defects
that cannot be effectively sealed by the hydration layer. These defects greatly increase the CO2 permeance, but also
decrease the selectivity. Therefore, GO-2 membranes are expected to have high CO2 permeance but lower CO2/N2
selectivity compared to the GO-1 membranes.
In addition to the hollow fiber GO-based membranes, the project team demonstrated for the first time an easy, fast, and
scalable printing method with advanced computational controls to deposit ultrathin, high-quality GO-based membranes
on a polymeric support for gas separation. A commercial ink cartridge was used to hold an appropriate GO dispersion
for printing (Figure 3a). Using only GO “ink,” ultrathin GO membranes for highly effective water nanofiltration have been
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
320 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
printed. To promote membrane separation performance for a CO2/N2 mixture, an extra cartridge was added that holds
various amine solutions, such as ethylene diamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA), to increase both CO2 permeance and CO2/N2
selectivity (Figure 3b). Uniform GO coatings with well-controlled thickness and a membrane area as large as 225 cm2 have
been printed (Figure 3c). Figure 3d shows a typical cross-sectional scanning electron microscopy (SEM) of the printed
membrane. Figure 3e indicates the thicknesses of the printed membranes are between 6 and 60 nm and can be well-
controlled by the GO concentration.
Figure 3: (a) Schematics of GO membrane fabrication by inkjet printing; (b) GO-based membrane preparation by printing from two
cartridges containing GO ink and additives; (c) a picture of a printed GO membrane (15 cm × 15 cm); (d) cross-sectional SEM of the
membrane; (e) dependence of membrane thickness on GO ink concentration.
The project team prepared GO-based flat-sheet membranes on a polyether sulfone (PES) substrate by printing. The
resulting membrane was sealed in a plate-and-frame module for characterization and CO2/N2 separation testing.
The project team coated GO-based membranes on 50- to 100-cm2 PES porous hollow-fiber modules by a vacuum
filtration process. The sub-recipient systematically synthesized and optimized single-layered GO flakes via different GO
synthesis methods. A variety of equipment was used to characterize the membrane morphology, thickness, composition,
and structural defects density. The CO2/N2 separation properties were measured using an existing laboratory-scale testing
system and simulated flue gas.
For coal-fired flue gas, the proposed GO2 technology is designed to capture 90% CO2 with greater than 95% CO2 purity.
The system will be installed downstream of flue gas desulfurization (FGD), as shown in Figure 4. It is a compact, stand-
alone, membrane-based process, enabling easy integration into the power plant.
Figure 4: Process flow diagram for the proposed GO2 process for CO2 capture.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 321
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — Graphene Oxide
Materials of Fabrication for Support Layer — Polyether sulfone
0.002-0.05 for GO-1 0.002-0.02 for GO-1
Nominal Thickness of Selective Layer m
0.005-0.1 for GO-2 0.005-0.05 for GO-2
Membrane Geometry — Hollow fiber and flat sheet Hollow fiber and flat sheet
Max Trans-Membrane Pressure bar <5 1
>200
Hours Tested without Significant Degradation — 20
(actual flue gas)
Manufacturing Cost for Membrane Material $/m2 TBD TBD
Membrane Performance
80 for GO-1
Temperature °C 65
70 for GO-2
1,020 for GO-1 1,000 for GO-1
CO2 Pressure Normalized Flux GPU
2,500 for GO-2 2,500 for GO-2
1/10 for GO-1 <1/10 for GO-1
CO2/H2O Selectivity —
N/A for GO-2 <1/10 for GO-2
680 for GO-1 >200 for GO-1
CO2/N2 Selectivity —
>30 for GO-2 >20 for GO-2
N/A for GO-1 <1/10 for GO-1
CO2/SO2 Selectivity —
N/A for GO-2 <1/10 for GO-2
Type of Measurement — mixed gas mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — Crossflow
Packing Density m2/m3 1,000
Shell-Side Fluid — CO2-rich permeate
Flue Gas Flowrate kg/hr TBD
CO2 Recovery, Purity, and Pressure %/%/bar 70-90%, >95%, TBD
Pressure Drops Shell/Tube Side psi/m Feed and permeate: <1.5
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
322 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – A vacuum pump is used on the permeate side to provide a vacuum of 2.9 pounds
per square inch absolute (psia; 0.2 bar). Because the GO-based membranes are highly water-permeable, the water vapor
in the flue gas permeates through the membrane and lowers the partial pressure of CO2 in the permeate side. Thus, the
applied vacuum provides enough driving force for CO2 permeation. The CO2-depleted residue leaving the GO-1 unit is
sent to a second membrane unit, GO-2, which also uses a vacuum on the permeate side to create the driving force for
separation.
Contaminant Resistance – GO is typically prepared under strong acid and oxidation conditions in an aqueous solution,
so it is expected to be very stable under these harsh conditions. Additionally, GO is hydrothermally stable at 150°C and
has good chemical stability and mechanical strength. Therefore, GO is expected to be stable under flue gas conditions
and with flue gas contaminants, such as nitrogen dioxide (NO2), SOX, etc.
Flue Gas Pretreatment Requirements – The proposed GO2 system will be installed downstream of FGD.
Membrane Replacement Requirements – TBD
Waste Streams Generated – No waste streams are generated. The GO-based membranes are selective for water (H2O)
over CO2, and the proposed GO2 technology can recover the water vapor from the permeate streams. The recovered,
mineral-free, high-purity water can be reused by the power plant.
technology advantages
• The technology achieves high CO2 capture rates (≥70%) with 95% CO2 purity.
• The water-permeable feature of the GO membrane overcomes the process pressure limitation issue, enhancing mass
transfer.
• GO membranes have high thermal/chemical stability and mechanical strength.
• Graphene-based materials such as GO have been considered next-generation membrane materials. They are only sub-
nanometer thick and thus may form ultrathin separation membranes to minimize transport resistance and maximize
flux.
• GTI’s printing method for GO membrane formation has several advantages, including:
o Low-cost, fast, and scalable deposition of ultrathin GO-based membranes.
o Capability of controlling coating properties by controlling printing parameters.
o High utilization efficiency of GO material without waste.
o Flexibility of forming GO-hybrid coatings by introducing desired additives.
R&D challenges
• When scaling-up GO-based membranes, the CO2 permeance and/or CO2/N2 selectivity may not scale with size.
• There is risk that membrane sealing issues will be encountered in the development process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 323
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
• The commercial PES substrate quality is not sufficiently high for scale-up of GO-based membranes yet.
status
The preparation conditions of GO- and GOQD-based membranes on both hollow-fiber support and flat sheet support
have been optimized.
A nitrogen-doped, GO-based membrane showed a CO2 permeance as high as 2,800 GPU with a CO2/N2 selectivity of 150
at 90°C, 100% feed humidity, and 0.3 bara pressure on the permeate side. This type of membrane can be employed as
the GO-1 membrane in the GO2 process.
Carbon dioxide separation performance was investigated by using different amines mixed with GO. For a GO-based
membrane prepared by printing, CO2 permeance of greater than 2,500 GPU with CO2/N2 selectivity of greater than 30
was achieved. This type of membrane can be employed as the GO-2 membrane in the GO2 process.
available reports/technical papers/presentations
Li, Shiguang, et al. “Bench-Scale Development of a Transformational Graphene Oxide-Based Membrane Process for
Post-Combustion CO2 Capture,” presented at the 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/Bench-
Scale%20Development%20of%20a%20Transformational%20Graphene%20Oxide-
Based%20Membrane%20Process%20for%20Post-Combustion%20CO2%20Capture%20Aug%202018.pdf.
Li, Shiguang, et al. “Energy Efficient GO-PEEK Hybrid Membrane Process for Post-Combustion Carbon Dioxide Capture,”
presented at the 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/S-Li-GTI-Energy-Efficient-GO-PEEK-Hybrid-Membrane-Process.pdf.
Li, Shiguang, et al. “Energy Efficient GO-PEEK Hybrid Membrane Process for Post-Combustion Carbon Dioxide Capture,”
presented at the 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/projects/files/FE0026383-March-22-2017-BP1-Review.pdf.
Li, Shiguang, et al. “Energy Efficient GO-PEEK Hybrid Membrane Process for Post-Combustion CO2 Capture,” presented
at the BP1 Review Meeting, Pittsburgh, PA, March 2017. https://www.netl.doe.gov/projects/files/FE0026383-March-22-
2017-BP1-Review.pdf.
Li, Shiguang, et al. “Energy Efficient GO-PEEK Hybrid Membrane Process for Post-Combustion CO2 Capture,” presented
at the presented at the 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/projects/files/S-Li-GTI-Go-Peek-Hybrid-Membrane-Process.pdf.
Li, Shiguang, et al. “Energy Efficient GO-PEEK Hybrid Membrane Process for Post-Combustion CO2 Capture,” presented
at the project kickoff meeting, Pittsburgh, PA, December 2015. https://www.netl.doe.gov/projects/files/FE0026383-
Kickoff-Presentation.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
324 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Scale-Up and Testing of technology maturity:
Advanced Polaris Membrane
Engineering-Scale, Actual
Flue Gas (equivalent to 1
CO2 Capture Technology
MWe)
project focus:
Polymeric Membranes
primary project goals
participant:
Membrane Technology and Research, Inc. (MTR) will design, build, and operate an Membrane Technology and
advanced Polaris™ membrane carbon dioxide (CO2) capture system at the Research, Inc.
Technology Centre Mongstad (TCM) using actual flue gas from a refinery catalytic
cracker, which simulates coal flue gas. This test system will validate recent project number:
membrane technology advancements and mitigate risk in future scale-up FE0031591
activities. The overall MTR membrane process will show the potential to meet the
2030 U.S. Department of Energy (DOE) target of $30/tonne CO2 captured from predecessor projects:
coal-fired power plants. This project will demonstrate a cost-effective advanced FE0005795
membrane process to capture CO2 from flue gas through slipstream tests at TCM FE0026414
using commercial-scale components. Results from this field test will provide
performance data to allow a thorough technical and economic evaluation of the NETL project manager:
proposed membrane process. Successful completion of this project will signify Isaac Aurelio
readiness to proceed to the next step – testing a larger proof-of-concept advanced [email protected]
membrane system on the scale of 10 to 25 megawatts-electric (MWe).
principal investigator:
Tim Merkel
technical goals Membrane Technology and
Research, Inc.
• Design the membrane test system and complete host site preparations. [email protected]
• Fabricate commercial-scale membranes and low-pressure-drop membrane
partners:
modules.
Technology Centre
• Fabricate membrane test system skid, with membrane modules incorporated Mongstad, Dresser-Rand,
into skid, and install system at TCM. Trimeric Corporation,
• Conduct a minimum six-month field test, including three months of steady- WorleyParsons/Advisian
state operation and parametric tests that focus on verifying system
performance at partial capture rates that minimize capture costs. start date:
08.01.2018
• Evaluate optimal integration of advanced compression into the membrane
capture process, including cost estimates.
percent complete:
• Complete a techno-economic analysis (TEA) and environmental, health, and 39%
safety (EH&S) assessment of the membrane capture technology.
technical content
In this project, no additional membrane development is required. A previously
validated second-generation (Gen-2) membrane will be scaled-up to commercial
manufacturing equipment. It is expected that this production scale-up process will
produce cost savings through bulk materials usage and application of automated
manufacturing equipment.
The goal of this project is to scale-up advanced Polaris Gen-2 membranes and
modules to a final form optimized for commercial use, and to validate their
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 325
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
transformational potential in an engineering-scale field test at TCM. This program will expand on work conducted by MTR
over the past decade with DOE support to develop efficient membrane CO2 capture technology. This effort has produced
the MTR Polaris class of membranes and a patented selective recycle process design that lowers the cost of capture.
Over the course of this development effort, key improvements made were higher-permeance membranes, low-pressure-
drop modules, and a process design that optimizes the efficiency of capture.
The Gen-2 Polaris membranes have demonstrated double the CO2 removal capacity of the original membrane in bench-
scale tests at the National Carbon Capture Center (NCCC) (Figure 1). They will be packaged into new modules designed
for low-pressure flue gas treatment. Prototypes of these modules have been validated in prior field trials that confirm
large energy and cost savings. Assemblies of these modules will be fitted into a standard container that represents the
final form factor for this technology, with future commercial systems simply utilizing large numbers of this modular repeat
unit.
Figure 1: A CO2/N2 trade-off plot showing data for two generations of MTR Polaris membrane. Data are pure-gas values at room
temperature.
These step-change material and device advances will be incorporated into a system design that takes advantage of the
inherent efficiency of membranes for bulk separations. Capture costs can be minimized by operating at partial capture
rates (50 to 75%), while still reducing coal plant CO2 emissions to that of a gas-fired power plant or less. Finally, the pairing
of Polaris Gen-2 membrane technology with advanced compression technology will be investigated. This technology
combination was previously featured in the DOE Pathways Study as an attractive way to reach future cost targets.
In addition to an advanced membrane material, this project will also utilize a new type of low-pressure-drop module. This
plate-and-frame module, in addition to its relatively compact size, had about four times lower pressure-drop at the same
test conditions as the spiral modules during field testing at NCCC (Figure 2), resulting in large energy savings.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
326 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 2: Difference in pressure-drop between spiral and plate-and-frame modules in NCCC field tests.
To reduce the cost of the membrane modules, MTR plans to fabricate them from structural plastics. During this project,
a mold flow analysis was completed for the new module design. With this analysis, any issues with the mold design can
be identified prior to actual fabrication of the mold and the molding company can determine how to operate their
machinery with the MTR mold. Various process parameters were profiled and optimized, including temperature, pressure,
number of gates, and gate locations.
Using the mold flow analysis, MTR, along with the domestic mold fabricator and custom plastics injection molding
companies, finalized a mold design. A detailed drawing of the new planar stack containing eight membrane modules is
shown in Figure 3.
Figure 3: Detailed drawing of a membrane module stack containing eight membrane modules.
Figure 4 shows a simple process flow diagram for the MTR engineering-scale system to be installed at TCM. A slipstream
of flue gas is sent to the membrane system (stream 1). After passing through a feed blower, the flue gas (stream 2) goes
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 327
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
to the first membrane skid, where a vacuum on the permeate is used to remove CO2. The membrane permeate (stream
4) is sent to a second-stage CO2 purification unit (stream 5). Some of this purified CO2 can be routed through a spillback
line (stream 9) to the front of the membrane system to increase the concentration of CO2 in the feed from 13 to ~20%.
In this way, the feed to the membrane system will mimic the fully integrated case without having to recycle CO2 to the
boiler. With this spillback option, the 20% CO2 membrane feed contains about 1 MWe worth of CO2. The partially treated
flue gas that leaves the first membrane step (stream 3) is then sent to the sweep membrane unit. Air (stream 6) flows on
the permeate-side of these membranes and removes additional CO2 from the flue gas. The CO2-enriched air (stream 7)
would be sent to the boiler in integrated operation, but here it is just vented after analysis. Finally, the cleaned flue gas
(stream 5) flows to the stack.
Figure 4: Simplified process flow diagram for the MTR skid operating at TCM.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer m <1 <1
Membrane Geometry — flat sheet flat sheet
Max Trans-Membrane Pressure bar 70 70
>13,000 (real and simulated
Hours Tested without Significant Degradation — >11,000 (real coal)
coal)
Manufacturing Cost for Membrane Material $/m2 50 10
Membrane Performance
Temperature °C 30 30
CO2 Pressure Normalized Flux GPU or equivalent 1,700 1,700
CO2/H2O Selectivity — 0.3 0.3
CO2/N2 Selectivity — 50 50
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — mixed gas mixed gas
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
328 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Proposed Module Design (for equipment developers)
Flow Arrangement — plate-and-frame (crossflow and countercurrent)
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flow rate kg/hr 2,676
CO2 Recovery, Purity, and Pressure %/%/bar 75, >85, 1 (test system conditions)
Pressure Drops Shell/Tube Side bar feed: <0.05/sweep: 0.05
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation through the Polaris membrane occurs by the passive solution-
diffusion mechanism.
Contaminant Resistance – The membranes are known to be unaffected by water (H2O), oxygen (O2), and sulfur dioxide
(SO2). The effect of trace contaminants, such as Hg, arsenic, etc., is still under investigation. Polaris modules exposed to
coal-fired fuel gas at NCCC for more than a year had no reduction in performance.
Flue Gas Pretreatment Requirements – When placed downstream of existing power plant flue gas emission treatment
unit operations to remove particulates (nitrogen oxide [NOX] and SO2). The MTR Polaris post-combustion CO2 capture
membrane process design does not require additional pretreatment.
Membrane Replacement Requirements – MTR has installed hundreds of commercial membrane systems in the
petrochemical, refinery, and natural gas industries over the past 30 years. The membrane module lifetime is estimated to be
three years, which is at the conservative end of the typical industrial gas separation module lifetime of three to five years.
Waste Streams Generated – The MTR capture process will produce a dry, CO2-depleted flue gas stream routed to the
stack and a liquid stream containing much of the moisture in the flue gas (because the MTR membrane captures water
as well as CO2). Prior studies have determined that this water can be recycled to existing flue gas desulfurization (FGD)
blowdown wastewater treatment.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 329
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
technology advantages
• Gen-2 Polaris membranes have a CO2 permeance approximately twice that of Gen-1 and about 20 times that of
conventional membranes.
• There are no hazardous chemicals or emissions in the membrane process.
• The plate-and-frame membrane module minimizes pressure-drop.
• A single-stage system allows for low-cost partial capture, while a novel two-step design efficiently captures CO2 at high
removal rates and high purity.
• The CO2 recycle increases feed concentration, reducing membrane area and energy requirements.
• High turndown, rapid response to dynamic conditions.
• The membrane module stack reduces module space and cost, which translates into additional cost savings in the
system due to reduced ductwork and system complexity.
R&D challenges
• Optimizing CO2 capture rate to minimize capture cost.
• Long-term stability of Gen-2 membranes.
• High-permeance membrane is required to lower capital cost.
• Pressure-drops must be minimized to reduce energy losses.
• Balance of plant equipment cost/efficiency, particularly for rotating equipment, are critical to system performance.
• Scale-up and integration issues (and operational complications from multiple vacuum pumps and valves, and
complicated ductwork in multiple flow banks) likely given the large number of membranes needed to service a 550-
MWe plant.
status
A full hazard and operability (HAZOP) review of the MTR test system has been completed with MTR and TCM
representatives. The results of the HAZOP were incorporated into the final system design; Progressive Recovery, Inc. of
Dupo, Illinois, has been chosen as the fabricator for the MTR test system that will be installed at TCM.
available reports/technical papers/presentations
Merkel, T., et al. “Scale-Up and Testing of Advanced Polaris Membrane CO2 Capture Technology,” presented at the 2019
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/T-Merkel-MTR-Advanced-Polaris-Membrane-r1.pdf
Merkel, T., et al. “Scale-Up and Testing of Advanced Polaris Membrane CO2 Capture Technology,” Project Kickoff
Presentation, Pittsburgh, PA, September 2018. https://www.netl.doe.gov/projects/plp-
download.aspx?id=12053&filename=Scale-
Up%20and%20Testing%20of%20Advanced%20Polaris%20Membrane%20CO2%20Capture%20Technology%20Sept%2020
18.pdf.
Merkel, T., et al. “Scale-Up and Testing of Advanced Polaris Membrane CO2 Capture Technology,” presented at the 2018
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/plp-download.aspx?id=12054&filename=Scale-
Up%20and%20Testing%20of%20Advanced%20Polaris%20Membrane%20CO2%20Capture%20Technology%20Aug%2020
18.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
330 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Rational Development of technology maturity:
Bench-Scale, Actual Flue
Novel Metal-Organic Gas (5 kwe equivalent)
Polyhedra-Based Membranes project focus:
for CO2 Capture
Mixed Matrix Membranes
participant:
State University of New York
primary project goals (SUNY)–Buffalo
The objective of this proposed program is to rationally develop solubility-selective project number:
mixed matrix membranes (MMMs) comprising highly polar rubbery polymers and
soluble metal-organic polyhedra (MOPs) to achieve high carbon dioxide (CO2) FE0031736
permeance (3,000 gas permeation units [GPU]), high CO2/nitrogen (N2) selectivity
(75), and CO2/oxygen (O2) selectivity (30) at 60°C. Such membranes would predecessor projects:
outperform currently leading membranes by 50 to 100%, which can be N/A
implemented into Membrane Technology and Research Inc.’s (MTR’s) membrane
processes and may enable CO2 capture at less than $30/ton CO2 from coal power NETL project manager:
plants.
Isaac Aurelio
[email protected]
technical goals
principal investigator:
• Develop solubility-selective MMMs comprising polar rubbery polymers and Haiqing Lin
MOPs. SUNY–Buffalo
[email protected]
• Develop thin-film composite (TFC) membranes achieving high CO2 permeance
(3,000 GPU) and high CO2/N2 selectivity (75) at 60°C.
partners:
• Demonstrate separation performance and stability with raw flue gas at the
National Carbon Capture Center (NCCC). Membrane Technology and
Research Inc., National
• Perform techno-economic analysis (TEA) on the membrane processes. Carbon Capture Center,
Rensselaer Polytechnic
technical content Institute, California Institute
of Technology, Trimeric
Corporation
The State University of New York (SUNY) at Buffalo is developing transformative
solubility-selective MMMs containing MOPs and rubbery polar polymers. These
transformative MMMs are built upon three key unique approaches. First, rubbery start date:
polymers with CO2-philicity (and N2-phobicity) will be designed, in contrast with 7.01.2019
most of the literature approach in pursuing glassy polymers with strong size-
sieving ability. Second, MOPs with strong CO2 affinity will be designed and added percent complete:
to increase the CO2/gas solubility selectivity. In contrast to the commonly pursued 17%
insoluble metal-organic frameworks (MOFs), these MOPs are discrete nano-
cages and soluble in organic solutions, making it easier to prepare TFC
membranes with selective layers as thin as 100 nm. Third, the structure of
polymers and MOPs can be independently designed with enormous possibilities,
which can be accelerated using computational simulation.
A consortium of six organizations with complementary capabilities has been
assembled to achieve these goals, including University at Buffalo (UB),
Rensselaer Polytechnic Institute (RPI), California Institute of Technology
(Caltech), MTR, NCCC, and Trimeric Corporation (Trimeric). The UB team will
conduct fundamental and industrial membrane development and MOP synthesis
and application to develop the novel materials, perform laboratory parametric
tests, and scale-up the production. RPI will prepare functionalized polymers and
scale-up the production. Caltech will simulate gas permeation to guide the design
of the MMMs. MTR will prepare TFC membranes and bench-scale modules and
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
331
Post-Combustion Membrane Technologies
perform field tests at NCCC. Trimeric will update the membrane process design and economic analysis based on MTR’s
patented processes. The endpoint of this project will be a field test of bench-scale membrane modules, and a TEA of the
newly developed membranes elucidating their potential to meet U.S. Department of Energy’s (DOE) goals for CO2
capture.
Figure 1: The “rubbery polymers”: two macromonomers, poly(1,3-dioxolane) acrylate (PDXLA) and poly(1,3-dioxolane) ethyl ether
acrylate (PDXLEA) are highly polar polymers that exhibit CO2/N2 separation properties above the upper bound in the Robeson’s plot.
Figure 2: The highly branched amorphous polymers containing poly(1,3-dioxolane) (PDXL) in the branches interact favorably with
CO2, but not N2, allowing for the design of solubility-selective membrane materials with superior performance for gas separations.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
332 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — Mixed matrix materials of rubbery polymers and MOP
Materials of Fabrication for Support Layer — Glassy polymers such as PAN, PSf
Nominal Thickness of Selective Layer nm 200–1,000 100–300
Membrane Geometry — flat sheet flat sheet
Max Trans-Membrane Pressure bar 10 10
Hours Tested without Significant Degradation — 120 500
Membrane Performance
Temperature °C 60°C 60°C
CO2 Pressure Normalized Flux GPU 1,500–2,000 3,000
CO2/H2O Selectivity — 0.3 0.3
CO2/N2 Selectivity — 50 75
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — Mixed gas Mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — Spiral-wound modules
Packing Density m2/m3 300–600
Shell-Side Fluid — feed
Flue Gas Flowrate ft3/min –
CO2 Recovery, Purity, and Pressure %/%/bar –
Pressure Drops Feed/Permeate Side psi/m –
Estimated Module Cost of Manufacturing and __$__
–
Installation m2
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3/(cm2∙s∙cm mercury [Hg]) at 1 atmosphere (atm) and 0°C. For
non-linear materials, the dimensional units reported shall be based on flux measured in cm3/(cm2∙s) (at 1 atm and 0°C)
with pressures measured in cm Hg. Note: 1 GPU = 3.3464×10-6 kgmol/(m2∙s∙kPa) (SI units).
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities shall be for
mixture of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either co-current, counter-current, cross-flow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate or retentate stream.
technology advantages
• This membrane process builds upon innovative membrane process design using CO2-selective membranes developed
by MTR. If successfully developed, such membranes would outperform current leading membranes by at least 50%.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
333
Post-Combustion Membrane Technologies
R&D challenges
• This approach of solubility-selective MMMs based on soluble MOPs directly addresses the two key challenges for
membranes for CO2 capture: (a) transport phenomena in new membrane materials, and (b) fabrication and use of the
novel membrane systems in effective process designs.
status
Several batches of polymers, MOPs, and MMMs have been synthesized, and the characterization work has shown that
increasing the MOPs loading in the MMMs increases pure-gas permeability. MMMs were thoroughly characterized,
including density, glass transition temperature (Tg), and d-spacings. The morphology of the MMMs was characterized
using scanning electron microscopy (SEM). The team will continue to optimize the polymer and MOPs structure, and the
flat sheet membranes will be prepared.
available reports/technical papers/presentations
“Rational Development of Novel Metal Organic Polyhedra-based Membranes for CO2 Capture,” presented by Haiqing
Lin, University of Buffalo, The State University of New York, 2019 NETL CO2 Capture Technology Project Review
Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/H-Lin-UB-SUNY-Metalorganic-
Membrane.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
334 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Novel Transformational technology maturity:
Bench-Scale, Simulated and
Membranes and Process for Actual Flue Gas
CO2 Capture from Flue Gas project focus:
Polymeric Composite
Membranes
primary project goals
participant:
The Ohio State University (OSU), along with its partners Gas Technology Institute, The Ohio State University
the National Carbon Capture Center (NCCC), and American Electric Power, aims
to develop a cost-effective design and fabrication process for a novel
project number:
transformational membrane and its membrane modules that capture carbon
dioxide (CO2) from flue gas. The goal of this project is to achieve greater than 60 FE00031731
to 90% capture of the CO2 with greater than 95% CO2 purity ready for compression
to 152 bar (2,200 pounds per square inch [psi]) for storage or enhanced oil predecessor projects:
recovery (EOR). For less than 90% capture, the goal is to achieve less than N/A
$30/tonne CO2 captured.
NETL project manager:
technical goals Isaac Aurelio
[email protected]
• Optimize and characterize the transformational membrane (including
morphology, transport properties, and stability). principal investigator:
• Synthesize an improved polymer support with a CO2 permeance greater than w.S. winston Ho
23,000 gas permeation units (GPU) for the membrane. The Ohio State University
[email protected]
• Develop a polymeric composite membrane with CO2 permeance greater than
3,300 GPU and CO2/nitrogen (N2) selectivity more than 140 at 77°C. partners:
• Design and construct an integrated bench-scale testing system to be tested at Gas Technology Institute,
OSU and NCCC. National Carbon Capture
• Complete a techno-economic analysis (TEA) of the project. Center (NCCC), American
Electric Power
technical content
start date:
07.01.2019
OSU and its partners will develop a cost-effective design and fabrication process for
a novel transformational membrane and its membrane modules that capture CO2
from flue gas. Based on density functional theory (DFT) calculations indicating a percent complete:
new carrier with high reactivity with CO2, OSU will synthesize novel transformational 9%
polymer membranes with the new carrier, showing a very high CO2 permeance of
about 3,300 GPU (1 GPU = 10-6 cm3[STP (Standard Temperature and
Pressure])/(cm2/s/cm mercury [Hg]) and a very high CO2/N2 selectivity of greater
than 140. Optimization of the novel transformational membrane, scale-up of the
membrane to a prototype size of about 14 inches wide in continuous roll-to-roll
fabrication, and construction and testing of a bench skid for the integrated
membrane process will be performed.
For the design of this membrane, OSU will use a cost-effective polyethersulfone
(PES) support and coat a thin top layer of the membrane (Figure 1). This membrane
design offers a low cost for the membrane element in commercial spiral-wound
configuration (less than $2.00/ft2 or $21/m2). The prototype membrane will be used
to fabricate at least six pilot-size membrane modules (each about 20-inch length
and 35-m2 membrane area) for testing with simulated flue gas at OSU and
subsequently with actual flue gas at NCCC (Wilsonville, Alabama), using the skid to
capture the CO2 (at 60 to 90%) with at least 95% CO2 purity (Figure 2). The prototype
membrane modules will be in commercial spiral-wound configuration with a minimal
pressure drop (less than 0.103 bar/meter or 1.5 psi/meter).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
335
Post-Combustion Membrane Technologies
After the skid testing, OSU will determine the identity and concentration of any possible contaminates on the membrane via
laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy (FTIR),
X-ray photoemission spectrometry (XPS), and nuclear magnetic resonance spectroscopy (NMR).
Figure 1: Schematic of thin-film composite membrane consisting of an amine-containing cover layer on a nanoporous PES support.
Figure 2: Process concept for two-stage membrane system.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — amine-containing polymer
Materials of Fabrication for Support Layer — polyethersulfone on non-woven fabric
Nominal Thickness of Selective Layer nm 170 150–250
Membrane Geometry — flat sheet flat sheet
Max Trans-Membrane Pressure bar 4 4
Hours Tested without Significant Degradation — 1,600 hours 500 hours
Manufacturing Cost for Membrane Material $/m2 20 20
Membrane Performance
Temperature °C 57–77°C 57–77°C
CO2 Pressure Normalized Flux GPU 3,500 GPU >3,300 GPU
CO2/H2O Selectivity — 1 1
CO2/N2 Selectivity — 170 >140
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
336 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Proposed Module Design (for equipment developers)
Flow Arrangement — Spiral-wound
Packing Density m2/m3 about 2,000
Permeate-Side Fluid — vacuum or retentate recycle
Flue Gas Flowrate ft3/min 10.3
CO2 Recovery, Purity, and Pressure %/%/bar >60%–90%, >95%, 1 bar
Pressure Drops Feed/Permeate Side psi/m 1.5/1.5
Estimated Module Cost of Manufacturing and __$__
40
Installation m2
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm Hg). For non-linear
materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures
measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in desulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Permeate-Side Fluid – Either vacuum or a sweep gas.
Estimated Cost – Basis is m2 membrane area.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Membrane Permeation Mechanism – Facilitated transport for amine-containing selective layer.
Contaminant Resistance – Resist up to 3 parts per million volume (ppmv) sulfur dioxide (SO2).
Flue Gas Pretreatment Requirements – Removal of particulates and SO2 polishing to 3 ppmv.
Membrane Replacement Requirements – Estimated approximately four years.
Waste Streams Generated – Nitrogen with water (H2O), about 1% CO2, and minor impurities.
Process Design Concept – See Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
337
Post-Combustion Membrane Technologies
technology advantages
This membrane consists of a thin selective polymer layer on a polymer support so that it can be made efficiently in
continuous roll-to-roll manufacturing. The membrane offers high CO2/N2 selectivity at greater than 57°C, which does not
require flue gas cooling or cryogenic distillation. The simplicity of this membrane design offers a low cost for the
membrane element in commercial spiral-wound configurations. If successful, the proposed process can achieve less
than $30/tonne CO2 for 70% recovery.
R&D challenges
• Membrane stability in the presence of high-level contaminants, SO2 and nitrogen oxide (NOX).
• Design and fabrication of prototype spiral-wound membrane module with 8-inch diameter.
• Requires two membrane stages.
status
The project has commenced.
available reports/technical papers/presentations
Ho, W., Han, Y., “Novel Transformational Membranes and Process for CO2 Capture from Flue Gas,” poster presented at
the 2019 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019.
Ho, W., Han, Y., “Novel Transformational Membranes and Process for CO2 Capture from Flue Gas,” presented at the 2019
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/Y-
Han-OSU-Transformational-Membrane.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
338 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Commercial-Scale Front-End technology maturity:
Engineering Design Study for
Front-End Engineering
Design (FEED)
Membrane Technology and project focus:
Research’s Membrane Carbon
Polaris™ Polymeric
Membrane-Based Process
Dioxide Capture Process
Retrofit
participant:
Membrane Technology and
primary project goals Research, Inc.
Membrane Technology and Research, Inc. (MTR) is conducting a front-end project number:
engineering design (FEED) study for an ~400-megawatt-electric (MWe) membrane FE0031846
carbon dioxide (CO2) capture system installed at Basin Electric’s Dry Fork Station
in Gillette, Wyoming. The project builds on prior work in advancing MTR’s predecessor projects:
membrane capture technology through small pilot testing and a pre-FEED study. FE0026414
DE-NT0005312
technical goals FC26-07NT43085
FE0005795
FE0007553
• Complete FEED study of MTR capture process applied to the 400-MWe Dry Fork FE0013118
Station.
• Complete an environmental review of full-scale MTR membrane capture at Dry NETL project manager:
Fork Station. Sai Gollakota
[email protected]
• Provide a path to commercialization (detailed costs and construction plan) for a
full-scale membrane capture plant based on actual equipment costs with a
principal investigator:
reliability of ±15%.
Tim Merkel and Brice
Freeman
technical content Membrane Technology and
Research, Inc.
[email protected]
The project team is performing a FEED study of MTR’s membrane CO2 capture
[email protected]
technology applied at commercial-scale as the next step in the development of
the process, after the successful completion of small pilot testing and execution of partners:
a full-scale pre-FEED study. The study includes an estimate of the cost and
Sargent & Lundy (S&L), Basin
performance of a first-of-its-kind commercial-scale membrane capture plant and Electric, Trimeric
a plan for its construction. The plant will be designed to capture approximately Corporation, Electric Power
5,600 tonnes per day (TPD) of CO2 (approximately 2.0 million tonnes/year of CO2), Research Institute (EPRI),
representing 70% of the Dry Fork Station power plant’s CO2 emissions. The system Efficient Fuel Additives (EFA)
incorporates the innovative high-performance Polaris™ membrane, low-pressure-
drop membrane modules, and a patented selective-recycle sweep module design. start date:
Earlier research has shown that the MTR process has the potential to capture CO2 10.01.2019
from coal-fired flue gas at the U.S. Department of Energy (DOE) capture cost target
of less than $40/tonne CO2. percent complete:
10%
A preliminary process flow diagram of the membrane capture process to be
examined in the FEED study is shown in Figure 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 339
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 1: Preliminary design for full-scale membrane capture plant.
The main challenge of membrane technology for CO2 capture is the low partial pressure of CO2 in flue gas, resulting in a
large membrane area being required due to the small driving force for separation. MTR’s process includes three
innovations that address this problem:
• A new class of membranes called Polaris that exhibit 10 times the CO2 permeance of conventional gas separation
membranes, leading to a large decrease in required membrane area and reduced capital cost.
• A membrane selective-recycle process that uses combustion air as a sweep stream to generate a driving force for
transmembrane CO2 transport. Separated CO2 is recycled to the boiler, increasing the concentration of CO2 in the flue
gas, which reduces the energy and capital required for subsequent capture.
• A low-pressure-drop, low-cost membrane module design. The pressure differentials, and therefore the energy
required, to circulate gas through the module is a fraction of that measured in conventional modules.
Single-stage membrane designs are unable to produce high-purity CO2 combined with high CO2 capture rates because
the system performance is limited by the small pressure ratio across the membrane. MTR’s multi-stage membrane process
design (Figure 2) addresses the pressure ratio constraint to efficiently capture 50 to 75% of the CO2 in flue gas. First, the
combustion flue gas enters a primary capture module, which produces a permeate containing ~55 to 60% CO2. This gas
is then treated by a second membrane stage to further enrich the CO2 stream to greater than 85% CO2. The CO2-rich
permeate from the second-stage module is dehydrated and compressed. An optional selective-recycle membrane step
can boost the CO2 capture rate to 90% with the retentate from the primary capture module being fed into a countercurrent
sweep module, from which the permeate is recycled back to the boiler via an air sweep. This increases the CO2
concentration of the flue gas entering the initial module.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
340 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 2: MTR CO2 capture process.
MTR’s Polaris membranes, developed in a previous DOE-funded project, DE-NT43085, exhibit high CO2 permeance and
high CO2/nitrogen (N2) selectivity for post-combustion flue gas applications. The thin-film composite membrane utilizes
hydrophilic polymers. Commercial Polaris membranes offer a step-change improvement over typical commercial CO2-
selective membranes used for natural gas treatment, with an average CO2 permeance of 1,000 gas permeation units (GPU)
and a CO2/N2 selectivity of 50. Recent studies have improved membrane performance, demonstrating a CO2 permeance
of 3,000 GPU at lab-scale. The combination of these membranes with a novel sweep module design that utilizes incoming
combustion air to generate a separation driving force greatly reduces the projected cost of CO2 capture.
Membranes packed into spiral-wound modules is the most commonly used module design for commercial membrane
installations today. Spiral-wound modules are robust, resistant to fouling, and economical; they are used in 95% of the
reverse osmosis (RO) desalination industry and more than 70% of the membrane market for CO2 removal from natural
gas. Figure 3 shows the general design features of a spiral-wound membrane module. The module consists of a permeate
collection tube with a spiral formation of permeate spacers and feed spacers, which allow the flue gas and separated CO2
to flow through the device. Each module contains 20 to 50 m2 of membrane, meeting high packing-density performance
targets. A total membrane area of about 0.5 to 1 million m2 is required to achieve 90% CO2 capture for a 550-MWe plant.
Figure 4 shows a proposed design for efficient module packing in a full-scale membrane system that consists of seven
tubes nested in a single pressure vessel. Each set of modules is stacked on a skid and connected together to form a single
“mega-module.” About 130 mega-module skids are required for a 550-MWe power plant. The process parameters for
the Polaris membranes in a spiral-wound module configuration are shown in Table 1.
Figure 3: Schematic diagram of a spiral-wound membrane module.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 341
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 4: Full-scale membrane system design using spiral-wound modules.
TABLE 1: MEMBRANE PROCESS PARAMETERS IN SPIRAL-WOUND MODULE CONFIGURATION
Materials Properties Units Design Value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer m <1
Membrane Geometry — spiral
Max Trans-Membrane Pressure bar 70
Hours Tested without Significant Degradation — 11,000
Manufacturing Cost for Membrane Material $/m2 10
Membrane Performance
Temperature °C 30
CO2 Pressure Normalized Flux gpu or equivalent 1,000
CO2/H2O Selectivity — 0.3
CO2/N2 Selectivity — 30
CO2/SO2 Selectivity — 0.5
Type of Measurement — Mixed gas
Module Design
Flow Arrangement — crossflow and countercurrent
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flow rate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar 90% / >96% / 140
Pressure-Drops Shell/Tube Side bar 0.1
Estimated Module Cost of Manufacturing and Installation __$__ 50
m2
Under a previous DOE-funded project, DE-FE0005795, a membrane skid designed to capture 1 tonne of CO2 per day from
a 7,000-standard-m3/day (250,000 standard cubic feet per day [scfd]) flue gas slipstream was installed and tested at the
National Carbon Capture Center (NCCC; Figure 5). The skid held up to eight (four crossflow and four countercurrent
sweep), 8-inch-diameter Polaris membrane modules. The system accumulated more than 11,000 hours of operation with
flue gas testing spiral-wound modules in both steps of the MTR process: a capture step operating with permeate vacuum
and a selective-recycle step that uses air sweep to provide driving force for CO2 removal. The test demonstrated
membrane operation in commercial-scale modules and determined typical membrane lifetimes under coal combustion
flue gas operating conditions.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
342 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 5: Membrane skid used for 1-TPD bench-scale slipstream testing at NCCC.
Scale-up of the Polaris capture system from the 1-TPD bench-scale unit to a 20-TPD small pilot system using commercial-
scale membrane components was also completed in FE0005795. The 20-TPD system is a two-level design, with membrane
modules located on the upper level, and all rotating and associated equipment on the lower level. Like the 1-TPD unit,
the 20-TPD unit was designed for slipstream operation at NCCC and is shown in Figure 6.
Figure 6: 20-TPD small pilot system installed at NCCC.
Pilot-scale operation of the existing 1-MWe (20-TPD) membrane CO2 capture system, integrated with a Babcock & Wilcox
(B&W) 0.6-MWe coal-fired research boiler, was performed in the DOE-funded project DE-FE0026414 to determine how
various membrane parameters impact the performance of a boiler system. Operation of the integrated membrane-boiler
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 343
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
system involves the recycling of CO2-laden air back to B&W’s boiler via a countercurrent sweep membrane. A modest
reduction in boiler efficiency due to recycled CO2 was measured (1.8%) at 90% capture, showing that the selective-recycle
process is feasible and the impact on boiler performance is relatively small.
While previous tests have shown that recycle to the boiler is feasible, operation at ~70% capture without recycle is of
most interest, because it offers lower capture costs and still reduces coal plant emissions to less than that of a natural gas
power plant. Therefore, the FEED study focuses on a two-stage membrane system that captures 70% of the CO2 in the
flue gas without selective recycle and concentrates the gas to about 85% CO2. A CO2 purification unit is then used to
produce greater than 99% CO2 at 150 bar. For the full-scale capture plant, container-sized skids will be used as the basic
modular building block. An evaluation of the most efficient arrangement of the membrane capture skids is being
conducted in the FEED study.
MTR applied an alternative approach to membrane packing to develop plate-and-frame modules optimized for low-
pressure operation. Testing of the small pilot-scale 20-TPD system at NCCC and B&W incorporated this novel large-area
membrane module designed by MTR in project DE-FE0007553. A single 100-m2 membrane module element has the
equivalent membrane area of five 8-inch spiral-wound membrane modules. Figure 7 shows the plate-and-frame module
design and Figure 8 shows a full-scale mega-module, which consists of a pressure vessel with five module elements,
reducing the footprint of the plant. The simple, straight flow path of the new module design results in a pressure-drop
that is almost four times lower than that measured for the spiral-wound module, as shown in Figure 9, resulting in energy
and cost savings. At full-scale, this reduced pressure-drop represents about a 10-MWe savings in fan power. The plate-
and-frame module skids are projected to cost $30/m2 of membrane at full commercialization stage. Process parameters
for the Polaris membranes in a plate-and-frame module configuration are shown in Table 2.
Figure 7: Plate-and-frame module.
Figure 8: Prototype plate-and-frame module during testing at NCCC.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
344 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Figure 9: Measured pressure-drop in plate-and-frame module, compared to spiral-wound module.
TABLE 2: MEMBRANE PROCESS PARAMETERS IN PLATE-AND-FRAME MODULE CONFIGURATION
Materials Properties Units Design Value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer m <1
Membrane Geometry — plate-and-frame
Max Trans-Membrane Pressure bar 2
Hours Tested without Significant Degradation — 1,500
Manufacturing Cost for Membrane Material $/m2 30
Membrane Performance
Temperature °C 30
CO2 Pressure Normalized Flux gpu or equivalent 1,700
CO2/H2O Selectivity — 0.5
CO2/N2 Selectivity — 30
CO2/SO2 Selectivity — 0.5
Type of Measurement — Mixed gas
Module Design
Flow Arrangement — crossflow, partial countercurrent
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flow rate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar 70% / >96% / 150
Pressure-Drops Shell/Tube Side bar 0.1
Estimated Module Cost of Manufacturing and Installation __$__ 50
m2
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 345
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Further improvements to the membrane module design to reduce fabrication costs resulted in a 3D-printed module
prototype based on injection-molded, fiber-reinforced thermoplastics. The modules are designed to fit one on top of
another to create a module stack, which is placed on a container-sized skid, as shown in Figure 10. The large membrane
capture system will consist of multiple container-sized membrane module skids that will be prefabricated using advanced,
high-volume manufacturing and shipped to the plant site. This approach minimizes expensive site assembly and
installation work and enhances fabrication quality. The FEED study will evaluate and quantify savings based on the
modular construction approach.
Figure 10: Drawing of container-sized skid housing six module stacks. Eight individual modules are connected together to form each
stack.
MTR also previously evaluated a hybrid membrane-absorption process system combining Polaris membranes and an
amine solvent-based capture system under DOE-funded project DE-FE0013118. The integrated system combines MTR’s
plate-and-frame sweep module with a CO2 capture system developed by the University of Texas at Austin (UT-Austin)
that uses a piperazine (PZ) solvent and advanced high-temperature/high-pressure regeneration. This hybrid design
requires significantly less membrane area for a two-step CO2 capture process, compared to MTR’s all-membrane process.
In the hybrid design, MTR’s Polaris membrane recycle stage enriches flue gas from ~13 to ~20% CO2 and a 5 molal PZ
advanced flash stripper with cold-rich bypass is optimized to take advantage of the higher CO2 concentration. Both series
and parallel configurations were considered with the hybrid design, as shown in Figure 11. Process modeling of MTR’s
plate-and-frame skid integrated with UT-Austin’s Separations Research Program (SRP) 0.1-MWe pilot plant showed that
a hybrid-parallel configuration offers a lower cost of capture than the series configuration. However, the benefits of a
hybrid system do not outweigh the costs.
Figure 11: Two hybrid configurations for membrane-absorption CO2 capture process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
346 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
MTR is also currently working on three additional DOE-sponsored projects related to this study. DE-FE0031587 is a three-
phase project for the design, construction, and operation of a large-scale pilot system to treat 10 MWe of flue gas at
Wyoming’s Integrated Test Center, with support from Basin Electric’s Dry Fork Station power plant. The Phase I feasibility
program is completed and the project is now in Phase II. The National Environmental Policy Act (NEPA) review and
Environmental Information Volume (EIV) that were completed in Phase I can be leveraged in this FEED project. The second
project currently underway (DE-FE0031589) is a pre-FEED study led by the Electric Power Research Institute (EPRI), in
collaboration with MTR, Nexant, and Bechtel, to evaluate a full-scale (640-MWe) membrane capture technology applied
to Duke Energy’s East Bend Station. The general configuration from the pre-FEED capture plant design is being used as
the starting point for the Dry Fork Station FEED study. In project DE-FE0031591, MTR and its partners are scaling-up the
next-generation Polaris membranes and modules to a final form optimized for commercial use, and validating their
performance in an engineering-scale field test at Technology Centre Mongstad.
The Dry Fork Station power plant is an ideal location for installation of a membrane CO2 capture system due to:
• High CO2 content (~15% on dry basis) in the flue gas increases efficiency of membrane capture system.
• Cool, dry climate allows cooling water operation at ~25°C, resulting in an energy savings of 25 MWe/tonne of CO2
captured.
• Dry Fork Station generates electricity at a low cost, which is important for a capture process powered only by electricity.
• CO2 utilization opportunities with nearby oil fields and CO2 pipeline.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow-fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed- or pure-gas measurements; target permeance and selectivities should be for
mixture of gases found in desulfurized flue gas.
Flow Arrangement – Typical gas separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 347
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation through the Polaris membrane occurs by the passive solution-
diffusion mechanism.
Contaminant Resistance – The membranes are known to be unaffected by water (H2O), oxygen (O2), and sulfur dioxide
(SO2). The effect of trace contaminants, such as Hg, arsenic, etc., was examined in the field tests at NCCC and no major
issues were found.
Flue Gas Pretreatment Requirements – The greatest concern of species present in flue gas is that particulate matter will
foul the membranes, reducing module lifetimes. The field tests at NCCC treated post-FGD flue gas, and in extended
testing (more than 13,000 hours), fouling was not a significant issue.
Membrane Replacement Requirements – The target membrane module lifetime is three years, which is at the conservative
end of the typical industrial gas separation module lifetime of three to five years.
Waste Streams Generated – The membrane process will recover greater than 95% of the H2O in flue gas as liquid. The
quality of this H2O and its potential to be reused in the plant will be studied in future work.
Process Design Concept – See Figure 1.
technology advantages
• The Polaris membranes developed are more than 10 times more permeable to CO2 than conventional membranes,
which reduce the required membrane area and capital costs.
• A membrane system does not contain any chemical reactions or moving parts, making it simple to operate and
maintain.
• The membrane material has a high tolerance to wet acid gases and is inert to O2.
• The membrane system has a compact footprint and low energy cost.
• The membrane capture system can recover water from flue gas.
• The use of an existing air stream to generate a CO2 partial-pressure gradient in the countercurrent sweep membrane
stage reduces the need for compressors or vacuum pumps, thus reducing the overall energy cost.
• The recycled CO2 from the air sweep to the boiler increases the CO2 partial-pressure driving force for separation in the
initial CO2 separation step (either membrane or absorption/stripper unit), reducing total system cost.
R&D challenges
• Uncertainty in vacuum pumps and compression equipment efficiency and stability treating flue gas.
• Potential performance problems with the CO2 purification equipment.
• Scale-up of advanced Polaris membranes that exhibit a CO2 permeance of 3,000 GPU to reduce the capital cost of the
membrane system.
status
MTR is reviewing the preliminary heat and mass balances and process flow diagrams that were previously prepared, and
then will decide on the design basis for the full-scale capture plant. Based on the design basis, the team will prepare a
preliminary process design for the full-scale capture plant, focusing on design of the capture plant equipment (direct
contact cooler columns, evaporative coolers, number and layout of the membrane skids, compression equipment, and
the design and size of the CO2 purification unit and refrigeration equipment, etc.).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
348 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
available reports/technical papers/presentations
Freeman, B., Kniep, J., Merkel, T., “Commercial-Scale FEED Study for MTR’s Membrane CO2 Capture Process (FE0031846),”
DOE Kickoff Meeting, October 29, 2019. https://netl.doe.gov/project-information?p=FE0031846.
Freeman, B., et al. “Bench Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” presented at the
2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA. August 2018.
https://netl.doe.gov/sites/default/files/netl-file/B-Freeman-MTR-Hybrid-Membrane-Absorption-Capture-Process.pdf.
Merkel, T., “Integrated Testing of a Membrane CO2 Capture Process with a Coal-Fired Boiler,” presented at the 2017 NETL
CO2 Capture Technology Project Review Meeting, Pittsburgh, PA. August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-Tuesday/T-Merkel-MTR--Integrated-Testing-of-a-
Membrane.pdf.
Freeman, B. and Rochelle, G., “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,”
presented at the 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA. August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-Thursday/B-Freeman-MTR-Hybrid-Membrane-
Absorption.pdf.
Freeman, B., et al. “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” Project review
meeting presentation, June 2017. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/FE0013118-Project-Review-Meeting-2017-06-13.pdf.
Merkel, T., Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” Final Report, September 2016.
https://www.osti.gov/servlets/purl/1337555.
“Merkel, T., “Integrated Testing of a Membrane CO2 Capture Process with a Coal-Fired Boiler,” presented at the 2016 NETL
CO2 Capture Technology Project Review Meeting, Pittsburgh, PA. August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/1-Monday/T-Merkel-MTR-Integrated-
Membrane-Testing.pdf.
Freeman, B., “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” presented at the 2016
NETL CO2 Capture Technology Meeting, Pittsburgh, PA. August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/B-Freeman-MTR-Hybrid-
Membrane-Absorption.pdf.
Merkel, T., et al. “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” Final project review meeting
presentation, August 2016. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/fe0005795-final-review-08-24-2016.pdf.
Freeman, B., “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” presented at the 2015
NETL CO2 Capture Technology Meeting, Pittsburgh, PA. June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/B-Freeman-MTR-Hybrid-Membrane-
Absorption-CO2-Capture.pdf.
Merkel, T., et al. “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” presented at the 2015 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA. June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/T-Merkel-MTR-Pilot-Membrane-CO2-
Capture.pdf.
Freeman, B., “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” presented at the 2014
NETL CO2 Capture Technology Meeting, Pittsburgh, PA. July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/B-Freeman-MTR-Bench-Hybrid-
Absorption-Membrane.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 349
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Membrane Technologies
Merkel, T., “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” presented at the 2014 NETL CO2
Capture Technology Meeting, Pittsburgh, PA. July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/T-Merkel-MTR-Pilot-Testing-
of-a-Membrane-System.pdf.
Merkel, T., et al. “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture, Project Status Meeting,
Pittsburgh, PA. April 2014. http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/MTR-5795-DOE-review-April-2014-non-confidential.pdf.
Freeman, B., et al. “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process,” Project kickoff
meeting presentation, December 2013. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/Kickoff-Presentation-
fe0013118.pdf.
Merkel, T., et al. “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” presented at the 2013 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA. July 2013.
https://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/T-Merkel-MTR-Slipstream-Testing-of-Membrane-
CO2-Capture-Proc.pdf.
Merkel, T., et al. “Slipstream Testing of a Membrane CO2 Capture Process,” presented at the 2012 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA. July 2012. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/T-
Merkel-MTR-Membrane-Process.pdf.
Merkel, T., et al. “Pilot Test of an Efficient Membrane Process for Post-Combustion CO2 Capture,” presented at the 2011
NETL CO2 Capture Technology Meeting, Pittsburgh, PA. August 2011.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/22Aug11-Merkel-MTR-Efficient-Membrane-Pilot-
Test.pdf.
Merkel, T., et al. “Membranes for Power Plant CO2 Capture: Slipstream Test Results and Future Plans,” presented at the
Tenth Annual Conference on Carbon Capture and Sequestration, Pittsburgh, PA. May 2011.
Merkel, T., et al. “Pilot Testing of a Membrane System for Post-Combustion CO2 Capture,” presented at the 2010 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA. September 2010.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/Tim-Merkel---Membrane-Technology-and-Research-
Inc.pdf.
Wei, X., “Membrane Process to Capture Carbon Dioxide from Coal-Fired Power Plant Flue Gas,” presented at the 2010
NETL Review Meeting. September 2010. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/Xiaotong-Wei-
--NT0005312-and-NT43085.pdf.
Merkel, T., et al. “Power Plant Post-Combustion Carbon Dioxide Capture: An Opportunity for Membranes,” Journal of
Membrane Science, Volume 359, Issues 1-2, 1 September 2010, pages 126-139.
Merkel, T., et al. “Opportunities for Membranes in Power Generation Processes,” Gordon Research Conference
Presentation, July 27, 2010.
Merkel, T., et al. “Membrane Process to Capture CO2 from Coal-Fired Power Plant Flue Gas,” Second Quarterly Progress
Report, May 2009.
Merkel, T., et al. “A Membrane Process to Capture CO2 from Coal-Fired Power Plant Flue Gas,” presented at the Annual
NETL CO2 Capture Technology for Existing Plants R&D Meeting, Pittsburgh, PA. March 2009.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/5312-MTR-membrane--Merkel--mar09.pdf.
Merkel, T., et al., “Membrane Process to Sequester CO2 from Power Plant Flue Gas,” First Semi-Annual Technical Report,
October 2007.
Merkel, T., et al. “The Membrane Solution to Global Warming,” presented at the 6th Annual Conference on Carbon Capture
and Sequestration, Pittsburgh, PA, May 2007.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
350 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
POST-COMBUSTION
NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
351
Post-Combustion Novel Concepts
Advanced Manufacturing to technology maturity:
Laboratory-Scale
Enable Enhanced Processess project focus:
and New Solvents for Carbon Encapsulation of Solvents in
Capture
Permeable Membrane for
CO2 Capture
participant:
primary project goals Lawrence Livermore
National Laboratory
Lawrence Livermore National Laboratory (LLNL), Harvard University, and Carnegie
Mellon University (CMU) teamed up to develop processes that enhance and enable project number:
the use of new solvents to capture carbon dioxide (CO2). Primarily, the project FwP-FEw0194
aimed to develop and evaluate the concept of Micro-Encapsulated CO2 Sorbents
(MECS) and to develop new concepts for absorber packings for solvent-based CO2 predecessor projects:
capture (advanced packings). The technology uses advanced manufacturing N/A
techniques to reduce the cost of carbon capture for coal-fired power plants and
supports the U.S. Department of Energy’s (DOE) Carbon Capture Program's goal NETL project manager:
of advancing the technical, economic, and environmental performance of second- Isaac Aurelio
generation and transformational systems and technologies for future deployment. [email protected]
principal investigator:
technical goals
joshuah Stolaroff
Lawrence Livermore
• Develop processes to enhance and enable the use of thermodynamically National Laboratory
favorable solvents to capture CO2 using advanced manufacturing techniques to [email protected]
encapsulate the solvents in a permeable membrane.
• Identify and assess improvements to the design of industrial CO2 absorbers partners:
made possible by advanced manufacturing. Harvard University,
Carnegie Mellon University
• Identify the best process configuration for encapsulated solvents.
• Measure the properties of potential solvents using LLNL’s microfluidic start date:
technique for rapid characterization of solvent properties. 03.01.2015
technical content percent complete:
100%
LLNL, Harvard University, and CMU formed a team to develop processes that
enhance and enable the use of advanced solvents to capture CO2 from coal-fired
power plants using advanced manufacturing techniques. New solvents for the
capture of CO2 pose challenges for conventional equipment due to slow kinetics,
high viscosity, phase changes, corrosivity, or other issues. The team formed to
develop processes to enhance and enable the use of these otherwise
thermodynamically favorable solvents to capture CO2 using advanced
manufacturing techniques to encapsulate the solvents in a permeable membrane to
overcome these challenges.
One of the key goals of the project was to take the micro-encapsulation concept,
which had previously been demonstrated with sodium and potassium carbonate,
and apply it to new solvents, especially water-lean solvents. Compatibility among
the solvent, shell material, and production methods turned out to be a critical
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
352 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
challenge, and extensive efforts to solve this challenge ran the course of the project.
The primary selection criterion for a MECS shell material is high permeability to CO2. Further criteria include heat stability
at the regeneration temperature of the solvent (typically 80 to 120°C), mechanical robustness in the chosen process
conditions (e.g., fluidized bed), and chemical compatibility with the solvents (CO2-binding organic liquid [CO2BOL],
nanoparticle-organic hybrid material [NOHM], ionic liquid [IL], carbonates). For microfluidic production, ultraviolet (UV)-
curable polymers with precursors that are liquid at room temperature are particularly suitable. Silicones have among the
highest CO2 permeabilities of common polymer classes, with typical values on the order of 3,000 barrer. After extensive
screening and through past and concurrent work on encapsulation, two commercial silicones were identified as promising
shell materials (Semicosil 949 and Tego-Rad 2650). Two new, in-house polymer classes, identified as Thiolene and SiTRIS,
were developed for capsule screening. During the project, variations of Thiolene have been formulated by slightly
changing the compositions for more robust capsule production and better suitability with scale-up production.
The shell materials tested in this project are summarized in Table 1, showing some of their relevant properties.
TABLE 1: SUMMARY OF SHELL MATERIAL CANDIDATES WITH BASIC PROPERTIES
Several core solvents (Koechanol, 1,8-diazabicyclo[5.4.0]-undec-7-ene [DBU]/hexanol, five ILs, and an NOHM) were tested
for compatibility with shell material candidates. The screening process involved three main tasks: (1) a solubility test, to
determine whether the solvent would dissolve solid shell material; (2) a test of interfacial stability, to determine if the solvent
and shell material precursor maintain distinct liquid phases; and (3) a curing test to determine if the shell material cures by
UV in the presence of the solvent. Results of the screening are summarized in Figure 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
353
Post-Combustion Novel Concepts
Figure 1: Summary of IL/shell material compatibility screening tests. “X”s mark unsuccessful capsule production; checks mark successful
capsule production.
Multiple options to synthesize larger quantities (~1 kg) of encapsulated ILs were explored. Of those, the most successful was
a new process developed specifically for the project. Figure 2 shows the In-Air Drop Encapsulation Apparatus (IDEA) built at
LLNL. The system pumps fluids out of a coaxial nozzle to form a core-shell fluid jet in air. The jet of fluid is broken into drops
with the use of an external device (a contact speaker in this case), which causes the nozzle to vibrate. When a sinusoidal
wave with a certain frequency (related to fluid properties, flow rate, and nozzle size) is applied, monodisperse drops are
formed. Capsules are produced when the drops are exposed to sufficient UV to crosslink the polymer shell. This method
does not require a carrier fluid and potentially provides better control and reproducibility than the parallel microfluidic
approach. IDEA was the leading option for scale-up of carbonate and IL capsules, with a maximum rate up to 400 g/hr per
nozzle.
Figure 2: (A) Overview of in-air drop generator box; (B) a device example that was used to produce core-shell droplets; (C) production
of carbonate SiTRIS droplets.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
354 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
After developing formulations for the previously discussed solvents, six candidate MECS were selected for inter-
comparison. The solvents were sodium carbonate (Na2CO3) solution, uncatalyzed and with two different promoters; two
IL solvents; and one CO2BOL. It was found that 17 wt% Na2CO3 capsules containing cyclen as a promoter outperformed
Na2CO3 capsules with no promoter or with sarcosine as a promoter in terms of absorption rate. It was also discovered
that the CO2BOL liquid permeated or broke the capsule shell, and thus these MECS were not cycled. Both of the IL MECS
outperformed the Na2CO3 capsules, having roughly twice the capacity and higher absorption rates. However, production
of the IL MECS proved much more difficult to scaleup while maintaining multicycle performance.
One of the key innovations in this project is the development of printed composite sorbents, a variation of the capsule-
based MECS that originated the research. The composites combine the same or similar silicone shell materials used for
capsules with Na2CO3 or other solvents; however, rather than making core-shell spherical capsules, filaments or meshes
of homogeneous material were produced.
The composite sorbents are similar to MECS in that the final material is composed of aqueous Na2CO3 solutions
surrounded by CO2 permeable silicone. Both materials use fine feature sizes (less than 500 µm) to enable high mass
transfer rates into the carbonate solutions. However, the composite sorbents have the benefit of being 3D-printable,
which enables geometric control of the material that can be optimized for parameters, such as pressure drop, though the
system. The impact of geometry on CO2 absorption rate was investigated. The smallest filament sizes were able to achieve
slightly better rates than core-shell MECS.
These initial investigations of composites applied 3D printing. However, in follow-on projects, production was generalized
to use either a simple extrusion of random mats or waffle patterns cast to make thin sheets. Thus, composites can achieve
similar surface areas and mass transfer rates as spherical MECS and similar or better loading, but their production is more
scalable. For this reason, composite MECS are the focus of several follow-on commercialization efforts.
One of the key goals of the fourth project year was to develop an integrated, automated, bench-scale packed-bed
apparatus for testing extended cycles of absorption-desorption and for testing realistic regeneration conditions with
steam. This apparatus was built and successfully tested. It contains twin jacked reactor columns (see Figure 3), which can
be operated simultaneously to cycle between absorption and regeneration. The design enables the use of steam to
directly or indirectly heat up sorbents.
Figure 3: Detail of the automated sorbent testing system.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
355
Post-Combustion Novel Concepts
A process diagram is shown in Figure 4. A gas line can also be used to purge a column depending on cycling requirements.
Figure 4: Process diagram of the automated sorbent testing system.
Steam, nitrogen (N2), and/or a 10% N2/CO2 mixture can flow through the main columns. Steam can also flow through the
jacketed portion of the column to indirectly heat the microcapsules. After passing through the column, the gas stream
passes through a heat exchanger to condense any water and steam. The gas/condensed water mixture then passes
through a gas splitter to separate the two phases. Lastly, the gas stream is passed through a flow meter and CO2 meter.
After constructing the sorbent testing system, absorption-desorption tests on Na2CO3 MECS were conducted, focusing
on direct steam regeneration. The gram-scale and smaller column experiments of prior test apparatuses could not be
configured for these tests.
The CO2 breakthrough curves for eight sequential cycles and the resulting integrated absorbed CO2 amounts are shown
in Figure 5. In the first cycle, just after loading the capsules into the column, breakthrough was nearly instantaneous,
though there was a long tail to reach the final outlet concentration, suggesting slow absorption kinetics. In following
cycles, breakthrough and equilibrium were both obtained more quickly. The result of this is that the amount of CO2 that
was able to be absorbed decreased over time.
Figure 5: (a) CO2 breakthrough curves for 10% CO2/N2 at ~500 sccm through the MECS column, followed by desorption in steam. (b)
Cumulative absorbed CO2 as a function of time.
Despite the initial setbacks with the material, the system can perform cyclic absorption and steam desorption. In future
work, consistent performance should be demonstrated, such as that observed in the previously mentioned gram-scale
experiments, using a different MECS formulation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
356 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
In the second half of the project, much of the focus for MECS was on process design and measurements to enable techno-
economic analysis (TEA). From the beginning, fluidized-bed, fixed-bed, and moving-bed configurations had been
considered. It remained difficult to down-select among these options. In an absorber sizing study and a separate process
design and TEA, it was found that capsule MECS-based fixed beds or fluidized beds were generally larger than solvent
towers with monoethanolamine (MEA) for carbon capture from a coal power plant. The TEA also found that the MECS
system had higher overall costs than an MEA system. Because of this, and even allowing that better process configurations
for MECS may be achievable, it is still unlikely that MECS will outperform second-generation solvents for carbon capture
at power plants. Solids handling and heat integration with solids is a major challenge for MECS and for any sorbent system
to outperform commercial solvents.
However, Na2CO3-based MECS have some special properties that may make them commercially attractive in niche
applications. Chief among these is bio-compatibility (low toxicity). Also, as a sorbent, MECS downscale to small capture
applications much better than solvents and, unlike most sorbents, are water-tolerant. MECS are also inexpensive
compared to many other chemisorbents, like metal-organic frameworks (MOFs). Leveraging these advantages, MECS
commercialization efforts are ongoing.
TABLE 2: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 980–1,050 —
Bulk Density kg/m3 ~650 —
Average Particle Diameter mm 0.5 0.3
Particle Void Fraction m3/m3 0 —
Packing Density m2/m3 — —
Solid Heat Capacity @ STP kJ/kg-K — —
Crush Strength kgf — —
Manufacturing Cost for Sorbent $/kg 100–1,000 5—10
Adsorption
Pressure bar 0.05–10 —
Temperature °C 20–60 —
Equilibrium Loading mol CO2/kg 0.8–2 2–3
Heat of Adsorption kJ/mol CO2 ~44–90 —
Desorption
Pressure bar 1 1–80
Temperature °C 80–100 80–160
Equilibrium CO2 Loading g mol CO2/kg — —
Heat of Desorption kJ/mol CO2 — —
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — packed bed or fluidized bed
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 1--140
Adsorber Pressure Drop bar <0.5
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
357
Post-Combustion Novel Concepts
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure; if it is
a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of CO2 is roughly 0.132
atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Chemical.
Sorbent Contaminant Resistance –Water tolerant.
Sorbent Attrition and Thermal/Hydrothermal Stability – Lowered CO2 capture capacity is seen with cyclic absorption
and steam desorption in the bench-scale system. In future work, the team would most likely be able to demonstrate more
consistent performance, such as that observed in the gram-scale experiments, using a different MECS formulation.
Process Design Concept – See above
technology advantages
• Microcapsules are high surface area, permeable microreactors that enable advanced solvents to achieve
transformational carbon capture.
• MECS may overcome all or many of the characteristics inherent in some new CO2 capture sorbents, which include slow
kinetics, high viscosity, phase changes, corrosivity, or other issues.
• Overcomes mass transfer limitations of advanced solvents, reducing size and capital cost of absorber.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
358 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
R&D challenges
• Selection of suitable shell materials.
• Testing packing methods.
• Developing capsule production scale-up.
• Capsule curing.
• Determining thermodynamic properties of micro-scale solvents.
status
This project has concluded.
available reports/technical papers/presentations
Saraf Nawar, Congwang Ye, Joshuah K. Stolaroff, Du Thai Nguyen, Lu Mi, and David A. Weitz. “Spatially Patterning
Microfluidic Device Wettability using Sequential Microfabrication.” Lab on a Chip (in review).
Nguyen, Du; Murialdo, Maxwell; Hornbostel, Katherine; Ye, Congwang; Smith, William; Baker, Sarah; Bourcier, William;
Knipe, Jennifer; Aines, Roger; Stolaroff, Joshuah. "3D Printed Polymer Composites for CO2 Capture." (2019) Industrial
and Engineering Chemistry Research. 58, 48, 22015-22020.
Chu, Albert, Du Nguyen, Sachin S. Talathi, Aaron C. Wilson, Congwang Ye, William L. Smith, Alan D. Kaplan, Eric
B. Duoss, Joshuah K. Stolaroff, and Brian Giera. “Automated Detection and Sorting of Microencapsulation via Machine
Learning.” Lab on a Chip 19, no. 10 (2019): 1808–17. https://doi.org/10.1039/C8LC01394B.
Kotamreddy, Goutham, Ryan Hughes, Debangsu Bhattacharyya, Joshuah Stolaroff, Katherine Hornbostel, Michael
Matuszewski, and Benjamin Omell. “Process Modeling and Techno-Economic Analysis of a CO2 Capture Process Using
Fixed Bed Reactors with a Microencapsulated Solvent.” Energy & Fuels, July 17, 2019.
https://doi.org/10.1021/acs.energyfuels.9b01255.
Hornbostel, K., D. Nguyen, W. Bourcier, J. Knipe, M. Worthington, S. McCoy, and J. Stolaroff. “Packed and Fluidized Bed
Absorber Modeling for Carbon Capture with Micro-Encapsulated Sodium Carbonate Solution.” Applied Energy 235
(February 1, 2019): 1192–1204. https://doi.org/10.1016/j.apenergy.2018.11.027.
Stolaroff, J., “Advanced Manufacturing to Enable New Solvents and Processes for Carbon Capture,” presented at the
2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-Thursday/2J-Stolaroff2-LLNL-
Microencapsulation.pdf.
Stolaroff, J. K.; Ye, C.; Oakdale, J. S.; Baker, S. E.; Smith, W. L.; Nguyen, D. T.; Spadaccini, C. M. & Aines, R. D. (2016).
Microencapsulation of advanced solvents for carbon capture. Faraday Discuss., The Royal Society of Chemistry, 192, 271-
281.
Stolaroff, J., “Advanced Manufacturing to Enable New Solvents and Processes for Carbon Capture,” presented at the 2016
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13078&filename=J-Stolaroff-LLNL-Advanced-Manufacturing-for-
New-Solvents.pdf.
Stolaroff, J., “Advanced Manufacturing to Enable New Solvents and Processes for Carbon Capture,” presented at the 2015
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2015.
https://www.netl.doe.gov/projects/plp-download.aspx?id=13077&filename=J-Stolaroff-LLNL-Microencapsulation-and-
Advanced-Manufacturing.pdf.
Vericella, J. J.; Duoss, E. B.; Stolaroff, J. K.; Baker, S. E.; Hardin, J. O.; Lewicki, J.; Glogowski, E.; Floyd, W. C.; Valdez, C. A.;
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
359
Post-Combustion Novel Concepts
Smith, W. L.; Jr., J. H. S.; Bourcier, W. L.; Spadaccini, C. M.; Lewis, J. A. & Aines, R. D. "Encapsulated liquid sorbents for
carbon dioxide capture." Nature Communications, 2015, 6, 1-7.
Stolaroff, J.K., Bourcier, W.L., “Thermodynamic assessment of microencapsulated sodium carbonate slurry for carbon
capture.” Energy Procedia 63 ( 2014 ) 2331 – 2335.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
360 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Process Intensification for technology maturity:
Prototype-Scale, Actual Flue
Carbon Capture Gas (equivalent to 0.2-1.0
kwe)
primary project goals project focus:
Molecular Basket Sorbents on
Altex Technologies Corporation, in partnership with Pennsylvania State University Microchannel Heat
(PSU), have previously developed the integrated temperature and pressure swing Exchangers
(ITAPS) carbon capture system. The ITAPS system utilizes advanced molecular
basket sorbents (MBSs) on microchannel heat exchangers, which can be quickly participant:
cycled between carbon dioxide (CO2) sorption from coal-derived syngas and Altex Technologies
desorption into low-pressure steam exhausted from steam turbines in an Corporation
integrated gasification combined cycle (IGCC) power system. This would replace
project number:
the typical three-stage Selexol system (for acid gas removal and pre-combustion
carbon capture in the context of IGCC) with smaller and energy-efficient SC0013823
desorption and sorption units.
predecessor projects:
The project is currently in Phase IIB, with the goal of developing the Compact N/A
Rapid Cycling CO2 Capture (CRC3) system that would extend the concept of using
the MBSs on microchannel heat exchangers to post-combustion applications. NETL project manager:
Also, work is continuing to reduce the size (and therefore costs) of the Altex CO2 Katharina Daniels
capture system by coating both sides of the heat exchanger with a sorbent with [email protected]
rapid sorption-desorption kinetics. Current objectives are to design a prototype-
scale system for CRC3 to improve the MBSs for higher heat- and mass-transfer principal investigator:
rates, to fabricate and test a prototype-scale CRC3 sorbing unit on actual flue gas, Kenneth Lux
and to perform techno-economic analysis (TEA) of the CRC3 system integrated Altex Technologies
Corporation
into a large-scale power plant.
[email protected]
technical goals partners:
Pennsylvania State University,
• Improve sorbent capacity and sorption/desorption rates. NCCC
• Demonstrate heat integration of sorption and desorption processes.
start date:
• Conduct prototype-scale testing of a post-combustion capture-geared 06.08.2015
prototype unit on actual flue gas at 10 to 50 standard liters per minute (slpm),
equivalent to 0.2 to 1.0 kilowatt-electric (kWe). percent complete:
75% (combined Phases I, II, &
technical content IIB)
The Altex team previously developed the ITAPS process with a view to produce a
low-cost CO2 capture technology that leverages process intensification principles
(i.e., process capital and energy costs of the capture systems are shared with other
unit operations of the power plant). In ITAPS, Altex-developed microchannel heat
exchangers were wash-coated with PSU's advanced MBSs. By wash-coating the
MBS on the microchannel heat exchanger, high heat- and mass-transfer rates were
obtained. These high rates allow for quick cycling between CO2 sorption and
desorption. This should allow smaller sorption units with a lower capital cost than
a typical three-stage Selexol system. Operating costs are also lower than a three-
stage Selexol system because the system can operate at lower pressures and does
not require circulation of a liquid amine sorbent. The system can also be integrated
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
361
Post-Combustion Novel Concepts
with the power plant steam loop to improve energy efficiency; the heat of sorption can be used to preheat the boiler
feedwater, while the heat of desorption can be used to condense about 50% of the steam turbine exhaust. In terms of
process integration, Figure 1 depicts the ITAPS units’ process with boiler feed water flows and steam turbine flows (for
sorption and desorption modes, respectively), which would be encountered in integrating an ITAPS system within the
context of an IGCC cycle or a traditional power plant.
a)
Capture Mode
SYNGAS
OR
FLUE GAS
BOILER BOILER
FEED FEED
WATER WATER
Contactor
CLEAN
SYNGAS OR FLUE GAS
b)
Regeneration Mode
TURBINE TURBINE
EXHAUST EXHAUST
Contactor
SYNGAS
OR
FLUE GAS
Figure 1: Simplified process flow diagram for Altex’s integrated temperature and pressure swing carbon capture process. a) Capture
mode – cooling provided by boiler feed water; b) Regeneration mode – heating provided by turbine exhaust.
PSU has been responsible for development of the sorbents they term as MBSs. The idea is to load CO2-philic polymers
such as polyethyleneimine (PEI) onto high-surface-area nano-porous inorganic materials such as MCM-41 and SBA-15,
thereby increasing the accessible sorption sites per weight/volume of sorbent and improving the mass-transfer rate in
sorption/desorption processes by increasing the gas-PEI interface. These sorbents can selectively adsorb large quantities
of CO2 compared to typical sorbents such as zeolites or activated carbons. The sorbents also pack CO2 in a condensed
form in the mesoporous molecular sieve basket and hence show a high CO2 capacity and selectivity. The basic idea for
preparation of MBS is illustrated in Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Figure 2: Principle for preparation of “molecular basket” sorbent (MBS).
The sorbents are applied by wash-coating the surfaces of microchannel heat exchangers. Altex is leveraging their expertise
in design of these heat exchangers, which have been deployed in a wide range of sizes (fractions of kW to multiple
megawatt [MW] capacities); materials (aluminum, copper, stainless steel, high-temperature alloys, corrosion-resistant
alloys); counter-flow and cross-flow configurations; for various types of fluid flows; and in many fields, including oil and
gas platform processes, separators, liquefied natural gas (LNG) processing, chillers, heat pumps, fuels reforming, waste
heat power systems, and electronics cooling applications. For ITAPS, Altex developed the bench-scale prototype depicted
in Figure 3. Note that finned inserts within the unit provide ample surface area onto which MBS can be wash-coated. In
the pre-combustion capture case, the process stream of syngas containing CO2 passes through the channels, and on the
utility side, cooling water provides withdrawal of heat; in regeneration, steam would be passed through the channels to
purge out the captured CO2. Extensive surface area facilitates efficient heat transfer needed to accomplish the sorption
and desorption steps for capture of CO2.
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Post-Combustion Novel Concepts
Figure 3: Illustration of ITAPS microchannel heat exchanger units/reactors.
In earlier project phases, PSU advanced the MBS material to improve the CO2 capacity, and Altex demonstrated and
established the feasibility of wash-coating this sorbent onto the microchannel heat exchanger. Advancements were made
in both improving the mechanism of loading of the polymer into the solid matrix of the sorbent (low-cost fumed silica
has been used in place of high-cost mesoporous silica, and sorbent performance improved by incorporating 3-
aminopropyl triethoxysilane [APTES] along with PEI in the polymer formulation) and in improving the process for wash-
coating the reactor (a single-step wash-coating method incorporating fumed silica, APTES, and PEI was devised,
eliminating a separate impregnation step).
The bench-scale system prototype was tested for multiple cycles of CO2 sorption/desorption, validating the feasibility of
cycling and heat recovery. Data from these tests were used to determine the required wash-coat thickness needed to
meet the target cost of electricity (COE) and ensure that this thickness can maintain a high effectiveness. From findings
of the testing, analysis showed that the ITAPS process could significantly reduce cost of capture and COE.
Currently, the project is extending application of this technology into the area of post-combustion CO2 capture. Figure 4
depicts the process concept for the CRC3 system, which deploys the Altex technology to capture of CO2 from post-
combustion flue gas.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
364 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
CRC3
Figure 4: Process concept for the Compact and Rapid Cycling CO2 Capture (CRC3) system.
Within this post-combustion capture context, current work is targeting better process approaches to integrate heat of
sorption with the heat of desorption and to further improve sorbent performance, all of which are intended to reduce
capture costs and enable the commercial potential of this technology.
technology advantages
• The CRC3 approach of applying sorbent to the high surface area, wash-coated minichannel reactor walls enables
indirect heating and cooling of the sorbent.
• The sorbent on the minichannel reactor walls remains fixed in place and is not subject to particle attrition resulting
from particle-particle contact, as would occur in a fluidized bed.
• The dispersion of sorbent over the high surface area of the walls of the minichannel reactor enables high mass-transfer
rate of CO2 to the sorbent.
• The pressure drop through the minichannel reactor can be reduced relative to a packed-bed absorber, much in the
same way that monolith-supported catalysts reduce the pressure drop in selective catalytic reactors (SCRs) and, more
commonly, in automobile catalytic converters. This will enable ITAPS to handle high gas-flow rates.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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365
Post-Combustion Novel Concepts
• The CO2 MBSs developed by PSU exhibit high capacity and operate at low-desorption temperatures and with lower
heat of sorption, requiring less parasitic energy draw and thereby boosting plant net efficiency.
• The MBSs are engineered with specific chemical surface functionality, which allows for high CO2 sorption capacities in
high-humidity conditions.
• Sorbent performance and the CRC3 approach enable lower round-trip energy costs for a complete sorption-desorption
cycle.
• Enabling the production of CRC3 reactors at low cost and integrating a carbon capture system with existing unit
operations should result in lower capital and operating costs for CO2 capture from coal-fired power plants.
R&D challenges
• Operation at lower CO2 partial pressures in flue gas as compared to syngas used in Phase I and Phase II.
• Implementing sorbent on both sides of the contactor and coordinating heat transfer between them.
• Operating on real flue gas.
status
Project Phase I and Phase II have been previously completed, in which ITAPS technology was developed and feasibility
demonstrated for pre-combustion capture. Phase IIB is underway, in which the MBSs integrated in microchannel heat
exchangers are to be improved, evaluated, and tested for post-combustion capture from flue gas.
available reports/technical papers/presentations
“Process Intensification for Carbon Capture,” Altex Technologies Corporation and Pennsylvania State University, DE-
SC0013823 (Phase IIB) Kickoff Meeting presentation (proprietary), September 5, 2019.
“Process Intensification for Carbon Capture,” Phase II Final Report, Kenneth Lux, Tahmina Imam and Mehdi Namazian of
Altex Technologies Corporation, Xiaoxing Wang and Chunshan Song of Pennsylvania State University, Submitted to the
U.S. Department of Energy Office of Science (SBIR) / Office of Fossil Energy under Assistance Agreement Number DE-
SC0013823, November 12, 2018.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
366 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Lab-Scale Development of a technology maturity:
Laboratory-Scale, Simulated
Hybrid Capture System with Flue Gas
Advanced Membrane, Solvent project focus:
System, and Process
Solvent-Membrane Hybrid
Capture System
Integration participant:
Liquid Ion Solutions
primary project goals project number:
FE0026464
Liquid Ion Solutions LLC, with Penn State University and Carbon Capture Scientific
(CCS), LLC, will develop and validate a transformational hybrid membrane/solvent predecessor projects:
system for post-combustion carbon dioxide (CO2) capture from flue gas. The N/A
hybrid technology is a two-stage CO2 capture system combining a membrane
separation process and an absorption/stripping process with heat integration NETL project manager:
between the absorption column and stripping column through a heat pump cycle. Andrew jones
Process air is used to sweep the stripper, resulting in much lower regeneration [email protected]
temperatures and enabling heat integration to the point that no process steam is
required. To reduce capital cost, a next-generation membrane technology with principal investigator:
higher permeance will be developed. The interfacially controlled envelope (ICE) Hunaid Nulwala
membrane will make use of a transport zone neglected in conventional mixed Liquid Ion Solutions
matrix membranes (MMMs). By carefully controlling the interface between the [email protected]
polymer and inorganic particles within the MMM, CO2 transport will be
partners:
encouraged and nitrogen transport diminished in the gap between the two
phases. Since permeance is directly tied to membrane area and capital cost, the Carbon Capture Scientific,
LLC, Pennsylvania State
development of the ICE membranes will reduce the capital cost of the hybrid
University
process below that of the baseline technologies. The research team will combine
computer simulation with lab-scale experimentation using simulated flue gas to start date:
develop, optimize, and test ICE membranes; test the absorption column and air
10.01.2015
stripper; and provide data to complete a techno-economic analysis (TEA) of the
hybrid technology. percent complete:
100%
technical goals
• Conduct computer simulations to better understand the various unit operations
in the hybrid process and set experimental conditions for project testing.
Integrate the simulations and optimize the hybrid system.
• Conduct initial testing of the Generation 0 ICE (neat polymer) membrane
formulations. Develop and optimize polymers, select and modify necessary filler
particles, examine and validate fabrication techniques, and construct an
isochoric test unit.
• Modify and install an existing lab-scale, packed-bed absorption column, and
then use it to investigate the absorption column performance at a reduced
operating temperature.
• Prepare and characterize the Generation 1 ICE membranes using the isochoric
membrane testing unit.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
• Modify the absorption column based on computer simulation results, then install and test.
• Fabricate the two optimal Generation 1 ICE membrane compositions for simulated flue gas testing in the isobaric
membrane test system.
• Conduct an initial technical and economic feasibility study.
technical content
The objective of the project was to achieve lab-scale demonstration of a transformational hybrid membrane/solvent system
for the capture of CO2 from flue gas. A novel process integration scheme was proposed to overcome the low partial pressure
of CO2 present in flue gas. This scheme took advantage of the potential synergies inherent in the membrane and solvent
capture systems. The proposed hybrid technology replaced the second-stage membrane with a methyl diethanolamine
(MDEA) solvent capture process. The combustion air was used as a sweeping gas in the solvent stripper. This overall
configuration had the major advantages of requiring much less air and eliminating the problems associated with oxygen
slip in the membrane-based systems. Even more importantly, because of the presence of the air sweep in the stripper, much
lower temperatures were required for solvent regeneration, which enabled heat integration to the point that no process
steam was required.
Twenty-two poly(phosphazenes) were synthesized and fully characterized to identify the most optimal candidate matrix
poly(phosphazene) polymer for ICE membrane development. The team performed detailed chemical analysis, solvent
solubility studies, film formability, adhesion studies, membrane casting procedures, and thermal characterization studies on
the 22 candidate polymers.
The base polymer material, called MM16, was not a film former, and it lacked the needed mechanical properties. To
overcome these challenges, a cross-linker chemistry was developed and introduced in MM16 (CO2/nitrogen [N2] selectivity
of 90 and permeability of 900 was observed for the MM16 polymer). The crosslinked material was termed MM19, which
achieved a CO2/N2 selectivity of 50 and a CO2 permeability of 500 barrer. MM19 had good film forming, as well as mechanical
properties needed to cast membranes, and was selected as the base polymer for developing the ICE-1 membranes
incorporating surface modified nanoparticles.
A variety of nanoparticles were evaluated, including surface-modified Quantum dots (QD). However, it was clear during the
project that surface-modified silica nanoparticles are optimal for making ICE membranes. A synthesis methodology was
developed to place a variety of functional groups on the surface of nanoparticles. Overall, there were three different
functional groups placed on 10- to 15-nm silica particles. The functional groups used were cyclohexyl, octadecyl, and
ethylene glycol. It was found that MM19 and the cyclohexyl surface-modified silica particles were compatible with each
other. These colloidal nanoparticles were obtained from Nissan chemicals and are available in large quantities. The surface
modification reaction is scalable. Figure 1 illustrates the general synthesis scheme.
Surface modified silica
R
Si R
R Si
Si O O
O R
∆ Si
R O
R Si
Si + -MeOH O
O O Si R
O
Si
R
Figure 1: General synthesis scheme of surface modification for silica-nano material.
Additional membrane improvements were carried out by the team to optimize the mechanical and film casting properties.
This included identifying the best support and lift-off procedures, as well as figuring out the additional types of crosslinker
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
in the polymeric film. The team studied the impact of the support and determined which support would be ideal for this
class of material. The team further improved the mechanical properties of the MM19 polymer by introducing a secondary
crosslinking moiety. The addition of this crosslinking moiety resulted in interpenetrating networks (IPN) and improved
membrane performance. The IPN approach is illustrated in Figure 2 with the chosen crosslinker. The team also developed
an ultraviolet (UV)-initiator to cure the membranes extremely fast. Upon forming the IPN, the membranes obtained were
mechanically robust. The implications of the vastly improved mechanical stability cannot be overstated, and lead to far more
robust films. Synthesis of MM19 was routinely carried out at 20- to 40-gram scale.
Figure 2: Accessing robust films using interpenetrating approach.
The membrane testing had many interdependent variables, and understanding them was important to developing an
optimal membrane material. The team performed detailed design of experiment studies and built a test matrix to yield
statistically relevant data. This matrix evaluated 30 different membrane compositions and was used to determine the most
optimal composition for these membranes. These results are summarized in Figure 3. The membrane compositions number
1, 4, 9, 20, and 25 showed promise for the application. These materials show permeability of over 1,200 barrer and CO2/N2
selectivity over 35. The team was able to achieve 5X higher permeability that the current state-of-the-art materials.
Figure 3: Testing results obtained from the isobaric unit. The blue line is the cutoff for the permeability (1,200 barrers), and the red line is
the cutoff for selectivity (35 CO2/N2). Five compositions have permeability over 1,200 and selectivity over 35.
The initial simulation work for the membrane system, absorption/air stripping system, heat pump cycle, and optimization of
the hybrid process was conducted by CCS LLC. On the membrane side, the team determined that it was economical to
choose a one-stage compression unit over two-stage compression and refrigeration steps due to lack of additional
performance and increased cost. On the solvent side, it was determined that an operating temperature of 25°C was the most
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
economical temperature for the absorption process. The initial simulation provided the guidelines to perform the CO2
absorption experiments.
Absorption and air stripping simulations were conducted using the ProTreat software package. Industrial operating
conditions were used in the simulations to study the effect of several parameters on packing height, including operating
temperature, gas-to-liquid (G/L) ratio, and air flow rates for CO2 stripping in the desorption step. A simulation program that
integrated an absorber and a stripper into the heat pump cycle was created, and further optimization work was carried out
to reduce the energy consumption of the heat pump cycle. Preliminary optimization work revealed that the moisture
contained in the stripping air would impact the performance of the heat pump cycle.
An existing lab-scale, packed-bed absorption column was modified and installed to investigate the absorption column
performance at a reduced operating temperature. The installed absorption column can be seen in Figure 4. Parametric tests
were performed to investigate the influence of G/L ratio and operating temperature on the CO2 removal rate. Tests were run
at three operating temperatures (15, 25, and 35°C). For each operating temperature, three G/L ratios were studied. For the
hybrid process to work successfully, the absorption process needed to achieve at least 85% CO2 removal. The parametric
test results were in reasonable agreement with the computer simulations, showing that 85% CO2 removal was achievable.
Figure 4: Installed absorption column.
On the membrane side of the simulation, an internally developed program was used to simulate the membrane separation
step. Simulation work confirmed that major improvements in membrane performance were needed to produce CO2 with
95% purity via one-stage membrane separation. Adding a simple compression and refrigeration step after the membrane
separation allowed CO2 with 95% purity to be produced in a more practical way.
The absorption column previously used was modified by CCS LLC based on computer simulation results to form the air
stripper column. The modified air stripping column was installed and tested. This stripper column was then used to perform
parametric testing. Preliminary parametric tests were carried out by the CCS LLC team. The variables to be investigated
include stripping operating temperature, stripping air flow rate, and G/L ratio. For each test condition, data was collected
once the operation reached steady-state. The parametric tests were mainly performed to investigate the influence of G/L
ratio and operating temperature on CO2 desorption. The tests were conducted at different operating temperatures (45 to
65°C) with different G/L ratios (80 to 160 L air/L solvent).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Several successful absorption/desorption cycles were identified: they were cycles with absorption temperature/desorption
temperature of 15/55°C, 25/55°C, and 35/65°C. By combining the experiments and computer simulation results in the hybrid
process, the following optimal processing conditions were obtained:
• Absorption temperature: 30°C.
• Desorption temperature: 60°C.
• Lean loading: 6.0 wt%.
• G/L ratio: 92 L air/L solvent.
• Number of inter-stage heating: 2.
The systematic parametric tests and computer simulations revealed that an absorption/stripping cycle between 30/60°C was
optimal for the hybrid process. A heat pump cycle with a temperature lift of 40°C was enough for the absorption/stripping
cycle when 80% of the combustion air was used in the stripping column, fulfilling the success criteria. In addition, the column
heights of both the absorber and stripper were reasonable, at 25 meters or less for the Case B12B-scale power plant.
A considerable effort was spent on figuring out how the MM19 could be scaled-up. The synthesis of MM19 included multiple
purification steps that were never a problem at smaller scales. However, the team’s attempts at synthesizing polymers over
40 grams ran into difficulty. The general synthesis scheme is provided in Figure 5. It is also important to note that the
chloropolymer is extremely reactive to air. The formation of the sodium salts are separate synthesis steps.
Figure 5: General scheme for the synthesis of MM19 polymer.
There were other problems that also started to show up, such as batch-to-batch variation from the chemical suppliers. The
chloro-precursor for poly(phosphazene) quality became an issue as well. A significant effort was spent on the scale-up of
these polymers and benchmarking them against the originally obtained polymers. However, the team was unable to
benchmark the large-scale material with small-scale synthesized results.
The team evaluated the impact of contaminants on the membrane performance. It was found that upon introduction of
contaminants, the permeability and selectivity is lowered. However, the membranes recovered upon removal of the
contaminants.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Figure 6: Simulated flue gas studies on ICE-1 membranes.
Figure 6 illustrated that despite the problems with synthesis, the overall ICE membrane concept holds true. The ICE
membranes were not affected by the addition of contaminants to the simulated flue gas (50 parts per million [ppm] sulfur
dioxide [SO2] and 70 ppm nitrogen dioxide [NO2] with 7.8 g of water [H2O]/kg of air [16% relative humidity]), and upon
removal, they recover.
The performances of the power plant equipped with the hybrid process and Baseline Case B12B were compared. Results
showed that the power plant equipped with the hybrid CO2 capture process had a thermal efficiency of 33.4%. This was
better than the Baseline Case B12B, which was 32.5%. However, the cost of electricity (COE) for the hybrid process was
$146.3/megawatt-hour (MWh), which was higher than the $142.8/MWh for Case B12B. It is important to note that these
analyses were performed based on building a new power plant. For a retrofitting case, since the hybrid CO2 capture
technology would not require steam from an existing power plant, no modifications of the existing power plant would be
needed. In the case of a retrofit, the capital cost of the hybrid CO2 capture process could be lower and potentially a better
fit for a CO2 capture case.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 109.255 N/A
Normal Boiling Point °C N/A N/A
Normal Freezing Point °C - N/A
Vapor Pressure @ 15°C bar 《1Pa N/A
Manufacturing Cost for Solvent $/kg 《3 N/A
Working Solution
Concentration kg/kg 1/1 N/A
Specific Gravity (15°C/15°C) - 1.09 N/A
Specific Heat Capacity @ STP kJ/kg-K 2.978 N/A
Viscosity @ 15°C cP 10.2 N/A
Absorption
Pressure bar 1 1
Temperature °C 30 30
Equilibrium CO2 Loading mol/mol 0.494 0.348
Heat of Absorption kJ/mol CO2 55.99 55.99
Solution Viscosity cP 10.2 10.2
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Desorption
Pressure bar 1 1
Temperature °C 60 60
Equilibrium CO2 Loading mol/mol 0.347 0.347
Heat of Desorption kJ/mol CO2 55.99 55.99
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr -
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 ~20
Absorber Pressure Drop bar <0.1
Estimated Absorber/Stripper Cost of Manufacturing __$__
—
and Installation kg/hr
TABLE 2: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — proprietary polymer
Materials of Fabrication for Support Layer — proprietary polymer
Nominal Thickness of Selective Layer µm <1 <1
Membrane Geometry — plate-and-frame plate-and-frame
Max Trans-Membrane Pressure bar 1.1 1.1
Hours Tested without Significant Degradation — - (simulated coal) - (simulated coal)
Manufacturing Cost for Membrane Material $/m2 - -
Membrane Performance
Temperature °C 40 40
CO2 Pressure Normalized Flux GPU or equivalent 5,000 5,000
CO2/H2O Selectivity — 2 2
CO2/N2 Selectivity — 44 44
CO2/SO2 Selectivity — - -
Type of Measurement — simulated coal simulated coal
Proposed Module Design (for equipment developers)
Flow Arrangement — crossflow and countercurrent
Packing Density m2/m3 -
Shell-Side Fluid — -
Flue Gas Flowrate kg/hr -
CO2 Recovery, Purity, and Pressure %/%/bar 50, 95,140
Pressure Drops Shell/Tube Side bar feed: <0.05/sweep: 0.05
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing
cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical.
Solvent Foaming Tendency – For a flue gas environment, no foaming should be expected.
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Post-Combustion Novel Concepts
Flue Gas Pretreatment Requirements –SO2 removal is required.
Solvent Makeup Requirements – Without water wash at the tops of both absorber and stripper, the makeup rate is
about 10kg/hr MDEA and 20kg/hr piperazine (PZ).
Waste Streams Generated – A waste stream will be created only if a solvent reclamation process is installed.
Process Design Concept –
Makeup
Clean Flue Gas Solvent Air +CO2
To
Combustor
Lean Solution Rich Solution
Expansion
Valve
Heat
Membrane Pump
Cycle
Unit
Stripper
Stripper
Absorber
Flue Gas
Vapor
Compressor
Vacuum
Pump Cross Heat
Exchanger
Air
CO2
Lean
Solution
Rich
Solution
Figure 7: Overall membrane/solvent integrated process.
Membrane Permeation Mechanism – The membranes developed under this project are polar, rubbery/elastic with very
low glass transition temperatures allowing higher permeabilities. The overall separation occurs mainly due to the solubility
of CO2 in the polymer, which is further facilitated by interfaces of the surface modified nano particles resulting in improved
permeabilities.
Contaminant Resistance – The surface-modified nanoparticles are not affected by the addition of simulated flue gas
and the addition of contaminants (50 ppm SO2 and 70 ppm NO2 with 7.8g of H2O/kg of air [16% relative humidity]).
Membrane Replacement Requirements – Outside project scope.
technology advantages
• Polyphosphazenes have excellent chemical and thermal stability.
• Steam extraction is not required.
• Stripper operating pressure is flexible (depending on low-quality heat).
• The high-permeance membrane reduces capital costs.
• The heat pump cycle and use of air sweep for stripping eliminate the need for steam extraction, reducing parasitic
power and operating expenditures.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
375
Post-Combustion Novel Concepts
R&D challenges
• Polyphosphazene performance is uncertain.
• Scale-up is a problem.
• The heat pump has high energy consumption.
• The long-term durability of the membrane in actual flue gas and variable conditions has not been determined.
status
This project has concluded.
available reports/technical papers/presentations
Nulwala, H. “Lab-Scale Development of a Hybrid Capture System with Advanced Membrane, Solvent System and
Process Integration,” Final Report, December 2018. https://www.osti.gov/servlets/purl/1484714/.
Nulwala, H. “Lab-Scale Development of a Hybrid Capture System with Advanced Membrane, Solvent System and
Process Integration,” Budget Period 2 Review, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/sites/default/files/2017-12/FE0026464-BP2-Review-Presentation-08-03-17.pdf.
Nulwala, H. “Lab-Scale Development of a Hybrid Capture System with Advanced Membrane, Solvent System and
Process Integration,” Project Kickoff Meeting, Pittsburgh, PA, October 2015.
https://www.netl.doe.gov/sites/default/files/2017-12/FE0026464-Kickoff-Presentation.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
376 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Advanced Carbon Dioxide technology maturity
Compression with Supersonic
Pilot-Scale, 1.5 MTPA (million
tons per annum) of CO2
Technology project focus:
Supersonic Compression
primary project goals participant:
Dresser-Rand, A Siemens
Dresser-Rand, a Siemens Business, is developing a unique compressor technology Business
based upon flight-based supersonic/shockwave compression principles for use as
a carbon dioxide (CO2) compressor. Advancing supersonic compressor technology project number:
will help meet overall goals of lower capital costs, smaller footprints, and improved FE0026727
energy efficiencies of carbon capture systems.
predecessor projects:
technical goals FE0000493
FC26-06NT42651
• Increase the performance of CO2 supersonic compression from a previously
NETL project manager:
demonstrated single-stage pressure ratio of 11.5:1 to the goal of efficient 100:1
Robin Ames
total pressure ratio CO2 compression across two stages. [email protected]
• Operate at a compressor CO2 flow rate of 100 pounds per second, suitable for
carbon capture applications in 125-megawatt-electric (MWe) coal-fired power principal investigator:
plants and be scalable to higher flowrates. Kirk Lupkes
• Validate compressor performance of pilot-scale compressors, testing on gas Dresser-Rand
[email protected]
representative of a CO2 capture system.
• Perform techno-economic analysis (TEA) of the integration of supersonic CO2 partners:
compression in a 550-MWe power plant to quantify economic benefits of the N/A
technology for scenarios of large-scale power generation with carbon capture.
start date:
technical content 03.10.2016
Dresser-Rand (which acquired the assets of Ramgen Power Systems in 2014) is percent complete:
developing supersonic shockwave compression technology, similar in concept to 100%
an aircraft supersonic engine inlet, for use in a stationary compressor. This
compressor design features a rapidly rotating enclosed disk that generates
supersonic speeds at its rim, generating shockwaves, and thereby compressing
gases introduced into a channel surrounding the rim. Compared to conventional
compressor technologies, supersonic compression offers several potential
advantages: high compression efficiency, high single-stage compression ratios,
opportunity for waste heat recovery, and low capital cost. For example, Dresser-
Rand’s shock compression has the potential to develop compression ratios from
2.0 to 12.0 per stage. For CO2 compression applications, a nominal two-stage 100:1
compression ratio is envisioned, featuring a pair of 10:1 compression stages with
an intercooler located between the stages.
Figure 1 provides a cross-sectional view of an early concept for a single-stage
supersonic compressor, which gives some idea of the engineering embodied in a
compressor of this type.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 377
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Figure 1: Cross-sectional model of a single-stage supersonic compressor.
When shockwaves pass through a gas, they cause a localized compression. Figure 2 shows that the rotating rotor rim has
small, shallow angles that, when rotating at supersonic speed, will produce a series of oblique shocks terminating in a
final normal shock. These shockwaves can be seen in the 3D Euler computational fluid dynamics (CFD) image shown in
Figure 2.
Figure 2: Schematic of rotor rim and engine case and 3D Euler CFD image depicting shockwave behavior.
Additionally, strakes (ridges) are incorporated into the design of the rotor to form sidewalls. The strakes are utilized to
segregate individual shock compression ducts, as well as to separate high-pressure discharge gas from low-pressure
suction. The combination of shocks and strakes result in a compressed fluid delivered from a stationary discharge duct
with compression efficiencies comparable to conventional industrial turbo-compressors, but with much higher single-
stage pressure ratios. The heat generated during this single stage of shockwave compression is higher than that generated
during conventional compression, yielding gas discharge temperatures exceeding 290°C (550°F). This is a relatively high-
quality source of waste heat that can be recovered and utilized gainfully in optimizing overall system thermal efficiency.
The high mechanical efficiency and waste heat recovery opportunity combine to deliver significant installed and
operational cost savings versus existing turbo-compressors.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
378 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
The project includes testing of the high-pressure compressor in a CO2 test loop and the design, build, and testing of a
high-flow coefficient low-pressure stage to complete the 100:1 total pressure ratio testing, along with the completion of
a TEA for the integration of the supersonic compressor technology and heat integration into a 550-MWe power plant.
The 10-MW high-pressure compressor on the close-loop CO2 test stand is shown in Figure 3.
Figure 3: High-pressure CO2 compressor on test stand.
technology advantages
• Competitive operating efficiency and reduced installed capital cost (approximately 50%) over multistage bladed turbo-
compressors.
• Lowered footprint of the CO2 compression island in the plant, less piping and fewer intercoolers.
• High-stage discharge temperature enables cost-effective recovery of heat of compression:
o Improves carbon capture system efficiency.
o Reduces power plant de-rate.
R&D challenges
• Complicated shockwave aerodynamics in the gas flow path require intensive computing capabilities and model
development.
• High rotational speeds and the resulting loads and stresses.
• High-speed rotordynamic stability that meets industry standards.
• High-pressure ratio compressors yield high rotor thrust loads on bearings and structure.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 379
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
status
Testing for the high-pressure CO2 compressor was concluded with the final test phase achieving a 11.5:1 compression
ratio, better than the required 10:1 ratio. Testing of a high-flow, low-pressure compressor was completed at a 12.0:1
pressure ratio. A TEA was completed, including integration of waste heat showing benefits for carbon capture applications,
with a 28% reduction in cost of electricity (COE) for the cost of compression duty and 21,000-gallon reduction in cooling
water.
available reports/technical papers/presentations
Srinivasan, R., “Advanced CO2 Compression with Supersonic Technology,” presented at 2018 NETL CO2 Capture
Technology Project Review Meeting. Pittsburgh, PA, August 2018. https://www.netl.doe.gov/projects/files/R-Srinivasan-
DRC-Advanced-Carbon-Dioxide-Compression.pdf.
Kuzdzal, M.J., “Advanced CO2 Compression with Supersonic Technology (FE0026727),” presented at 2017 NETL CO2
Capture Technology Project Review Meeting. Pittsburgh, PA, August 2017. https://www.netl.doe.gov/projects/files/M-
Kuzdzal-Dresser-Rand-CO2-Compression-with-Supersonics.pdf.
Saretto, S., “Advanced CO2 Compression with Supersonic Technology,” presented at the 2016 NETL CO2 Capture
Technology Project Review Meeting, Pittsburgh, PA, August 2016. https://www.netl.doe.gov/projects/files/S-Saretto-
DresserRand-CO2-Compression-with-Supersonic-Tech.pdf.
Koopman, A., “Design and Testing of CO2 Compression Using Supersonic Shock Wave Technology,” Final Report, August
2009 through March 2015, DOE Award Number: DE-FE0000493, Seattle Technology Center, Dresser-Rand Company,
Bellevue, WA, June 2015.
Lupkes, K., “Ramgen Supersonic Shock Wave Compression and Engine Technology,” presented at the 2012 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2012.
Grosvenor, A.D.; Zheltovodov, A.A.; Derunov, E.K.; 2012; “Numerical Prediction of 3-D Shock-Induced Turbulent Flow
Separation Surrounding Bodies of Revolution Adjacent to a Flat Surface,” EUCASS Book Series on Advances in
Aerospace Sciences, Progress in Flight Physics, Eds. Ph. Reijasse, D. Knight, M. Ivanov, and I. Lipatov, Torus Press,
ISBN/ISSN: 978-2-7598-0674-4, pp. 119-140.
Baldwin, P., “Ramgen Supersonic Shock Wave Compression and Engine Technology,” presented at the 2011 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, August 2011.
Grosvenor, A.D.; Zheltovodov, A.A.; Matheson, M.A.; Sailer, L.M.; Krzysztopik, M.; Gutzwiller, D. P.; 2011; “Verification for a
Series of Calculated 3-D Shock Wave/Turbulent Boundary Layer Interaction Flows,” Proceedings 4th European
Conference for Aerospace Sciences (EUCASS 2011). July 4–8, 2011, Saint Petersburg, Russia. Paper 578.
Lawlor, S., “CO2 Compression Using Supersonic Shock Wave Technology,” presented at the 2010 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, September 2010.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
380 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Cryogenic Carbon Capture technology maturity:
Skid-Scale, Actual Flue Gas
Development project focus:
Cryogenic Carbon Capture
primary project goals Process
The objective of this project is to increase the reliability, efficiency, and scalability participant:
of the Cryogenic Carbon Capture™ (CCC) process to prepare for a pilot-scale (up Sustainable Energy Solutions
to 5 megawatt-electric [MWe], or 100 tonnes/day [tpd] of carbon dioxide [CO2]
captured) demonstration. project number:
FE0028697
technical goals
predecessor project:
DE-AR0000101 (ARPA-E)
• Improve key areas of the process through iterative design and experimentation,
culminating with recommendations for improvements to be integrated into the
NETL project manager:
existing skid-scale CCC External Cooling Loop (CCC-ECL™) system developed
David Lang
under previous funding.
[email protected]
• Integrate the recommended improvements into the CCC-ECL system and
confirm their contributions through experimental process testing. principal investigator:
• Perform modeling and estimation analyses to improve the techno-economic Larry Baxter
analyses (TEAs). Sustainable Energy Solutions
[email protected]
technical content partners:
PacifiCorp, Brigham Young
Sustainable Energy Solutions (SES), in partnership with PacifiCorp, Brigham Young University, Electric Power
University, Electric Power Research Institute, Inc., and Tri-State Generation & Research Institute, Inc., Tri-
Transmission Association, Inc., has implemented process improvements to the ECL State Generation &
version of their CCC technology, further advancing it. SES developed the CCC-ECL Transmission Association,
Inc., Press Technology and
technology under previous research funded by the Advanced Research Projects
Manufacturing, Sargent &
Agency-Energy (ARPA-E) project "Cryogenic Carbon Capture" (DE-AR0000101),
Lundy
the state of Wyoming, and others. Previous analyses and field tests of skid-scale
(1-tpd) versions of the CCC process have shown that the technology reduces CO2 start date:
emissions by more than 95% and has a parasitic load of less than 15% for coal- 10.01.2016
fired power plants. This project addressed issues discovered during the previous
field tests at power plants, cement kilns, and heating plants, resulting in the percent complete:
implementation of various process improvements. 100%
The foundation of the CCC process relies on refrigeration to cryogenic
temperatures, rather than a chemical reaction, to separate CO2 from flue gas from
a power plant or industrial source. Typically, refrigeration cycles consume large
amounts of energy, but this is only true if the final products are at lower
temperature than the incoming streams (e.g., air conditioning). While the CCC
process relies on refrigeration process principles, the products are at nominally the
same temperature as the incoming flue gas, and thus the energy efficiency is much
higher than for typical refrigeration processes. The CCC technology, shown in
Figure 1, separates CO2 and other pollutants from coal-derived flue gas by cooling
the flue gas to approximately -130°C, at which temperature CO2 forms a solid
(desublimates). The CCC process utilizes a large amount of recuperative heat
exchange through commercially available heat exchangers to cool the flue gas to
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
381
Post-Combustion Novel Concepts
the verge of CO2 desublimation before it enters a proprietary desublimating heat exchanger that desublimates, or freezes,
the CO2 out of the carrier gas stream. In the CCC-ECL system, an external refrigeration loop is used to provide cooling to
the desublimator (Figure 2). The process separates the solid CO2 from the carrier gas and recovers heat as the solids warm
and melt under pressure. The process delivers a high-pressure (150 bar), high-purity (99+%) liquid. The process
compresses liquid CO2 rather than a gas, so the energy input for CO2 compression is minimal. The cold, light gasses
(nitrogen [N2], oxygen [O2], and others) do not condense, but they do return through the recuperator for energy recovery,
which, in turn, minimizes the cooling load on the desublimator. The CCC process is minimally invasive and represents a
bolt-on carbon capture retrofit technology, allowing it to be easily retrofitted to existing plants. Additionally, the process
recovers water from flue gas and robustly handles impurities in the flue gas stream. It also requires 50% less energy and
costs about 50% less than an amine absorption process (Figure 3). Additional energy and cost savings ($14/tonne CO2
avoided) can be achieved through integration with steam cycle and control methods for sulfur oxides (SOX), nitrogen
oxides (NOX), and mercury (Hg).
Figure 1: CCC process.
Figure 2: CCC process implemented using an ECL system.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
382 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Figure 3: CO2 capture costs for CCC process compared to amine absorption process (NETL 2013 amine costs).
In this project, the team used existing CCC equipment and analytical tools to optimize the CCC unit operations and
improve technical performance through iterative design and experiment. The project explored issues affecting process
reliability, efficiency, and scalability, culminating in recommended improvements that will enhance the performance of
commercial CCC systems. The investigation of unit operation improvements to the CCC-ECL system included: (1) state-
of-the-art adsorption and phase-change drying processes, as well as alternative drying techniques, to decrease the energy
consumption and CO2 absorption in the flue gas drying stages of CCC; (2) options to mitigate potential heat exchanger
fouling to eliminate the accumulation of dissolved CO2, solid CO2, and other possible impurities in the CCC process; (3)
alternative solid-liquid separation operations to improve the reliability and performance and to decrease the energy
consumption of the separation process; (4) three alternative heat exchanger designs for commercial-scale implementation
of CCC; (5) skid modifications to implement measurements and controls that can extend the skid testing time; (6) several
options for managing the light gas stream produced by the CCC process; and (7) models that describe CCC capture of
pollutants other than CO2, validated with experimental data. The project integrated the recommended alternatives into
the existing skid-scale CCC-ECL system and operated the modified skid at PacifiCorp’s Hunter Power Plant using a
slipstream of flue gas for approximately 600 cumulative hours during a series of tests over several months. Photos of the
CCC-ECL skid are shown in Figure 4. Test results and process modeling informed an updated TEA of the CCC technology.
The primary figures of merit for improving unit operations are as follows:
• Reliability: The ability of the unit to operate without maintenance or performance degradation for a period of 18 to
24 months (average time between scheduled power plant maintenance).
• Efficiency: The energy or other resource consumption of the unit operation and its effect on overall process energy
efficiency.
• Scalability: The performance or existence of the unit operation at scales up to 1 gigawatt-electric (GWe) equivalent
and the impact of such scalability on cost, efficiency, and reliability.
• Techno-Economic Performance: Energy demand and ancillary pollutant capture efficiency as a function of CO2
capture fraction and cost estimates for retrofit and greenfield installations as measured by the increase in cost of
electricity (COE) and cost per unit mass of CO2 avoided.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
383
Post-Combustion Novel Concepts
Figure 4: CCC-ECL process test skid.
technology advantages
• The CCC process retrofits existing plants or provides a greenfield solution to any continuous CO2 source (coal-based
power, natural gas, cement, integrated gasification combined cycle, refineries, etc.).
• The CCC process captures 90 to 99+% of the CO2, and most pollutants (e.g., SOX, NOX, Hg), at half the cost and energy
of alternative carbon capture technologies and recovers more water from flue gas than it requires for operation
(reduces overall water demand).
• The CCC process integrates with renewables through grid-scale energy storage, which can result in further reductions
in cost and substantial value added for renewables.
• An increase in the process reliability, efficiency, and scalability represents significant progress toward the U.S.
Department of Energy’s (DOE) goal of $40/tonne of CO2 captured by 2025.
R&D challenges
• Innovative desublimating heat exchangers can be further optimized.
• Solids handling and other process equipment must avoid fouling, plugging, and level upsets.
• Innovative, scalable flue gas dryer requires demonstration.
• Effectiveness of solid-liquid separation is critical for pilot-scale implementation.
status
SES refined the CCC process in several areas, including flue gas drying, mitigating heat exchanger fouling, managing light
gas dispersal, and developing predictive capability for the capture of pollutants other than CO2. The individual unit
improvements were implemented, and the modified skid was operated at Hunter Power Plant for more than 600
cumulative hours, consistently capturing more than 90% CO2 and reaching 1 tpd CO2 capture capacity during short-term
tests.
available reports/technical papers/presentations
“Cryogenic Carbon Capture – Development Project DE-FE0028697,” Final Briefing – Public, September 2019.
https://www.netl.doe.gov/projects/files/CCC-Dev%20Final%20Briefing%20-%20Public.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
384 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Baxter, L., “Cryogenic Carbon Capture Development Progress and Field Test Data,” presented at the 2019 NETL CCUS
Integrated Project Review meeting, Pittsburgh, PA, August 2019.
https://www.netl.doe.gov/projects/files/Cryogenic%20Carbon%20Capture%20Development%20(FE0028697).pdf.
Baxter, L, et al., “Cryogenic Carbon Capture Development,” presented at the 2018 NETL CO2 Capture Technology Project
Review Meeting, August 2018. https://www.netl.doe.gov/projects/files/L-Baxter-SES-BYU-Cryogenic-Capture-
Development.pdf.
Baxter, L. and Stitt, K., “Cryogenic Carbon Capture Development,” presented at the 2017 NETL CO2 Capture Technology
Project Review Meeting, Pittsburgh, PA, August 2017. https://www.netl.doe.gov/projects/files/L-Baxter-SES-Cryogenic-
Carbon-Capture.pdf.
Sayre, A., Frankman, D., Baxter, A., Stitt, K., and Baxter, L., “Field Testing of Cryogenic Carbon Capture,” Carbon Management
Technology Conference, Houston, Texas, July 17-20, 2017. https://www.osti.gov/servlets/purl/1412681.
Baxter, L. and Stitt, K., “Cryogenic Carbon Capture Development,” Project Kickoff Meeting, December 2016.
https://www.netl.doe.gov/projects/files/SES-FE0028697-kick-off.pdf.
Jensen, M. J., C. S. Russell, D. Bergeson, C. D. Hoeger, D. J. Frankman, C. S. Bence and L. L. Baxter (2015). "Prediction and
validation of external cooling loop cryogenic carbon capture (CCC-ECL) for full-scale coal-fired power plant retrofit."
International Journal of Greenhouse Gas Control, Vol. 42: 200-212.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
385
Post-Combustion Novel Concepts
Additively Manufactured technology maturity:
Bench-Scale, Simulated Flue
Intensified Device for Gas
Enhanced Carbon Capture project focus:
Additively Manufactured
Intensified Device for
primary project goals Solvent-Based CO2 Capture
Oak Ridge National Laboratory (ORNL) is developing intensified devices participant:
combining multiple thermodynamic operations for improved efficiency for Oak Ridge National
solvent-based carbon dioxide (CO2) capture. These additive-manufactured Laboratory
packing structures combine heat and mass transfer, simultaneously increasing the
reactive surface area and enhancing heat exchange efficiency. project number:
FwP-FEAA130
technical goals predecessor projects:
N/A
• Utilize a computational fluid dynamics (CFD) model to realize a design and
perform a parametric study on key design and operational parameters. NETL project manager:
• Demonstrate the manufacturability of an equivalent geometry of a widely used David Lang
packing structure (Mellapak 250) and intensified device design with additive [email protected]
manufacturing techniques.
• Validate the core-scale metrics of the additively manufactured device to
principal investigator:
compare to its commercial counterpart. xin Sun
Oak Ridge National
• Design and print a device-scale prototype. Laboratory
• Test the device-scale prototype with a commercially available solvent and [email protected]
simulated flue gas to evaluate overall capture performance.
partners:
N/A
technical content
start date:
ORNL is developing intensified CO2 capture devices, which can combine multiple
07.01.2017
thermodynamic operations into one unit. Improvements in solvent-based CO2
capture devices are targeted through analysis of monoethanolamine (MEA) percent complete:
absorption and desorption of CO2. The multi-functionality of these intensified
100%
devices is envisioned to be achieved through graded packing structures with built-
in heat exchanging channels made by additive manufacturing technologies,
namely 3D printing.
Conventional carbon capture systems are configured with multiple unit operations
that use sequentially coupled stages for mass and heat transfer. Since solvent- and
sorbent-based capture intrinsically couples mass and heat transfer at the
fundamental length scales, multiple stages of single-purpose unit operations
would result in larger equipment size, higher equipment costs, and potentially less
than optimal operating conditional for the equipment. This project aims to use
additive manufacturing technologies to develop a graded packing structure to
allow for the integration of heat exchange, reaction, and potentially mass
exchange in one multi-functional structure, and then to optimize the geometry to
maximize the capture performance. By combining these operations in the single
unit, this device would lead to intensification of the capture process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
386 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
To execute this project, ONRL applied capabilities in CFD, additive manufacturing, and absorber-scale
demonstration/validation experiments. The team utilized a Carbon Capture Simulation for Industry Impact (CCSI2)-
developed CFD model to enable optimization of an additive-manufactured intensified carbon capture device. This
computational tool was used for design realization and for a parametric study on key design and operational parameters.
The target structured packing control was the commercial Mellapak 250 (shown in Figure 1). ORNL fabricated 3D-printed
devices with different cell densities (Figure 2). The test packing was 8 inches in diameter and 5.57 inches tall. Cell sizes of
25.4 millimeter (mm), 12.7 mm, and 6.3 mm were printed.
Figure 1: Mellapak (commercial) structured packing.
Figure 2: Packing with different cell densities, 3D-printed at ORNL.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
387
Post-Combustion Novel Concepts
ORNL fabricated a second-generation intensified device (Figure 3) for use in heat and mass transfer studies. The solvent-
based reactive test system, shown in Figure 4, included the 3D-printed intensified device within a column containing
commercial packing elements.
Figure 3: Second-generation intensified device.
Figure 4: Reactive system test facility.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
388 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
technology advantages
• Improvement of CO2 capture efficiency by simultaneously increasing reactive surface area and enhancing heat
exchange efficiency in order to maintain the forward absorption reaction in the absorber column.
R&D challenges
• Fabrication of a benchmark geometry for a conventional packing structure, interpreting the computationally derived
intensified device requirements, and demonstrating the manufacturability of the intensified device design additive
manufacturing techniques.
status
ORNL has successfully designed, printed, characterized, and tested a 3D-printed intensified packing device. The intensified
device had hydrodynamic behavior that was not much different than that of the commercial-structured packing elements.
The intensified device was capable of substantially reducing the amine solvent temperature in situ. Experiments showed
enhanced CO2 capture rates using the intensified device.
available reports/technical papers/presentations
Sun, X., et al. “Additively Manufactured Intensified Device for Enhanced Carbon Capture,” Presented at Final Project
Review Meeting, Pittsburgh, PA, November 2019. https://www.netl.doe.gov/projects/files/ORNL%20FWP-
FEAA130%20final%20project%20review_110819.pdf.
Bolton, S., Kasturi, A., Palko, S., Lai, C., Love, L., Parks, J., Sun, X., and Tsouris, C., “3D Printed Structures for Optimized
Carbon Capture Technology in Packed Bed Columns,” Separation Science and Technology, 54, 2047-2058 (2019).
Sun, X., et al. “Additively Manufactured Intensified Device for Enhanced Carbon Capture,” Presented at the 2019 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/X-Sun-
ORNL-Additively-Manufactured-Device.pdf.
Sun, X., et al. “Additively Manufactured Intensified Device for Enhanced Carbon Capture,” Presented at the 2018 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, August 2018. https://netl.doe.gov/sites/default/files/netl-file/X-Sun-
ORNL-Additive-Manufacturing-Utilization.pdf.
Sun, X., et al. “Additively Manufactured Intensified Device for Enhanced Carbon Capture,” Presented at Project Kickoff
Meeting, Pittsburgh, PA, October 2017. https://www.netl.doe.gov/projects/files/FWP-FEAA130-Kickoff-101917.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
389
Post-Combustion Novel Concepts
High-Efficiency, Integrated technology maturity
Bench-Scale, Simulated Flue
Reactors for Sorbents, Solvents, Gas
and Membranes Using project focus:
Additive Manufacturing
Additively Manufactured
High-Efficiency Reactors for
Sorbents, Solvents, and
Membranes
primary project goals
participant:
Lawrence Livermore National Laboratory (LLNL), as part of the Discovery of Carbon Lawrence Livermore
Capture Substances and Systems (DOCCSS) initiative, is designing and fabricating National Laboratory
high-efficiency reactors supporting advanced sorbents, solvents, or membranes
for transformational carbon capture. An integrated design process coupling project number:
computational design optimization with additive manufacturing (AM) is creating FwP-FEw0225
novel reactor geometries customized for new carbon dioxide (CO2) capture
materials. predecessor projects:
N/A
technical goals NETL project manager:
Andy Aurelio
• Assess new reactor geometries and identify design principles. [email protected]
• Assess AM for each reactor type.
• Identify the most promising reactor class (sorbent, solvent, or membrane) for principal investigator:
the next phase of development. joshuah Stolaroff
LLNL
• Design and test the first-generation bench-scale reactor. [email protected]
• Evaluate a small-scale integrated prototype of the first-generation reactor
design with simulated flue gas. partners:
• Design and test a second-generation bench-scale reactor. N/A
• Design an integrated prototype of the second-generation reactor concept.
start date:
08.01.2017
technical content
percent complete:
LLNL is designing high-efficiency reactors to support advanced sorbents, solvents, 60%
or membranes for CO2 capture. An integrated design process utilizing
computational design optimization combined with AM is utilized to create new
reactor geometries designed for advanced carbon capture materials resulting in
efficient, low-cost carbon capture. The reactors can offer a range of improvements
for CO2 capture, including absorbers and fixed beds with integrated heat
exchange, enabled by the unique structure of the triply periodic minimal surfaces
(TPMS). They can also enable membrane-based separators with minimal pressure
drop and strippers capable of extreme high pressure. The bases of these novel
reactors are hierarchical networks and TPMS, shown in Figure 1. These new
geometries will be fabricated using AM techniques at LLNL. An example of a TPMS
structure fabricated using AM at LLNL is shown in Figure 2. The TPMS geometries
can be made into packing for columns. These printed plastic packings allow TPMS
geometries with integrated heat exchange. LLNL has demonstrated printed
packing in multiple different plastics, including acrylonitrile butadiene styrene
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
390 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
(ABS), high-density polyethylene, and polycarbonate. The ABS-based packing with TPMS showing the same geometry as
conventional stainless-steel packing is shown in Figure 3.
LLNL will evaluate novel geometries and identify the design principles for these new reactor types. AM techniques will be
assessed. The most promising reactor class, either sorbent, solvent, or membrane, will be identified to move forward with
in the development process. A first-generation reactor will be designed, fabricated with the AM techniques, and tested
on simulated flue gas at the bench-scale. Based on the test results, the team will design a more advanced second-
generation reactor. Integrated prototype testing for both will include adsorption and desorption with continuous
operation.
Figure 1: Design features focused on at LLNL: triply periodic minimal surface (l), hierarchical flow channels (r).
Figure 2: TPMS structure printed using AM at LLNL.
Figure 3: Conventional stainless-steel packing (l) and ABS-printed packing (r).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
391
Post-Combustion Novel Concepts
technology advantages
• Novel reactor geometries enable absorbers and fixed beds with integrated heat exchange, membrane separators with
minimal pressure drop, and extremely high-pressure-capable strippers.
• TPMS geometries enhance fluid mixing.
• Lower cost of plastic printed packings compared to stainless steel.
R&D challenges
• Optimizing geometry of TPMS for best performance.
• Identifying new material or fabrication strategy for TPMS membrane reactors.
• Part-scale fabrication using AM.
status
LLNL has concluded that for single-phase flow, smaller feature sizes are better, to the limits of fabrication. Printed plastic
packings using multiple materials were demonstrated. Hydrophobic surfaces in the stripper are promising for polarity-
swing solvents.
available reports/technical papers/presentations
Stolaroff, J., “High-Efficiency, Integrated Reactors for Sorbents, Solvents, and Membranes Using Additive
Manufacturing,” Presented at 2019 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/J-Stolaroff-LLNL-Additive-Manufacturing.pdf.
Stolaroff, J., “High-Efficiency, Integrated Reactors for Sorbents, Solvents, and Membranes Using Additive
Manufacturing,” Presented at 2018 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2018.
https://netl.doe.gov/sites/default/files/netl-file/J-Stolaroff-LLNL-Reactor-Additive-Manufacturing.pdf.
Stolaroff, J., “High-Efficiency, Integrated Reactors for Sorbents, Solvents, and Membranes Using Additive
Manufacturing,” Presented at 2017 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2017.
https://netl.doe.gov/sites/default/files/event-proceedings/2017/co2%20capture/4-Thursday/1J-Stolaroff1-LLNL-High-
Efficiency--Integrated-Reactors.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
392 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Rapid Design and Testing of technology maturity:
Laboratory-Scale, Simulated
Novel Gas-Liquid Contacting Flue Gas
Devices for Post-Combustion project focus:
CO2 Capture via 3D Printing:
Gas-Liquid Contacting
Devices for Post-Combustion
Modular Adaptive Packing
CO2 Capture
participant:
ION Clean Energy, Inc.
primary project goals
project number:
ION Clean Energy, Inc. (ION) is developing advanced gas-liquid contacting
devices that enable more efficient capture of carbon dioxide (CO2) with reduced FE0031530
process footprints. The Modular Adaptive Packing (MAP) design incorporates a
mathematically driven model for creating a contacting device built for integrated predecessor project:
mass transfer and heat transfer based on computational fluid dynamics (CFD). SC0012056
The overall objective of this project is to design, fabricate, and evaluate packing
internals in a packing characterization rig. NETL project manager:
Katharina Daniels
[email protected]
technical goals
principal investigator:
• Design MAP modules for testing at ION’s pilot facility.
Erik Meuleman
• Use 3D-printing techniques to fabricate MAP modules in plastic for design ION Clean Energy, Inc.
verification, including but not limited to fit, performance, and stress testing. [email protected]
• Use 3D-printing techniques to fabricate metal MAP module prototypes for
packing characterization. partners:
• Modify ION’s capture rig to a packing characterization rig for suitable evaluation 3D Systems, ANSYS,
of packings regarding pressure drop, active surface area, and liquid hold-up Optimized Gas Treating, Inc.,
measurements. Sulzer Chemtech USA
• Perform baseline testing in the modified rig using a commercially available
start date:
packing.
01.19.2018
• Install the 3D-printed metal MAP modules into the packing characterization rig
and perform systematic testing to verify packing design performance.
percent complete:
• Incorporate experimental test results into process models and perform
85%
simulations on new structured packings.
• Implement simplified packing models that are descriptive of the MAP with
monoethanolamine (MEA) in the acid-gas software modeler, ProTreat®, for
further data analysis and concept evaluation.
technical content
Standard CO2 absorption technologies create heat (i.e., exothermic) upon reacting
CO2 with a liquid absorbent. When optimizing for process efficiency, the greatest
amount of heat released occurs towards the top of the absorber in close proximity
to the clean flue gas exit and as such carries the risk of solvent loss through
evaporation at an elevated temperature. Therefore, the program described herein
addresses the challenges of internal gas-liquid contactors and novel methods for
controlling evaporative solvent loss risks.
The internals of process columns (e.g., distributors, packing, and collectors), heat
exchangers, and emissions control measures are among the highest capital costs
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
393
Post-Combustion Novel Concepts
in CO2 capture plants. ION’s MAP technology provides a way to lower the cost of column internals in CO2 capture
systems, while simultaneously reducing degradation rates and emissions of typical amine-based capture solvents,
thereby allowing for more economically sustainable capture plant operations. The use of 3D printing to fabricate packing
internals reduces the costs, which allows for the total freedom of design of the gas-liquid interaction area and the complete
integration of intra-column cooling. 3D printing is an “additive” fabrication technique that offers unprecedented advantages
in accelerating the design cycles of gas-liquid contacting devices, minimizing manufacturing costs, and expediting the
deployment timeline for CO2 capture commercially.
Through the use of 3D printing, ION can maximize the surface area to void volume of the contactor surface through
complete geometric freedom. The flow domain consists of a cylindrical tube that encapsulates a hollow structure. The
hollow structure forms a network of channels filled with cooling water, where CO2-containing air and liquid absorbent can
chemically react in the space outside the cooling water channels for heat transfer. The design essentially combines the
absorber gas-liquid contactor with an in-situ heat exchanger.
This project is a continuation of a previous U.S. Department of Energy (DOE)-funded Small Business Innovation
Research (SBIR) project, DE-SC0012056. Phase I results of the SBIR project showed that the mass transfer increases
with increasing surface area to volume ratios in the packing. In Phase II, ION developed a dual-function mass and heat
transfer packing medium to incorporate heat transfer into the design. The design team first 3D-printed plastic prototypes
to test for overall fit, check for design flaws, and evaluate the potential for commercialization. ION engineers landed with
a final design using metal and then tested in ION’s 0.001-megawatt-electric (MWe) lab pilot (Figure 1) CO2 capture unit
using a common benchmark solvent of 30 wt% MEA and synthetic flue gas. The results were compared to commercially
available and optimized structure packing (Sulzer Mellapak 350X) tested in the same unit under the same process
conditions. The results of the testing showed more than a 10°C reduction in absorber maximum temperature compared
to baseline structured packing, which leads to significantly reduced emissions. Additionally, the mass transfer was
comparable and within 5% of the benchmark results. As expected, the MAP was shown to have inferior pressure drop
properties, mainly due to the addition of cooling channels. Other contributing factors to the increased pressure drop were
the internal support structures within the additive packing, which were necessitated by the metal printing process and
had to be added to the design prior to printing. However, when cooling was implemented, the pressure drop was lower
(~15%) compared to the uncooled version. At a larger scale, important for commercial viability, the pressure drop will
decrease since a much lower volume fraction will be occupied by the cooling channel and its wall thicknesses. During
Phase II, ION also designed a CFD model to simulate the CO2 capture process. The model predicted the flow and energy
dynamics of coolant water, the gas flow, and the distribution of liquid solvent in the domain, as well as the CO2 absorption
for a various geometries and operating conditions. CFD lends itself to parameterization—wherein geometry, flow rates,
and other tunable variables, such as the reaction mechanism and rate, can be changed to understand the entire design
space available and optimize the model before the fabrication of prototypes. Figure 2 shows a computer model and the
resulting plastic and metal printed prototypes. Overall, the SBIR project successfully demonstrated the commercial
viability of customizable and modular packing devices that incorporate both heat and mass transfer for CO2 capture and
other applications where exothermic reactions are involved.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
394 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Figure 1: ION’s lab-pilot (0.001 MWe) CO2 capture test unit.
Figure 2: Design model, metal prototype, and plastic prototypes from SC0012056.
This Phase III project consists of advanced manufacturing efforts that will result in a 3D-printed commercial prototype of
a gas-liquid contacting device that is modular and adaptable to both small- and large-scale applications. Further
enhancements are being made to the heat exchange, which will allow for further improved mass transfer and a significant
decrease in pressure drop. ION is utilizing the design work from the previous SBIR project and incorporating expertise
from commercial experts such as ANSYS and 3D Systems to produce an optimized MAP prototype design. Parameters
that are being evaluated include the shape of inner walls and structures to promote primary and secondary mixing, liquid-
gas mass transfer contact area, liquid-liquid heat exchange area, wall thickness and integrity, material choice, and the
ratio of area for gas and liquid flow versus coolant flow. These design parameters are being evaluated across a range of
process parameters, such as pressure drop, mass and heat transfer between gas and liquid phases, heat transfer
between cooling or heating medium and liquid-gas channel, heat transport within a module and within a range of modules,
connectivity, safeguards in event of leakage, wall-effects, entrainment, and flooding.
Prototypes were printed in plastic using a stereolithographic apparatus for design and structural verification and metal
prototypes were printed based on the final design. Successfully printed metal MAP modules are being tested at ION’s
packing characterization rig that has been modified to accommodate the MAP modules, as well as a standard column
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
395
Post-Combustion Novel Concepts
that incorporates a commercial structure packing. The characterization aims to empirically determine packing
characteristics, including pressure drop over the height of the packing as a function of gas- and liquid-load and viscosity;
packed-bed liquid hold-up over a broad range of column gas and liquid loads; and effective surface area of the packings
as a function of gas and liquid load. Development strategies focus on optimal designs for the MAP from three angles by
computational analyses:
• Optimized heat transfer by liquid flow design (using CFD), inlet and outlet positioning, material choice, and vanes.
• Optimized specific area by vanes and printing surface roughness.
• Optimized pressure drop on the gas side.
o Incorporate aerodynamic principles and circumvent channeling.
o Incorporate considerations on gas volumetric flow changes throughout packing (temperature, CO2 removal).
Figure 3: 3D-printed columns in plastic and metal.
TABLE 1: SOLVENT PROCESS PARAMETERS
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr > 600
CO2 Recovery, Purity, and Pressure % / % / bar 95% 99% 1.0
Absorber Pressure Drop bar < 0.020
Estimated Absorber/Stripper Cost of __$__
TBD
Manufacturing and Installation kg/hr
Definitions:
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
396 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
technology advantages
• Lower cost of column internals, including distributors, packing, and collectors.
• Reduces degradation rates and emissions of typical amine-based capture solvents.
• Modular and scalable, which allows for customization of temperature profiles, mass transfer, and pressure drop.
• The use of 3D printing allows for the use of lower-cost materials and minimizes manufacturing costs.
• It allows for control of absorber profile temperatures, which leads to reduced emissions-related issues and lower
energy consumption. This allows for significant capital savings in the water wash by reducing packing height
requirements and results in lower operating expenses due to reduced solvent makeup.
• The rapid and flexible feedback loop between design, fabrication, and testing provided through 3D printing advances
the performance and lowers the costs of gas-liquid contacting devices for CO2 capture.
R&D challenges
• Module leakage.
• Blockage of the intercooling tubes.
• Structural integrity of 3D-printed modules.
status
CFD modeling efforts have resulted in an advanced 3D design model incorporating mass transfer, reaction, heat transfer,
and pressure drop calculations for CO2 capture. ION has completed a redesign of the module internals to reduce the
calculated printing time from 100 days to the design limit of the machine, which is under 10 days. Full-size 3D prototypes
have been printed in plastic by 3D Systems for design and structural verification. After the final design was selected, two
modules were printed in metal for quality assurance testing and then were put together for fitting and leak testing. The
remaining metal modules have been printed by 3D Systems and shipped to the ION facility for testing. ION has
coordinated with a third-party fabrication shop to assemble the in-house packing characterization rig.
available reports/technical papers/presentations
Meuleman, E., Panaccione, C., et al., “Rapid Design and Testing of Novel Gas-Liquid Contacting Devices for Post-
Combustion CO2 Capture via 3D Printing: Modular Adaptive Packing (MAP),” presented at the 2019 Carbon Capture,
Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting, Pittsburgh, PA, August 2019.
https://netl.doe.gov/sites/default/files/netl-file/E-Meuleman-ION-Novel-Contacting-Devices.pdf.
Meuleman, E., Atcheson, J., and Panaccione, C., “Rapid Design and Testing of Novel Gas-Liquid Contacting Devices for
Post-Combustion CO2 Capture via 3D Printing: Modular Adaptive Packing (MAP),” presented at the 2018 NETL CO2
Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018. https://netl.doe.gov/sites/default/files/netl-
file/E-Meuleman-ION-Rapid-Design-and-Testing-of-Contacting-Devices.pdf.
Meuleman, E., Atcheson, J., and Panaccione, C., “Rapid Design and Testing of Novel Gas-Liquid Contacting Devices for
Post-Combustion CO2 Capture via 3D Printing: Modular Adaptive Packing (MAP),” Project Kickoff Meeting. July 2018.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
397
Post-Combustion Novel Concepts
A Process with Decoupled technology maturity:
Large Bench-Scale (0.1
Absorber Kinetics and Solvent Mwth), Actual Flue Gas
Regeneration Through project focus:
Membrane Dewatering and
Integrated Advanced
Solvent Process
In-Column Heat Transfer participant:
University of Kentucky
Center for Applied Energy
primary project goals Research (UK CAER)
The University of Kentucky Center for Applied Energy Research (UK CAER) has project number:
teamed with Media and Process Technology Inc. and Lawrence Livermore
National Laboratory (LLNL) through support project FWP-FEW0242 to develop an FE0031604
intensified, innovative carbon dioxide (CO2) capture process. The project goals (support project FwP-
are to increase system efficiency and enable significant reductions in capital and FEw0242)
operating costs of solvent-based post-combustion capture through: (1) the use of
3D-printed, two-channel structured packing material to control absorber predecessor projects:
temperature profile and increase the CO2 absorption rate, thereby allowing N/A
decreases in absorber size; (2) implementation of a zeolite membrane dewatering
unit capable of substantial dewatering of carbon-rich solvent to decouple solvent NETL project manager:
concentrations that are optimum for CO2 absorption and desorption; and (3)
David Lang
utilization of a two-phase flow heat exchanger prior to the stripper, providing a
[email protected]
secondary point of vapor generation for CO2 stripping resulting in significant
energy savings.
principal investigator:
Project scope is to design and fabricate advanced structured packing and a Kunlei Liu
dewatering membrane module, and retrofit and test the intensified process on UK University of Kentucky
CAER’s small and large (0.1-megawatt-thermal [MWth]) bench-scale post- [email protected]
combustion CO2 capture facilities with simulated and coal-derived flue gas.
Results will underpin a process techno-economic analysis (TEA), an partners:
environmental, health, and safety (EH&S) risk assessment, and a technology gap
analysis to advance the technology toward further scale-up and Media and Process
commercialization. Technology Inc., Lawrence
Livermore National
Laboratory (LLNL)
technical goals
start date:
• Enable reduction of absorber size (compared to baseline conventional 05.01.2018
absorber) by up to 50% through application of the in-situ heat removal
structured packing material. percent complete:
• Attain at least 15% dewatering of the carbon-rich solvent in the process loop. 55%
• Attain 30% energy savings in the solvent reboiler-specific energy consumption.
• Demonstrate the process at 0.1 MWth bench-scale on coal-derived flue gas.
• Collect data to perform the detailed TEA of CO2 capture process integration to
a full-scale coal-fired power plant.
• Advance this technology to meet U.S. Department of Energy (DOE) capture
goals of 95% CO2 purity at a cost of approximately $30 per tonne of CO2
captured.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
398 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
technical content
UK CAER’s starting point for development of this technology was consideration of the drivers for capital and operating
costs of aqueous post-combustion capture process systems. While still utilizing the general process arrangement of CO2
absorption-desorption by contacting the flue gas with solvent (which might even be a commonly used aqueous solvent
such as an amine) in the absorber and water vapor stripping the rich solvent in the regenerator, UK CAER has postulated
that significant efficiency and cost savings could be obtained by deploying several design improvements in this process
and innovations in certain units. The basic process arrangement and units involved are depicted in Figure 1.
Figure 1: UK CAER CO2 capture process.
Improvement of Temperature Profile in the Absorber—3D-Printed Packing
The absorber for contacting flue gas with solvent to remove the CO2 from the flue gas is a packed column type containing
either random or structured packing to increase mixing/contacting of the gas and liquid solvent. The diameter of the
absorption column is determined by the flooding point at the liquid/gas (L/G) ratio; the diameter must be large enough to
prevent flooding. The highest flooding potential for a fast-reacting solvent occurs at a characteristic temperature bulge,
which typically occurs in the top packing section, 15 to 30% of packing height from the top. A measured temperature
profile for UK CAER’s 0.7-megawatt-electric (MWe) small pilot-scale absorber is shown in Figure 2 for contacting flue
gas with amine solvent. With L/G ~3.2, a temperature rise of ~50°F is observed ~10 feet below the lean amine feed.
Because the driving force for CO2 absorption is inhibited by high temperature, temperature excursions like this decrease
performance, which means that larger internal column diameter and increased column height (translating directly into
increased column cost) would be necessary to accomplish a given required amount of CO2 capture. However, if internal
temperatures in the column can be aggressively managed, column size can be substantially reduced.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
399
Post-Combustion Novel Concepts
Figure 2: Absorber temperature profile (solid lines indicate model predictions for liquid and gas, experimental data in dots).
The UK CAER team’s approach for temperature management in the absorber is to deploy innovative, 3D-printed
structured packing that incorporates heat transfer channels in the packing. This would provide in-process substantial
cooling at appropriate locations without the need for separate, multiple external inter-stage cooling sections (reducing
column height). Use of 3D printing/additive manufacturing provides the capability to fabricate the packing with the
complex dimensional patterns required at reasonable cost.
Polymeric materials, such as acrylonitrile butadiene styrene (ABS), polystyrene, and high-density polyethylene, were
investigated for use. They are stable in the presence of loaded amine solvent at operating temperature, while they are
readily amenable to 3D printing via methods such as fused deposition modeling and stereolithography. Figure 3 shows
the design (left) and a fabricated unit printed in ABS via stereolithography (middle). Instances of leakage, structural
integrity issues, and fouling have occurred with certain polymeric materials made by certain methods; recently, use of
direct metal laser sintering to fabricate packing from 316 stainless steel (Figure 3, right) has delivered promising results.
Figure 3: 3D-printed packing.
Evaluation of the performance of the packing for improving the temperature profile in the absorber column has been
ongoing using the bench-scale unit at UK CAER. Figure 4 shows results of putting the new packing material into the
column. The solid line is the baseline without the heat transfer packing, and the dotted and dashed lines are with it in
place. Thermocouples are located at regular intervals from position 1 at the top of the column (lean solvent inlet) to
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
400 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
position 7 at the bottom (flue gas inlet). Note that the typical temperature increase at positions 2 and 3 in the baseline
has been greatly improved when the heat transfer packing is deployed.
Figure 4: Heat transfer packing effect on absorber column temperature profile.
Dewatering Rich Solvent—Membrane-Based Dewatering Unit
Another element of this innovative process approach is tackling the conflicting requirements for solvent concentrations
between the absorber and stripper. In terms of transport phenomena, it is well accepted that the stripper is equilibrium-
controlled while the absorber is mass transfer/diffusion-controlled. For the equilibrium-controlled stripper, the carbon
loading via CO2 partial pressure will determine the size of the stripper as well as the energy associated with stripping
gases, which typically accounts for approximately 40% of the overall energy required for solvent regeneration. Higher
solvent concentrations typically produce higher carbon loadings per kilogram solution at a given temperature compared
to a diluted solvent, so more concentrated solvents are preferable for stripper applications. However, higher solvent
concentrations always correspond to higher viscosities. For a diffusion-controlled absorber using any advanced fast
solvent, the mass transfer coefficient is dominated by the resistance from the chemical reaction of CO2 and amine in the
reaction film and diffusion of unreacted amine and carbamate between the reaction interface and bulk solvent.
Unfortunately, the diffusivity between the reaction interface and the bulk solvent is governed by a mildly exponential
relationship in which higher solvent viscosity increases the diffusion resistance, thereby reducing mass transfer.
To better attain desired solvent concentrations between the absorber and stripper, a dewatering unit using zeolite
membranes is being developed and evaluated. The unit receives rich solvent from the absorber and permeates it through
membranes, resulting in concentrated solvent retentate and a permeate stream of mostly water. The target is to
accomplish at least 15% dewatering of the solvent coming from the absorber in this membrane-based dewatering unit.
The permeate water is returned to the absorber, leaving a carbon- and solvent-concentrated solution to enter the stripper
for regeneration. This has the dual desired result of lowering energy consumption in the stripper, while simultaneously
maintaining more dilute solvent in the absorber so as not to negatively impact CO2 absorption rates there. The dewatering
step is indicated in Figure 1 as Zeolite Dewatering; note that the recovered water is mixed with the lean solvent from the
stripper and the combined stream goes to the top of the absorber.
Design and fabrication of the zeolite membrane dewatering modules is an important aspect of technology development.
The membranes themselves consist of a thin zeolite layer on a sublayer of dense alumina, all of which is supported on
tubes of highly porous conventional alumina. The very dense alumina layer is needed to confine the molecular seed
particles to the surface of the alumina, from which the zeolite layer is grown. Figure 5 shows a scanning electron
microscopy (SEM) cross-section of a membrane showing the juxtaposition of these layers, with a fully formed 3.5 µm
layer of zeolite on the outside. The membrane tubes are to be deployed in bundles in modules, per the design depicted
in Figure 6 for the intended bench-scale testing. Membrane packing density can reach ~322 m2/m3 in these modules.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
Figure 5: Dewatering membrane structure.
Figure 6: Dewatering membrane module design.
Advanced Stripping and Secondary Vapor Generation Point
An additional improvement in this process approach targets reduction of steam consumption by considerations of phase
transitions occurring in the stripper and optimization of heat exchange and points of solvent feed to the stripper. In a
conventional stripping process, the stripper reboiler uses extracted steam to evaporate water in the solvent both as a
carrier gas to strip CO2 out of the solvent and as an energy carrier to heat the stripper to a desired temperatures profile
as required by the solvent and stripper operating pressure. During this process, significant exergy is lost. Secondarily,
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
high rich solvent temperature from the rich/lean heat exchanger entering the stripper prevents the gaseous phase from
condensing at the top of the stripper, reducing heat recovery within the system as more water vapor is lost with the
gaseous exhaust. Consequentially, the typical temperature profile (left) and CO2 and water fluxes (right) as a function of
height in the stripper have been observed on UK CAER’s 0.7-MWe post-combustion capture facility and modeled as
plotted in Figure 7. This clearly indicates that most of the CO2 is liberated from the solvent in the bottom 14 feet or so of
the 30-foot-long stripper (corresponding with the nearly flat plateau seen in the right-side panel).
Figure 7: Temperatures and mass fluxes in solvent stripper.
To overcome these inefficiencies characteristic of the conventional stripper regenerator, UK CAER is evaluating a
process design using a secondary entry point for rich solvent feed. The multi-point rich solvent feed is accomplished by
dividing the traditional lean/rich (L/R) heat exchanger into two sections – a low-end L/R exchanger and a high-end L/R
exchanger (which essentially creates a second source for vapor generation). The basic arrangement of these is
diagrammed in Figure 1. The feed to the stripper from the dewatering unit is split into two streams: (1) after the low-end
exchanger, about half of the total rich flow with a temperature (solvent and carbon loading dependent) is fed to the top of
stripper packing as a heat sink to condense water vapor and subsequently reduce the water (H2O)/CO2 ratio; and (2) the
remaining rich flow is heated through the high-end exchanger so that two-phase flow is achieved with 5 to 6% vapor
entering the middle of the stripper packing. This vapor will act as a secondary source of carrier gas for CO2 stripping. UK
CAER modeling indicates the H2O/CO2 ratio in the stripper exhaust will be significantly reduced from 0.8 to 1.0 as
experienced conventionally, to 0.3 to 0.4, allowing an ~26% reduction in steam consumption.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
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403
Post-Combustion Novel Concepts
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 Amine Amine
Normal Boiling Point °C 155-170 155-170
Normal Freezing Point °C -2 -2
Vapor Pressure @ 15°C bar 0.0007 0.0007
Manufacturing Cost for Solvent $/kg 14.74 14.74
Working Solution
Concentration kg/kg 0.35-0.45 0.35-0.45
Specific Gravity (15°C/15°C) - ~1.0 ~1.0
Specific Heat Capacity @ STP kJ/kg-K 2.7-3.3 2.7-3.3
Viscosity @ 15°C cP 5-7 5-7
Absorption
Pressure bar 1.01 1.01
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.5 0.45
Heat of Absorption kJ/mol CO2 ~-65 ~-70
Solution Viscosity cP 3-5 3-5
Desorption
Pressure bar 3-5 3-5
Temperature °C 110-130 110-130
Equilibrium CO2 Loading mol/mol 0.20 0.20
Heat of Desorption kJ/mol CO2 ~85 ~85
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 24
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 ~20
Absorber Pressure Drop bar <20”WC
Estimated Absorber/Stripper Cost of __$__
$36K
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of inorganic salt and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120°C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2%. Therefore, the partial pressure of
CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted otherwise, flue gas pressure, temperature, and composition leaving the flue
gas desulfurization (FGD) unit (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOX NOX
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – The solvent is an aqueous solution of a hindered primary amine. A carbamate
species is formed upon CO2 absorption. In a CO2 capture absorber, the absorption rate, R, as a function of temperature,
T, and carbon loading, C/N, can be expressed as: R(T, C/N) = kG·a·(PCO2 – P*CO2) where kG is mass transfer coefficient,
a is effective wetted surface area, and (PCO2 – P*CO2) is the driving force, the difference in the concentration of CO2 in
liquid from the gas. Significant increase in R, via kG and a, and corresponding reduction of capital cost comes from the
mass transfer enhancement of the proposed aqueous system compared to any second-generation technology because
there is an order of magnitude greater effective wetted surface area n in the top of the absorber.
Solvent Contaminant Resistance – UK CAER analysis show the solvent is more resistant to degradation, 40 to 50%
improvement than 30 wt% MEA. Accumulation of metals within the solvent is expected to be equivalent to that within 30
wt% MEA.
Solvent Foaming Tendency – The experimental data from a packed column (2-inch ID mini-scrubber) and large-bench
(4-inch ID column) indicate the foaming tendency of proposed solvent is very low.
Flue Gas Pretreatment Requirements – The flue gas pretreatment requirement is sulfur dioxide (SO2) removal to less
than 5 parts per million (ppm) to minimize heat stable salt formation. This can be done with a standard counter-current
pretreatment column with a circulating solution of either of soda ash (Na2CO3) or sodium hydroxide (NaOH). The solvent
used is a hindered primary amine and does not form stable nitrosamine species; therefore, no additional nitrogen oxide
(NOX) removal is required. No additional moisture removal is required, as it is for ionic liquids.
Solvent Makeup Requirements – Two factors contributing to solvent makeup rate are degradation and emission. UK
CAER analysis shows the solvent has degradation rates less than 30 wt% MEA, and when the UK CAER developed
solvent recovery technology is applied, the solvent emission will be about 0.5 ppm. The anticipated solvent makeup rate
is less than 0.5 kg/tonne CO2 captured.
Waste Streams Generated – The waste streams of the post-combustion CO2 capture process using the proposed
compact absorber are the same as any other post-combustion CO2 capture process. There will be a blowdown stream
from the SO2 pretreatment column and a reclaimer waste stream from the solvent loop.
Process Design Concept – See Figure 1.
technology advantages
• Reduction in absorber column size, reducing both capital and operating costs.
• Reduction in stripper column size and steam demand for solvent regeneration, reducing both capital and operating
costs.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
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Post-Combustion Novel Concepts
• Applicability to a variety of solvents in absorption-based capture process implementation.
R&D challenges
• Innovative absorber packing fabrication cost, structural/performance integrity, fouling.
• Dewatering membrane unit zeolite membrane fabrication, module integrity.
• Increased controls and control schemes, mainly because of more complicated process flows and heat exchange
around the dewatering unit.
status
Absorber testing with deployment of 3D-printed packing material has resulted in 10°C temperature reductions, proving
the concept for the structured packing enabling column size reductions. The zeolite membrane-based dewatering has
been validated on amine solvent at 10 kg/m2/hr, and modules with required membrane packing density have been
established. Individual components in the UK CAER bench-scale unit have been evaluated, paving the way for the larger-
scale testing in continued work.
available reports/technical papers/presentations
“A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-
Column Heat Transfer,” BP1 project review meeting presentation, October 2, 2019.
“A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-
Column Heat Transfer,” presentation by James Landon, University of Kentucky, 2019 NETL CCUS Integrated Project
Review Meeting, Pittsburgh, PA, August 2019.
“A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-
Column Heat Transfer,” presented by James Landon, University of Kentucky, 2018 NETL CO2 Capture Technology
Project Review Meeting, Pittsburgh, PA.
“A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-
Column Heat Transfer,” Project kickoff meeting presentation, May 18, 2018.
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406 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Novel Concepts
Flue Gas Aerosol Pretreatment technology maturity:
Pilot-Scale, Actual Flue Gas
Technologies to Minimize PCC project focus:
Solvent Losses Flue Gas Aerosol
Pretreatment
primary project goals participant:
Linde Gas North America,
Linde Gas North America, LLC and their project partners will evaluate three flue LLC
gas aerosol pretreatment technologies that have the potential to significantly
reduce high flue gas aerosol concentrations, which have been shown to contribute
project number:
to amine losses in solvent based post-combustion carbon dioxide (CO2) capture
(PCC) processes. The options that will be evaluated are: (1) a novel high-velocity FE0031592
water spray concept previously tested at a Rheinisch-Westfälische
Elektrizitätswerk (RWE) power plant in Niederaussem, Germany; (2) an innovative predecessor projects:
electrostatic precipitator (ESP) with optimized operating conditions; and (3) a non- N/A
regenerative sorbent-based sulfur oxide (SOX) and nitrogen oxide (NOX) removal
technology with potential for aerosol particle reduction. The objectives of this NETL project manager:
project are to design, build, and independently test these technologies at a coal-
fired power plant host site using a slipstream of flue gas containing high Isaac Aurelio
[email protected]
concentrations of aerosol particles (greater than 107 particles/cm3). The results will
be used to benchmark the performance and cost of these technologies against
existing options for pretreatment of coal-based flue gas for aerosol mitigation. The principal investigator:
impact of this reduction in aerosol concentrations could be leveraged across a Devin Bostick
variety of solvent-based PCC systems to minimize solvent losses. Linde Gas North America,
LLC
[email protected]
technical goals
partners:
• Perform a literature study to identify mechanisms that contribute to aerosol University of Illinois at
particle nucleation and growth in flue gas streams.
Urbana-Champaign,
• Develop a model to simulate the mechanisms and assess the impact of washington University in St.
aerosols on amine losses based on particle size distribution and particle Louis, InnoSepra LLC,
number concentration. Affiliated Construction
• Complete basic engineering and design and provide cost estimates for the Services
three aerosol pretreatment technologies selected for testing at the Abbott
Power Plant. start date:
• Fabricate, install, and commission the high-velocity water spray-based system, 06.01.2018
ESP system, and sorbent technology system at the host site.
• Perform independent parametric testing of each aerosol pretreatment percent complete:
technology, evaluate test results, and identify the optimum operating and 70%
design conditions for maximum performance of each technology.
• Compare test results against predefined targets and standard capabilities of
conventional aerosol treatment methods described in literature and complete a
techno-economic evaluation for each system to compare system costs at scale.
• Dismantle and remove pilot equipment from the host site.
technical content
Aerosol mitigation methods to reduce aerosol-driven amine losses include: (1)
baghouse installation in the flue gas upstream of the PCC plant; (2) amine wash
sections and wash section operating conditions for the PCC plant absorber; (3)
specific absorber operating temperature and pressure conditions that can also
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
negatively impact specific regeneration energy; and (4) flue gas aerosol pretreatment, which is the focus of the proposed
technologies and testing.
Figure 1 shows the range of upstream flue gas aerosol particle number concentrations able to be managed by current
methods used today to achieve less than 0.3 kg amine emitted per tonne of CO2 captured for solvent-based PCC processes.
For power plants without baghouses producing flue gas containing particle concentrations greater than 107 particles/cm3,
the only realistic option available to mitigate aerosol-driven amine losses from PCC plants is flue gas aerosol pretreatment.
Flue gas aerosol pretreatment has traditionally been performed using simple ESPs and Brownian filters, but no systematic
study has been performed yet to evaluate the performance of these systems over the complete range of possible operating
conditions, aerosol particle number concentrations, and aerosol particle sizes. It is important to note that even with lower
flue gas aerosol number concentrations (fewer than 107 particles/cm3), there is still a sizeable benefit to using pretreatment
systems to minimize amine losses for the entire range of solvent-based PCC operating conditions. Hence, this project
focuses on evaluation of flue gas aerosol pretreatment solutions to determine an optimum technology that can minimize
aerosol-driven amine losses for any power plant, including plants producing flue gas with the highest range of possible flue
gas aerosol concentrations and size distributions. Based on previous 1.5-megawatt-electric (MWe) pilot-scale tests of the
Linde-BASF PCC technology at the National Carbon Capture Center (NCCC) in Wilsonville, Alabama, from 2015 to 2016,
high aerosol concentrations in the size range of 70 to 200 nm contribute most significantly to amine losses. Hence, this
technology development project targets high removal efficiency for particles in and around this size range. Additionally,
previous aerosol number concentration measurements performed at the Abbott Power Plant host site, a power generating
unit without a baghouse, show the presence of very high aerosol concentrations (greater than 107 particles/cm3). The ability
to apply pretreatment technologies on the wide range of aerosol concentrations measured at Abbott will enable
demonstration of the performance of each technology as applied at most coal-fired power plants in the world based on
aerosol measurement data collated from scientific literature.
1.E+10 Technology Flue gas
developed in
(# of particles/cm3) for which technology can adequately
pretreatment
1.E+09 this project
Baghouse in
Inlet flue gas aerosol particle concentration
power plant Absorber operating
1.E+08 upstream of PCC conditions
plant Dry bed (no baghouse)
1.E+07
operation
(no baghouse)
remove particles
1.E+06
1.E+05
1.E+04
1.E+03
1.E+02
1.E+01
1.E+00
0.009 <0.3 <0.3 <0.3
Amine Losses (kg amine/tonne CO2)
Figure 1: Flue gas aerosol particle number concentration ranges for which aerosol mitigation technologies are applicable and sufficient.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
408 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Post-Combustion Novel Concepts
The first aerosol pretreatment technology tested in this work is a novel high-velocity water spray-based system originally
developed by RWE and previously tested by RWE in Niederaussem, Germany. A process flow diagram of this system is
shown in Figure 2. The high-velocity water spray provided by the specialized nozzle distributor design enables rapid growth
and collection of aerosol particles in the liquid phase through water condensation before further removal by the demister at
the top of the spray column. In addition, the perforated tray at the midsection of the column optimizes vapor-liquid distribution
to enhance aerosol removal. Aerosol particles collected in the liquid-phase are discharged in the process condensate
removed from the column, effectively removing the aerosols from the treated flue gas exiting the top of the vessel. The
project team has designed, constructed, and tested the water spray-based system on up to 1,000 standard cubic feet per
minute (scfm) of actual flue gas emitted from two coal-fired boilers at the Abbott Power Plant host site. Parametric tests
have been performed to evaluate the impact of specific spray nozzle and perforated tray designs and operating conditions
to determine the optimal system configuration and design conditions maximizing aerosol particle removal efficiency for very
high flue gas particle concentrations (up to and greater than 107 particles/cm3) for aerosol particles in the 70 to 200 nm
diameter size range.
Flue Gas Outlet
Flue Gas
Downstream
Blower
Aerosol
Measurement
Equipment
Demister
Spray
Makeup water
Nozzle
Cooling
water
Perforated
tray
Flue Gas Inlet Cooling
water
Recirculating
water
flow
Upstream Process
Aerosol Condensate
Measurement High-velocity water
Equipment circulation pump
Figure 2: Process flow diagram of high-velocity water spray-based aerosol pretreatment system.
The second aerosol pretreatment technology tested in this project is an advanced ESP system developed by Washington
University in St. Louis (WUSTL) that incorporates a patented photo-ionizer technology to enhance aerosol removal
efficiency. The ESP functions by applying a high voltage between a plate and a wire. This voltage ionizes aerosol particles
in the entering flue gas. Due to electrostatic force, ionized particles are diverted from the gas towards collecting plates,
removing them from the gas. The specific collection area (SCA) of an ESP is the most important design parameter in terms
of achieving required aerosol removal efficiency. A typical SCA for an ESP capable of obtaining 98 to 99% removal efficiency
for 1,000 scfm gas flow is ~95 m2/(m3/s); the area can be increased further to remove particles in the range of 10 to 500 nm
at very high efficiencies. The pilot-scale ESP system will be tested to remove aerosol particles from flue gas at a capacity
of 500 scfm. The photo-ionizer device is expected to greatly enhance the capture efficiency of nano-sized particles. In full-
scale applications, the photo-ionizer developed by WUSTL can be retrofitted to existing ESPs at commercial power plants,
reducing the capital costs of implementation.
A process flow diagram of the WUSTL ESP is shown in Figure 3. Specific ESP voltages may increase particle concentrations
for certain particle sizes due to secondary aerosol generation inside the ESP from nucleation of water-sulfuric acid (H2O-
H2SO4) aerosols when sulfur dioxide (SO2) present in the flue gas is oxidized. Hence, the ESP voltage needs to be carefully
optimized during pilot tests. This project will determine the optimum design and operating conditions for the ESP system to
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
treat flue gas with high aerosol concentrations. Through parametric testing, the performance of the advanced ESP will be
compared against predefined aerosol removal efficiency targets. In addition, the costs to incorporate the ESP technology
upstream of a PCC plant will be assessed.
Figure 3: Conceptual flow diagram of the advanced ESP system developed by WUSTL.
The third technology tested in this project is a non-regenerative sorbent filter system developed by InnoSepra LLC. It has
been proven to remove residual sulfur trioxide (SO3), SO2, nitrogen dioxide (NO2), hydrogen chloride (HCl), and hydrogen
fluoride (HF) from flue gas after the power plant flue gas desulfurization (FGD) unit to limit the detrimental impact of PCC
solvent components reacting with flue gas contaminants. In addition to contaminant removal, the aerosol removal efficiency
of the InnoSepra sorbent filter technology will be evaluated as a potential means to limit aerosol-driven amine losses as
well. A process flow diagram of the InnoSepra sorbent-based filter technology is depicted in Figure 4.
Outlet
Sample
Flue Gas
Outlet
Inlet Sample
Flue Gas
Inlet
Sorbent
Vessel
Figure 4: Process flow diagram of the InnoSepra sorbent-based filter technology.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
The host site chosen for the testing is the University of Illinois’ Abbott Power Plant located in Champaign, Illinois. As shown
in Figure 5, Abbott’s own ESPs and a wet jet bubbling FGD scrubber are used to remove some SO2 and large particulate
matter from the flue gas. The pilot testing will withdraw the flue gas from the outlet of the reheat burner at the flue gas stack
and return downstream, as Figure 5 depicts. Abbott flue gas composition, temperature, and pressure at the inlet to the
aerosol pretreatment units are listed in Table 1 (based on data collected when two out of three boilers are in operation).
Each technology will be built in modules and installed at the Abbott site connected to common flue gas inlet and outlet
piping.
ID Fans
Boiler #5 ESP
Reheat
Booster Burner
Fan
Jet
Boiler #6 ESP Bubbling
FGD
Flue gas
stack
Flue gas
Boiler #7 ESP aerosol
pretreatment
test skid
Figure 5: Abbott Power Plant layout and connection to flue gas aerosol pretreatment test skid.
TABLE 1: ABBOTT FLUE GAS PROPERTIES
Valu
Parameter Unit
e
Temperatu
°F 200
re
Pressure psig 0.75
Gas composition
H2O vol% 19.2
CO2 vol %, dry 9.2
O2 vol%, dry 7.35
SO2 ppmv, wet 177
NOX ppmv, wet 211
Preliminary performance targets for the three flue gas aerosol pretreatment systems are listed in Table 2. Cost
competitiveness and environmental sustainability targets will be based on scaled-up commercial versions of each
technology for performance comparison with the U.S. Department of Energy’s (DOE) National Energy Technology (NETL)
Case B12B reference excluding baghouse capital and operating costs. From an allotted test period of eight weeks, four
consecutive weeks of parametric testing are planned for the water spray-based system, two consecutive weeks of testing
are planned for the ESP system, and one to two weeks of testing are planned for the InnoSepra sorbent filter system.
Each technology will undergo parametric testing to examine their impact on particle removal efficiency, overall capital
and operating costs, and environmental sustainability performance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
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Post-Combustion Novel Concepts
TABLE 2: PRELIMINARY PERFORMANCE TARGETS FOR AEROSOL PRETREATMENT TECHNOLOGIES
TESTED AT ABBOTT
Target for High-
Target for InnoSepra
Velocity Water Target for ESP-Based
Filter Aerosol
Performance Parameter Spray Aerosol Aerosol Pretreatment
Pretreatment
Pretreatment Technology
Technology
Technology
Particle removal efficiency (%) for 500
to 1,000 scfm flue gas slipstream.
(# of particles/cm3 before aerosol >98% for aerosol particles 70-200 nm in diameter
treatment - # of particles/cm3 after
aerosol treatment) / (# of particles/cm3
before aerosol treatment)
Cost competitiveness when integrated
with PCC technology for 550-MWe
COE < $133.20/MWh and cost of CO2 captured < $58/tonne CO2 when compared to
pulverized coal supercritical power
DOE-NETL Case B12B without a baghouse
plants without a baghouse (COE = cost
of electricity).
Environmental sustainability when Energy consumption
integrated with PCC technology for 550- < 14 MWe; process Energy consumption < 14 Energy consumption < 14
MWe pulverized coal supercritical power condensate MWe; ESP solids MWe; sorbent material
plants without a baghouse. adequately removed adequately removed inventory safely managed
and treated
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD unit (wet
basis) should be assumed as:
Composition
Pressure Temperature vol%, wet ppmv, wet
psia °F CO2 H2O N2 O2 Ar SOX NOX
15.45 200 7.4 19.2 66.6 5.9 0.80 200 211
Other Parameter Descriptions:
Flue Gas Pretreatment Requirements – The proposed work will provide as a test option effective flue gas SOX and
NOX removal achieved using the already pilot-validated, low-cost, high-capacity, non-regenerative InnoSepra sorbent
material installed in a packed bed upstream of the test skid. In addition to the physical effects of the sorbent bed on
aerosol removal, the InnoSepra sorbent can improve aerosol reduction performance by reducing nucleation of H2SO4
aerosols in the flue gas by minimizing its SOX content.
Waste Streams Generated – Acidic process condensate is generated by the high-velocity water spray-based system in
a similar manner to how a direct contact cooler operates upstream of a solvent-based PCC plant. This condensate
contains nitric acid (HNO3) and H2SO4 from reaction of NOX and SOX in the flue gas with the circulating process water
used in the spray column. This water is sent to Abbott’s onsite water pretreatment facility where it is neutralized. The ESP
plates collect a very small mass of solid particles during operation on coal-fired flue gas. The solids collected include
metal oxides, dust, and other contaminants. These can be easily removed from the plates and discarded in the power
plant’s gypsum pile. The InnoSepra sorbent material must be removed after use and sent to the vendor’s processing
facility to either be specially processed for reuse or discarded in an approved manner compliant with all waste
management regulations.
Process Design Concept – See above.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
412 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
technology advantages
• Mitigates a wide range of flue gas aerosol concentrations and size distributions, including very high concentrations (up
to and above 107 particles/cm3) in the 70 to 200 nm particle size range.
• Reduced solvent makeup requirements lower operating expenditures for solvent-based PCC processes, enhance
PCC performance in terms of energy consumption, reduce the need for solvent reclamation units, and improve solvent
inventory logistics for full-scale operations.
• Reduced solvent emissions to the environment and aerosol contaminant exposure to personnel and environment.
• Smaller process footprint, more cost-effective, flexible operation, and higher aerosol removal efficiency compared to
installing a baghouse at a coal-fired power plant.
R&D challenges
• Waste management.
• Effects of variability in flue gas composition, temperature, and pressure, as well as power plant load changes on
aerosol measurements.
• Material compatibility with corrosive flue gas contaminants.
status
A comprehensive summary of the results from the aerosol-driven amine loss mechanisms study and modeling effort, as
well as the environmental health and safety (EHS) analysis, have been completed. Basic and detailed engineering for
the Linde spray-based system, ESP-based system, and InnoSepra filter system were completed by Affiliated Construction
Services (ACS), WUSTL, and InnoSepra, respectively. All pilot equipment procurement and fabrication activities have
been completed, and all pilot system components were delivered to the Abbott site and installed on a concrete pad. Pilot
system commissioning and test-readiness checks were completed.
Since mid-January 2020, pilot tests of the spray-based system have been completed and testing of the InnoSepra filter
and ESP systems are currently underway. The full parametric test campaign for all pilot systems is expected to be
completed by late March 2020, followed by data analysis and evaluation of aerosol removal efficiency and cost
performance for each technology
available reports/technical papers/presentations
Bostick, D. “Flue Gas Aerosol Pretreatment Technologies to Minimize Post-Combustion CO2 Capture (PCC) Solvent
Losses,” NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2019.
https://www.netl.doe.gov/projects/files/Flue%20Gas%20Aerosol%20Pretreatment%20Technologies%20to%20Minimize
%20PCC%20Solvent%20Losses%20(FE0031592).pdf.
Bostick, D. “Flue Gas Aerosol Pretreatment Technologies to Minimize Post-Combustion CO2 Capture (PCC) Solvent
Losses,” Budget Period 1 Review Meeting, Pittsburgh, PA, January 2019.
https://www.netl.doe.gov/projects/files/FE0031592%20%e2%80%93%20Flue%20Gas%20Aerosol%20Pretreatment%2
0Technologies%20to%20Minimize%20Post-Combustion%20CO2%20Capture%20(PCC)%20Solvent%20Losses.pdf.
Bostick, D. “Flue Gas Aerosol Pretreatment Technologies to Minimize PCC Solvent Losses,” NETL CO2 Capture
Technology Project Review Meeting, Pittsburgh, PA, August 2018.
https://www.netl.doe.gov/projects/files/Flue%20Gas%20Aerosol%20Pretreatment%20Technologies%20to%20Minimize
%20PCC%20Solvent%20Losses%20Aug%202018.pdf.
Bostick, D. “Flue Gas Aerosol Pretreatment Technologies to Minimize PCC Solvent Losses,” Project Kickoff Meeting,
Pittsburgh, PA, July 2018.
https://www.netl.doe.gov/projects/files/Flue%20Gas%20Aerosol%20Pretreatment%20Technologies%20to%20Minimize
%20PCC%20Solvent%20Losses%20July%202018.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
413
Post-Combustion Novel Concepts
Inexpensive and Sustainable technology maturity:
Up to 100-Gallon
Anti-Corrosion Coating for Electroplating Bath Tank
Sizes
Power Generation project focus:
Applications Corrosion-Resistant Coated
Carbon Steel Components
in CO2 Capture Processes
primary project goals
participant:
LumiShield Technologies is developing and demonstrating durable and LumiShield Technologies Inc.
inexpensive anti-corrosion coatings for application on carbon steel, which is used
extensively in power plant boilers’ and capture systems’ vessels and piping. By project number:
reducing corrosion and allowing substitution of coated mild or carbon steel for FE0031659
expensive stainless steel, capital and maintenance costs of power plant systems
could be significantly reduced, helping to enable cost-effective carbon dioxide predecessor projects:
(CO2) capture for coal- and natural gas-fired power generation. N/A
The multi-layer coating structure consists of a novel mixed metal oxide coat NETL project manager:
covered with an organic anti-corrosion coating. Project objectives are initially
Sai Gollakota
focusing on optimizing the metal oxide base layer for applying the organic [email protected]
coatings and proving the effectiveness of a prototype two-layer coating in
preventing corrosion. Subsequently, the objectives are for optimization through principal investigator:
identification of the organic coatings that give the best performance in john watkins
combination with the optimized metal oxide base layer and showing the economic LumiShield Technologies Inc.
advantage of using the coatings through cost-benefit analysis. [email protected]
partners:
technical goals
AECOM, Southern
Company—NCCC
• Improve the corrosion resistance of organically coated steel (by at least 10% in
terms of higher salt spray hours) by addition of the LumiShield metal oxide base start date:
coat underneath the conventional organic top coat. 10.01.2018
• Perform lab-scale testing of LumiShield-coated carbon steel samples in
simulated amine capture system conditions (CO2 saturated 30% percent complete:
monoethanolamine [MEA] solution at 60°C) and realistic flue gas conditions 75%
(slipstream bench-scale testing at the National Carbon Capture Center [NCCC]).
• Optimize top-coating chemistry to maximize adhesion to LumiShield aluminum
oxide coating under exposure to acids and amines, as evidenced by no change
in appearance or adhesion, including blistering or swelling of organic coatings
under realistic testing/exposure conditions.
• Provide a cost-benefit analysis for completed composites and compare with
existing coatings and materials, making quantified estimates of: (1) how much
stainless steel is replaceable by carbon steel with LumiShield coating in a
baseline system, and (2) savings in capital and operating costs for the baseline
system (with the quantitative target that at least one of the coatings should
result in a decrease in cost per tonne of CO2 by 1% or greater).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
414 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
technical content
In fabrication of piping and vessels in power plants, carbon steel is the preferred material of construction given its
relatively high strength and relatively low cost. However, in applications for corrosive environments (e.g., acid gas-
containing flue gas streams, amine solutions in capture systems, and wet CO2 captured by amine systems), carbon steel
may not provide suitable corrosion resistance. Stainless steel provides high corrosion resistance, but it is expensive.
Conventional organic-coated steel initially confers corrosion resistance but tends to develop defects though which
diffusion of water and gas species can occur, leading to corrosion of the substrate and delamination of the coating (as
illustrated in Figure 1). Therefore, better anti-corrosion coatings are needed in applications such as corrosive solvent-
containing carbon capture systems.
Figure 1: Mechanism for corrosion of coated metallic substrates.
The approach to this problem involves utilization of previously developed LumiShield metal oxide coating technology to
establish a base metal oxide layer on carbon steel, on which organic coatings tailored for resistance to amine solutions
could be applied. The basic geometry of the dual coating concept is depicted in Figure 2. The presence of the LumiShield
coating improves the adhesion of the organic coating, preventing the coating from being undermined and considerably
increasing the overall coating performance. The LumiShield coating was initially developed as a stand-alone anti-
corrosion coating to replace toxic metal coatings like chromium and cadmium. However, realization occurred that the
metal oxide surface would allow excellent adherence of organic coating molecules and that the resulting composite
coating could make use of a thinner organic layer with fewer defects, improving corrosion resistance performance and
reducing cost. The metal oxide layer itself may be applied in a single step using equipment and expertise well-known to
the industry. These characteristics allow competitive or even lower costs than conventional primed steel coatings, which
sometimes require multiple layers at increased cost.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
415
Post-Combustion Novel Concepts
Figure 2: Coating structure.
Metal Oxide Base Layer
The metal oxide layer consists mainly of aluminum oxide applied via electroplating, utilizing water-stable aluminum
complexes (with proprietary additions) in the electroplating bath, which form a coherent and highly adherent aluminum
oxide layer on steel via a proprietary cathodic electroplating process. It has been observed that the aluminum oxide layer
formation allows for some degree of metal-to-metal bonding between aluminum centers and the steel substrate, giving
the coating excellent adhesion. The LumiShield alumina electrodeposition process takes place in an aqueous system,
offering significant cost advantages over non-aqueous methods of alumina deposition that require processes to be free
of atmospheric water and oxygen. The process is analogous to the electroplating of common metals like zinc and can be
applied using standard equipment present in every electroplating facility.
The LumiShield approach makes use of pulse-plating methods (in which electrical field strength is varied to improve
control over electroplating processes). By adopting a pulsed-plating procedure (example illustrated in Figure 3), the
LumiShield coating is further improved in adhesion and density. Also, the nature of the coating process allows a large
degree of control of the morphology of the coating. By adjusting the electroplating conditions of pulse, pH, temperature,
and solution composition and concentrations, it is possible to create morphologies ranging from plate-like growth with
a so-called cracked glass appearance under magnification (Figure 4, left side) to granular growth structures (Figure 4,
right side). The cracked glass morphology is valuable because its high surface area will improve the adhesion of organic
layers deposited on top of it.
Figure 3: Complex electroplating pulse scheme.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
416 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Figure 4: Variation in metal oxide coating morphology.
A major focus at the start of the project was optimization of the LumiShield metal oxide base layer. This was accomplished
by varying process and electroplating solution conditions in forming the metal oxide coatings, which were then
characterized for morphology and adhesion through physical and optical methods. Polarization testing to determine
corrosion rates, electrochemical impedance spectroscopy to determine corrosion mechanisms, and salt spray exposure
testing were conducted. LumiShield has identified plating solution parameters (temperature, pH, concentrations), as well
as electrochemical process variables (pulse scheme, current density, timing), which result in thin, rough, adherent metal
oxide coatings that will promote organic top-layer adhesion.
Organic Top Layer
For the essential organic top layer, LumiShield has surveyed existing/available organic anti-corrosion coating materials
and identified epoxy resins, phenolic resins, and fluoropolymer resins as the three types for consideration for applications
involving amine solutions, flue gas, and wet CO2, given their formulation flexibility, robustness at elevated temperatures
(as high as 180 to 250°C for epoxy coatings and 120 to 200°C for phenolic coatings), chemical resistance, and physical
characteristics. Project work has involved testing of these three types with and without the LumiShield base coat to
establish baselines for each polymer class for corrosion resistance, adhesion and scribe creep, and measure improvement
of corrosion resistance in salt spray tests. Testing has shown significant improvement in corrosion performance with both
epoxy and phenolic coatings, both of which likely have enhanced adhesion on the LumiShield metal oxide base layer that
is improving corrosion protection. Specifically, epoxy coatings appear to be the best candidate for modification and
further work to improve performance as the project progresses. On the other hand, it has been concluded that
fluoropolymer coatings (which show poor adhesion to many materials) will probably not meet performance goals. Figure
5 shows interim results on these evaluations for the more promising epoxy and phenolic coating choices.
Figure 5: Comparisons of performance of epoxy and phenolic top coats with and without LumiShield metal oxide base coat.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
417
Post-Combustion Novel Concepts
To facilitate the attachment of top layer to the aluminum oxide base coating, several organic treatments have been
considered based on silane treatment (silane is an inorganic compound with the chemical formula SiR4). Silanes are used
in a large variety of high-performance coatings as a binding agent between organic resins and inorganic substrates. The
aim is to bind silanes to the pendant hydroxide functionality of the aluminum oxide layer (refer to Figure 2 depicting this
idea) to create a synthetic handle for incorporation of the silane into the polymer top layer. To this end, several silane
candidates will be investigated.
Non-Capture Applications
Although LumiShield’s project focus has been application of the coatings for carbon capture systems, it has two customers
that are interested in piloting LumiShield technology with specific modifications to their specific paints:
• An automotive company interested in high-temperature paint adhesion for heat shields.
• Expansion of an oil and gas program towards other markets and corrosion sites using heavy brine solutions.
There is also interest in corrosion resistance to other corrosive amines to serve the needs of the broader chemical industry.
Cost-Benefit Analysis
The LumiShield team includes AECOM, who have performed a preliminary cost-benefit analysis of LumiShield’s coating
technology. An initial objective was to determine the highest value targets in the carbon capture system for materials
replacement with the developed aluminum oxide coating over incumbent construction methods. Initial analysis has found
that stainless steel currently used for fabrication of both the absorber and stripper could be replaced by LumiShield-
coated mild steel with powder-coating at a capital cost saving of 13% and 17%, respectively. They also note that the
replacement of stainless steel parts with mild steel may have additional nonquantifiable benefits (e.g., improved materials
of construction may allow a wider range of operating conditions or allow use of amine species previously ruled out due
to their effects on the stainless steel construction materials). Furthermore, cost savings might be improved significantly
based on increasing part lifetime by using a new coating system.
technology advantages
• Coated mild steel can cost-effectively replace stainless steel constructions.
• Coatings can be made acid- and amine-resistant with suitable topcoats.
• Coatings can be readily fabricated using straightforwardly implemented aqueous electroplating methods.
• Coatings of the type being developed are non-toxic and can replace heavy metal-based processes.
• May be used to avoid chloride stress cracking of stainless steel in some services.
R&D challenges
• Achieving a dense base metal oxide coating layer with high roughness suitable for securely attaching the upper coating
layer, and the general difficulties of controlling results in utilization of electroplating methods.
• Achieving chemical and physical compatibility between the metal oxide base layer and upper organic layer.
• Attaining substantially improved performance of prototype organic coatings on the metal oxide base layer.
• Larger electroplating bath tank sizes are needed for coating of large steel equipment items.
• Developing surface repair technique for coatings when damaged during shipping or installation.
status
Optimization of the parameters for fabrication of dense metal oxide base coatings with high surface roughness,
characterization of prototype organic coatings, and a preliminary cost-benefit analysis have been completed.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
418 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
available reports/technical papers/presentations
“Inexpensive and Sustainable Anti-Corrosion Coating for Power Generation Applications,” presented by John Watkins,
LumiShield Technologies Incorporated, 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies
Integrated Review Meeting, Pittsburgh, PA, October 2019.
LumiShield Technologies, “Inexpensive and Sustainable Anti-Corrosion Coating for Power Generation Applications,”
kickoff meeting presentation, January 2019.
“Electrochemical Deposition of Aluminum-Based Coatings from Aqueous Systems,” presented by John Watkins,
LumiShield Technologies Incorporated, SSPC Coatings+ 2020, Long Beach, CA, February 2020. Also submitted as a
proceeding of the same title.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
419
Post-Combustion Novel Concepts
Advancing Post-Combustion technology maturity:
Bench-Scale, Actual Flue
CO2 Capture Through Gas
Increased Mass Transfer and project focus:
Lower Degradation
Solvent Enabling Techniques
participant:
University of Kentucky
primary project goals
project number:
The University of Kentucky Center for Applied Energy Research’s (UK CAER) project FE0031661
will develop three techniques to enable aqueous post-combustion carbon dioxide
(CO2) capture technologies to meet the U.S. Department of Energy (DOE) predecessor projects:
performance and cost targets of 90% CO2 capture, 95% purity, at a cost of less N/A
than $30/tonne CO2 captured. To reduce the cost of CO2 capture, critical elements
need to be addressed, including how to increase CO2 mass transfer (reduce capital NETL project manager:
cost), how to reduce solvent makeup (lower the operational cost) resulting from Naomi O’Neil
degradation, and how to address the potential environmental issues (permitting [email protected]
hurdles) from nitrosamine formation. The specific objectives of this project are to
develop a 3D-printed dynamic polarity packing material with increased turbulent principal investigator:
liquid flow and controlled gas-liquid bubble formation to increase CO2 mass jesse Thompson
transfer into amine solvents; investigate the impact of additives on the physical University of Kentucky
[email protected]
properties of solvents and their relationship to bubble formation to boost mass
transfer while reducing aerosol formation; and destruct nitrosamines derived from
partners:
amine solvents through development of an electrochemical treatment process.
Lawrence Livermore
The project team will develop and fabricate customized dynamic packing using
National Laboratory
advanced manufacturing techniques, install the packing into UK CAER’s bench-
scale (less than 0.1-megawatt-thermal [MWth]) CO2 capture unit, and conduct
start date:
parametric and long-term testing with additive-modified solvents. Additionally, an
10.01.2018
electrochemical cell with stationary carbon electrodes will be designed and
evaluated for the adsorption and decomposition of nitrosamines from wash water percent complete:
solutions collected from UK CAER’s 0.7-megawatt-electric (MWe) small pilot CO2
50%
capture system located at Kentucky Utilities’ E.W. Brown Generating Station.
technical goals
• Develop a library of structure/property relationships that can be used as a
guideline for choosing effective additives for a given solvent or blend.
• Design and fabricate dynamic polarity packing based on a range of solvent
property parameters for a given liquid-gas ratio.
• Evaluate selected solvents in UK CAER’s bench-scale CO2 capture unit with
conventional structured packing to serve as a baseline.
• Replace the conventional packing in the bench-scale unit with 3D-printed
dynamic packing and test the selected solvents under the same operating
conditions to determine mass transfer enhancement.
• Test selected solvent additives in the bench-scale unit to evaluate mass transfer
enhancement and reduced energy demand.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
420 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
• Evaluate the electrochemical cell using wash water collected at UK CAER’s 0.7-MWe small pilot CO2 capture system to
measure the ability to maintain nitrosamine levels below 0.5 parts per million (ppm).
• Conduct parametric testing of the combined dynamic packing solvent/additive system and identify optimum operating
conditions to achieve an increase in mass transfer.
• Perform a long-term testing campaign under optimized operating conditions to evaluate the stability of dynamic
packing and electrochemical cell and examine aerosol formation, corrosion, and solvent degradation.
• Perform a high-level techno-economic analysis (TEA) based on the collected bench-scale test data.
technical content
This UK CAER and Lawrence Livermore National Laboratory (LLNL) project will involve the development and fabrication of
customized 3D-printed dynamic packing to increase CO2 mass transfer in the absorber column. UK CAER will design,
fabricate, and test an electrochemical cell to adsorb and decompose nitrosamines from the water wash. After both systems
have been constructed, they will be tested on UK CAER’s bench-scale CO2 capture unit. The specific activities is this proposal
include: (1) quantifying the CO2 mass transfer improvement from the customized 3D-printed dynamic polarity packing in
the absorber by utilizing UK CAER’s existing less-than-0.1-MWth 3-inch ID CO2 capture column; (2) quantifying the energy
consumption saving associated with mass transfer enhancement from the dynamic polarity packing; (3) conducting detailed
studies to understand how solvent physical property can be utilized to form controllable gas bubbles to boost the mass
transfer area and impact wettability, degradation, and aerosol formation; (4) quantity the benefits of UK CAER’s
electrochemical cell to decompose nitrosamines; and (5) collect the necessary information/data to conduct a high-level TEA
of the proposed technologies.
A systematic approach was taken to develop understanding of the structure/function relationships for additives in a rational
series of amine solvents in terms of bubble formation, the stability of gas-liquid interface film, and solvent polarity. First,
physical properties such as surface tension, viscosity, elasticity, and contact angle were measured in aqueous amine solvents
with different pKa, polarity, and functional groups (i.e., –OH, -N, -R). Commercially available amines, including primary,
secondary, and tertiary amines, as well as amines with different functional groups, were prepared and examined at various
concentrations (e.g., 3 to 5 M) and at lean (~0.2 carbon/nitrogen ratio) and rich CO2 loading (~0.4 carbon/nitrogen ratio).
Water-soluble chemical additives were then selected with different functionality and chemical structures (surfactants,
inorganic metal corrosion inhibitors, organic oxidation inhibitors, and metal-ligand CO2 hydrolysis catalyst) and added to
the amine solvents. The physical properties of the amine solvents with the additives were then measured at lean and rich
CO2 loading to assess how the additives changed the solvent physical properties. The main physical property modification
came from addition of a surfactant, which resulted in a decrease in the surface tension of the solvent and a reduction in
the contact angle relative to a hydrophobic surface, such as a polymeric material. The decrease in contact angle implied
better wetting (coating) on the packing by the solvent, leading to better gas-liquid contact. This result has implications
when considering the use of plastic 3D-printed packing material as a substitute for steel structure packing in the absorber
column.
One important factor when exploring the use of polymer packing is the stability of the polymer when exposed to the caustic
CO2-loaded amine solution at elevated temperatures. The stability of the polymeric packing material after exposure to CO2-
loaded amine solvent at absorber temperature (60°C) was examined through an estimated 5,000 hours. Changes to mass,
thickness, and contact angle (°) versus water and the amine solvent were monitored every 1,000 hours. The results are shown
in Figure 1. The three polymer materials examined showed minimal changes in mass, thickness and contact angles versus
both water and the CO2-loaded amine solvent. Based on the amine stability studies, acrylonitrile butadiene styrene (ABS),
Nylon, and high-density (impact) polystyrene (HDPS) were shown to be stable upon exposure to CO2-loaded amine solvent
at anticipated absorber temperatures.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
421
Post-Combustion Novel Concepts
Figure 1: Contact angle (°) changes of polymeric materials after long-term exposure to CO2-loaded amine solvent.
To compare the wettability of the polymer packing, polished coupons of the HDPS, ABS, Nylon, and stainless steel (SS) were
collected, and contact angles were measured with water and an amine solution (Figure 2). The contact angle (wettability)
versus water of HDPS and ABS are similar, while Nylon and SS are lower and closer to each other. All the packing materials
showed a lower contact angle with the amine solvent compared to water. The contact angle of Nylon was the closest to SS,
with both ABS and HDPS having two to three times larger contact angles.
Figure 2: Contact angle of water and aqueous amines (at different CO2 loadings) on different packing material surfaces.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
422 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Post-Combustion Novel Concepts
Next, the contact angles of an amine solvent with the surfactant additive (0.1 wt.%) at different CO2 loadings were also
measured on all the packing material surfaces (Figure 3). The addition of the surfactant in the amine solvent lowered the
contact angle of the solutions versus the HDPS, Nylon, and ABS surfaces. This observation indicated that the wettability of
the aqueous amine solvent on these polymeric packing could be enhanced by adding a surfactant.
Figure 3: Contact angle of amine solvent with Tween 20 additive at variable CO2-loading on different packing materials surfaces.
To address the potential environmental concerns associated with nitrosamine formation in CO2 capture systems, an
electrochemical treatment cell is being developed to destruct nitrosamines from the absorber water wash. The
electrochemical cell is being evaluated using wash water solutions collected at UK CAER’s 0.7-MWe small pilot CO2 capture
system. The liquid under investigation represents the actual composition of wash water from an operating pilot CO2
capture system that treats coal flue gas. A preliminary design of a flow-through electrochemical cell with carbon xerogel
(CX) electrodes was generated (Figure 4) and fabrication has been completed. Recent testing demonstrated the ability to
continuously reduce at least 85% of the nitrosamines present in the water wash with an efficiency above 15%, well above
the original target values.
Figure 4: Flow-through electrochemical cell schematic with CX electrodes.
technology advantages
• Increased CO2 mass transfer and lower solvent regeneration energy.
• Enhanced CO2 absorption rate reduces absorber size, lowering capital and operating costs.
• Use of solvent additives increases solvent wetting on packing.
• Electrochemical treatment process addresses environmental concerns at high selectivity with very low operational cost.
• Technology can extend over a broad spectrum of CO2 capture systems, including many solvent-based systems.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
423
Post-Combustion Novel Concepts
R&D challenges
• Compatibility of packing material with actual flue gas and solvent impurity.
• Foaming with additives in long-term operation.
status
Experiments are being performed to gather data on solvent physical properties, dynamic packing development, and
performance of the nitrosamine decomposition electrochemical cell.
available reports/technical papers/presentations
Thompson, J. and Liu, K., “Advancing Post-Combustion CO2 Capture through Increased Mass Transfer and Lower
Degradation,” presented at the 2019 NETL Carbon Capture, Utilization, Storage, and Oil and Gas Technologies
Integrated Review Meeting, Pittsburgh, PA, August 2019. https://netl.doe.gov/sites/default/files/netl-file/J-Thompson-
UKY-CAER-Increased-Mass-Transfer.pdf.
Thompson, J. “Advancing Post-Combustion CO2 Capture through Increased Mass Transfer and Lower Degradation,”
Project Kickoff Meeting, Pittsburgh, PA, November 2018.
https://www.netl.doe.gov/projects/files/31661%20Kickoff%20Nov%202018_Public.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
424 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
PRE-COMBUSTION
SORBENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
425
Pre-Combustion Sorbent Technologies
Pilot Testing of a Highly technology maturity:
Effective Pre-Combustion
Pilot-Scale, Actual Syngas
Slipstream (equivalent to 0.1
Sorbent-Based Carbon
MWe)
project focus:
Capture System High-Capacity Regenerable
Sorbent
primary project goals participant:
TDA Research, Inc.
TDA Research, Inc., is continuing development of a new sorbent-based pre-
combustion carbon capture technology for integrated gasification combined cycle project number:
(IGCC) power plants. The process uses an advanced physical adsorbent that FE0013105
selectively removes carbon dioxide (CO2) from coal-derived synthesis gas (syngas)
above the dew point of the gas. The project aims to prove the viability of the new predecessor projects:
technology by using data collected from the pilot plant tests to complete high- FE0000469
fidelity engineering and cost analyses to calculate the impact of the carbon capture
system on the cost of electricity generation at a coal-fired IGCC power plant and NETL project manager:
the potential of the technology to meet the U.S. Department of Energy (DOE) goals Andrew O'Palko
of 90% CO2 capture and 95% purity at a cost of less than $40/tonne CO2 captured. [email protected]
Having shown promise under a previously-funded DOE project (FE0000469), this principal investigator:
sorbent is being evaluated at a larger scale, for longer durations, and under
Gökhan Alptekin
conditions that are more representative of a coal gasification-based application. TDA Research, Inc.
Current research objectives are to collect performance data for this advanced [email protected]
sorbent, including: two 0.1-megawatt-electric (MWe) tests with a fully equipped
prototype unit using actual syngas to prove the viability of the new technology; partners:
long-term sorbent life evaluation in a bench-scale setup; the fabrication of a pilot- Gas Technology Institute,
scale testing unit that will contain eight sorbent reactors; and the design of a CO2 CDM Smith, Inc., University
purification subsystem. of California at Irvine (UCI),
University of Alberta,
Sinopec
technical goals
start date:
Enable pre-combustion CO2 capture from syngas at 200 to 250°C and pressures 10.01.2013
up to 60 bar, with greater than 90% recovery and CO 2 purity of at least 95%
using a functionalized carbon sorbent in a pressure swing adsorption (PSA)- percent complete:
based cycle. 80%
Improve adsorber reactor design, including the optimized reactor internals and
bed geometry through computational fluid dynamics (CFD) analysis and PSA
cycle optimization with adsorption modeling.
Complete pilot-scale field tests on syngas slipstreams at 0.1 MWe equivalent,
at design conditions and for extended durations (e.g. greater than 3,000 hours),
to demonstrate capability to meet all performance objectives (e.g., CO 2 removal
efficiency, hydrogen [H2] recovery, sorbent life, and performance).
Validate long-term performance and lifetime of the sorbent through 60,000
cycles with no more than 2% decrease in adsorption capacity over fresh sorbent
(enabling projected lifetime of five years for the sorbent).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
426 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Sorbent Technologies
Enable improved IGCC plant efficiency (3 to 4 percentage points) over IGCC plants using conventional CO 2 removal
technology, thereby improving cost of electricity in coal-based power production.
technical content
TDA Research, Inc. is designing, constructing, and operating a slipstream 0.1-MWe pilot-scale process for pre-combustion
CO2 capture to assess their novel adsorbent for the selective removal of CO 2 from syngas. The adsorbent consists of a
mesoporous carbon grafted with surface functional groups that remove CO 2 via an acid-base interaction. The novel
process is based on TDA’s high-temperature PSA technology, using the new adsorbent to selectively remove CO 2 from
syngas in an IGCC power plant. The integration of the CO2 separation unit into the IGCC plant is shown in Figure 1.
Figure 1: TDA’s CO2 capture system integration in an IGCC power plant.
The CO2 capture system uses multiple sorbent beds that switch operating modes between adsorption and regeneration.
In adsorption mode, which is operated isothermally (temperature of about 240 to 250°C) and at syngas pressure of about
500 pounds per square inch absolute (psia), the sorbent removes CO 2 via strong physical adsorption. The CO2 surface
interaction is strong enough to allow operation at these elevated temperatures.
In regeneration mode, also operated isothermally (temperature of about 240 to 250°C), CO 2 is recovered via combined
pressure and concentration swing by contacting the sorbent with a steam purge stream. The operating pressure ranges
from 150 to 158 psia and partial pressure of CO2 ranges from 0 to 75 psi. Because the CO2 is recovered at ~150 psia,
energy requirement for CO2 compression for storage is reduced. Also, the isothermal operation eliminates heat/cool
transitions, and rapid cycling reduces cycle times and increases sorbent utilization. Because the CO 2 is not bonded via a
covalent bond, the energy input to the regeneration is low—only 4.9 kcal/mole of CO 2 removed (comparable to Selexol™).
This energy requirement is much lower than that of the chemical absorbents (e.g., sodium carbonate [Na 2CO3] requires
29.9 kcal/mol) and amine solvents (≈14 kcal/mol). The energy output loss of the IGCC plant is expected to be similar to
that of Selexol’s; however, a higher overall IGCC efficiency can be achieved due to higher temperature CO 2 capture.
The pilot plant design includes a gas conditioning unit and a high-temperature PSA-based CO 2 separation unit, as shown
in Figure 2. The gas conditioning unit allows for adjustment of the concentration and purity of the syngas. The CO 2
separation unit consists of eight high-temperature sorbent beds. The design of the CO 2 capture skid for the 0.1-MW pilot
unit is shown in Figure 3.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
427
Pre-Combustion Sorbent Technologies
Figure 2: Flow diagram for TDA’s pilot test unit.
Figure 3: Overhead view of carbon capture skid.
In 2017, TDA’s 0.1-MWe pilot-scale eight-bed PSA unit was installed at the National Carbon Capture Center (NCCC; Figure
4) and tested in real coal-derived syngas. The pilot unit ran for 707 hours of continuous operation at up to 97.3% carbon
capture at 53 standard cubic feet per minute (SCFM) of syngas flow, exceeding design specifications. The summary results
are given in Figure 5. This table also shows the upcoming design performance parameters for the Sinopec oxygen-based
gasifier testing at considerably increased throughput.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
428 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Sorbent Technologies
Figure 4: TDA’s 0.1-MWe pilot unit installed in the test pad at the NCCC (Wilsonville, AL).
Figure 5: Summary performance results of pilot-scale testing.
In 2018 and 2019, TDA shipped, installed, and performed shakedown testing
on field units at Sinopec (see Figure 6), which allow oxygen-based gasifier
testing at considerably increased throughput.
Very early testing results at 88 SCFM syngas flow have resulted in ~85% CO 2
removal efficiency at a rate of ~110 kg/hr CO2.
TDA has also performed preliminary techno-economic analyses (TEAs) of
cases assuming application of TDA’s sorbent-based CO2 capture system in
IGCC plant cycles, based upon performance data available to date from recent
testing. The comparisons involve a baseline of conventional cold-gas cleanup
and Selexol™ acid gas removal, compared to TDA’s assumption of warm-gas
cleanup combined with the sorbent units for CO2 capture. Results are shown
in Figure 7. Overall, the findings are as follows:
TDA system achieves higher efficiencies (34.5% and 34.1%) than IGCC
with Selexol™ (32.0% and 31.0%) for E-Gas™ and GE gasifier-based
plants.
Cost of CO2 capture is calculated as $31 and $30/tonne for GE and E-
Gas™ gasifier-based plants, respectively (16 to 30% reduction against
Figure 6: Field test units at Sinopec, China.
Selexol™).
Cost of CO2 capture is calculated as $40 and $28/tonne for Shell and TRIG gasifier-based plants, respectively (15 to
28% reduction against Selexol™).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
429
Pre-Combustion Sorbent Technologies
Figure 7: Preliminary Techno-economic comparisons.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D Value Target R&D Value
True Density @ STP kg/m3 1,314 1,314
Bulk Density kg/m3 620 620
Average Particle Diameter mm 0.42–1.68 0.42–1.68
Particle Void Fraction m3/m3 0.368 0.368
Packing Density m2/m3 4.59E+08 4.59E+08
Solid Heat Capacity @ STP kJ/kg-K 0.93 0.93
Crush Strength kgf 3 3
Manufacturing Cost for Sorbent $/kg 3.88 3.88
Adsorption
Pressure bar 33.8 33.8
Temperature °C 198 198
Equilibrium Loading g mol CO2/kg 1.04 1.04
g mol CO2/m3 645 645
Heat of Desorption kJ/mol CO2 -28.5 -28.5
Desorption
Pressure bar 10 10
Temperature °C 195.5 195.5
Equilibrium CO2 Loading g mol CO2/kg 0.005 0.005
g mol CO2/m3 3.22 3.22
Heat of Desorption kJ/mol CO2 28.5 28.5
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
430 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Sorbent Technologies
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — radial-flow fixed bed/cyclic
Syngas Flowrate kg/hr 668,083
CO2 Recovery, Purity, and Pressure+ %/%/bar 90.0% 96.0% 10
Adsorber Pressure Drop bar 1.41
Estimated Absorber/Stripper Cost of __$__
212.8
Manufacturing and Installation kg/hr
+ CO2 is recovered at 10 bar from TDA's CO2 capture system, which is further purified and compressed to 152.7 bar with a final CO2 purity of 99.96%.
Definitions:
STP – Standard temperature and pressure (15°C, 1 atmosphere [atm]).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are
process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO 2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO 2.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Surface functionalized mesoporous carbon removing CO2 via weak
interactions similar to physical adsorption at temperatures above the dew point of the syngas.
Sorbent Contaminant Resistance – The sorbent is highly resistant to contaminants such as hydrogen sulfide (H2S),
carbonyl sulfide (COS), ammonia (NH3) and trace metals such as mercury (Hg), arsenic (As), etc. If needed, additional
functionalities can be incorporated into the sorbent to remove these contaminants simultaneously with CO 2. Results of
the 707-hour-long testing with coal-derived syngas with the 0.1-MWe pilot unit at the NCCC in Wilsonville, Alabama,
showed excellent resistance to contaminants that could be present in syngas.
Sorbent Attrition and Thermal/Hydrothermal Stability – The sorbent has good thermal/hydrothermal stability; it is
stable in nitrogen up to 900°C and in steam stable up to 400°C. The attrition index for the sorbent is estimated to be 0.1%
loss per 1,000 hours of operation.
Syngas Pretreatment Requirements – Syngas needs to be shifted to convert carbon monoxide (CO) present into CO 2
and H2 via water-gas shift (WGS) reaction and sulfur content needs to be reduced to less than 100 parts per million (ppm)
before CO2 removal.
Sorbent Makeup Requirements – The expected life of the sorbent is five years. The annualized sorbent makeup
requirement is expected to be 261.5 tonnes on the 550-MWe process plant basis.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
431
Pre-Combustion Sorbent Technologies
Waste Streams Generated – Condensate from cooling the raw CO2 stream.
Process Design Concept – See Figure 1.
Proposed Module Integration – TDA’s CO2 separation, purification, and compression system is located downstream of
the warm-gas sulfur removal and the WGS processes as shown in Figure 1.
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H 2O H2 S
497.5 388.4 30.28 0.73 2.04 0.45 39.11 26.59 <10
technology advantages
Warm-gas CO2 capture above dew point of syngas leads to more steam in the hydrogen-rich gas entering the turbine.
o Improved efficiency.
o Higher mass throughput to gas turbine.
o Lower-gas turbine temperature, which lowers the need for high-pressure nitrogen (N 2) dilution and lowers nitrogen
oxide (NOX) formation.
High steam content feed more suited for next-generation hydrogen turbines under development.
High working capacity and cycle life of sorbent.
Carbon dioxide recovered at pressure reduces compression costs for storage.
A weak CO2 surface interaction allows fast regenerations at lower temperature with minimal or no heat input.
Short adsorption/regeneration cycles reduce bed size and weight, corresponding to reduced adsorber vessel size and
costs.
R&D challenges
Assuring consistency in sorbent material and minimizing batch-to-batch variation for large-scale manufacture.
Reducing the use of purge gas during regeneration.
Confirming resistance to syngas contaminants.
status
Pilot-scale testing at the NCCC was completed in mid-2017, with successful attainment of 90%+ carbon capture at greater
than design flows of syngas. Testing of the sorbent over 60,000 cycles has successfully demonstrated that the sorbent
maintains stability and retains high CO2 capacities over long-term cycling.
A CFD model to support reactor design was developed and tuned/optimized using the data from 1-kilowatt (kW) and
0.1-MW systems evaluated at Wabash River IGCC Plant and NCCC field tests.
TDA completed installation of field test units at Sinopec in mid-2019 and very early testing has subsequently begun,
which is expected to run six to 12 months from late-2019.
Preliminary TEAs of cases assuming application of TDA’s sorbent-based CO 2 capture system in IGCC plant cycles have
been completed.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
432 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Sorbent Technologies
available reports/technical papers/presentations
“Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System,” presented by Gökhan Alptekin
of TDA Research, Inc. at the 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review
Meeting – Capture and Utilization Sessions, Pittsburgh, Pennsylvania, August 2019.
“PSA Based CO2 Capture Above the Dew Point of Synthesis Gas for IGCC Power Plants,” presented at the 2017 AIChE
Annual Meeting, Minneapolis, MN, November 2017.
“Highly Efficient Warm Gas Carbon Capture System for IGCC Power Plants,” presented at the 2016 AIChE Annual
Meeting, Minneapolis, MN, November 2016.
“Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System,” presented by Gökhan
Alptekin, TDA Research, Inc., 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
“Pilot Testing of a Highly Efficient Pre-Combustion Sorbent-Based Carbon Capture System,” presented by Gökhan
Alptekin, TDA Research Inc., 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
“Pilot Testing of a Highly Efficient Pre-Combustion Sorbent-Based Carbon Capture System,” presented by Gökhan
Alptekin, TDA Research Inc., 2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
Alptekin, G., et. al. “A Low Cost, High Capacity Regenerable Sorbent for Pre-Combustion CO 2 Capture,” Final Report,
September 30, 2012.
“Pilot Testing of a Highly Efficient Pre-Combustion Sorbent-Based Carbon Capture System,” presented by Gökhan
Alptekin, TDA Research Inc., 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
“Pilot Testing of a Highly Efficient Pre-Combustion Sorbent-Based Carbon Capture System,” Project Kick-Off Meeting,
January 2013.
Alptekin, G., Jayaraman, A., Dietz, S., Bonnema, M., Rao, A., “Low Cost, High Capacity Regenerable Sorbent for
Precombustion CO2 Capture,” Final Report, September 2012.
Alptekin, G., “A Low Cost, High Capacity Regenerable Sorbent for CO 2 Capture,” presented at the International
Colloquium on Environmentally Preferred Advanced Power Generation (ICEPAG), Costa Mesa, CA, February 2012.
Alptekin, G., Jayaraman, A., Dietz, S., and Schaefer, M., “High Capacity Regenerable Sorbent for Pre-Combustion CO 2
Capture,” presented at the 28th Annual International Pittsburgh Coal Conference (IPCC), Pittsburgh, PA, September
2011.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 433
Pre-Combustion Sorbent Technologies
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NATIONAL ENERGY TECHNOLOGY LABORATORY
434 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
PRE-COMBUSTION
MEMBRANE TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
435
Pre-Combustion Membrane Technologies
Zeolite Membrane Reactor for technology maturity:
Bench-Scale, Actual Syngas
Pre-Combustion Carbon (2 kg per day equivalent to
2 kwth)
Dioxide Capture project focus:
Zeolite Membrane Reactor
primary project goals
participant:
Arizona State University’s (ASU) project objectives are to develop tools and Arizona State University
methods for scaling-up zeolite membrane fabrication and water-gas shift (WGS)
zeolite membrane reactors (ZMRs), and to construct bench-scale zeolite
project number:
membrane modules and test their performance for WGS with carbon dioxide (CO2)
capture on coal-derived syngas. FE0026435
This will be the first effort to study ZMRs for high-temperature chemical reaction predecessor projects:
and gas separation at this scale. The process design and techno-economic
N/A
analysis (TEA), with the input of the experimental findings, will validate the
effectiveness of the ZMR for WGS reaction and CO2/hydrogen (H2) separation.
The results of this project will provide a foundation and guide for further scaling- NETL project manager:
up of the membrane reactor technology for pre-combustion CO2 capture at pilot- Andrew jones
scale. [email protected]
principal investigator:
technical goals
jerry Lin
Arizona State University
• Identify structure and operation conditions for a bench-scale membrane reactor [email protected]
through modeling and experimental study of the WGS reaction in a single-tube
ZMR. partners:
• Fabricate chemically and thermally stable alumina tubule supports and zeolite Media and Processes
membranes of suitable quantity in consistent quality. Technology Inc., University
• Design and fabricate multiple-tube zeolite membrane modules with adequate of Cincinnati, Nexant Inc.
seals for H2 separation and WGS reaction at high temperature and pressures.
• Assemble and test the bench-scale zeolite membrane modules with desired start date:
catalyst for WGS reaction. 10.01.2015
• Demonstrate effective production of H2 and CO2 capture by the bench-scale
ZMR from coal gasification syngas at temperatures of 400 to 550°C and percent complete:
pressures of 20 to 30 atmosphere (atm), to produce 2 kg H2/day (equivalent to 95%
2 kilowatt-thermal [kWth] integrated gasification combined cycle [IGCC] power
plant).
• Perform process design and techno-economic and environmental, health, and
safety (EH&S) risk analyses to evaluate performance and cost-effectiveness of
the ZMR integrated in a 550-megawatt-electric (MWe) IGCC plant with CO2
capture.
technical content
The working hypothesis of this project is that the conventional WGS unit found in
a coal gasification process plant (for shifting the syngas toward primarily H2 and
CO2) and downstream conventional amine absorption unit for capturing the CO2
from the shifted syngas could be replaced, in whole, by a novel WGS shift reactor
that integrates zeolite-based H2 separation membranes. Within the zeolite
membrane WGS reactor, H2 would be withdrawn directly from the reaction
chamber, efficiently increasing the driving force for the WGS reaction to
completion. As such, the multiple stages of the conventional WGS unit are
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
436 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Pre-Combustion Membrane Technologies
replaced by a single, elegantly performing reactor. This process concept, with the ZMR replacing the conventional WGS
process stages and amine absorption unit, is depicted in Figure 1.
Figure 1: Zeolite membrane reactor for WGS reaction and CO2 capture in context of coal gasification plant cycle.
However, the operating environment in the reactor is challenging. Past findings have suggested that zeolite membranes,
which are inorganic and can be tailored or selected for specific gas-separation applications, can meet the functional
requirements and operational conditions as follows:
• Operation at 350 to 550°C.
• Chemically stable in hydrogen sulfide (H2S), thermally stable at ≈400°C.
• Hydrogen permeance = 2 × 10-7 mol/m2.s.Pa (600 GPU).
• Hydrogen/CO2 selectivity = 20 to 40.
In ASU’s previous work, Mobil-type 5 (MFI) zeolite (an aluminosilicate zeolite belonging to the pentasil family of zeolites)
was used in a laboratory-scale zeolite membrane WGS reactor and continues as the basis in current work. See Figure 2
for the zeolite structure and a highly magnified view of the zeolite layer deposited on an alumina substrate. Although this
zeolite has been traditionally used as a catalyst for hydrocarbon isomerization and the alkylation of hydrocarbons, it
serves in the current work as an H2-permeable membrane layer suitable for deposition on alumina, which can be formed
into the desired tubes for fitting into WGS reactor modules.
The MFI zeolite pores have an effective diameter of ~0.56 nm, which is large enough for the small gas molecules involved
in the WGS reaction to permeate through by gaseous diffusion mechanism. Therefore, pristine MFI-type zeolite
membranes offer high H2 permeance but with limited H2/CO2 selectivity defined by the Knudsen factor (~4.75) at high
temperatures where the permeating gases become non-adsorbing to the zeolite. The MFI-type zeolite membranes can
be modified by in situ deposition of mono silica species to the internal pore wall that narrows down the effective zeolite
pore diameter from ~0.56 nm to less than 0.36 nm. Such a reduced pore size enables the highly selective size-exclusion
effect between the small H2 molecule (kinetic diameter dk = 0.289 nm) and other slightly larger molecules like CO2 (dk =
0.330 nm), carbon monoxide (CO) (dk = 0.376 nm), and methane (CH4) (dk = 0.380 nm).
ASU and the University of Cincinnati have developed an on-stream catalytic cracking deposition (CCD) method for
modification of the MFI-type zeolite membrane that effectively controls the silica deposition within a small portion of the
zeolitic channels near the membrane surface. This well-controlled modification avoids excessive loss in H2 permeance
while achieving substantially improved H2 selectivity over CO2, CO, and water (H2O).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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437
Pre-Combustion Membrane Technologies
Figure 2: MFI-type zeolite (ZSM-5 or silicalite) (on left); magnified view of zeolite membrane (on right).
Figure 3 depicts the laboratory-scale tubular membrane reactor for testing separation performance and WGS reaction of
a zeolite membrane tube containing a WGS catalyst. Feed gas is passed to the bore side of the tube, and as the gas
passes over the catalyst, increasing amounts of H2 are generated. The zeolite allows H2 to readily pass through the
membrane tube, while keeping the larger CO, H2O, and CO2 molecules inside. Retentate is enriched in CO2 after the
WGS reaction.
Figure 3: Zeolite membrane tubular WGS reactor.
Previously, CCD-modified MFI zeolite membranes showed long-term stability in WGS reaction at 400 to 550°C with a
high H2S content of ~400 parts per million (ppm) in feed. Modified MFI zeolite membranes with an H2/CO2 selectivity
higher than 10 showed the ability to achieve CO-conversion well exceeding the equilibrium conversion in WGS reaction.
In this project, ASU reported the first experimental demonstration of near-complete CO conversion (~99.9%) in a single
high-temperature and high-pressure WGS-ZMR that uses a CCD-modified MFI zeolite membrane supported on a
commercially available low-cost small diameter alumina tube (outer diameter: 5.7 mm, provided by Media and Processes
Technology Inc.).
This basic arrangement persists in the multi-tube reactors for bench-scale testing (these modules are depicted in Figure
4). The housing accommodates a full-length, 21-tube bundle, and the main feed port can be completely removed to
permit catalyst packing/removal.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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438 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Pre-Combustion Membrane Technologies
Figure 4: Zeolite membrane bundles and modules.
ASU performed a 425-hour challenge test on the 21-tube ZMR bundle and seals to evaluate performance and durability.
Testing conditions were at temperatures from 400 to 450°C, pressure from 100 to 400 pounds per square inch (psi), and
steam content from 60 to 100%. No deterioration was noted throughout the duration of the testing, as depicted in Figure
5.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
439
Pre-Combustion Membrane Technologies
Figure 5: Challenge testing on zeolite tube bundles.
ASU completed fabrication and installation of the bench-scale reactor test skid at the University of Kentucky facility, and
testing is underway.
Preliminary performance results of the WGS-ZMR have been used in process modeling and a TEA of a ZMR-based
IGCC plant scenario; the results were compared to a National Energy Technology Laboratory (NETL) baseline case
(conventional WGS and Selexol acid gas removal [AGR]) and the Nexant IGCC case. Compared to the NETL baseline,
which has a cost of electricity (COE) of 141.5 mills/kilowatt-hour (kWh), including CO2 transportation, storage, and
monitoring (TS&M), the ZMR COE was higher at 147.3 mills/kWh. Notwithstanding somewhat lower capital costs,
auxiliary power consumption is higher in the ZMR case, chiefly causing the higher COE.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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440 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value * Target R&D value
Materials of Fabrication for Selective Layer — modified MFI zeolite modified MFI zeolite
Materials of Fabrication for Support Layer — α-alumina α-alumina
Nominal Thickness of Selective Layer µm ~10 ~5
Membrane Geometry — discs tubes
Maximum Trans-Membrane Pressure bar ~20 ~30
Hours Tested without Significant Degradation — ~100 >200
Manufacturing Cost for Membrane Material $/m2 ~800 ~600
Membrane Performance
Temperature °C 400-500 400-500
H2 Pressure Normalized Flux GPU or equivalent ~300 300-600
H2/H2O Selectivity — >100 >100
H2/CO2 Selectivity — 10–30 20-45
H2/H2S Selectivity — >60 >60
Sulfur Tolerance ppm 1,000 10,000
Type of Measurement — mixed-gas mixed-gas
Proposed Module Design
Flow Arrangement — Counter-current
Packing Density m2/m3 50-200
Shell-Side Fluid — Retentate, CO2-rich flow
Syngas Gas Flowrate kg/hr 5-20
CO2 Recovery, Purity, and Pressure %/%/bar 90 95 ** ~30
H2 Recovery, Purity, and Pressure %/%/bar 92 95 ~20
Pressure Drops Shell/Tube Side bar 10-30
Estimated Module Cost of Manufacturing and __$__
kg/hr ~1,000
Installation
* For the Current R&D Value, the calculation is based on lab-scale zeolite membranes reported in literature. Palladium-based membranes
have high hydrogen selectivity but low sulfur tolerance, which is not presented here.
** Gasifier, coal feedstock, and upstream unit operation (e.g., syngas pretreatment) specifications dependent.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivity should be for mixture
of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
441
Pre-Combustion Membrane Technologies
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – At temperatures above 400°C, the separation of H2 and CO2 through modified
zeolite membranes is governed by translational gas diffusion in micropores.
Contaminant Resistance – Zeolite membranes and catalysts have excellent resistance to syngas contaminants.
Syngas Pretreatment Requirements – Particulate removal is required.
Membrane Replacement Requirements – The multiple-tube membrane bundle will be applied in the ZMR continuously
over 200 hours without replacement.
Waste Streams Generated – There are no waste streams generated in the flowsheet. All potential waste streams are
recycled and used in the process somewhere. For example, the condensed water at the outlet of retentate side is recycled
back as makeup water for the WGS reaction.
Process Design Concept – As presented in Figure 1. A skid for bench-scale ZMRs consisting primarily of a flow control
system and a high-temperature oven is connected into a coal-to-liquids facility by replacing the WGS unit.
Proposed Module Integration – The proposed bench-scale study of ZMRs will be conducted at the University of
Kentucky, Center for Applied Energy Research. The multiple-tube membrane bundle will be located downstream of a
Coal/Biomass-to-Liquids (CBTL) pilot facility that produces syngas with a rated feed capacity of 1 ton/day. The pressure
and temperature of syngas entering the membrane module are 435 pounds per square inch absolute (psia) and 845°F,
respectively. The composition of the gas mixture is assumed:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H2O H2S
435 845 32.3 34.1 0 2.8 25.7 3.4 >400
technology advantages
• The membrane reactor process could replace a conventional two-stage WGS reactor system requiring intercooling
and a separate CO2 capture unit, with a single WGS membrane reactor unit with potential for energy efficiency increase
and equipment cost savings.
• Modified MFI zeolite membranes have remarkable resistance to sulfur species in the syngas feed and good thermal
and hydrothermal stability and show superior hydrogen permeance and high H2/CO2 selectivity.
• These tubular membranes can be fabricated into robust and stable multiple-tube modules at a high packing density.
• The ZMR-based process will create a high-pressure CO2 stream, capturing greater than 90% of CO2 in post-shift
syngas.
R&D challenges
• Low reproducibility of laboratory fabrication of long-tube zeolite membranes in large quantity with H2 separation
performance the same as a single, short-tube membrane.
• High-temperature hydrothermal stability of membrane bundle components and seals.
• Deterioration of strength of membrane tubes in use.
• WGS catalysts’ thermal stability, poison resistance, and product selectivity maintained at high pressures (greater than
15 atm) and temperatures (up to 550°C).
• Removal of particulate matter from the syngas to reduce its potential impact on the membrane lifetime.
• Cost reductions for the membrane module materials if the technology is to become economically viable.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
442 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
status
Zeolite membranes have been fabricated on cost-effective industrial tubular alumina substrates, and high-pressure and
high-temperature intermediate-scale zeolite membrane modules have been built and tested. WGS on ZMR was studied
by experiments and modeling. Also, a process concept for ZMR integration into an IGCC power plant system has been
identified and will serve as the basis for eventual cost and performance estimates for this technology.
available reports/technical papers/presentations
“Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture,” presented by Jerry Lin, Arizona State
University, 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review Meeting -
Capture and Utilization Sessions, Pittsburgh, PA, August 2019.
“Zeolite Membrane Reactor for Pre-Combustion CO2 Capture,” MPT Site Visit, February 2019.
“Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture,” presented by Lie Meng, Arizona State
University, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
A. Arvanitis, X. Sun, S. Yang, D. Damma, P. Smirniotis, J. Dong, “Approaching complete CO conversion and total H2
recovery for water gas shift reaction in a high-temperature and high-pressure zeolite membrane reactor,” Journal of
Membrane Science, 549 (2018) 575–580.
“Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture,” presented by Jerry Lin, Arizona State
University, 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
“Zeolite Membrane Reactor for Pre-Combustion CO2 Capture,” presented by Jerry Lin, Arizona State University, 2016
NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
443
Pre-Combustion Membrane Technologies
Sorption Enhanced Mixed technology maturity:
Bench-Scale, Actual Syngas
Matrix Membranes for (10 lb/hour equivalent to
0.007 Mwe)
Hydrogen Purification and project focus:
Carbon Dioxide Capture Mixed Matrix Membranes
participant:
primary project goals State University of New York
(SUNY)–Buffalo
The overall objective is to combine crosslinked polymers having molecular size-
sieving ability, and palladium (Pd)-based nanomaterials with very high hydrogen project number:
(H2)/carbon dioxide (CO2) solubility selectivity, to achieve membranes with
superior gas-separation performance relative to stand-alone polymeric FE0026463
membranes. This project may lead to a new generation of membrane materials
that combine robust performance with good processability to significantly predecessor projects:
decrease the cost of CO2 capture, utilization, and storage (CCUS), enabling N/A
environmentally responsible energy production from abundant domestic coal.
NETL project manager:
technical goals Andy Aurelio
[email protected]
• Identify mixed matrix materials with H2 permeability of 50 Barrers and H2/CO2
principal investigator:
selectivity of 30 at 150 to 200°C with simulated syngas.
Haiqing Lin
• Prepare thin-film mixed matrix composite membranes with H2 permeance of
State University of New York
500 gas permeation units (GPU) and H2/CO2 selectivity of 30 at 150 to 200°C
(SUNY)–Buffalo
and perform parametric testing of these membranes using simulated syngas in
[email protected]
the laboratory.
• Conduct a 20-day field test of membrane stamps with real syngas from a partners:
gasifier, providing duration testing as well as assessing effects of exposure to
Membrane Technology and
syngas contaminants.
Research Inc.
technical content start date:
10.01.2015
The State University of New York (SUNY) at Buffalo is developing a membrane-
based process to capture CO2 from coal-derived syngas. The key advancement percent complete:
of this technology is a series of novel sorption-enhanced mixed matrix membranes
95%
(MMMs) with high H2 permeance (500 GPU) and high H2/CO2 selectivity (30) at
temperatures up to 200°C. The approach combines highly crosslinked polymers
with strong molecular size-sieving ability and Pd-based nanomaterials with high
H2/CO2 selectivity to achieve membranes with performance superior to stand-
alone polymeric membranes.
The working hypothesis explored in this technology development is that Pd
nanoparticles exhibit extraordinary H2 sorption, and therefore would confer
favorable H2/CO2 solubility selectivity to thin-film composite (TFC) membranes into
which they are incorporated (allowing H2 to “hop” along the particle array). Such
membranes, consisting of metallic Pd particles dispersed in a polymer matrix, are
termed MMMs. Figure 1 depicts this approach, in which an MMM should improve
both permeance and selectivity for H2 separation above those typical of base
polymer membranes.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
444 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 1: Mixed matrix materials approach.
One of the most suitable choices of polymeric material for
membranes intended for H2 separation from hot syngas is
poly[2,2’-(m-phenylene)-5,5’-bisbenzimidazole] (m-PBI),
which has been widely investigated for elevated
temperature H2/CO2 separation. One of the strategies to
enhance the size-sieving ability in m-PBI is to crosslink the
polymer chains to increase chain rigidity and/or decrease
free volume, and in this work, the m-PBI is crosslinked using
terephthaloyl chloride. SUNY also discovered that by
doping with phosphoric acid (H3PO4), the PBI is favorably
modified toward greater H2/CO2 selectivity while decreasing
H2 permeability. The H3PO4 tightens the polymer structure
and increases size-sieving ability while exhibiting stability
up to 200°C. The improvement in PBI polymer properties
thus demonstrated is depicted in Figure 2.
An important aspect of development of this technology is
synthesis of the Pd nanoparticles for incorporation in the
MMMs. Both solution-phase (colloidal) synthesis and gas-
phase (aerosol) synthesis using a high-temperature
reducing jet (HTRJ) reactor developed by SUNY were
investigated. This reactor is depicted in Figure 3. The
solution-phase synthesis directly provides nanoparticles
Figure 2: Polymer development and scale-up.
that are dispersible in common organic solvents, including
those from which the polymer membranes are cast.
However, the HTRJ process can more readily produce alloy nanoparticles and is likely to be a more scalable and cost-
effective process at larger scale. Pd-copper (Cu) (60/40) alloy nanoparticles with typical size of 4 to 8 nm were
successfully prepared using the HTRJ reactor; when tested, these evidenced extremely high H2/CO2 solubility selectivity
(≈840), and H2 chemisorption independent of gas pressure.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
445
Pre-Combustion Membrane Technologies
Figure 3: HTRJ reactor.
Particles prepared in the gas phase are collected as dry powders. For incorporation into polymer membranes, these
nanoparticles must be stably dispersed in solvents that are also capable of dissolving the polymers of interest. The Pd
alloy nanoparticles are suspended in toluene solvent and mixed with 5.0 wt% PBI in dimethylacetamide (DMAc) solvent.
The combined dual solvent system incorporating both the dissolved PBI and nanoparticles is sonicated, then placed on
a plate or support and allowed to dry at elevated temperature and under vacuum. Currently, the mixed matrix PBI/Pd
layer is created directly on a support structure of polydimethylsiloxane (PDMS) silicone on pure PBI support, all of which
is underlain by stainless steel mesh. In Figure 4, a very thin mixed matrix layer only 900 nm thick with embedded
nanoparticles is visible on the silicone gutter layer, with porous PBI support underneath. In this image, the mixed matrix
layer is 58 wt% or 13 vol% of Pd nanoparticles (designated PBI-Pd-58/13). Syntheses have increased Pd nanoparticle
content up to 70 wt%; the point depicted in red in Figure 2 shows early performance properties of the 70 wt% Pd/PBI
MMM.
Figure 4: Cross-sectional scanning electron microscopy (SEM) of membranes.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
446 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 5 shows the final laboratory-scale testing results for MMM permeability and selectivity for H2/CO2 separation.
Behavior of optimized membranes at temperatures ranging from 150 to 225°C is show for three loadings of nanoparticles
(22%, 46%, and 58% nanoparticles by weight). Note that the target performance region has been attained with the PBI-
PD-58/13 MMM.
Figure 5: Effect of increasing Pd nanoparticle content on H2/CO2 separation in MMMs.
Also, stability of the MMMs in the presence of hydrogen sulfide (H2S) and water (H2O) was experimentally evaluated by
measuring any changes of membrane permeability and selectivity with and without these species added to the simulated
syngas mixtures. Satisfactory stability was observed in long-term laboratory-scale testing.
An important performance target of H2 permeance of 500 GPU or greater at 150 to 200°C (with selectivity at least 30)
had been set for this technology. Figure 6 shows the laboratory-scale permeances attained in this project (red) for a 70-
nm thin-film MMM and various other competing H2 separation membranes’ permeance performance for comparison. Note
that a thin-film MMM at 230°C would have more than adequate selectivity; however, with permeance of 400 GPU, it does
not attain the target field.
Figure 6: Hydrogen permeance target performance.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
447
Pre-Combustion Membrane Technologies
Final project work involves testing of field stamps of MMMs using real syngas. Testing is to be conducted at the University
of Kentucky’s Center for Applied Energy Research (CAER), using syngas from the opposed multi-burner entrained flow
coal gasifier at CAER.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — polymers
Materials of Fabrication for Support Layer — polysulfone, polyethersulphone, etc.
Nominal Thickness of Selective Layer µm 0.1–0.2 0.1
Membrane Geometry — Flat sheet or hollow fiber Flat sheet
Maximum Trans-Membrane Pressure bar 50 50
Hours Tested without Significant Degradation — 1 month 3 weeks
Manufacturing Cost for Membrane Material $/m2 10-50 20-50
Membrane Performance
Temperature °C 100-300 250
H2 Pressure Normalized Flux GPU 200 500
H2/H2O Selectivity — 0.1-0.5 —
H2/CO2 Selectivity — 20 30
H2/H2S Selectivity — 10-20 20
Sulfur Tolerance ppm 50 10
Type of Measurement — mixed-gas mixed-gas
Proposed Module Design
Flow Arrangement — spiral-wound modules
Packing Density m2/m3 1,000-5,000
Shell-Side Fluid — syngas
Syngas Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure %/%/bar — — —
H2 Recovery, Purity, and Pressure %/%/bar — — —
Pressure Drops Shell/Tube Side bar —
Estimated Module Cost of Manufacturing and __$__
kg/hr —
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
448 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Barrer – Gas permeability unit of membrane selective materials, 10-10 cm3 (STP)/(cm2 s cm Hg)
Other Parameter Descriptions:
Membrane Permeation Mechanism – Solution-diffusion mechanism.
Contaminant Resistance – Resistant to water, high-pressure CO2. However, the effects of sulfur and carbon monoxide
(CO) on gas separation properties are to be determined.
Syngas Pretreatment Requirements – Sulfur removal and temperature adjustment.
Membrane Replacement Requirements – Not determined.
Waste Streams Generated – None identified.
Process Design Concept – Not determined.
Proposed Module Integration – The membrane system is after the low-temperature shift reactor.
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H2O H2S
750 480-750 35-45 1-2 1-2 1-2 50-60 2-5 5-100
technology advantages
• Synergism created by incorporating Pd in a polymer membrane, taking advantage of the well-understood properties
and performance of PBI in membrane gas separations with the extremely high H2 selectivity and permeability of Pd.
• Cost savings over pure Pd membranes, using relatively little expensive Pd metal, but still taking advantage of its H2
sorption properties and stability against sulfur compounds.
• Good processability derived from polymer-based materials for the fabrication of the industrial thin-film composite
membranes.
R&D challenges
• Membrane stability at operating conditions (elevated pressure and temperature).
• Fabrication of thin-film composite membranes consistently to specification and without defects.
• Scaled-up production of high-purity Pd nanoparticles and improving process yield.
• Attaining target region of selectivity vs. permeability in MMMs.
• Particulate matter needs to be controlled to reduce its potential impact on the membrane lifetime.
• Cost reductions for the membrane module materials will be needed if the technology is to become economically viable.
• Scale-up and integration issues are a possibility given the large number of membranes needed to service a 550-
megawatt-electric (MWe) plant.
status
Mixed matrix materials with superior H2/CO2 separation properties, and polymers and nanomaterials with promising
H2/CO2 separation properties, were identified and prepared. Laboratory-scale testing of MMM-based membranes has
been completed, from which adequate H2/CO2 selectivity, targeted gas permeability, and stability in the presence of
simulated syngas has been confirmed. Current work is on readying the field test unit to perform testing on membrane
samples in actual coal syngas.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
449
Pre-Combustion Membrane Technologies
available reports/technical papers/presentations
“Sorption Enhanced Mixed Matrix Membranes for Hydrogen Purification and CO2 Capture,” presented by Haiqing Lin,
State University of New York (SUNY) - Buffalo, 2019 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2019.
“Sorption Enhanced Mixed Matrix Membranes for Hydrogen Purification and CO2 Capture,” presented by Haiqing Lin,
State University of New York (SUNY) - Buffalo, 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018.
“Sorption Enhanced Mixed Matrix Membranes for Hydrogen Purification and CO2 Capture,” presented by Haiqing Lin,
State University of New York (SUNY) - Buffalo, 2017 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2017.
“Sorption Enhanced Mixed Matrix Membranes for Hydrogen Purification and CO2 Capture,” presented by Haiqing Lin,
State University of New York (SUNY) - Buffalo, 2016 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2016.
“Sorption Enhanced Mixed Matrix Membranes for Hydrogen Purification and CO2 Capture,” project kickoff meeting
presentation, Pittsburgh, PA, October 5, 2015.
L. Zhu, M. Swihart and H. Lin, Unprecedented size-sieving ability in polybenzimidazole doped with polyprotic acids for
membrane H2/CO2 separation, Energy & Environmental Science, 2018, DOI: 10.1039/c7ee02865b
L. Zhu, M. Swihart and H. Lin, Tightening nanostructure of PBI for membrane H2/CO2 separation, Journal of Materials
Chemistry A, 5, 19914-19923, 2017, DOI: 10.1039/C7TA03874G
Lingxiang Zhu, Maryam Omidvar and Haiqing Lin. “Manipulating Polyimide Nanostructures via Crosslinking for
Membrane Gas Separation,” Chapter 6 in Membranes for Gas Separation, pp. 243-270, World Scientific, Aug 11, 2017.
H. Lin, “Molecularly Engineering Membrane Materials for Separations through Enhanced Interactions: A Road Less
Traveled,” Department of Chemical and Materials Engineering and Center of Membrane Science, University of
Kentucky, Lexington, KY, March 1, 2017.
Adams and Chen, Materials Today, 14 (2011) 282-289.
H. Lin et al., J. Membr. Sci. 457, 149-161 (2014).
Merkel, Zhou and Baker, J. Membr. Sci., 389, 442 (2012).
Wijmans and Baker, J. Membr. Sci., 107, 1 (1995).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
450 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Integrated Multichannel technology maturity:
Laboratory-Scale, Simulated
Water-Gas Shift Catalytic Syngas (5 kg/day)
Membrane Reactor for Pre- project focus:
Combustion Carbon Capture
water-Gas Shift Catalytic
Membrane Reactor
participant:
primary project goals Bettergy Corporation
The Bettergy Corporation team is developing an integrated catalytic membrane project number:
reactor (CMR) system that combines, in a one-stage process, a high-temperature SC0018853
water-gas shift (WGS) reaction with a hydrogen (H2) separation membrane to
produce H2 while simultaneously delivering carbon dioxide (CO2) at high pressure, predecessor projects:
minimizing the cost of CO2 compression. The core of the novel process is built N/A
upon a robust modularized membrane supported on catalytic substrates, which is
based on Bettergy’s patented nanopore engineering membrane (NEM) platform NETL project manager:
technology. Previously, a lab-scale WGS-CMR system was successfully tested, David Lang
achieving high WGS conversion, high-purity H2 through membrane separation, [email protected]
and enriched CO2 in the retentate stream. Currently, the main project goals are to
optimize the process, develop and test a multichannel prototype system, and principal investigator:
generate a commercialization plan. Zhong Tang
Bettergy Corporation
[email protected]
technical goals
partners:
• Optimize the formulation for the catalytic membrane substrate. University of Cincinnati,
• Develop and optimize the fabrication processes for making both tubular and Dawnbreaker, Inc.
multichannel membrane substrates.
start date:
• Optimize membrane synthesis procedures on the substrates.
07.02.2018
• Optimize CMR performance to attain carbon monoxide (CO) conversion
exceeding the thermodynamic limit at high temperature (up to 500°C) and percent complete:
pressure of 450 pounds per square inch (psi).
50%
• Investigate the effect of impurities (e.g., hydrogen sulfide [H2S]) on membrane
performance, and achieve stability of at least 500 hours without appreciable
degradation.
• Demonstrate prototype performance at syngas (simulated) flow rate of 5
kg/day.
• Enable improvement of energy efficiency of a CMS reactor system integrated in
a 550-megawatt-electric (MWe) integrated gasification combined cycle (IGCC)
plant with CO2 capture by 25 to 30%, relative to a multistage WGS reaction with
amine-based carbon capture and pressure swing adsorption (PSA) H2
purification.
technical content
The working hypothesis of this project is that the conventional WGS unit found in
a coal gasification or steam reforming plant (for shifting the syngas toward
primarily H2 and CO2) and downstream conventional amine absorption unit (for
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
451
Pre-Combustion Membrane Technologies
capturing the CO2 from the shifted syngas) could be replaced in whole by a one-stage WGS-CMR process unit. In this
one-stage process, the WGS reaction occurs in the CMR, which incorporates H2 separation membranes that permit pure
H2 to be drawn off, efficiently increasing the driving force for the equilibrium WGS reaction to go to completion. Carbon
dioxide exiting the WGS-CMR remains at relatively high pressure, reducing subsequent CO2 compression costs. As a result,
the multiple stages of the conventional WGS unit would be replaced by a single-stage reactor (or banks of reactors in
parallel as syngas throughput requires). The process concept is depicted in Figure 1 (for a natural gas reforming scenario).
Figure 1: WGS-CMR (in green shadow) replacing two-stage shift, amine CO2 capture, and PSA systems (in blue envelope) in natural gas
steam reforming H2 production process.
The basic structure of the WGS-CMR will consist of tubular channels having a configuration of the sort illustrated in Figure
2. Each reactor gas channel consists of a porous tubular support on which two different active layers are applied. The
internal tube layer is made of WGS catalyst, while the outer layer is an H2-selective zeolite. Pressurized syngas flows
through the bores of the tubes, where it contacts the WGS catalyst layer inducing increased H2 production. The H2
permeates through the support and can exit through the outside selective layer. Other syngas species do not readily
permeate through the outside zeolite layer and remain at pressure inside the tubes. Given suitable WGS kinetics and gas
flow rates, high levels of syngas conversion can be obtained, and a large fraction of H2 can be recovered on the permeate
side of the reactor. Retentate from the reactor can be made to contain most of the carbon in the incoming syngas in the
form of CO2. An alternate WGS-CMR configuration is similar but dispenses with the WGS layer and has only an H2-selective
layer on a porous substrate of WGS catalyst. In this case, the WGS catalyst might be in monolith form with many channels,
and the H2-selective zeolite layer will be on the outside surface of the monolith.
The dimensions of the gas channels may be made very small, and as such the WGS-CMR is a type of microchannel
membrane reactor. Microchannel reactors offer multiple benefits, including better control over temperature profiles,
minimal catalyst loading for given levels of gas throughput, moderate pressure drop, and favorable trade-off between
capital cost and performance.
This novel WGS-CMR does pose developmental challenges, including optimizing the formulation of the high-temperature
WGS catalyst (as either a layer on an inert porous support, or itself as the catalytically active porous substrate), preparing
the H2-selective composite zeolite thin layer membrane on the support/substrate, and development and optimization of
WGS-CMR assemblies.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
452 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 2: WGS-CMR tubular configuration.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — composite composite
Materials of Fabrication for Support Layer — WGS catalyst WGS catalyst
Nominal Thickness of Selective Layer µm 10-20 10-20
Membrane Geometry — tubular multichannel
Max Trans-Membrane Pressure bar 10 30
Hours Tested without Significant Degradation — 500 1,000
Manufacturing Cost for Membrane Material $/m2 1,200 355-657
Membrane Performance
Temperature °C 350-550 400-500
H2 Pressure Normalized Flux GPU or equivalent 150 50-250
H2/H2O Selectivity — N/A N/A
H2/CO2 Selectivity (Dense layer thickness) — >75 >75
H2/H2S Selectivity (Dense layer thickness) — N/A N/A
Sulfur Tolerance ppm 200 500
Type of Measurement — mixed mixed
Proposed Module Design (for equipment developers)
Flow Arrangement — counter flow
Packing Density m2/m3 n/a
Shell-Side Fluid — retentate
Syngas Flowrate kg/hr 0.21
CO2 Recovery, Purity, and Pressure %/%/bar 80%, 80%, 20 bar
H2 Recovery, Purity, and Pressure %/%/bar 80%, >95%, 30 bar
Pressure Drops Shell/Tube Side* bar 1/1.5
Estimated Module Cost of Manufacturing and __$__
TBD
Installation kg/hr
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
453
Pre-Combustion Membrane Technologies
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, monolith, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for
mixture of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Molecular sieving and activated diffusion.
Contaminant Resistance – TBD.
Syngas Pretreatment Requirements – Tar removed.
Membrane Replacement Requirements – TBD.
Waste Streams Generated – Hydrogen sulfide would remain in the retentate and must be separated. This may result in
a waste stream containing H2S.
Process Design Concept – See Figure 1.
Proposed Module Integration – TBD.
The composition of the gas entering the module:
Composition (Dry)
Pressure Temperature vol%
psia °F CO2 CO CH4 N2 H2 H2O H2S
435.1 842 15.95 49.75 0.12 1.15 32.55 0.46 0.02
technology advantages
• The novel pre-combustion CO2 capture technology can be used in current gasification plants or future IGCC plants for
industrial H2 production while simultaneously capturing CO2.
• Bettergy’s CMR system offers substantial simplification of the CO2 capture process, reduction in the cost of CO2 capture,
and increased energy efficiency, providing economic and environmental benefits for the general public.
• Microchannel reactors facilitate favorable operating temperature profiles in the reactor.
• Microchannel reactors minimize catalyst loading and limit pressure drop.
• Microchannel reactors provide optimized balance between capital cost and performance.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
454 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
R&D challenges
• Optimizing the formulation of the high-temperature WGS catalyst (as either a layer on an inert porous support, or itself
as the catalytically active porous substrate).
• Preparation of the H2-selective composite zeolite thin layer membrane on the support/substrate.
• Development and optimization of WGS-CMR assemblies.
status
Proof-of-Concept has been successfully accomplished. Tubular and multichannel modules are being developed.
available reports/technical papers/presentations
“Integrated Multichannel WGS Catalytic Membrane Reactor for Pre-Combustion Carbon Capture,” Phase I final
briefing/Phase II kickoff meeting, August 2019.
“Integrated Multichannel WGS Catalytic Membrane Reactor for Pre-combustion Carbon Capture,” Phase l kickoff meeting
presentation, July 2018.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
455
Pre-Combustion Membrane Technologies
Bench-Scale Development of technology maturity:
Bench-Scale, Actual Syngas
a Transformative Membrane (equivalent to 0.015 Mwe)
Process For Pre-Combustion project focus:
CO2 Capture
Polymeric Membranes
participant:
Membrane Technology and
primary project goals Research, Inc.
Membrane Technology and Research, Inc. (MTR) and partners Susteon and the project number:
Energy and Environmental Research Center (EERC) are maturing technology
based on a novel, hydrogen (H2)-selective, multi-layer composite polymer FE0031632
membrane called Proteus™ for use in the separation of H2 from post-shifted
syngas. The current project focuses on the scale-up of a second-generation predecessor projects:
Proteus™ membrane, including fabrication of high-temperature prototype FE0001124
modules using Gen-2 membranes and validating module performance in
laboratory tests. A prototype module test system will be designed, built, and NETL project manager:
installed at EERC for parametric and lifetime testing of the modules with actual
Andy Aurelio
coal-derived syngas. The process will be optimized, and a techno-economic
[email protected]
analysis (TEA) will be updated based upon the results of testing.
principal investigator:
technical goals jay Kniep
Membrane Technology and
• Optimize the Gen-2 Proteus™ membrane and develop modules capable of Research, Inc.
operation up to 200°C. [email protected]
• Demonstrate membrane module performance while processing coal-derived
syngas during a field test at EERC by demonstrating an H2/carbon dioxide partners:
(CO2) selectivity = 30 and recovering 2.5 lb/h H2 at 75% purity at a syngas flow Susteon Inc., Energy and
rate of 20 lb/h. Environmental Research
• Advance the Gen-2 Proteus™ membrane pre-combustion membrane capture Center
technology from Technology Readiness Level (TRL) 4 to TRL 5.
• Optimize processes for integrating membrane modules into the integrated
start date:
gasification combined cycle (IGCC) process with carbon capture (including 10.01.2018
evaluating sulfur treatment options), showing the potential via a TEA to reduce
the cost of capture by more than 30% compared to Selexol. percent complete:
40%
technical content
MTR is developing composite membranes for application in pre-combustion
carbon capture where essential membrane characteristics include high H2/CO2
selectivity and high H2 permeance rates. The MTR composite membrane for H2
separation is called Proteus™. Figure 1 illustrates the membrane structure and
some characteristic composite membrane layers. Note that the key to competitive
industrial performance is a very thin selective layer, which is required to allow high
gas fluxes (or permeances) for given membrane surface areas.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
456 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 1: Proteus™ membrane multi-layer composite structure.
The H2-selective Proteus™ membranes were first developed by MTR in work funded by the U.S. Department of Energy
(DOE; DE-FE0001124). The first-generation membrane (Gen-1 Proteus™) had an upper temperature limit of 150°C.
Semi-commercial modules made from this membrane demonstrated stable operation for extended periods in the
presence of sulfur and other contaminants in slipstream tests of actual coal-derived syngas from an air-blown gasifier at
the National Carbon Capture Center (NCCC). By the end of testing in 2017, Gen-1 Proteus™ was evaluated in more
than 15 different gasification campaigns accumulating 5,500 hours of run time for membrane stamps or lab-scale modules
and 3,625 hours for semi-commercial modules at NCCC.
The recently developed Gen-2 Proteus™ has a higher temperature limit compared to the Gen-1 membrane (200°C versus
150°C), which allows for better heat integration into pre-combustion processes. The Gen-2 membrane also has improved
H2/CO2 selectivity compared to the Gen-1 membrane, with an average value of 32 measured in membrane stamp testing
at NCCC (compared to 15 to 20 for Gen 1 in the same tests). In ongoing work, a new membrane treatment technique
has been developed that improves the membrane H2/CO2 selectivity to 50, which significant exceeds the project success
criteria of 30. This improved selectivity will reduce energy use and the required purification equipment size, thereby
lowering operating and capital expenses.
To highlight the improved permeation performance of the Gen-2 Proteus™ membrane, Figure 2 compares the selectivity
and permeance of this membrane with other polymers on a Robeson tradeoff plot.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
457
Pre-Combustion Membrane Technologies
Figure 2: Robeson plot with Gen-2 Proteus™ membrane performance.
Process Scenarios
A simplified process flow diagram for carbon capture with membranes in an IGCC power cycle is depicted in Figure 3.
Coal is converted by oxygen-based pressurized gasification resulting in a raw syngas. This syngas is shifted via the
water-gas shift (WGS) reaction to produce syngas consisting mostly of H2 and CO2. This shifted syngas is introduced at
the high-pressure feed side of the membrane capture unit. The high-partial pressure driving force, combined with a
nitrogen (N2) sweep on the lower-pressure permeate side of the membrane, causes selective H2 permeation into the N2
sweep, which serves as fuel gas in a combustion turbine. The high-pressure membrane retentate is enriched in CO2 that
can then be further purified, compressed, and sent to storage.
Figure 3: Overall process design for the pre-combustion capture membrane system.
Figure 4 shows additional process details for the MTR pre-combustion CO2 capture process. After using the Proteus™
membrane to recover H2, a series of steps are used to purify CO2. These steps include (1) sulfur removal, (2) gas drying,
(3) refrigeration to produce liquid CO2, (4) additional CO2 recovery with the MTR Polaris™ membrane, and (5) pumping
liquid CO2 to storage pressure. The CO2 purity can be readily increased to greater than 99% in this process. In comparison
to a baseline case (GE Gasifier with two-stage Selexol [i.e., Case 2 of DOE Bituminous Baselines Study]), prior studies
showed that the MTR membrane process provides a 27-megawatt-electric (MWe) net power improvement and a 7.4%
lower cost of energy (COE) using Gen-1 Proteus™ membrane properties. Both the warm (H2 membrane) and cold (CO2
membrane) portions of the MTR process have been validated in independent skid field tests at NCCC.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
458 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 4: MTR dual-membrane process for H2 recovery and CO2 capture in IGCC power generation.
For industrial applications, Proteus™ membranes will be packed into spiral-wound membrane modules, a commonly
used module design for commercial membrane installations. Spiral-wound modules are robust, resistant to fouling, and
economical; they are used in 95% of the reverse osmosis (RO) desalination industry and more than 70% of the membrane
market for CO2 removal from natural gas. Figure 5 shows the general design features of a spiral-wound membrane
module. The module consists of a permeate collection tube with a spiral formation of permeate spacers and feed spacers,
allowing separated H2 to be swept by N2 on the permeate side and CO2 retained on the feed site to flow through the
device. In bench-scale work, modules have membrane area of 1 to 4 m2, and accommodate gas flow of about 50 lb/h.
Commercial modules have membrane area of 20 to 50 m2, and accommodate gas flow of about 500 lb/h.
Figure 5: Schematic diagram of a spiral-wound membrane module.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
459
Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — Proprietary polymers
Materials of Fabrication for Support Layer — Proprietary polymers
Nominal Thickness of Selective Layer µm < 1 micron < 1 micron
Membrane Geometry — Flat sheet Flat sheet
Maximum Trans-Membrane Pressure bar 75 75
Hours Tested without Significant Degradation — 1 month 3 months
Manufacturing Cost for Membrane Material $/m2 500 250
Membrane Performance
Temperature °C 200 200
H2 Pressure Normalized Flux GPU 225 200
H2/H2O Selectivity — 0.4 0.4
H2/CO2 Selectivity — 50 30
H2/H2S Selectivity — >50 50
Sulfur Tolerance ppm Inert to Sulfur Inert to Sulfur
Type of Measurement — mixed-gas mixed-gas
Proposed Module Design
Flow Arrangement — Spiral-wound modules
Packing Density m2/m3 1,000
Shell-Side Fluid — Syngas
Syngas Gas Flowrate kg/hr 717,000
CO2 Recovery, Purity, and Pressure %/%/bar 90 99.5 152.7
H2 Recovery, Purity, and Pressure %/%/bar 99.4 44 % in N2 as fuel 30
Pressure Drops Shell/Tube Side bar feed: 1 /sweep: 1
Estimated Module Cost of Manufacturing and __$__
kg/hr 15
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for
mixture of gases found in syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (syngas) stream.
Estimated Cost – – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
460 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Permeation through the Proteus™ membrane occurs by the passive solution-
diffusion mechanism.
Contaminant Resistance – The MTR membranes and membrane module components are compatible with the species
found in coal-derived syngas. This is one of the major findings from syngas field tests conducted at NCCC between 2009
and 2017 for both the Polaris™ (5,200 cumulative hours online) and Proteus™ (9,125 cumulative hours online)
membranes.
Syngas Pretreatment Requirements – The MTR pre-combustion CO2 capture membrane process design does not
require syngas pretreatment.
Membrane Replacement Requirements – The target membrane module lifetime is three years, which is at the conservative
end of the typical industrial gas separation module lifetime of three to five years.
Waste Streams Generated – No additional waste streams are generated when adding the MTR pre-combustion CO2
capture system to an IGCC process. Similar to the stand-alone IGCC process, water removed from the MTR process
can be recycled to process demand and the removed sulfur species can be sent to a Claus plant for processing. The
high-purity CO2 product can be used for enhanced oil recovery or other industrial applications.
technology advantages
• The Proteus™ membrane allows separation of H2 from syngas at elevated temperatures. This ability to operate
warm/hot reduces the need for heat exchange (e.g., membrane modules operate at a higher temperature than
conventional acid gas removal processes like Selexol, reducing the need for syngas cooling and water condensation).
• A membrane system does not contain moving parts or involve chemical reactions, making it simple to operate and
maintain.
• The membrane material has a high tolerance to acid gases and is inert to all primary syngas species.
• The membrane capture system has a compact footprint and low energy cost.
• The membrane capture system permeates water in syngas (increase mass to turbine and reduces CO2 dehydration
costs).
• Membrane modules downstream from pressurized WGS maintain CO2 effluent at pressure; therefore, less
compression of CO2 product is required compared to conventional acid gas removal processes.
• The proposed N2 sweep on the H2 permeate side increases the partial-pressure driving force for separation and
decreases the required membrane area.
R&D challenges
• Countercurrent sweep module design could result in several potential inefficiencies, including sweep-side pressure
drop, concentration polarization, poor utilization of the membrane area due to module geometry, and non-
countercurrent flow patterns.
• Feed and permeate side pressure drops could lead to excessive energy losses if modules are not designed properly.
• Membrane module cost reductions will be needed if the technology is to become economically viable.
• Scale-up and integration issues are a possibility given the large number of membranes needed to service a 550-MWe
plant.
status
A second-generation Proteus™ membrane has been made with performance that exceeds H2/CO2 selectivity targets,
and robust membrane module components have been identified for use in syngas environments at high temperatures.
Development work underway includes mixed-gas module testing at MTR and fabrication of a field test skid for prototype
commercial-scale module testing on oxygen-blown, gasifier-produced syngas at EERC.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
461
Pre-Combustion Membrane Technologies
available reports/technical papers/presentations
“Bench-Scale Development of a Transformative Membrane Process for Pre-Combustion CO2 Capture,” presented by
Jay Kniep, Membrane Technology and Research, Inc., 2019 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2019.
“Bench-Scale Development of a Transformative Membrane Process for Pre-Combustion CO2 Capture,” presented by
Jay Kniep, Membrane Technology and Research, Inc., 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018.
“Bench-Scale Development of a Transformative Membrane Process for Pre-Combustion CO2 Capture,” Project kick-off
meeting presentation, December 2018.
“Novel Polymer Membrane Process for Pre-combustion CO2 Capture from Coal-fired Syngas,” Final Report for DE-
FE0001124, Membrane Technology and Research, Inc., December 2011.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
462 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Development and Testing of a technology maturity:
High-Temperature PBI Hollow-
Bench-Scale, Actual Syngas
(equivalent to 50 kWth)
Fiber Membrane Technology project focus:
for Pre-Combustion CO2
PBI Polymer Membrane
Capture
participant:
SRI International
project number:
primary project goals
FE0031633
SRI’s overall goal is to develop a technically and economically viable carbon
predecessor projects:
dioxide (CO2) capture system based on a high-temperature polybenzimidazole
FC26-07NT43090; FE0012965
(PBI) polymer hollow-fiber membrane separation technology. This is intended for
deployment at elevated temperatures to separate hydrogen (H 2) and CO2 in shifted
NETL project manager:
syngas, enabling pre-combustion carbon capture in integrated gasification
Andrew Jones
combined cycle (IGCC) power plants. Current project goals are to extend previous
[email protected]
work on PBI hollow-fiber membranes and bench-scale test skids with second-
generation (Gen-2) fibers having improved selectivity. These are to be deployed in principal investigator:
bench-scale testing on actual coal-derived syngas from an oxygen-blown gasifier. Indira Jayaweera
Results are to demonstrate if Gen-2 PBI-based hollow-fiber membranes provide a SRI International
pathway to achieving the U.S. Department of Energy’s (DOE) pre-combustion [email protected]
capture targets.
partners:
Enerfex, Inc., PBI
technical goals
Performance Products,
University of Kentucky
Produce at least 100 kilometers of Gen-2 fibers that provide an H 2/CO2 Research Foundation
selectivity of about 40 and H2 permeance of 80 to 120 gas permeation units
(GPU) at greater than 150°C at a 150 pounds per square inch (psi) pressure start date:
differential. 10.01.2018
Modify the existing 50-killowatt-thermal (kWth) bench-scale test skid
(fabricated and used in FE0012965) with Gen-2 hollow-fiber modules of 4- to percent complete:
6-inch diameter, and complete bench-skid acceptance testing for 50 hours 40%
achieving H2/CO2 selectivity greater than 35.
Perform bench-scale testing at temperatures ≈225°C and up to a pressure of 30
bar under various operating conditions, including long-term steady-state
conditions using actual coal-derived syngas (throughput equivalent to 50 kWth)
from the entrained flow oxygen-fed gasifier at the University of Kentucky’s Center
for Applied Energy Research (CAER).
Prepare techno-economic analysis (TEA) based on latest Gen-2 bench-scale
testing results to re-evaluate technology performance to achieve DOE’s pre-
combustion capture targets.
technical content
SRI’s PBI membrane-based technology is being developed for high-temperature
pre-combustion separation of H2 from shifted syngas, leaving a high-
concentration, high-pressure CO2-rich stream in the retentate and yielding a high
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
463
Pre-Combustion Membrane Technologies
H2-content permeate stream. SRI’s membranes are asymmetric hollow-fiber PBI (molecular structure of the polymer
shown in Figure 1), which is chemically and thermally stable at temperatures up to 300°C and pressures up to 55
atmospheres (atm; 800 pounds per square inch gauge [psig]). PBI membranes are also sulfur tolerant. These characteristics
permit the use of the PBI membrane for CO2 capture downstream of a sour water-gas shift (WGS) reactor without requiring
further gas cooling before the PBI membrane, significantly increasing plant efficiency. In addition, the CO 2 is recovered at
high pressure, decreasing CO2 compression requirements.
Figure 1: m-polybenzimidazole molecular structure.
Single-bore PBI-based hollow fibers have been shown to be highly durable, with near-constant levels of permeability and
selectivity over the course of 330 days while in the presence of H2, carbon monoxide (CO), methane (CH4), nitrogen (N2),
CO2, and hydrogen sulfide (H2S) at 250°C. Therefore, PBI fiber modules can be successfully used in pre-combustion CO 2
capture applications.
PBI-based hollow fibers, as seen in various magnified views in Figure 2, offer a considerable advantage over coated
stainless-steel tubes. They require as much as 24 times less membrane surface area and 305 times less membrane volume
when using a 0.1 to 0.5 micrometer separation layer (the dense layer). Ease of large-scale manufacturability, high packing
density, and the cost are notable advantages of hollow-fiber membrane systems.
Figure 2: PBI hollow-fiber membranes and details of physical structure.
Fiber Fabrication and Modules
Hollow-fiber membrane fabrication is accomplished in a spinning line as depicted in Figure 3. An important part of
technology maturation involves improvements in fiber spinning technology enabling an improved and robust spinning
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
464 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
process that can be transferred to industry. Improvements in the spinning line have enabled use of multiple coagulation
solvents, increased productivity (one-gallon reservoir size), process monitoring and data collection, precise flow controls
and draw ratios, optimization of fiber diameter, and optimization of the fiber dense-layer thickness.
SRI has been improving its developed protocols to enable spinning <0.3-μm dense layer hollow-fiber membranes with
membrane OD 450 to 650 μm. Figure 2 includes photographs of a hollow-fiber membrane well within this range, with
~0.1-μm dense layer fibers having ~600-μm OD. Optimization of OD and dense layer has been supported through testing
of more than 100 fiber bundles (1-inch). Fabrication of the Gen-1 hollow-fiber membrane with a very thin, dense layer
(<0.3 μm) in kilometer lengths has been accomplished with very good reproducibility. In previous work, more than 100
kilometers of Gen-1 fibers have been spun for both Generon and SRI modules (4-inch diameter size fiber modules). In
latest work, more than 10 kilometers of the improved performance Gen-2 fibers have been produced so far for
deployment in the new modules to be used in upcoming testing at the University of Kentucky’s CAER.
Figure 3: SRI hollow-fiber membrane spinning line.
Large bundles of hollow fibers are potted in tube sheet modules (currently in 4- or 6-inch diameters), which can then be
assembled into larger-scale gas separation units/skid for process implementation. Figure 4 shows the cross-section of an
actual 4-inch fiber module as fabricated at SRI (on the left); these are the type that had been incorporated in the bench-
scale skid, which was deployed in past testing at the National Carbon Capture Center (NCCC) on a syngas slip stream. SRI
fiber modules are designed for easy fabrication, easy handling, and easy drop-in replacement. A new tube sheet module
design is being deployed (images on right side of Figure 4). These will enable faster module swapping and reduced gas
bypass characteristics.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
465
Pre-Combustion Membrane Technologies
Figure 4: Potted module cross-section (left-most); new tube sheet module design (right).
Testing Results
Results of testing PBI modules at NCCC on air-blown gasifier syngas have established performance characteristics of both
the Gen-1 and Gen-2 PBI modules. Specifically, membrane element TS-1 (consisting of SRI Gen-1 fibers having GPU ~150,
H2/CO2 selectivity ~25 at 150°C) was tested for about 500 hours. Membrane element TS-2 (consisting of SRI Gen-2 fibers
having GPU ~100, H2/CO2 selectivity ~40 at 200°C, and at 200 psi) was tested for 48 hours. Figure 5 plots selectivity results
of various testing runs for both Gen-1 and Gen-2 testing campaigns. Selectivity of Gen-2 shows definite improvement
with potential for superior performance at target operating temperatures of ~200°C. Taken with gas permeance
measurements (Figure 6), the Gen-2 modules evidence significant performance advantages over Gen-1.
Figure 5: Comparison of measured H2/CO2 selectivity for Gen-1 and Gen-2 PBI modules.
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Figure 6: Measured H2 and CO2 permeances for the Gen-2 module at varying temperatures under a pressure differential of 145 to 155 psi.
Preliminary Techno-Economic Analysis Findings
SRI has previously made estimations of cost of electricity (COE) reductions that should be possible by application of the
PBI membrane technology in process implementation in the context of an IGCC power plant cycle. From testing of Gen-
1 and Gen-2 membranes, performance parameters have been quantified. Given expected Gen-1 and Gen-2 gas
selectivities and different gas permeance assumptions, it is possible that the PBI membrane technology can meet National
Energy Technology Laboratory (NETL) targets, assuming the membrane system has capital cost reductions that are
expected to emerge in industrial-scale economies and savings associated with high levels of system optimization, which
are anticipated as higher Technology Readiness Levels (TRLs) are attained.
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TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer PBI PBI
Materials of Fabrication for Support Layer PBI PBI
Nominal Thickness of Selective Layer m 0.3–2 <0.5
Membrane Geometry hollow fiber hollow fiber
Max Trans-Membrane Pressure bar ≈14 >20
Hours Tested without Significant Degradation hr. 1,000 1,000
Manufacturing Cost for Membrane Material $/m2 30–80 TBD
Membrane Performance
Temperature °C 200–250 225
H2 Pressure Normalized Flux GPU or equivalent 80–120 80–120
H2/H2O Selectivity — <1 <1
H2/CO2 Selectivity (Dense layer thickness) — 40 (>1 µm) and 22 (<0.3 µm) 40 (<0.3 µm)
H2/H2S Selectivity (Dense layer thickness) — >200 (>1 µm) >200 (<0.3 µm)
Sulfur Tolerance ppm 300 300
Type of Measurement pure and mixed mixed gases
Proposed Module Design (for equipment developers)
Flow Arrangement countercurrent
Packing Density m2/m3 >3,000
Shell-Side Fluid retentate or permeate
Syngas Flowrate kg/hr 22
CO2 Recovery, Purity, and Pressure %/%/bar TBD
H2 Recovery, Purity, and Pressure %/%/bar >98%, >49%, 30 bar
Pressure Drops Shell/Tube Side* bar <0.007/0.03
Estimated Module Cost of Manufacturing and __$__
—
Installation kg/hr
*A commercial 4-inch module design with 200 µm bore diameter and 28–48 bar feed pressure was assumed.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm 3 (1 atm, 0 °C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for
mixture of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
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Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Molecular sieving and activated diffusion.
Contaminant Resistance – PBI is resistant to acidic contaminants.
Syngas Pretreatment Requirements – Tar removed.
Membrane Replacement Requirements – Required frequency of membrane replacement to be determined.
Waste Streams Generated – Gaseous waste stream generated includes CO2 and H2S separated from the syngas. This
stream will be further treated to remove H2S.
Process Design Concept – Flowsheet/block flow diagram is shown in Figure 7. Note that the PBI hollow-fiber membrane
is both a water and H2 transporting membrane, so most water vapor/steam in the shifted syngas will segregate into the
permeate stream along with the H2.
Figure 7: Flowsheet/block flow diagram showing PBI membrane module integration in the IGCC plant process.
Proposed Module Integration – Module design is tubular with 4-inch diameter and 36-inch length. Figure 8 shows the
simulated module performance: the pressure, temperature, and composition of the gas entering the module, assuming
H2/CO2 selectivity of 40. Note that the module feed gas is from an oxygen-blown gasifier with a shifted syngas feed to
the membrane. In an oxygen-blown gasifier (assumed in TEA), the permeate recovers 98.4% of the feed H 2 and the
retentate captures 90% of the feed CO2. The retentate stream is further processed in a Claus plant to remove H2S and a
catalytic oxidizer to convert CO and CH4 to CO2 and H2 to water (H2O). The final retentate dry basis CO2 purity is 96.88%.
The composition of the gas entering the module:
Composition
Pressure Temperature vol%
psia °F CO2 CO CH4 N2 H2 H 2O H2 S
691.1 437 31.01 0.67 0.07 0.96 43.83 22.99 0.47
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N2 sweep at 30 psia
% slpm
N2 100.00 133.52
Feed at 691.6 psia Permeate at 30 psia
% slpm % slpm
CO2 31.01 218.82 CO2 3.54 21.96
CO 0.67 4.73 CO 0.03 0.19
CH4 0.07 0.49 CH4 0.00 0.01
N2 0.96 6.77 N2 0.05 0.29
H2 43.83 309.28 H2 49.10 304.44
H2O 22.99 162.23 H2O 25.75 159.69
H2S 0.47 3.32 H2S 0.00 0.01
Retentate at 691.1 psia
100.00 705.64 N2 swp 21.53 133.52
% slpm
100.00 620.11
CO2 89.87 196.86
CO 2.07 4.54
CH4 0.22 0.48
N2 2.96 6.48
H2 2.21 4.84
H2O 1.16 2.54
Membrane parameters: H2S 1.51 3.31
H2 permeance = 80 GPU 100.00 219.05
H2/CO2 Selectivity = 40
Dense layer thickness = 1.0 µm
Membrane area = 8.5 m2
Operating parameters:
Feed temperature = 437°F
50 kWth Shifted Syngas Feed
Permeate H2 recovery = 98.4%
Retentate CO2 capture* = 90.0%
* Retentate CO2 dry basis purity = 96.88% after H2S removal and catalytic oxidation of CO, H2 and CH4
Figure 8: Simulation of a PBI module performance with an oxygen-blown gasifier and a 50-kWth shifted syngas feed.
technology advantages
PBI combines both useful throughput (permeability) and degree of separation (selectivity).
PBI is thermally stable up to 300°C and is sulfur tolerant.
PBI asymmetric hollow fibers can be fabricated at increasingly small diameters, allowing increased fiber packing
densities in modules realistically consistent with 7,000 m2 of membrane surface area per m3 of module volume.
Membrane gas separation systems have reduced costs for syngas cooling.
Membrane gas separation systems should result in reduced CO 2 compression costs.
Membrane gas separation systems are emissions-free (i.e., they use no solvents such as amines).
Membrane gas separation systems may have decreased capital costs (assuming membrane costs are managed).
Membrane gas separation systems have relatively low maintenance demands.
Membrane gas separation systems are scalable and modular.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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470 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Pre-Combustion Membrane Technologies
R&D challenges
Maintaining fiber and module fabrication quality/performance (avoiding membrane pinholes, macrovoids; module seal
integrity) in scale-up/transfer of technology to larger-scale manufacturing.
Designing and synthesizing materials structure and configurations.
Integration and optimization of membrane-based CO 2 separation systems in coal gasification-based plants.
status
SRI is currently refurbishing the bench-scale test skid for eventual deployment at CAER and a long-term test campaign of
Gen-2 modules on oxygen-blown gasifier syngas. Large quantities of Gen-2 fibers are being spun for incorporation in the
larger Gen-2 modules required. New module designs are being developed for improved module handling and
performance.
available reports/technical papers/presentations
“Development and Testing of a High-temperature PBI Hollow-fiber Membrane Technology for Pre-combustion CO 2
Capture,” presented by Elisabeth Perea, SRI International, 2019 Carbon Capture, Utilization, Storage, and Oil and Gas
Technologies Integrated Review Meeting - Capture and Utilization Sessions, Pittsburgh, PA, August 2019.
“Development and Testing of a High-temperature PBI Hollow-Fiber Membrane Technology for Pre-Combustion CO 2
Capture,” presented by Indira Jayaweera, SRI International, Final Project Review (FE0012965) and Project Kickoff
(FE0031633), January 2019.
“Development and Testing of Polybenzimidazole (PBI) Hollow-Fiber Membrane Technology for Pre-Combustion CO 2
Capture (FE0031633),” presented by Indira Jayaweera, SRI International, 2018 NETL CO 2 Capture Technology Project
Review Meeting, Pittsburgh, PA, August 2018.
“Development of a Pre-Combustion CO2 Capture Process Using High-Temperature PBI Hollow Fiber Membranes,”
presented by Indira S. Jayaweera, SRI International, 2017 NETL CO 2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2017.
“Development of Pre-Combustion CO2 Capture Process Using High-Temperature PBI Hollow-Fiber Membranes (HFMs),”
presented by Indira S. Jayaweera, SRI International, 2016 NETL CO 2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2016.
“Development of Pre-Combustion CO2 Capture Process Using High-Temperature PBI Hollow-Fiber Membranes,” presented
by Indira S. Jayaweera, SRI International, 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
“Development of a Pre-Combustion Carbon Dioxide Capture Process Using High Temperature Polybenzimidazole Hollow-
Fiber Membrane,” presented by Gopala Krishnan, SRI International, 2014 NETL CO 2 Capture Technology Meeting,
Pittsburgh, PA, July 2014.
“Development of a Pre-Combustion Carbon Dioxide Capture Process Using High Temperature Polybenzimidazole Hollow-
Fiber Membrane Fact Sheet,” July 2014.
“Development of a Pre-Combustion CO2 Capture Process Using High-Temperature PBI Hollow-Fiber Membranes,” Project
Kickoff Meeting Presentation, Pittsburgh, PA, June 9, 2014.
Krishnan, G.; Steele, D.; O’Brien, K.; Callahan, R.; Berchtold, K.; and Figueroa, J., “Simulation of a Process to Capture CO 2
From IGCC Syngas Using a High Temperature PBI Membrane,” Energy Procedia, Volume 1, Issue 1, February 2009, pp.
4079-4088.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
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Pre-Combustion Membrane Technologies
Gopala Krishnan; Indira Jayaweera; Angel Sanjurjo; Kevin O'Brien; Richard Callahan; Kathryn Berchtold; Daryl-Lynn
Roberts; and Will Johnson,” Fabrication and Scale-up of Polybenzimidazole (PBI) Membrane Based System for
Precombustion-Based Capture of Carbon Dioxide,” DOE Contract Number: FC26-07NT43090, 2012-March 31.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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472 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Pre-Combustion Membrane Technologies
High-Temperature Ceramic- technology maturity:
Laboratory-Scale, Simulated
Carbonate Dual-Phase Syngas (0.25 kg per day
equivalent to 0.007 kwth)
Membrane Reactor for Pre- project focus:
Combustion Carbon Dioxide Ceramic-Carbonate Dual-
Capture
Phase Membrane Reactor
participant:
Arizona State University
primary project goals
project number:
Arizona State University (ASU), in collaboration with the University of South
FE0031634
Carolina (USC), seeks to develop technology for a high-temperature, high-
pressure, ceramic-carbonate dual-phase (CCDP) membrane reactor in this project. predecessor projects:
The reactor is intended to perform the water-gas shift (WGS) reaction on syngas
N/A
(maximizing hydrogen [H2] content of the syngas) while simultaneously separating
a high-purity carbon dioxide (CO2) stream from the reactor for capture. Project NETL project manager:
goals include designing and fabricating CCDP membranes with improved CO2 Andrew O'Palko
permeance and mechanical strength for testing in a lab-scale reactor with [email protected]
simulated coal-derived syngas. The results will inform a mathematical model used
to support process design and a techno-economic analysis (TEA) for a scenario of principal investigator:
incorporation of a CCDP membrane reactor in a full-scale integrated gasification jerry Lin
combined cycle (IGCC) plant. Arizona State University
[email protected]
technical goals partners:
University of South Carolina
• Synthesize chemically and thermally stable CCDP membranes with CO2
permeance greater than 2,000 gas permeation units (GPU) (6.5x10-7 start date:
mol/m2∙s∙Pa), CO2/H2 selectivity greater than 500, and resistant to poisoning 10.01.2018
from hydrogen sulfide (H2S) to the extent that CO2 flux drops less than 5% after
24 hours of exposure to typical levels of H2S. percent complete:
• Fabricate tubular CCDP membrane modules suitable for lab-scale WGS reactor 40%
operation (i.e., functional and durable at temperatures in excess of 700°C) and
at pressures in excess of 20 atmosphere (atm), and experimentally verify
performance at simulated syngas flow rate of 0.25 kg per day equivalent to
0.007 kilowatt-thermal (kWth).
• Determine CCDP membrane WGS reactor process conditions/protocols
enabling 99% carbon monoxide (CO) conversion for the WGS reaction, 90% CO2
recovery, 99% purity of the CO2 permeate stream, and 90% purity of the H2
retentate stream.
technical content
The working hypothesis of this project is that the conventional WGS unit found in
a coal gasification-based power plant (for shifting the syngas toward primarily H2
and CO2) and downstream conventional amine absorption unit for capturing the
CO2 from the shifted syngas could be replaced, in whole, by a novel WGS shift
reactor that integrates CO2-selective CCDP membranes and WGS catalyst. Within
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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the CCDP membrane WGS reactor, CO2 would be withdrawn directly from the reaction chamber, efficiently increasing the
driving force for the WGS reaction to completion. As such, the multiple stages of the conventional WGS unit are replaced
by a single, elegantly performing reactor. This process concept, with the unified CCPD membrane reactor (depicted in
callout) replacing the multistage conventional WGS process and amine absorption unit (both within red dotted line), is
depicted in Figure 1.
Figure 1: CCDP membrane reactor for WGS reaction and CO2 capture in context of coal gasification plant cycle.
CCDP membranes are composed of a porous ceramic phase as the structural support matrix, infiltrated with a molten
carbonate phase, as illustrated in Figure 2. At working temperatures of 600 to 900°C, the CCDP membrane possesses
extremely high CO2 selectivity and high CO2 permeance.
Figure 2: Physical structure of CCDP membrane.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Pre-Combustion Membrane Technologies
Scanning electron microscopy (SEM) images of actual CCDP membranes are shown in Figure 3. Note that the bright areas
in the SEM images are the ceramic phase, while dark zones consist of carbonate mixture. These illustrate the formation
of a dense, highly gas-tight dual-phase membrane, which has been verified by pre- and post-infiltration gas permeation
measurements.
Figure 3: SEM images of CCDP membrane cross-section at 250x (left) and 1,000x (right).
The high selectivity and permeance for CO2 in the CCDP membrane are a result of the electrochemical transport
mechanism illustrated in Figure 4. At elevated process operating temperatures, CO2 tends to form carbonate ions (CO32-)
by combining with oxygen ions (O2-), the latter readily transporting through the ionically conducting ceramic phase in the
membrane. At the same time, carbonate ions readily transport through the molten carbonate phase in the opposite
direction. Syngas on the feed side is at high pressure, resulting in high partial CO2 pressure on that side. The permeate
side is at ambient pressure (and possibly swept), resulting in low partial CO2 pressure. The CO2 partial pressure differential
provides the driving force for the ionic transport behavior in the membrane. High CO2 permeance values are expected
for the CCDP membrane if the functional layer is made of suitably thin (10 to 100 µm) ceramic with high oxygen ionic
conductivity.
Figure 4: CO2 separation mechanism in CCDP membrane.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Pre-Combustion Membrane Technologies
The novel choice of ceramic-carbonate membrane in a WGS reactor overcomes various problems observed with possible
alternatives. Theoretically, H2 could be removed from the WGS reactor through H2-selective membranes, which would
also constitute removal of product of the WGS reaction to drive conversion forward to completion. Inorganic membranes
with good H2 perm-selectivity at high temperatures do exist, and include amorphous microporous carbon, amorphous
silica, microporous crystalline zeolite, and dense perovskite-type proton-conducting ceramics. However, all of those
choices are hampered by one or more serious issues, including insufficient H2 permeance (particularly at the elevated
temperatures involved in the WGS reactor), poor H2 stability, poor hydrothermal stability, and membrane fabrication
difficulty and high cost, which translate into high costs for a membrane WGS reactor solution. Finally, organic membranes
of any type are simply incapable of application at the high operating temperatures involved. Considering these
shortcomings, a CO2-selective ceramic-carbonate membrane offers a favorable choice for this application.
An important aspect of technology development for the CCDP membrane concerns optimizing the choices of ceramic
and carbonate materials deployed in the membrane, characterization of membrane morphologies and properties, and
membrane fabrication. For the ceramic phase of the membrane, desired characteristics include high ionic conductivity,
long-term chemical stability in presence of characteristic syngas species and contaminants (particularly H2S), compatibility
with molten carbonate, and controllability of pore size and porosity.
ASU has previously investigated several ceramics for application in the CCDP membrane. The ceramics are in the family
of perovskite- or fluorite-structured metal oxides with oxygen vacancy defects:
• La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)
• Yttria-stabilized zirconia (YSZ)
• La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)
• Ce0.8Sm0.2O2-δ (Samarium Doped Ceria-SDC). Note: Figure 3 SEM images are of an SDC-based membrane.
• Bi1.5Y0.3Sm0.2O3 (BYS)
In ongoing developmental work, improved materials are being sought, mainly to deliver improved CO2 permeances and
improved stability to H2S. ASU is currently evaluating Sc2O3-doped ZrO2 (ScSZ) as the preferred material for the
membrane’s ceramic phase; it avoids the tendency to form compounds with sulfur that is characteristic of cerium (Ce)-
containing ceramics. Fabrication methods are being optimized to deliver the desired microstructure. The
ethylenediaminetetraacetic acid (EDTA)-citric acid method is effective; this involves dissolving Sc2O3 in nitric acid and
mixing with ZrO(NO3)2, to which EDTA and citric acid are added to the stirred solution in sequence. The solution is pH
adjusted and then heated until a clear, viscous gel is formed after water evaporation. The gel is dried and calcined,
resulting in almost pure-phase ScSZ with good microstructure.
Tubular membranes for incorporation in modules are formed by establishing thin layers on suitable supports. The ScSZ-
based CCDPs are established on BYS support tubes by dip coating them in ScSZ slurry, sintering, and infiltrating the
molten carbonate (MC). Essential steps are diagrammed in Figure 5.
Figure 5: Tubular CCDP membrane fabrication.
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Pre-Combustion Membrane Technologies
For the molten carbonate phase, mixtures of common alkali metal carbonates (i.e., Li2CO3/Na2CO3/K2CO3) have been
found to be suitable. Varying ratios of the alkali metal carbonates have been evaluated (e.g., a Li/Na/K ratio of 43.5/31.5/25
offers both relatively low melting point [less than 400°C] and good carbonate ion conductivity [1.24 S/cm]). In current
work, a binary eutectic mixture of 52% Li2CO3 and 48% Na2CO3 is being used with the ScSZ ceramic.
An apparatus for characterizing CCDP membrane performance has been developed and is operated in laboratory-scale
work, as depicted in Figure 6. Synthetic syngas can be mixed up and flowed to the tubular reactor module enclosed in a
high-temperature furnace, while resulting gas compositions of permeate and retentate can be measured in a gas
chromatograph. The fabrication of the tubular membrane reactor module itself is a challenge (see enlarged view of the
reactor in Figure 6), with a notable point of development concerning seals able to withstand the high-targeted operating
pressures and temperatures.
Figure 6: Laboratory-scale apparatus for CCDP membrane CO2 permeation studies.
With this test bed, various experiments and evaluations are possible, which provide invaluable data for optimizing
membrane and module materials and fabrication methods. For example, the reactor module with SDC ceramic infiltrated
with Li2CO3/Na2CO3/K2CO3 carbonate mixture was evaluated under the following test conditions:
• Temperature: 800 to 900°C.
• Feed and sweep side pressure: 1 atm.
• Simulated syngas: 49.5% CO, 36% CO2, 10% H2, 4.5% N2.
• Feed-side flow rate: syngas 10 to 30 mL/min and N2 10 mL/min.
• Steam to CO molar ratio: 1.0-3.0.
• Sweep-side flow rate: He 60 mL·min-1.
Results of CO conversion as a function of temperature, syngas flow rate, and ratio of steam to CO are shown in Figure 7,
along with behavior of CO conversion, CO2 permeation, and flux over long-term steady-state operation.
Also, the test bed allows long-term testing to evaluate changes to morphology of CCDP that may occur. For example,
Figure 8 shows surfaces on both sides of a tubular membrane after long-term testing.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Figure 7: Measurements from tubular CCDP modules in high-temperature WGS testing.
Figure 8: SEM images of CCDP surfaces after long-term WGS testing—sweep side (left); reaction side (right).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Ce0.8Sm0.2O2-δ(SDC)- Sc-doped ZrO2 (ScSZ)
Materials of Fabrication for Selective Layer — (42.5/32.5/25 Li/Na/K)2CO3 (42.5/32.5/25 Li/Na/K)2CO3
(MC) (MC)
Materials of Fabrication for Support Layer — BYS BYS
Nominal Thickness of Selective Layer µm 1,500 50-200
Membrane Geometry — tubes tubes
Maximum Trans-Membrane Pressure bar 1 30
Hours Tested without Significant Degradation hour 120 >200
Manufacturing Cost for Membrane Material $/m2 1,000 500
Membrane Performance
Temperature °C 700-900 700-900
CO2 Pressure Normalized Flux GPU 300-600 >2,000
CO2/H2O Selectivity — >500 >500
CO2/H2 Selectivity — >500 >500
CO2/H2S Selectivity — >500 >500
Sulfur Tolerance ppm <5 ppm >400 ppm
Type of Measurement — mixed-gas mixed-gas
Proposed Module Design
Flow Arrangement — Counter-current
Packing Density m2/m3 50-200
Shell-Side Fluid — Retentate, H2-rich flow
Syngas Gas Flowrate kg/hr 0.005-0.01
CO2 Recovery, Purity, and Pressure %/%/bar 90 99 ~1
H2 Recovery, Purity, and Pressure %/%/bar 99 90* ~ 10
Pressure Drops Shell/Tube Side bar 10-30
Estimated Module Cost of Manufacturing and __$__
kg/hr ~1,000
Installation
* Gasifier, coal feedstock, and upstream unit operation (e.g., syngas pretreatment) specifications dependent.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivity should be for mixture
of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
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Pre-Combustion Membrane Technologies
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate or retentate (syngas) stream.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – At temperatures above 600oC, the separation of H2 and CO2 through CCDP
membranes is governed by ionic transport of carbonate ion in MC phase in meso/macropores and oxygen ion in the
ceramic phase support.
Contaminant Resistance – The developed CCDP membranes have resistance to syngas contaminants such as H2S.
Syngas Pretreatment Requirements – Particulate removal is required.
Membrane Replacement Requirements – The multiple-tube membrane bundle is intended to operate in the membrane
reactor continuously over 1,000 hours without replacement.
Waste Streams Generated – There are no waste streams generated in the flowsheet. All potential waste streams are
recycled and used in the process somewhere.
Process Design Concept –
Proposed Module Integration – The composition of the gas mixture is assumed:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H2O H2S
435 1500 11.6 26.7 0.08 2.8 25.7 33.6 >400
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
480 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
technology advantages
• The membrane reactor process could replace a conventional two-stage WGS reactor system requiring intercooling and
a separate CO2 capture unit, with a single WGS membrane reactor unit with potential for energy efficiency increase
and equipment cost savings.
• WGS reactors containing CO2-selective membranes to recover CO2 have potential to achieve higher H2 delivery to the
turbine in an IGCC cycle than if H2 were being selectively recovered from the syngas stream.
• Carbon dioxide removal through a membrane process in a WGS reactor retains the H2 at high pressure, maximizing
the efficiency of the combustion turbine in an IGCC cycle.
• Tubular membranes can be fabricated into robust and stable multiple-tube modules at a high packing density.
R&D challenges
• Loss of carbonate from CCDP at high temperatures (especially loss of lighter Li2CO3).
• Gas leakage through membrane from unsealed pores (imperfect carbonate infiltration).
• High-temperature stability of membrane bundle components and seals.
• Deterioration of strength of membrane tubes in use.
• CCDP thermal stability, poison resistance, and product selectivity maintained at high pressures (greater than 20 atm)
and temperatures (700 to 900°C).
• Removal of particulate matter from the hot syngas to reduce its potential impact on the membrane lifetime.
• Cost reductions for the membrane module materials if the technology is to become economically viable.
status
A laboratory-scale module of the high-temperature and high-pressure CCDP-based WGS membrane reactor has been
successfully fabricated, which involved development of new seals to avoid leakage. SDC tubular membranes have been
fabricated at 11 cm length, and their CO2 permeation fluxes were measured at high temperatures. The new ScSZ-based
CCDP membrane disks were fabricated and tested, with CO2 permeance at 650oC measured at 1,200 GPU.
available reports/technical papers/presentations
“High-Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-Combustion Carbon Dioxide Capture,”
presented by Oscar Ovalle-Encinia, Arizona State University, 2019 NETL CO2 Capture, Utilization, Storage, and Oil & Gas
Technologies Integrated Review Meeting, Pittsburgh, PA, August 2019.
“High Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-Combustion Carbon Dioxide Capture,”
Kick-off meeting presentation, November 2018.
“High Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-combustion Carbon Dioxide Capture,”
presented by Lie Meng, Arizona State University, 2018 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2018.
M Anderson & YS Lin, Proc. ICIM 2006, pp. 678-681 (2006); J. Membr. Sci. 357, 122 (2010).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
481
Pre-Combustion Membrane Technologies
Transformational Membranes technology maturity:
for Pre-Combustion Carbon
Laboratory-Scale, Simulated
Syngas (equivalent to 0.58
Capture
kWe)
project focus:
Amine-Containing
primary project goals Polymeric Membranes
Ohio State University (OSU) will develop cost-effective design and fabrication participant:
methods for a novel amine-containing membrane to capture carbon dioxide (CO 2) Ohio State University
from coal gasification-derived syngas. The membrane is to be used in a single-
stage membrane process utilizing modules in commercial spiral-wound project number:
configuration with a minimal pressure drop. Work towards optimization and scale- FE0031635
up of transformational membranes with high CO2/hydrogen (H2) selectivity and
CO2 permeance, along with testing of spiral-wound membrane modules using predecessor projects:
simulated syngas, will make progress towards CO2 capture with improved N/A
performance to meet U.S. Department of Energy (DOE) targets for cost of
electricity and efficiency in advanced power generation plants. NETL project manager:
David Lang
[email protected]
technical goals
principal investigator:
Synthesize and characterize membranes, scale-up the best performing W. S. Winston Ho
membrane using a continuous roll-to-roll fabrication method, and fabricate at Ohio State University
least nine prototype membrane modules, each with an approximate membrane [email protected]
area of 800 cm2.
Establish module stability by testing of the modules at 31.7 bar and 107°C for
partners:
at least 200 hours on simulated syngas at 34 standard liter per minute (slpm) American Electric Power
flowrate. Microdyn-Nadir US Inc.
Enable CO2 capture at 95% CO2 purity, with greater than 99% H2 recovery from start date:
syngas.
10.01.2018
Optimize processes for integrating membrane modules into integrated
gasification combined cycle (IGCC) with carbon capture, showing potential via percent complete:
techno-economic analysis (TEA) to reduce the cost of electricity by 30% relative 40%
to conventional/baseline approaches (Selexol).
technical content
Many common membranes for gas separations are based on simple rubbery
polymers, which are simple to fabricate and low in cost. However, these
membranes face considerable performance limitations, along with the inevitable
trade-off between selectivity and permeability. Figure 1 illustrates this for polymer
membrane separation of CO2 and H2. In order to exceed the upper bound,
utilization of selective facilitated transport is essential.
OSU’s technological approach for the membrane focuses on a CO 2-selective and
permeable membrane layer on top of a polymer support, with amino groups
added to facilitate CO2 transport. The basic structure of the membrane is depicted
in Figure 2. Because this membrane is to be deployed to remove CO 2 from coal-
derived syngas, it is required to exhibit chemical stability to hydrogen sulfide (H 2S)
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
482 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
gas, which is always present in at least trace amounts in coal syngas. Also, it is preferred that it can function at elevated
temperatures, such as are characteristic of warm syngas cleanup regimes. The top layer of the membrane is the selective
layer containing amine in the form of amino groups, while the support layer is made of nanoporous polysulfone, which
is both highly permeable to gases and is mechanically robust. Some details of composition of the selective polymer layer
are proprietary.
Figure 1: Typical performance of polymer membranes for CO2/H2 separations. Figure 2: Membrane structure.
The facilitated transport mechanism involves enhancement of CO 2 transfer or flux through the membrane via chemical
reaction with amino groups located in the selective layer. The reversible reaction of CO 2 with amino groups is as follows:
CO2 + R-NH2 + H2O → R-NH3+ + HCO3-
The facilitated transport mechanism is depicted in Figure 3. Other non-acid gases, including H 2, carbon monoxide (CO),
methane (CH4), and nitrogen (N2), are non-reactive with the membrane, and can therefore only slowly permeate through
the membrane by a physical solution-diffusion mechanism. This results in high selectivities for CO 2 relative to these non-
reactive gases. In contrast, the acid gas H2S has even higher rates of permeation through the membrane than CO 2. This
means that high levels of sulfur removal from the syngas will be accomplished in a membrane separation module, with
less than 10 parts per million (ppm) H2S remaining in the syngas retentate on the feed side. The CO 2 permeate does
require further treatment to remove the sulfur from the CO 2 before the latter could be stored or used.
Figure 3: Mechanism of facilitated transport.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
483
Pre-Combustion Membrane Technologies
Process Scenario
One scenario for an overall plant process context is depicted in Figure 4. In order to enable greater than 90% carbon
capture in coal gasification-based IGCC processes, the preferred method is oxygen-based pressurized gasification
resulting in low nitrogen content raw syngas. Syngas is shifted via the water-gas shift (WGS) reaction in a WGS unit,
resulting in syngas containing large fractions of H2 and CO2. This shifted syngas is introduced at the high-pressure feed
side of the membrane unit. Carbon dioxide and H2S permeate to the low-pressure permeate side of the membrane unit;
H2S can be subsequently separated from the permeate mixture in a single-stage Selexol unit, while the purified CO 2 is
compressed and sent to storage. The high-pressure syngas retentate serves as fuel gas for a combustion turbine.
Figure 4: Process integration of membrane separation unit.
For industrial applications, it is intended that the polymeric membrane would be packed into spiral-wound membrane
modules, a commonly used module design for current commercial membrane installations. Spiral-wound modules are
robust, resistant to fouling, and economical; they are used in 95% of the reverse osmosis (RO) desalination industry and
more than 60% of the membrane market for CO2 removal from natural gas. Figure 5 shows the general design features
of a spiral-wound membrane module. The module consists of a permeate collection tube with a spiral formation of
permeate spacers and feed spacers. In current testing, the laboratory-scale membranes are in the form of flat-sheet
stamps with a membrane area of about 50 cm2. In future project work, the membrane will be scaled-up to 14 inches in
width by 20 feet in length in roll-to-roll manner, and then used for prototype spiral-wound membrane module fabrication.
Each of the laboratory-scale modules has a membrane area of 0.08 m2, and three modules in series in the process
accommodate syngas flow of about 34 slpm. Each of commercial modules has a membrane area of 20 to 50 m 2, and three
modules in series in the process accommodate syngas flow of about 8,500 to 21,250 slpm.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
484 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Figure 5. Schematic diagram of a spiral-wound membrane module [R. W. Baker, Membrane Technology and Applications, John Wiley &
Sons, West Sussex, United Kingdom (2012)].
Current Work and Results
A major technology development focus has been in improving performance of the membrane, chiefly in terms of
increasing CO2 permeance (while maintaining CO2/H2 selectivity in the range of greater than 100). Approaches for
improving permeance include the following:
Using sterically hindered amines as CO2 carriers: Comparing the mechanisms of reaction of CO 2 with both unhindered
and hindered amines, the latter can double the CO2 carrying capacity. In the latest work, a new alkanolamine has been
identified as an effective carrier to enhance both the chemisorption and physisorption of CO 2 at working temperature
of 107°C. Also, a series of aminosilanes containing various amino groups was used as coupling agents to graft amine
onto the polymer matrix. An aminoacid salt with severe steric hindrance was synthesized to explore the possibility of
effective H2S/CO2 separation by the membrane.
Incorporating certain molecular substituents or side chains in the membranes’ polymer molecular structure to improve
facilitated transport: Specifically, (1) ethylene oxide moieties and (2) amine-containing hydroxyethyl moieties are being
investigated in this respect.
Tuning the composition of the membrane polymers: Different molecular weights of the polymers and different carrier
structures in the membrane will have effects on performance. It is possible to optimize membrane polymer composition
for different ranges of CO2 partial pressures.
Incorporation of nanofillers: Linkages between molecular chains are not rigid in the polymer membrane. This means
that at working temperatures (e.g., 107°C), the crosslinked polymer network is rubbery and compressible. At high
syngas pressure, induced hydrostatic compression reduces the polymer free volume, causing reduced gas diffusivity
through the polymer. In order to mitigate the membrane compaction, nanofillers can be dispersed in the polymer
network as reinforcement. In current work, nanofiller in the form of perforated carbon nanosheet has been
economically synthesized in-house at OSU and is incorporated for this purpose.
Preliminary TEA of a single-stage membrane process based on the OSU-facilitated transport membrane in an IGCC plant
context has been made, informed by current membrane performance data. For the process designed to achieve 90% CO 2
removal with 95% purity, estimations are that the cost of electricity increases 15.4% over the non-capture baseline, and
that 99.4% of the H2 in the input syngas can be recovered.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
485
Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value * Target R&D Value
Materials of Fabrication for Selective Layer — polymer with amino groups polymer with amino groups
Materials of Fabrication for Support Layer — polysulfone polysulfone
Nominal Thickness of Selective Layer m ~15 – 25 15 – 25
Membrane Geometry — spiral wound spiral wound
Maximum Trans-Membrane Pressure bar 34 34
Hours Tested without Significant Degradation — 24 ≥200
Manufacturing Cost for Membrane Material $/m2 ~54 ≤54
Membrane Performance
Temperature °C 107 107
CO2 Pressure Normalized Flux GPU 327 275 – 350
CO2/H2O Selectivity — 1 1
CO2/H2 Selectivity — 139 120 – 140
H2S/CO2 Selectivity — 3 3
Sulfur Tolerance ppm >6,000 >6,000
Type of Measurement — mixed gas mixed gas
Proposed Module Design
Flow Arrangement — Counter-current
Packing Density m2/m3 2000
Shell-Side Fluid — Retentate, H2-rich flow
Syngas Gas Flowrate slpm 34
CO2 Recovery, Purity, and Pressure %/%/bar 90 95 1.1
H2 Recovery, Purity, and Pressure %/%/bar 99.4 94 31.7
Pressure Drops Shell/Tube Side psi/m 1.5
Estimated Module Cost of Manufacturing and __$__
m2 97
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm 3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10 -6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
486 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Facilitated transport mechanism.
Contaminant Resistance – Membrane is tolerant to greater than 6,000 ppm H2S.
Syngas Pretreatment Requirements – Thermal expansion for mild syngas cooling, and filtration to remove any
particulate matter.
Membrane Replacement Requirements – Spiral-wound membrane elements are expected to be replaced every five years.
Waste Streams Generated – Elemental sulfur recovered from the captured H2S and CO2 stream via the Claus process.
technology advantages
The simplicity of the amine-polymer membrane structure lowers its manufacturing cost.
Membrane modules do not contain moving parts or involve chemical reaction, simplifying operation and maintenance.
The membrane material has a high tolerance to acid gases and is inert to all primary syngas species.
The membrane capture system has a compact footprint and low energy cost.
The membrane capture system can operate warm/hot to reduce the need for heat exchange (e.g., membrane modules
operate at a higher temperature and pressure than conventional acid gas removal processes like Selexol, reducing the
need for syngas cooling and lowering the energy and capital cost required to convert captured CO 2 to liquid).
The membrane can remove H2S simultaneously with CO2, resulting in low-sulfur H2 for combustion or chemical
synthesis.
R&D challenges
Increasing the CO2 permeance of the membrane.
Assuring polymer support performance and properties.
Choice of spacer and glue for high-temperature membrane module fabrication.
Scale-up and integration issues are possible given the large number of membranes needed to service a 550-megawatt-
electric (MWe) plant.
status
Efforts in syntheses of improved membranes, membrane characterization, and TEA are in progress.
available reports/technical papers/presentations
“Facilitated Transport Membranes with Tunable Amine-CO2 Chemistry for Highly Selective CO2/H2 Separation,”
presentation by Yang Han and W.S. Winston Ho, 2019 AIChE (American Institute of Chemical Engineers) Annual
Meeting. Orlando, FL, November 2019, Paper 750a.
“Transformational Membranes for Pre-combustion Carbon Capture,” presentation by Winston Ho and Yang Han, The
Ohio State University, 2019 NETL CCUS Integrated Project Review Meeting. Pittsburgh, PA, August 2019.
“Transformational Membranes for Pre-combustion Carbon Capture,” project kickoff meeting presentation, November
2018.
“Transformational Membranes for Pre-combustion Carbon Capture,” Poster presentation by Yang Han, The Ohio State
University, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2018.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
487
Pre-Combustion Membrane Technologies
Development of Carbon technology maturity:
Molecular Sieves Hollow Fiber
Laboratory-Scale, Simulated
Syngas (equivalent to ~0.01
Membranes Based on
kWe)
project focus:
Polybenzimidazole Doped with Carbon Molecular Sieve
Polyprotic Acids with Superior
Hollow Fiber Membranes
H2/CO2 Separation Properties
participant:
State University of New York –
Buffalo
primary project goals project number:
FE0031636
The goal of this State University of New York (SUNY) – Buffalo project is to develop
scalable membrane technology by engineering polymers to achieve superior predecessor projects:
hydrogen (H2)/carbon dioxide (CO2) separation properties in readily fabricated and
N/A
easily deployed membranes. The application is for capture of CO 2 from coal-
derived syngas. Specifically, the approach is to derive carbon molecular sieve NETL project manager:
(CMS) membranes from polybenzimidazole (PBI) doped with polyprotic acids, with
Andrew O'Palko
the expectations that they will be chemically stable, be able to operate in [email protected]
temperatures up to 300°C, be easily scalable, and have high H2 permeance and
H2/CO2 selectivity. The scope of the work is to improve CMS hollow fiber principal investigator:
membrane characteristics, fabricate small membrane modules, and perform Haiqing Lin
testing with simulated syngas to establish module/membrane CO2 separation SUNY–Buffalo
performance and robustness. Data from testing is to inform techno-economic [email protected]
analysis (TEA) to determine process costs for large-scale carbon capture in an
integrated gasification combined cycle (IGCC) plant scenario. partners:
Los Alamos National
Laboratory
technical goals Trimeric Corporation
Develop CMS hollow fiber membranes having a H2 permeance of 1,000 gas start date:
permeation units (GPU) and an H2/CO2 selectivity of 40 at 200 to 300°C. 10.01.2018
Demonstrate membrane durability via testing of a pencil membrane module
under simulated syngas flow at 0.01 kilowatt-electric (kWe) equivalency for 120 percent complete:
hours. 40%
Characterize a CMS membrane-based system able to capture 90% CO2 from
coal-derived syngas with 95% CO2 purity at a cost of electricity 30% less than
baseline capture approaches (Selexol).
technical content
Conventional methods for pre-combustion carbon capture consist mainly of
solvent-based processes such as Selexol and Rectisol. Although enabling high
levels of capture at high gas purity, these processes have high capital and
operating costs and result in severe energy penalties. Membrane-based carbon
capture is of continued interest as an alternative, given its potential advantages in
simplicity, lower costs, and potential for large savings in energy use. Among
membranes for separation of CO2 from syngas, inorganic membranes such as
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
488 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
palladium alloys, ceramics, metal-organic frameworks (MOFs), and graphene oxide have been evaluated, given their
excellent H2/CO2 separation properties. However, they are faced with challenges in the cost and reliability, scale-up of
membrane production, and module fabrication. In contrast, polymer-based membranes are much easier to implement
than inorganic membranes, provided that the membrane materials demonstrate suitable separation properties.
Production scale-up and module fabrication using polymeric membranes have been widely practiced, creating a
substantial engineering knowledge base across the polymer membrane industry. Building on this foundation, the current
work targets development of scalable membranes by engineering polymers to achieve superior H 2/CO2 separation
properties.
Most work in H2/CO2 gas separations by polymeric membrane materials relies solely on strong size-sieving derived from
the rigid polymer chains. Polymers available commercially in this class include examples like poly(p-phenylene oxide)
(PPO), Matrimid, poly(bisphenol-A sulfone) (PSF), and cellulose acetate (CA). However, the commercially available
polymers have low H2 diffusivity and permeability, are limited by the permeability/selectivity trade-off, and are well below
the Robeson bound, as illustrated in Figure 1.
Figure 1: Pure-gas H2/CO2 separation performance of PBI-(H3PO4)X (x = 0.16-1.0) and PBI-(H2SO4)0.24 at 150°C versus Robeson’s upper
bound at 35°C and 150°C.
The SUNY team has demonstrated considerable improvement in polymer membrane performance by doping the polymer
PBI with polyprotic acids such as phosphoric acid (H3PO4) and sulfuric acid (H2SO4) to improve the size-sieving ability and
H2/CO2 separation properties at 120 to 180°C. As shown in the upper part of Figure 1, increasing the H 3PO4 doping level
(defined as the molar ratio of H3PO4 to the PBI repeating units) decreases the pure-gas permeability and drastically
increases the H2/CO2 selectivity at 150°C. For example, plain PBI shows an H2/CO2 selectivity of 16, while PBI-(H3PO4)1.0
exhibits a remarkable selectivity of 140, which is much higher than that of any previously studied polymers. Phosphoric
acid can strongly interact with multi-PBI chains via proton transfer from the acid to imidazole rings of PBI and hydrogen
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
489
Pre-Combustion Membrane Technologies
bonding, and thus it crosslinks the PBI. In comparison, a monoprotic acid such as hydrogen chloride (HCl) does not
crosslink the PBI chains and has minimal effect on H2/CO2 separation properties.
In current developmental work, the approach is to start with the already strongly size-sieving polymers (i.e., PBI doped
with polyprotic acids), and then carbonize them (by heating/pyrolysis at 500 to 800°C in inert nitrogen [N 2] for at least an
hour) to increase both permeability and selectivity into a range suitable for commercial deployment. This approach is
diagrammed in Figure 2. Carbonizing the acid-doped PBI results in CMS in which microcavities form, tending to increase
gas permeability, and ultra-microporous necks increasing size-sieving ability.
Figure 2: Steps to CMS membranes derived from PBI doped with polyprotic acids.
In past work, CMS membranes were made by carbonizing plain PBI. The pyrolysis increases the porosity and generates
graphite-like structure. As shown in Figure 3 in blue, the carbonization of PBI substantially increases H 2 permeability while
retaining or slightly increasing H2/CO2 selectivity at 100°C. All CMS samples have exhibited H2/CO2 separation properties
above the upper bound. For example, pure PBI exhibits an H 2 permeability of 12 Barrers and an H2/CO2 selectivity of 14
at 100°C, while the CMS prepared by pyrolysis of PBI at 800°C shows an H 2 permeability of 670 Barrers (which is 50 times
higher than pure PBI) and an H2/CO2 selectivity of 18 at 100°C.
Figure 3: Improvement in membrane performance upon carbonization to CMS.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
490 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
The SUNY team hypothesizes that the CMS membranes can meet targeted separation properties (H 2 permeance of 1,000
GPU and H2/CO2 selectivity of 40) if the starting polymers are PBI doped with polyprotic acids with strong size-sieving
ability. For example, PBI-(H3PO4)0.25 exhibits an H2 permeability of 8.6 Barrers and an H2/CO2 selectivity of 48 at 150°C. The
pyrolysis at 600°C increases the permeability to 100 Barrers while retaining an H 2/CO2 selectivity of 40 at 100°C, as shown
in red in Figure 3. During the pyrolysis, the H3PO4 gradually decomposes to polyphosphoric acid ((HPO 3)n), retaining the
rigid chains and strong molecular size-sieving ability. By optimization of the acid type, composition, and pyrolysis
temperature, the CMS should be able to achieve H2 permeability of 200 Barrers with an H2/CO2 selectivity of 40, which
can be used to prepare hollow fiber membranes with a selective layer thickness of 0.2 μm exhibiting an H 2 permeance of
1,000 GPU and an H2/CO2 selectivity of 40. This is feasible because carbonization has been demonstrated to increase H 2
permeability by 50 times, and Los Alamos National Laboratory (LANL) has successfully fabricated nearly defect-free PBI
hollow fiber membranes with a 0.2 μm selective layer.
Figure 4 shows images of (a) a base PBI hollow fiber membrane and (aʹ) carbonized hollow fiber. This illustrates that the
carbonized fiber retains the porous support morphology of the starting fiber.
Figure 4: Scanning electron microscopy (SEM) images of PBI hollow fibers, before (left) and after (right) carbonization.
CMS membranes are intended for incorporation in hollow fiber modules for deployment in gas separation systems. LANL
currently uses the hollow fiber spinning system depicted in Figure 5 to fabricate the hollow fibers. A custom micro-
machined spinneret forms the fiber. The steps resulting in CMS carbon fibers are also diagrammed.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
491
Pre-Combustion Membrane Technologies
Figure 5: LANL lab-scale continuous hollow fiber spinning system.
Process implementation of CMS membrane modules would follow the basic flow diagram shown in Figure 6. Shifted
syngas (1) containing mostly H2 and CO2 passes through membrane modules. Hydrogen selectively permeates and is
swept away by N2 (3), which is available in large quantities from the air separation unit producing oxygen for coal
gasification (not shown on this figure). The H2 and N2 mixture comprises fuel gas (4) to be combusted in the power
turbine. Retentate from the membrane modules is conditioned, dewatered, and compressed/pumped into liquid CO 2 for
storage or use (2).
Figure 6: Membrane process integration in process cycle.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
492 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value * Target R&D Value
Materials of Fabrication for Selective Layer — carbonized acid-doped PBI carbonized acid-doped PBI
Materials of Fabrication for Support Layer — carbonized acid-doped PBI carbonized acid-doped PBI
Nominal Thickness of Selective Layer m 0.1 0.1
Membrane Geometry — hollow fiber hollow fiber
Maximum Trans-Membrane Pressure bar 20 20
Hours Tested without Significant Degradation h 120 120
Manufacturing Cost for Membrane Material $/m2 20 20
Membrane Performance
Temperature °C 150 200-300
CO2 Pressure Normalized Flux GPU or equivalent 200 1,000
CO2/H2O Selectivity — 0.5 0.5
CO2/H2 Selectivity — 0.025 0.025
CO2/H2S Selectivity — 2 2
Sulfur Tolerance ppm 20 20
Type of Measurement — mixed gas mixed gas
Proposed Module Design
Flow Arrangement — Countercurrent
Packing Density m2/m3 ~1,000
Shell-Side Fluid — Permeate, CO2-rich flow
Syngas Gas Flowrate kg/hr 0.02
CO2 Recovery, Purity, and Pressure %/%/bar 90 95 20
H2 Recovery, Purity, and Pressure %/%/bar 90 50 15
Pressure Drops Shell/Tube Side bar 0.2
Estimated Module Cost of Manufacturing and __$__
kg/hr ~1,000
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atmosphere [atm], 0°C)/cm2/s/cm mercury (Hg). For non-
linear materials, the dimensional units reported should be based on flux measured in cm 3 (1 atm, 0°C)/cm2/s with
pressures measured in cm Hg. Note: 1 GPU = 3.3464 × 10 -6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either concurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
493
Pre-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Physical solution-diffusion.
Contaminant Resistance – Membranes are resistant to chemicals in the syngas.
Syngas Pretreatment Requirements – Removal of particles.
Membrane Replacement Requirements – Module lifetime is three to five years.
Waste Streams Generated – Water vapor will permeate with H2, and the water stream will be produced after the H2
combustion.
technology advantages
The capability of CMS membranes with high permeance and selectivity to operate at high temperature eliminates the
need for syngas cooling and avoids water vapor loss, which improves energy and cost efficiency of the carbon capture
process.
The simplicity of the membrane structure lowers its manufacturing cost.
A membrane system does not contain moving parts or involve chemical reactions, conferring some operation and
maintenance (O&M) advantages.
The membrane material has a high tolerance to acid gases and is inert to all primary syngas species.
Membrane capture systems (particularly those based on hollow fiber membrane modules) have compact footprint.
R&D challenges
Assuring polymer performance and properties.
Feed and permeate side pressure drops may lead to excessive energy losses.
Cost reductions for the membrane module materials will be needed if the technology is to become economically viable.
Durability and gas integrity of membrane modules (gas seals, fouling).
Scale-up and integration issues (and operational complications from multiple vacuum pumps and valves and
complicated ductwork in multiple flow banks) likely given the large number of membranes needed to service a 550-
megawatt-electric (MWe) plant.
status
Recently, PBI-(H3PO4)0.11 carbonized at 700°C was demonstrated to have an H2 permeability of 240 Barrer and an H2/CO2
selectivity of 54 at 225°C, which has met the target of an H2 permeability of 200 Barrer and an H2/CO2 selectivity of 40.
Work has just started in making the first generation of PBI-CMS hollow fiber modules needed for eventual parametric
testing and evaluation.
available reports/technical papers/presentations
“Development of Carbon Molecular Sieves Hollow Fiber Membranes Based on Polybenzimidazole Doped with Polyprotic
Acids with Superior H2/CO2 Separation Properties,” presentation by Haiqing Lin, SUNY Buffalo, 2019 NETL CCUS
Integrated Project Review Meeting. Pittsburgh, PA, August 2019.
“Development of Carbon Molecular Sieves Hollow Fiber Membranes Based on Polybenzimidazole Doped with Polyprotic
Acids with Superior H2/CO2 Separation Properties,” project kickoff meeting presentation, November 2018.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
494 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Membrane Technologies
“Development of Carbon Molecular Sieves Hollow Fiber Membranes Based on Polybenzimidazole Doped with Polyprotic
Acids with Superior H2/CO2 Separation Properties,” presented by Haiqing Lin, State University of New York (SUNY) at
Buffalo, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA. August 2018.
“Unexpectedly Strong Size-Sieving Ability in Carbonized Polybenzimidazole for Membrane H 2/CO2 Separation,” M. Omidvar,
H. Nguyen, L. Huang, C.M. Doherty, A.J. Hill, C.M. Stafford, X. Feng, M.T. Swihart, and H. Lin, ACS Appl. Mater. & Interfaces,
11 (50), 47365-47372 (2019)
“Ultraselective Carbon Molecular Sieve Membranes with Unprecedented Performance for H 2/CO2 Separation for Pre-
combustion CO2 Capture,” presented by Hien Nguyen, State University of New York (SUNY) at Buffalo, 2019 Materials
Research Society, Boston, MA. December 2019.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 495
Pre-Combustion Membrane Technologies
this page intentionally left blank
NATIONAL ENERGY TECHNOLOGY LABORATORY
496 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
PRE-COMBUSTION
NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 497
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
Bench-Scale Testing of a High- technology maturity:
Efficiency, Ultra-Compact
Bench-Scale, Actual Coal-
Derived Syngas (50.7-253 kg
Process for Pre-Combusion
per day equivalent to 3-14.9
kW)
CO2 Capture project focus:
Combined CMS
Membrane/WGS Reactor
primary project goals and Adsorption Reactor
The main objective is to scale-up and field-validate the technical feasibility of the participant:
University of Southern California's (USC) membrane- and adsorption-enhanced University of Southern
water-gas shift (WGS) process that employs a carbon molecular sieve (CMS) California
membrane reactor (MR), followed by an adsorption reactor (AR), for pre-
combustion carbon dioxide (CO2) capture. The project begins at Technology project number:
Readiness Level (TRL) 4, as the system prototype has already been validated in the FE0031737
laboratory on simulated syngas (under predecessor project FE0026423). The project
aims to end at TRL 5, via scaling-up of the prototype system and its testing on predecessor projects:
actual syngas at the University of Kentucky (UKy). Project tasks include designing, FE0026423
constructing, assembling, and validating the bench-scale experimental MR-AR
system; preparing suitable membranes, adsorbents, and catalysts needed for the NETL project manager:
bench-scale system; and deploying the unit at UKy and testing system performance Andrew Jones
using real syngas. Results are to be used to complete an updated process techno- [email protected]
economic analysis (TEA) and environmental, health, and safety (EH&S) risk
assessment. principal investigator:
Theodore Tsotsis
University of Southern
technical goals California
[email protected]
• Demonstrate CO2 capture from actual coal gasification syngas at a bench-scale
syngas flow rate of 50.7 to 253 kg/day, at a temperature of 250°C, at a pressure partners:
of 25 atmosphere [atm], and for 500 hours of testing. Media and Process
Technology Inc.,
• Increase stability of membranes and adsorbents in the process system in terms
University of California Los
of degradation by syngas constituents, with an interim target of less than 30%
Angeles
decline in performance over 500 hours of testing at typical syngas conditions. University of Kentucky
• Hydrogen (H2) permeance greater than 1 m3/m2.hr.bar for the H2-selective Research Foundation
membrane, with a target range for H2/carbon monoxide (CO) selectivity
exceeding 80. start date:
• Sorbent working capacity greater than 2.5 weight % CO2; sorbent attrition rate 06.01.2019
less than 0.2.
percent complete:
• Demonstrate progress (TRL 4 to TRL 5) toward enabling an MR-AR system in a
15%
550-megawatt-electric (MWe) integrated gasification combined cycle (IGCC)
plant, capable of CO2 capture with greater than 95% purity, while reducing the
cost of electricity (COE) by 30% over IGCC plants employing conventional
methods of CO2 capture.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
498 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
technical content
The working hypothesis of this project is that the conventional WGS unit found in a coal gasification process plant (for
shifting the syngas toward primarily H2 and CO2) and the downstream conventional amine absorption unit for capturing
the CO2 from the shifted syngas could be replaced in whole by a unique membrane- and adsorption-enhanced WGS
reactor system (previously developed for H2 production via methane steam reforming) that allows for in situ preferential
H2 permeation and simultaneous CO2 adsorption. The reactor system is depicted, in the context of a typical IGCC power
plant cycle, within the blue border-surrounded process block in Figure 1.
Figure 1: Proposed MR and AR system in the context of an IGCC plant process.
The system combines an MR and AR in tandem to continuously produce a pure H2 product (while attaining greater than
99% CO conversion) until the adsorbent (in the AR unit) is saturated. The AR unit must then be taken off-stream and
regenerated via steam-enhanced temperature swing adsorption (TSA). This unique reactor configuration can, therefore,
be viewed as a hybrid MR-AR system with TSA cycling. Compared to conventional WGS followed by CO2 capture using a
conventional amine process, the MR-AR system is more efficient and compact. Furthermore, the use of a TSA rather than
a pressure-swing CO2 recovery step (as commonly practiced in AR systems) allows the recovery of CO2 at higher pressures
aiding system efficiency.
The combined MR-AR process is shown in more detail in Figure 2. Here, the syngas first passes into the MR vessel,
consisting of WGS catalyst packed around an array of membrane tubes. The tubes are CMS-based membranes on ceramic
support, which are highly selective to H2. The MR permeate consists of high-purity H2. As the H2 is withdrawn from the
MR vessel, the WGS reaction equilibrium is pushed toward further H2 production. Retentate/rejected gases are passed to
an array of ARs operating in a periodic manner, whereby at any given time some ARs are fed retentate gases and operate
in reaction/adsorption mode, while the remaining ARs are fed steam and operate in a TSA regeneration mode. The ARs
contain additional WGS catalyst, in addition to CO2 sorbent. In this technology, hydrotalcite (HTC) is utilized as the CO2
sorbent. This co-location of the WGS reaction and CO2 separation functions in the AR allows traditional WGS reaction
equilibrium limitations to be overcome, thus enabling enhanced shifting of the syngas to occur until most of the carbon
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 499
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
as CO is converted into CO2 and adsorbed. This results in a relatively pure H2 gas exiting the AR at high pressure when
the ARs operate in reaction/adsorption mode, while a high-pressure steam/CO2 mixture exits the ARs when they operate
in regeneration mode. In summary, the proposed process configuration combining the MR and AR in tandem provides
significant process flexibility, efficient high-pressure and high-purity H2 production, and CO2 recovery.
Figure 2: Proposed MR-AR process.
The HTC sorbent mentioned previously is an anionic clay magnesium (Mg)/aluminum (Al)-layered double hydroxide, as
depicted in Figure 3. It has a relatively high CO2 capacity over a wide range of temperatures and pressures; can be easily
prepared by precipitation of Mg/Al from solution in sodium hydroxide; and is unaffected by hydrogen sulfide (H2S) and
simulated tars at anticipated operating temperature, thereby conferring process stability.
Figure 3: Hydrotalcite (HTC) adsorbent.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
500 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
The main accomplishments and findings of the USC team’s predecessor project included the following:
• CMS membranes were prepared and tested over the full range of expected operating temperatures (up to 300°C) and
pressures (10 to 25 bar). Performance targets for H2 permeance (350 to 550 gas permeation units [GPU]) and H2/CO
selectivity of greater than 80 were met.
• HTC sorbent was prepared, and adsorption/desorption kinetics and working capacity measured at expected operating
conditions of 300 to 450°C and pressure up to 25 bar. A performance target for working capacity of greater than 3
weight % CO2 was met.
• Kinetics of a commercially available sour-shift WGS catalyst were measured at expected operating conditions. This
information is essential in modeling and in preparing a TEA of the MR-AR process.
• An MR-AR system operating run of greater than 500 hours was carried out on simulated syngas at a flow rate of less
than 0.9 kg/day in a lab-scale integrated experimental apparatus. This effectively advanced the MR-AR technology to
TRL 4. Also, the membranes, sorbents, and catalysts were shown to be robust at expected operating conditions.
• Preliminary TEA study results comparing an MR-AR integrated system to a baseline Selexol system (both in the IGCC
context) show substantial reductions in required compression work and WGS catalyst requirements. The overall COE
target of 30% lower cost than the baseline COE would be closely approached or met given known performance
parameters and assumptions.
It should be noted that there are several major points of departure of the case of MR-AR within an IGCC power plant
context from the baseline IGCC case. These become important in process performance and cost analysis:
1. The WGS reaction occurs in the MRs and ARs alongside H2 removal (in the MRs) and CO2 removal (in the ARs).
2. The amount of steam needed in the MR-AR case is higher because steam not only serves as a feed in the AR, but it is
also used as a sweep stream to evacuate the WGS reaction products.
3. A single-stage Selexol unit is needed for H2S removal, as opposed to a dual-stage Selexol unit for H2S and CO2 removal
in the baseline case.
4. Steam is used as diluent in the combustion turbine, as opposed to nitrogen (N2) in the baseline case.
Clearly, item 3 is beneficial from both cost and efficiency considerations, but items 2 and 4 are not beneficial because of
the extra steam needed and its cost. If credit is taken for sale of N2 in the MR-AR case, economics are obviously better
than if N2 cannot be sold. In any case, the added complication of N2 marketing must be regarded as a negative aspect of
MR-AR process technology.
Current project work focuses on design and construction of a bench-scale unit. Ultimately, this will be sited at UKy’s
Center for Applied Energy Research (CAER) to enable testing on actual coal-derived syngas from CAER’s entrained-flow
coal gasifier. The bench-scale unit will utilize 30-inch membrane tubes in 2-inch outer diameter modules for the MR. Test
campaigns totaling 500 hours are planned, enabling determination of performance at this larger scale, affording an
opportunity to evaluate membrane, catalyst, and sorbent stability over time. The performance data will allow improved
TEA of the MR-AR system.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 501
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — carbon molecular sieve (CMS)
Materials of Fabrication for Support Layer — alumina
Nominal Thickness of Selective Layer m 2–3 2–3
Membrane Geometry — tubular tubular
Maximum Trans-Membrane Pressure bar >82 bar >82 bar
>16,000 hours in lab,
Hours Tested without Significant Degradation — —
>1,000 hours at NCCC
Manufacturing Cost for Membrane Material $/m2 <1,500 <750
Membrane Performance
Temperature °C 250–300 250–300
H2 Pressure Normalized Flux GPU or equivalent 500 900
H2/H2O Selectivity — 2–4 >3
H2/CO2 Selectivity — .200 >200
H2/H2S Selectivity — >100 >100
Sulfur Tolerance ppm >10,000 >10,000
Type of Measurement — mixed gas mixed gas
Proposed Module Design
Flow Arrangement — co/counter-current or cross-flow
Packing Density m2/m3 >450
Shell-Side Fluid — Permeate
Syngas Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure %/%/bar 90 95 >60
H2 Recovery, Purity, and Pressure %/%/bar >80 >90 Up to 20
Pressure Drops Shell/Tube Side bar —
Estimated Module Cost of Manufacturing and __$__
kg/hr 1,500
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0°C)/cm2/s/cm mercury (Hg). For non-linear materials,
the dimensional units reported should be based on flux measured in cm3 (1 atm, 0°C)/cm2/s with pressures measured in
cm Hg. Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture
of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
502 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Molecular sieving.
Contaminant Resistance – Resists all chemical contaminants in gasifier off-gas including H2S, ammonia (NH3), heavy
metals, organic vapors, tars, etc., based on bench-scale testing conducted at the National Carbon Capture Center (NCCC).
Syngas Pretreatment Requirements – Particulate removal should be practiced.
Membrane Replacement Requirements – Not known presently, but assumed to be five to 10 years. More than 16,000 hours
of laboratory thermal stability testing has been demonstrated with no failure. More than 1,000 hours of live syngas testing at
NCCC has been conducted with no failure.
Waste Streams Generated – None.
Process Design Concept – See Figure 1.
Proposed Module Integration – See below.
Composition
Entering Pressure Temperature vol% ppmv
Module psia. °F CO2 CO CH4 N2 H2 H2O H2S
MR 800 440-540 0.1089 0.2823 0.0010 0.0055 0.2689 0.3190 5700
AR 800** 440-540* 0.2480 0.1466 0.0009 0.0055 0.2590 0.3253 5700
* Species compositions shown for inlet temperature of 440°F; To match the exit gasifier conditions.
**
TABLE 2: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D Value Target R&D Value
True Density @ STP kg/m3 2,849–3,066 2,849–3066
Bulk Density kg/m3 1,322–1,423 1,322–1,423
Average Particle Diameter mm 0.6–0.8 2–3
Particle Void Fraction m3/m3 0.536 0.536
Packing Density m3/m3 0.406 0.406
Solid Heat Capacity @ STP kJ/kg-K 0.5–0.65 0.5–0.65
Crush Strength kgf N/A 10-15
Manufacturing Cost for Sorbent $/kg — —
Adsorption
Pressure bar 25 >25
Temperature °C 250–300 250–300
Equilibrium Loading g mol CO2/kg ~3 ~3
Heat of Adsorption kJ/mol CO2 ~10 kJ/mol ~10 kJ/mol
Desorption
Pressure bar 25 >25
Temperature °C 400–450 <400
Equilibrium CO2 Loading g mol CO2/kg 0.1-0.2 <0.1
Heat of Desorption kJ/mol CO2 — —
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 503
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — See Figure 2
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure % / % / bar >90 95 25
Adsorber Pressure Drop bar —
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15°C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing
cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading. Operating
pressure and temperature for the desorber/stripper are process dependent. Measured data at other conditions are
preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2.
Packing Density – Ratio of the active sorbent volume to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – See Figures 1 and 2.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
technology advantages
• Hybrid concept process allows the simultaneous removal from the reacting phase and recovery of both H2 and CO2,
resulting in significant reaction rate enhancement over the conventional WGS system.
• Significantly reduced catalyst weight usage requirements: reaction rate enhancement (over conventional WGS) permits
operation at lower weight of catalyst/inlet molar flow rate of CO (W/FCO), thus resulting in significant catalyst savings.
• No syngas pretreatment required given use of sour-shift catalyst and use of CMS membranes, which have
demonstrated stability to all gaseous contaminants present in coal-derived syngas.
• Efficient H2 production and superior CO2 recovery and purity: the synergy of the MR and AR units satisfies the CO2
recovery/purity, carbon utilization (CO conversion), and H2 recovery/purity goals.
R&D challenges
• Heat management in reactors.
• Process integration with IGCC.
• Particulate matter needs to be controlled to reduce its potential impact on the reactor units.
• Scale-up and integration issues, given the large number of reactor modules needed to service a 550-MWe plant.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
504 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
status
Design and construction of the bench-scale unit for testing at UK CAER is underway.
available reports/technical papers/presentations
“A High Efficiency, Ultra-compact Process for Pre-combustion CO2 Capture,” presentation by Theo Tsotsis, University of
Southern California, 2019 Carbon Capture, Utilization, Storage, and Oil and Gas Technologies Integrated Review
Meeting - Capture and Utilization Sessions, August 2019.
“Bench-Scale Testing of a High Efficiency, Ultra-Compact Process for Pre-Combustion CO2 Capture,” project kickoff
meeting presentation, May 2019.
“A High Efficiency, Ultra-compact Process for Pre-combustion CO2 Capture,” Final Report submitted to the U.S.
Department of Energy, National Energy Technology Laboratory. DOE Award Number DE-FE0026423, University of
Southern California, April 2019.
Karagöz, S., Tsotsis, T.T., and Manousiouthakis, V.I., “Multi-scale Modeling and Simulation of a Novel Membrane Reactor
(MR)/Adsorptive Reactor (AR) Process,” In Press, Chemical Engineering & Processing: Process Intensification, 137, 146,
2019.
Karagöz, S., Tsotsis, T.T., and Manousiouthakis, V.I., “Energy Intensification of H2 Generation and CO2 Capture/Utilization
by Carrying-out the Water Gas Shift Reaction in an Adsorptive Reactor: Multiscale Dynamic Modeling and Simulation,”
AIChE J., 2019.doi: 10.1002/aic.16608.
Pichardo, P., Karagöz, S., Ciora, R., Tsotsis, T.T., and Manousiouthakis, V.I., “Technical Economic Analysis of an Intensified
Integrated Gasification Combined Cycle (IGCC) Power Plant Featuring a Sequence of Membrane Reactors,” J. Membrane
Sci., 579, 266, 2019.
Garshasbi, A., Chen, H., Cao, M., Karagöz, S., Ciora, R.J., Liu, P.K.T, Manousiouthakis, V.I., and Tsotsis, T.T., “Membrane-
based Reactive Separations for Process Intensification during Power Generation”, Catalysis Today, 331, 18, 2019.
Pichardo, P., Karagöz, S., Ciora, R., Tsotsis, T.T., and Manousiouthakis, V.I., “Techno-Economic Analysis of an Intensified
Integrated Gasification Combined Cycle (IGCC) Power Plant Featuring a Combined Membrane Reactor - Adsorptive
Reactor (MR-AR) System,” DOI: 10.1021/acs.iecr.9b02027, Ind. Eng. Chem. Res., 2019.
Karagöz, S., Tsotsis, T.T., and Manousiouthakis, V.I., “Multi-scale Model based Design of Membrane Reactor/Separator
Processes for Intensified Hydrogen Production through the Water Gas Shift Reaction,” In Press, Int. J. Hydrogen Energy.
Garshasbi, A., Karagöz, S., Chen, H., Cao, M., Pichardo, P., Ciora, R., Liu, P.K.T, Manousiouthakis, V., and Tsotsis, T.T.,
“Membrane-Based Reactive Separations for Process Intensification During the Power Generation,” Presentation at the
25th International Symposium on Chemical Reaction Engineering, May 20-23, 2018, Florence, Italy.
Chen, H., Garshasbi, A., Karagöz, S., Cao, M., Pichardo, P., Ciora, R., Liu, P.K.T, Manousiouthakis, V., and Tsotsis, T.T.,
“Carbon Molecular Sieve-Based Reactive Separations for Power Generation Applications,” Presentation at the 15th
International Conference on Inorganic Membranes, June 18-22, 2018, Dresden, Germany
Tsotsis, T., Manousiouthakis, V., Ciora, R., “A High Efficiency, Ultra-Compact Process for Pre-combustion CO2 Capture
(FE0026423),” Presented at the CO2 Capture Technology Meeting, August 13-17, 2018, Pittsburgh, PA.
Karagoz S., Tsotsis, T., Manousiouthakis, V.I., “Process Intensification of Hydrogen Production Systems,” Session 185ag
Interactive Session: Systems and Process Design, presented at AIChE Annual Meeting, Pittsburgh, PA, 10-29-2018.
Karagoz S., Tsotsis, T., Manousiouthakis, V.I., “Effectiveness Factor Phenomena for the Transition between PBR and MR
via Coupled Heat and Mass Transfer,” Session 360g Process Intensification by Enhanced Heat and Mass Transfer,
presented at AIChE Annual Meeting, Pittsburgh, PA, 10-30-2018.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 505
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
Chen, H., Cao, M., Karagoz, S., Zhao, L., Manousiouthakis, V., and Tsotsis, T.T., “Experimental and Numerical Study of an
Intensified Water-Gas Shift (WGS) Reactor Process Using a Membrane Reactor (MR)/Adsorptive Reactor (AR) Sequence,”
Paper 464b, presented at the AIChE Annual Meeting, Pittsburgh, PA, 10-31-2018.
Karagöz, S., Da Cruz, F.E., Tsotsis, T.T., and Manousiouthakis, V.I., “Multi-Scale Membrane Reactor (MR) Modeling and
Simulation for the Water Gas Shift Reaction,” Chemical Engineering & Processing: Process Intensification, 133, 245, 2018.
Chen, H., Cao, M., Manousiouthakis, V.I., and Tsotsis, T.T., “An Experimental Study of an Intensified Water-Gas Shift
Reaction Process Using a Membrane Reactor/Adsorptive Reactor Sequence,” Ind. Eng. Chem. Res., 57, 13650, 2018.
Karagoz S., Tsotsis, T., Manousiouthakis, V., “Modeling and Simulation of a Hybrid Adsorptive-Membrane Reactor
(HAMR) for Intensification of the Water-Gas Shift (WGS) Reaction Process,” Presentation at 2017 AIChE Conference,
October 29 - November 3, Minneapolis, MN.
Karagoz S., Tsotsis, T., Manousiouthakis, V., “A Parametric Study of the Adsorption/Desorption Steps for an Adsorptive
Reactor (AR) Intensifying the Water Gas Shift (WGS) Reaction,” Presentation at 2017 AIChE Conference, October 29-
November 3, Minneapolis, MN.
Karagoz S., Tsotsis, T., Manousiouthakis, V., “Comparative Study of a Hybrid Adsorptive-Membrane Reactor (HAMR) with
a Membrane Reactor/Adsorptive Reactor Sequence,” Presentation at the 2017 AIChE Conference, October 29-
November 3, Minneapolis, MN.
Pichardo, P., Karagoz, S., Tsotsis, T.T., Ciora, R., Manousiouthakis, V. “Technical Economic Analysis of an Intensified
Integrated Gasification Combined Cycle Plant Design Featuring Membrane and Adsorptive Reactors,” Presentation at
2017 AIChE Conference, October 29-November 3, Minneapolis, MN.
Chen, H., Cao, M., Karagoz, S., Manousiouthakis, V., and Tsotsis, T.T., “Experimental and Numerical Study of an
Intensified Water-Gas Shift (WGS) Reaction Process Using a Membrane Reactor (MR)/Adsorptive Reactor (AR)
Sequence,” Presentation at the 2017 AIChE Conference, October 29-November 3, Minneapolis, MN.
Garshasbi, A., Chen, H., Cao, M., Karagöz, S., Ciora, R.J., Liu, P.K.T, Manousiouthakis, V.I., and Tsotsis, T.T., “Membrane-
Based Reactive Separations in Power Generation,” Presentation at ICOM 2017, San Francisco, CA, 29 Jul-4 Aug, 2017.
Tsotsis, T., Manousiouthakis, V., Ciora, R., “A High Efficiency, Ultra-Compact Process for Pre-combustion CO2 Capture
(FE0026423),” Presented at the CO2 Capture Technology Meeting, August 2017, Pittsburgh, PA.
Garshasbi, A., Chen, H., Cao, M., Karagöz, S., Ciora, R.J., Liu, P.K.T, Manousiouthakis, V.I., and Tsotsis, T.T., “Membrane-
Based Reactive Separations for Process Intensification During Power Generation,” Key-note Presentation at the
ICCMR13, Houston, TX, July 10-13, 2017.
Tsotsis, T., Manousiouthakis, V., Ciora, R., “A High Efficiency, Ultra-Compact Process for Pre-Combustion CO2 Capture,”
BP1 Project Review Meeting Presentation, Pittsburgh, PA, March 2, 2017.
Tsotsis, T., Manousiouthakis, V., Ciora, R., “A High Efficiency, Ultra-Compact Process for Pre-combustion CO2 Capture
(FE0026423),” Presented at the CO2 Capture Technology Meeting, August 8-12, 2016, Pittsburgh, PA.
Lowd, J., Tsotsis, T., Manousiouthakis, V., Ciora, R., “Experimental and Theoretical Studies of CO2 Adsorption on
Hydrotalcite,” Presentation at 2016 AICHE Conference, November 13-18, San Francisco, California.
Karagoz S., Tsotsis, T., Manousiouthakis, V., “Study of Adsorptive Reactor (AR): Dynamic Multi-Scale
(Catalyst/Adsorbent/Reactor Scale) Modeling and Simulation,” Presentation at 2016 AICHE Conference, November 13-
18, San Francisco, California.
Karagoz S., Tsotsis, T., Manousiouthakis, V., “Multi-Scale (Pellet-Reactor Scale) Membrane Reactor Modeling and
Simulation: Low Temperature and High-Pressure Water-Gas Shift Reaction,” Presentation at 2016 AICHE Conference,
November 13-18, San Francisco, California.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
506 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
Tsotsis, T., Manousiouthakis, V., Ciora, R., “A High Efficiency, Ultra-Compact Process for Pre-Combustion CO2 Capture,”
Project Kickoff Presentation, Pittsburgh, PA, Nov. 16, 2015.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
507
Pre-Combustion Novel Concepts
Combined Sorbent/WGS- technology maturity:
Laboratory-Scale, Simulated
Based CO2 Capture Process Syngas
with Integrated Heat project focus:
Management for IGCC
Combined CO2
Sorbent/water-Gas Shift
Systems
Reactor
participant:
Southern Research Institute
primary project goals
project number:
Southern Research Institute (SR) is developing a combined magnesium oxide FE0026388
(MgO)-based carbon dioxide (CO2) sorbent/water-gas shift (WGS) reactor that
offers high levels of durability, simplicity, flexibility, and heat management ability. predecessor projects:
The primary project goal is to develop a combined CO2 sorbent/WGS reactor- N/A
based process with advanced integrated heat management to capture 90% of the
CO2 from the Transport Reactor Integrated Gasifier (TRIG™) syngas for integrated NETL project manager:
gasification combined cycle (IGCC) applications. Andy Aurelio
[email protected]
technical goals
principal investigator/
responsible person:
• Identify sorbent and operation conditions for a combined CO2 sorbent/WGS
Santosh Gangwal/
reactor through modeling and experimental study of the WGS reaction at bench
Amit Goyal
scale.
Southern Research Institute
• WGS reaction conversion extent of 90 to 95% of equilibrium carbon monoxide [email protected]
(CO) conversion.
partners:
• Carbon dioxide capture from coal gasification syngas at a temperature of 350°C
and pressure of 40 atmosphere (atm), with syngas throughput at space velocity IntraMicron Inc., Nexant Inc.
of 500 to 2,000 standard cubic centimeter (scc)/g/hr (for sorbent), 1,000 to 4,000
start date:
scc/cc/hr (for catalyst).
10.01.2015
• Carbon dioxide capacity of sorbent 3 to 5 mol/kg, and regenerability and
durability of more than 500 cycles. percent complete:
• Progress toward enabling combined MgO-based CO2 sorbent/WGS reactor 100%
technology in a 550-megawatt-electric (MWe) IGCC plant, capable of 90%
capture of CO2 at over 95% purity, while reducing the cost of electricity (COE)
by 30% over IGCC plants employing conventional methods of CO2 capture.
technical content
The working hypothesis of this project is that the conventional WGS unit found in
a coal gasification process plant (for shifting the syngas toward primarily hydrogen
[H2] and CO2) and downstream conventional amine absorption unit for capturing
the CO2 from the shifted syngas could be replaced in whole by a combined MgO‐
based CO2 sorbent/WGS reactor unit. Within the WGS reactor, CO2 would be
withdrawn directly by the sorbent, efficiently increasing the driving force for the
equilibrium WGS reaction to completion. As such, the multiple stages of the
conventional WGS unit are replaced by a single, elegantly performing reactor (or
banks of reactors in parallel as syngas throughput requires).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
508 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
The CO2 sorbent is stabilized meso-porous high-surface area MgO promoted by alkali salts. Magnesium oxide captures
CO2 according to reactions 1 through 3. Carbon dioxide is present in the syngas from the original gasification reactions,
and is additionally formed as a product of the WGS reaction (reaction 4):
MgO(s) + CO2(g) ↔ MgCO3(s); ΔH = -100.7 KJ/mol (1)
MgO(s) + H2O(g) ↔ Mg(OH)2(s); ΔH = -81.1 KJ/mol (2)
Mg(OH)2(s) + CO2(g) ↔ MgCO3(s) + H2O(g); ΔH = -19.5 KJ/mol (3)
CO(g) + H2O(g) ↔ CO2(g) + H2(g); ΔH = -41.2 KJ/mol (4)
The MgO sorbent gradually transforms to carbonate in the forward reactions and must be regenerated to MgO in the
reverse reactions to enable ongoing operation. Accordingly, the reactor must be operated in cyclic mode, with combined
WGS reaction/CO2 capture interval followed by a regeneration interval, with multiple reactors needed to maintain
continual process operation. The regeneration is accomplished by reverse gas flow through the reactor at decreased
pressure (atmospheric). Therefore, this can be regarded as a pressure swing adsorption system for CO2 capture.
This technology takes advantage of IntraMicron’s technology of Microfibrous Entrapped Catalysts (MFECs). These are
based on microfibrous media (MFM), a highly porous structure (≈94%) that consists of randomly oriented microfibers.
The random orientation of the microfibers provides a uniform flow profile throughout the bed, which minimizes
channeling, assists with mixing, and generally allows improved fluid flow to facilitate mass transport at catalytic reaction
sites. MFECs are prepared using a proprietary method that locks small catalyst particles (0 to 35 vol. %, and with size 40
to 300 microns) within the microfibrous media, as depicted in Figure 1(a). The microfibrous structure can be formed from
a variety of materials, including metals (copper [Cu], nickel [Ni], etc.), alloys (stainless steel, brass), polymers, and glass,
allowing the support structure to be tailored to a given reaction system. Metals are typically used when enhanced heat
transfer is needed, because high-conductivity metal MFM enable rapid heat transfer to or from the embedded catalyst
particles. As such, this technology is helpful in intensifying catalytic processes where catalyst performance is otherwise
limited by heat transfer limitations. Also, distributing catalyst particles on a highly porous structure allows gas flow more
akin to a fluidized bed than a packed bed; this might be termed “frozen-fluidized bed” to distinguish it from the
conventional alternatives.
Conventional WGS reactors have the catalyst in traditional packed beds, and it is believed that significant advantages can
be realized by performing the WGS reaction using MFECs in the frozen-fluidized bed configuration (Figure 1(c), which
would reduce or eliminate intra-particle heat and mass transfer limitations experienced conventionally. For example,
Figure 1(b) shows the better heat transfer in MFM as compared to a conventional packed bed of alumina.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
509
Pre-Combustion Novel Concepts
Figure 1: (a) Images of catalyst and sorbent particles entrapped in sintered microfibrous media (top left); (b) comparison of thermal
conductivities of metal MFEC with alumina packed bed (bottom left); (c) improved gas flow through frozen fluidized bed configuration of
MFECs (on right).
In the SR application, commercial WGS catalyst is used as the source material for the catalyst particles in the MFECs.
Promoted MgO sorbent particles are also introduced into the MFM. The result consists of finely divided sorbent and
catalyst particles in close proximity, which allows good heat transfer characteristics and gas flow through the mesh holding
them.
Although combining the WGS reaction and CO2 capture in the same media provides intrinsic process intensification, it
does create challenges in terms of the inevitable regeneration cycle demanded by the sorbent. The WGS catalyst is present
in the reactor as the sorbent undergoes regeneration; the WGS catalyst obviously experiences no benefit from the
regeneration cycle and could experience degradation due to some conditions applied for regeneration.
Figure 2 depicts the laboratory-scale apparatus that SR has employed to determine performance characteristics of the
combined WGS/MgO sorbent media in a small MFEC reactor, operated on simulated syngas compositions resulting from
an air-blown TRIG™ gasifier and an oxygen-blown GE gasifier.
Figure 2: SR’s bench-scale CO2 reactor system.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
510 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
In experimental evaluation of the bench-scale MFEC reactor, SR discovered desulfidation of WGS catalyst resulting in
reduced CO conversion activity and observed structural changes in copper metal MFEC. The sulfidation caused reduction
of thermal conductivity and creation of hot spots. Desulfidation with steam caused degradation of fibrous structure. These
problems were addressed by modifications of the reactor system to prevent regeneration steam from affecting the
catalyst bed by changing MFEC materials from copper to stainless steel and further optimizing reaction conditions.
Under optimized conditions, the sorbents achieved up to 8 mmol/g of CO2 working capacity and remained stable over
500 cycles of adsorption and regeneration. The selected WGS process achieved 96% CO per pass conversion and remained
isothermal during the test duration that lasted more than 500 cycles.
Figure 3 shows the concept for integration of this technology in the context of a representative IGCC process cycle,
indicating the primary process flows and their temperatures for both absorption and regeneration of the WGS-MgO
reactors. Based on this general process arrangement for inclusion of the SR technology in an IGCC cycle with carbon
capture, techno-economic analyses (TEAs) have been prepared comparing this to U.S. Department of Energy
(DOE)/National Energy Technology Laboratory (NETL) baselines of a GE gasifier-based IGCC cycle with capture and a
subcritical pulverized coal plant with capture. Results are reported in Figure 4. Overall, given known performance
parameters and assumptions for costs, the SR MFEC-based WGS/CO2 capture process has lower overall investment costs
than the comparative IGCC baseline, but suffers from lower gross power output and therefore yields approximately the
same COE as the baseline IGCC case.
550C
375C Steam
950C 575C 575C 950C
Coal
Air Gasifier HCl Hot Gas
ATR
Precipitation Filter
Steam H2, CO,
H2O, CO2, WGS/ WGS/
Steam H 2S MgO MgO
Exothermic Endothermic
Absorption Regeneration
375C 450C
350C
375C
N2
H2, H2S 475C
ZnO
Air 325C
Pure CO2
300C
WGT
ZnO/ ZnO/
ZnS ZnS 375C H2
GT H 2O
ZnS + H2O WST
550C
ST
Figure 3: Integration of the combined sorbent/WGS-based CO2 capture process in context of an IGCC plant cycle.
At the end of technology and process development efforts, SR concludes that the combined WGS/CO2 capture process
has technical feasibility to replace conventional two- to three-stage WGS reactor systems with intercooling plus a separate
CO2 capture unit with a single WGS reactor unit, with potential for energy efficiency increase and equipment cost savings.
Notwithstanding the above finding, SR concluded that a single WGS reactor coupled to multiple CO2 sorbent beds would
be a preferred commercial approach compared to several mixed-adsorption/WGS reactors, after considering the
comparative implications of these process arrangements. It turns out that high-CO conversions approaching 96% can be
achieved in the WGS reactor containing only the WGS catalyst supported on MECS and thereby made to be isothermal.
In this case, sorbent-only reactors would be located downstream for CO2 capture. This configuration would meet capture
performance requirements but be less complicated in terms of sorbent regeneration (obviously, because regenerating a
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
511
Pre-Combustion Novel Concepts
dedicated sorbent-only reactor with steam is not problematic, which regenerating one containing combined WGS catalyst
and sorbent would deleteriously expose the WGS catalyst to steam).
In all cases, heat management using MFECs was demonstrated to enable thermodynamically favorable reaction
temperatures for both exothermic CO2 capture/WGS and endothermic regeneration.
The current state-of-the-art CO2 capture process involves scrubbing the gas stream at low temperature. SR’s elevated-
temperature CO2 capture technique eliminates the need to cool the gas stream coming from WGS reactor, resulting in
thermodynamic advantage.
SR’s high-capacity CO2 sorbent provides fast adsorption/desorption kinetics, but regeneration with steam causes slow
degradation that needs further investigation.
Figure 4: TEA case comparisons.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
512 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
Pellet Density kg/m3 1,700 1,600
Bulk Density kg/m3 1,100 1,050
Average Particle Diameter μm 150 150
Packing Density kg/m3 750 730
Sorbent Heat Capacity kJ/kg-K 0.93 0.93
Manufacturing Cost for Sorbent $/kg 0.47 TBD
Adsorption
Total pressure bar 40 40
Temperature °C 350 350
Equilibrium Loading g mol CO2/kg 7.2 5.6
Heat of Adsorption kJ/mol CO2 -130 -130
Desorption
Total pressure bar 1 1
Temperature °C 390 350
Heat of Desorption kJ/mol CO2 130 130
Definitions:
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading. Operating
pressure and temperature for the desorber/stripper are process-dependent. Measured data at other conditions are
preferable to estimated data.
Packing Density – Ratio of the active sorbent mass to the total adsorber volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – See Figure 3 above.
Syngas Conditions – Pressure, temperature and composition of the gas entering the reactor, TRIG™ (air-blown) case:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H2O H2S
615 662 8.5 17.5 2.6 50.5 11.7 9.2 500
Pressure, temperature, and composition of the gas entering the reactor, GE (oxygen-blown) case:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 H2O H2S
615 662 13.7 35.8 0.12 0.8 34.2 15.4 500
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
513
Pre-Combustion Novel Concepts
technology advantages
• Could replace conventional two-stage WGS reactor system with intercooling plus a separate CO2 capture unit with a
single WGS reactor unit, with potential for energy efficiency increase and equipment cost savings.
• Carbon dioxide capture drives equilibrium-limited WGS toward CO2 and H2.
• Integrated heat management maintains thermodynamically favorable reaction temperatures for both exothermic CO2
capture/WGS and endothermic regeneration.
• The current state-of-the-art CO2 capture process involves scrubbing the gas stream at low temperature. SR’s elevated-
temperature CO2 capture technique eliminates the need to cool the gas stream coming from WGS reactor
• SR’s high-capacity and highly regenerable CO2 sorbent provides fast adsorption/desorption kinetics, which can be
applied in a pressure swing process under minimum temperature swing condition.
R&D challenges
• High levels of CO and CO2 in syngas.
• Effect of contaminants in coal syngas on MFECs, MFECs’ thermal stability, and product selectivity maintained at high
pressures and temperatures.
• Sorbent capacity, kinetics, and durability.
• WGS catalyst degradation during cycling.
• Heat management in reactor.
• Process integration with IGCC.
• Scale-up and integration given the large number of reactor modules needed to service a 550-MWe plant.
status
The project is complete. The hybrid CO2 capture/WGS reactor has been run for hundreds of cycles at bench scale and
testing has shown the sorbent to meet both CO2 capture capacity and durability targets. WGS performance was close to
target. Reactor modeling and techno-economic evaluation have been completed, and a 1,000-cycle test has been
completed to gauge durability at optimum process conditions.
available reports/technical papers/presentations
Zhao S, McCabe K. and Gangwal, S. “Combined Sorbent/WGS-based CO2 Capture Process with Integrated Heat
Management for IGCC Systems,” Final Scientific/Technical Report, April 2019.
“Combined Sorbent/WGS-Based CO2 Capture Process with Integrated Heat Management for IGCC Systems,” presented by
Santosh Gangwal, Southern Research Institute, 2018 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh,
PA, August 2018.
“Combined Sorbent/WGS-Based CO2 Capture Process with Integrated Heat Management for IGCC Systems,” presented by
Andrew Lucero, Southern Research Institute, 2017 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh,
PA, August 2017.
“Combined Sorbent/WGS-Based CO2 Capture Process with Integrated Heat Management for IGCC Systems,” presented by
Andrew Lucero, Southern Research Institute, 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh,
PA, August 2016.
"Combined Magnesium Oxide/Water Gas Shift-Based CO2 Capture Process,” poster presentation at CO2 Summit II:
Technologies and Opportunities Conference, Santa Ana Pueblo, New Mexico, April 2016.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
514 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Pre-Combustion Novel Concepts
"Combined Sorbent/WGS-Based CO2 Capture Process with Integrated Heat Management for IGCC Systems,” project
kickoff meeting presentation, October 2015.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 515
Pre-Combustion Novel Concepts
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NATIONAL ENERGY TECHNOLOGY LABORATORY
516 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
517
R&D Collaborations
National Carbon Capture technology maturity:
Laboratory-Scale/Bench-
Center Scale/Pilot-Scale, Actual
Flue Gas
primary project goals project focus:
Carbon Capture Testing
The U.S. Department of Energy (DOE)/National Energy Technology Laboratory (NETL) Center
and Southern Company operate the National Carbon Capture Center (NCCC), a neutral
research facility working to advance technologies to reduce greenhouse gas emissions participant:
from natural gas- and coal-based power plants. Located in Wilsonville, Alabama, the
Southern Company
center offers a unique test bed for third-party technology evaluations of cost-effective
carbon dioxide (CO2) capture technologies—bridging the gap between laboratory research
and large-scale demonstrations. project number:
FE0022596
The NCCC offers exceptional benefits to technology developers by providing them with
testing opportunities in the real-world operating conditions of a power plant, thereby predecessor projects:
accelerating the commercialization of low-cost, carbon capture processes. The center has
surpassed 110,000 hours of technology testing for carbon capture innovators from the NT0000749
United States and six other countries. Through the testing of more than 60 technologies,
the center has directly participated in the reduction of the projected cost of carbon capture NETL Project Manager:
by one-third. Andrew O’Palko
[email protected]
The NCCC will continue to meet its objective of evaluating advanced technologies, both
domestic and international, to identify and resolve environmental, health and safety,
principal investigator:
operational, component, and system development issues, as well as to achieve scale-up
and process enhancements in collaboration with technology developers. Evaluations of john Northington
DOE-sponsored projects, as well as projects from industry, universities, and other Southern Company
collaborative institutions, will provide a full spectrum of technologies for testing at the [email protected]
center.
partners:
American Electric Power,
technical content
ClearPath Foundation,
Electric Power Research
The DOE Office of Fossil Energy’s NETL, in cooperation with Southern Company, Institute, ExxonMobil,
established the NCCC in 2009 to provide an independent, flexible, and cost-efficient NRECA, Peabody Energy,
carbon capture technology testing facility with industrial operating conditions. In Inc., Tennessee valley
undertaking its mission, the center and its staff have been involved in a range of activities
Authority, Total, wyoming
to develop the most promising carbon capture technologies for future commercial
Infrastructure Authority
deployment.
The NCCC provides numerous test bays for simultaneous bench- and pilot-scale operation start date:
of advanced carbon capture technologies at commercially relevant process conditions. 06.06.2014
These include two fully integrated processes for solvent evaluations—a pilot-scale test unit
(PSTU) and a bench-scale slipstream solvent test unit (SSTU)—as well as seven pilot- and percent complete:
bench-scale test bays. In addition to the flexible test site, the facility provides support for
design, procurement, construction, installation, operation, data collection and analysis, and 90%
reporting in compliance with environmental and government regulations.
The types of technologies tested at the NCCC include advanced enzymes, membranes,
sorbents, solvents, hybrids, and associated systems for carbon capture. Testing with the
PSTU and SSTU is conducted to provide extensive data on physical properties of solvents
and perform solvent emission and degradation studies.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
518 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
R&D Collaborations
Since its inception, researchers at the NCCC have conducted numerous tests for the advancement of post-combustion carbon capture
for pulverized coal or natural gas power plants, as well as gasification technologies and pre-combustion carbon capture. In mid-2017,
after completing more than 30 projects in the gasification and pre-combustion carbon capture areas, the center concluded that scope
of work. The gasification and pre-combustion carbon capture equipment is currently being decommissioned and dismantled.
While the demand for post-combustion carbon capture options grows, new projects are planned as the NCCC continues to bring
advanced post-combustion carbon capture technologies closer to the marketplace. Significant infrastructure expansion is underway
to increase carbon capture testing with flue gas under natural gas-fired conditions—research that will support the nation’s continued
reliance on natural gas as a reliable and affordable power generation resource. In addition, future testing at the NCCC will also include
CO2 utilization technologies.
Figure 1: Post-combustion test facilities at the National Carbon Capture Center.
technology advantages
The ability of the center’s facilities to support multiple technology developers and tests simultaneously at various scales, and to offer
flexibility in capacity and process conditions, provides a wide range of data and information to accelerate the commercialization of
carbon capture technologies and enable natural gas- and coal-based power plants to achieve near-zero emissions while reducing
capture costs. The NCCC project is instrumental in supporting the DOE objective of CO2 capture in advanced coal-fired power plants
at a cost of less than $30/tonne by 2030.
R&D challenges
As the need to reduce carbon emissions from fossil-fueled power generation continues to grow, adding carbon capture to fossil fuel-
based electricity generation using conventional technologies would significantly increase the cost of electricity. To utilize the nation’s
abundant fossil-fuel resources in a carbon-constrained future, power generation must be equipped with advanced, cost-effective
carbon capture technology. To address this challenge, the NCCC provides a highly skilled team, along with the infrastructure, realistic
operating conditions, and flexible testing needed for commercial application of carbon capture for natural gas- and coal-based power
generation.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
519
R&D Collaborations
status
Figure 2: Diagram of post-combustion test facilities at the National Carbon Capture Center.
Figure 3: 3D model of natural gas testing system at the National Carbon Capture Center.
The center’s post-combustion test facilities utilize a flue gas slipstream from Southern Company subsidiary Alabama Power’s Plant
Gaston Unit 5 (see Figure 2: Plant Gaston Flue Gas), a base-loaded, 880-megawatt (MW) supercritical pulverized coal boiler. The
unit meets all environmental requirements utilizing state-of-the-art controls (see Figure 2: Flue Gas Desulfurization [FGD]); thus, the
flue gas extracted for testing is fully representative of commercial conditions. As shown in Figure 2, the site houses up to four bench-
scale and three pilot-scale technology developer units, the PSTU and SSTU for comprehensive solvent characterization, and the lab-
scale test unit (LSTU) for bench-scale testing of mixed-matrix membranes and other technologies. An air dilution system is also
available for carbon capture testing under simulated natural gas flue gas conditions.
Construction of a new system for generating natural gas-derived flue gas for carbon capture testing is progressing and expected to
begin operation in 2020. This will create operational independence from the host coal unit, increase operational flexibility for the
center, and provide a contaminant-free flue gas source to allow expanded testing of new technologies on both natural gas- and coal-
derived flue gas.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
520 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
R&D Collaborations
Post-combustion operation has provided more than 60,000 hours of testing enzymes, membranes, sorbents, solvents, hybrids, and
associated systems, and included 37 technologies from 25 developers, with eight technologies scaled-up (or ready) to be demonstrated
at 10+ MW. More than 8,000 hours of testing has been conducted under simulated natural gas conditions. The PSTU has operated
for more than 19,000 hours in support of commercial developers and DOE’s Carbon Capture Simulation Initiative, with several
solvents progressing to larger-scale testing at other facilities and commercial demonstration. Since its creation, the NCCC has more
than doubled its plant capacity from 12,000 to 35,000 lb/hr flue gas and has added systems (SSTU, air dilution, etc.), along with
enhanced instrumentation, sampling methods, and analysis systems. The new natural gas infrastructure currently being installed (see
Figure 3: Natural Gas Testing System) will provide an equivalent capacity of natural gas-derived flue gas for carbon capture testing.
Prior to concluding the gasification and pre-combustion program, accomplishments in these areas included more than 50,000 hours
of testing by technology developers. Scale-up and process intensification was achieved for several technologies. Gasification testing
was conducted in both air- and oxygen-blown operation. Sensor testing involved tunable diode laser sensors, particulate monitors,
thermowells, and coal feeder instrumentation. Water-gas shift (WGS) catalyst tests showed that steam-to-carbon monoxide ratios can
be reduced, relative to traditional recommendations, which in turn increases the net power output of an integrated gasification
combined-cycle plant and reduces the cost of electricity with carbon capture. A number of advanced CO2-absorbing chemical and
physical solvents, various hydrogen- and CO2-selective membranes, WGS catalysts, high-temperature mercury capture sorbents, and
solid oxide fuel cells were tested.
Performance data generated in post-combustion, gasification, and pre-combustion technology testing at the NCCC has been used to
validate laboratory data allowing for engineering scale-up, in turn driving new breakthroughs in carbon capture solutions.
available reports/technical papers/presentations
Advanced Technology Testing at the National Carbon Capture Center, Presented by Michele Corser, Southern Company, 2019
NETL Carbon Capture, Utilization and Storage, and Oil and Gas Technologies Integrated Review Meeting, Pittsburgh, PA, Aug
2019.
Update on National Carbon Capture Center, Presented by Tony Wu, Southern Company, 2018 NETL CO2 Capture Technology
Project Review Meeting, Pittsburgh, PA, Aug 2018.
Advanced Technology Testing at the National Carbon Capture Center, Presented by John Carroll, Southern Company, 2017 NETL
CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, Aug 2017.
2017 Update on Technology Testing at the National Carbon Capture Center, Presented by Barry Shirley, Southern Company, 42nd
International Technical Conference on Clean Energy, Clearwater, FL, June 2017.
Advanced Technology Testing at the National Carbon Capture Center, Presented by Justin Anthony and John Carroll, Southern
Company, 2016 NETL CO2 Capture Technology Project Review Meeting, Pittsburgh, PA, Aug 2016.
Pre-Combustion Carbon Capture at the National Carbon Capture Center, Presented by John Socha, Southern Company, 2015
NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
National Carbon Capture Center: Post-Combustion, Presented by Patrick Crossley, Southern Company, 2015 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, June 2015.
National Carbon Capture Center: Pre-Combustion CO2 Capture, Presented by Tony Wu, Southern Company, 2014 NETL CO2
Capture Technology Meeting, Pittsburgh, PA. (July 2014)
National Carbon Capture Center: Post-Combustion, Presented by John Wheeldon, National Carbon Capture Center, 2014 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
Website: https://www.nationalcarboncapturecenter.com/.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 521
R&D Collaborations
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NATIONAL ENERGY TECHNOLOGY LABORATORY
522 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Completed Projects
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
APPENDIX:
Completed
Projects
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 523
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
POST-COMBUSTION
SOLVENT TECHNOLOGIES
NATIONAL ENERGY TECHNOLOGY LABORATORY
524 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Bench-Scale Process for Low- technology maturity:
Bench-Scale, Simulated Flue
Cost Carbon Dioxide Capture Gas
Using a Phase-Changing project focus:
Absorbent
Phase-Changing Absorbent
participant:
GE Global Research
primary project goals
project number:
GE Global Research is designing and optimizing a bench-scale process using a novel
FE0013687
phase-changing aminosilicone-based carbon dioxide (CO 2 )-capture solvent
(absorbent) to establish scalability and technical and economic feasibility of using a
phase-changing CO 2 -capture absorbent for post-combustion capture, with the predecessor projects:
ultimate goal of achieving an overall reduction in CO 2 capture cost. ARPA-E project DE-
AR0000084
technical goals NETL project manager:
David Lang
• Design and build a bench-scale system for post-combustion CO 2 capture using a [email protected]
phase-changing aminosilicone-based solvent.
• Develop preliminary process and cost models. principal investigator:
• Conduct bench-scale testing on unit operations to evaluate performance and Tiffany westendorf
define parameters for scale-up. GE Global Research
[email protected]
• Evaluate materials of construction, manufacturability of solvent, assemble
continuous bench-scale system, and update the process model.
partners:
• Perform testing on continuous system to optimize process parameters.
Coperion Corporation
• Perform EH&S and techno-economic assessments and devise a scale-up strategy.
start date:
technical content 01.01.2014
GE Global Research is designing and optimizing a new process for a phase-changing percent complete:
CO 2 capture solvent for use in post-combustion capture in coal-fired power plants. The 100%
process is based on the use of the silicone-based phase change solvent (GAP-0), which
was developed at the lab-scale in a previous ARPA-E project (DE-AR0000084). The liquid
solvent rapidly absorbs CO 2 at low temperatures (40–50 °C) with high loading
(>17 percent weight gain) to form a solid carbamate salt. The carbamate salt readily
decarboxylates at high temperatures. The innovative process is designed to make use
of the unique phase-change properties of the aminosilicone solvent.
The process as originally designed, shown in Figure 1, starts in the absorber, where the
liquid phase-changing solvent is sprayed in fine droplets into the flue gas, reacting with
the CO 2 to form solid particles. The solids are conveyed in an extruder, moving from the
low-temperature, low-pressure absorber to the high-temperature, high-pressure
desorber. The unique design of the extruder permits heating and compression of the
solids, allowing for continuous delivery of the solids into the pressurized desorber. The
solids are heated in the desorber, leading to decarboxylation. CO 2 is separated from the
liquid phase-changing solvent in the desorber, allowing for recovery of the CO 2 and
recycle of the solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
525
Appendix: Post-Combustion Solvent Technologies
Figure 1: Phase-changing absorbent process
During the project, the process was modified based on understanding water effects on the carbamate and thermal stability of
the carbamate. This revised process, as shown in Figure 2, produces a water-carbamate solids slurry in the spray absorber, which
is transferred to the desorber inlet by a slurry pump. The single stage desorber operates at near-atmospheric pressure.
Figure 2: Updated process using a slurry rich phase
Testing of the bench-scale system provided data, including mass transfer parameters, kinetic parameters, heat transfer
parameters, solvent stability, effects of flue gas contaminants, and recommended operating conditions, to perform a techno-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
526 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
economic assessment and develop a scale-up strategy. The project aimed to establish scalability and technical and economic
feasibility of using a phase-changing CO 2 -capture absorbent for post-combustion capture of CO 2 from coal-fired power plants.
The solvent and process parameters are provided in Table 1.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 248.51 248.51
Normal Boiling Point °C 258.7 258.7
Normal Freezing Point °C <0 <0
Vapor Pressure @ 15 °C bar 1.8 x 10-5 1.8 x 10-5
Manufacturing Cost for Solvent $/kg TBD TBD
Working Solution
Concentration kg/kg 1 0.9
Specific Gravity (15 °C/15 °C) - 0.891 0.891 (GAP-0)/1.0 (water)
Specific Heat Capacity @ STP kJ/kg-K 2.29 2.29 (GAP-0)/4.18 (water)
Viscosity @ STP cP 4.4 12.3 (10% water, 90% GAP-0)
Absorption
Pressure bar 1 1
Temperature °C 30 40-60
Equilibrium CO 2 Loading mol/mol 0.9 0.65
Heat of Absorption kJ/mol CO 2 -113.4 -113.4
Solution Viscosity cP N/A N/A
Desorption
Pressure bar 7 1
Temperature °C 160 130
Equilibrium CO 2 Loading mol/mol 0.34 0.23
Heat of Desorption kJ/mol CO 2 -113.4 -113.4
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,767,497
CO 2 Recovery, Purity, and Pressure % / % / bar 90 95 150
Absorber Pressure Drop bar TBD
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., the amine monoethanolamine [MEA} in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO 2 -free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
527
Appendix: Post-Combustion Solvent Technologies
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent
(e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the solution. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly
0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO 2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Chemical absorption
Solvent Contaminant Resistance – Solvent absorbs sulfur dioxide (SO 2 ), forming heat-stable salts.
Solvent Foaming Tendency – Limited.
Flue Gas Pretreatment Requirements – Flue gas desulfurization, cooling to <40 °C.
Solvent Make-Up Requirements – TBD.
Waste Streams Generated – In the commercial scale process, a small slipstream of the phase-changing absorbent may be purged
from the process to limit accumulation of sulfur compounds in the solvent.
Process Design Concept – See Figure 2 above.
technology advantages
• Non-aqueous, pure solvent.
• Superior properties compared to reference case (MEA) results in potential for cost reduction.
o Lower heat capacity.
o Low corrosivity.
o Low vapor pressure.
• High CO 2 loading and intensified mass transfer requires smaller equipment.
R&D challenges
• Cost and availability of the solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
528 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
• Thermal degradation of solvent.
• Development of an advanced low-temperature desorber.
• Development of correlations between the primary system variables and unit operations performance to determine scale-up
effects, particularly on heat transfer in the absorber and desorber.
status
GE and NETL mutually agreed to terminate the project prior to completion of the final task due to internal changes within GE. GE
had designed, built, and tested a bench-scale system to evaluate their phase-changing solvent system. A techno-economic
assessment based on bench-scale testing data indicated a first-year CO 2 capture cost of $52.1/tonne compared to $66.4/tonne
for an aqueous amine process, with cost improvement primarily due to higher working capacity, lower corrosivity, lower vapor
pressure, and lower heat capacity of the phase changing solvent. However, as much as $88/tonne could be added to the CO 2
capture cost for solvent make-up costs due to the thermal degradation of this solvent at the Continuous Stirred Tank Reactor
(CSTR) desorber operating temperatures, confirming the need for development of a low-temperature desorber.
available reports/technical papers/presentations
“Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” Final Report, May
2017. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/fe0013687-final-report.pdf
Westendorf, T., “Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” 2016 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/T-Westendorf-GE-Phase-
Changing-Absorbent.pdf
Westendorf, T., “Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” 2015 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, June 2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/T-
Westendorf-GE-Phase-Changing-Absorbent.pdf
Westendorf, T., “Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” Budget Period 1 Briefing
Presentation, Pittsburgh, PA, February 2015. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/2015-02-23-DE-FE0013687-BP1-briefing.pdf
Westendorf, T., “Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” 2014 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File Library/Events/2014/2014 NETL CO2 Capture/T-
Westendorf-GE-Phase-Changing-Absorbent.pdf.
Westendorf, T., “Bench-Scale Process for Low-Cost CO 2 Capture Using a Phase-Changing Absorbent,” Project Kick-Off Meeting
Presentation, Pittsburgh, PA, November 20, 2013. http://www.netl.doe.gov/File Library/Research/Coal/carbon capture/post-
combustion/2013-11-20-Kickoff-Meeting-GE-FE0013687.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 529
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Accelerating the technology maturity:
Development of
Laboratory Scale
“Transformational” Solvents for
project focus:
CO2-Binding Organic Liquid
CO2 Separations
(CO2BOL) Solvents
participant:
Pacific Northwest National
primary project goals Laboratory
Pacific Northwest National Laboratory (PNNL) developed transformational carbon project number:
dioxide (CO2) capture solvents based on their nonaqueous switchable organic solvents,
FWP-65872
known as CO2-binding organic liquids (CO2BOLs). The project focus used computation-
aided molecular design to optimize, synthesize, and characterize CO2BOLs with a CO2-
rich viscosity of less than 50 cP at a cost of less than $10/kg. predecessor projects:
FE0007466
technical goals NETL project manager:
Isaac Aurelio
• Develop a physical property model to predict the viscosity of CO2BOL compounds. [email protected]
• Develop a model to predict thermodynamic properties of CO2BOL compounds.
• Design and synthesize promising CO2BOL candidate compounds and compare principal investigator:
solvent properties with predicted molecular simulations. David Heldebrant
• Synthesize candidates meeting desired cost and viscosity targets for further Pacific Northwest National
Laboratory
evaluation to determine how molecular structure impacts solvent system viscosity.
[email protected]
• Update thermodynamic and process models using data from CO2BOL testing to
predict process performance and cost. partners:
N/A
technical content
start date:
Solvent Platform 04.01.2014
PNNL developed transformational CO2 capture solvents based on their nonaqueous percent complete:
switchable organic solvents, known as CO2BOLs. This project advanced the
development efforts of the previously funded DOE project DE-FE0007466. 100%
CO2BOLs are a class of switchable ionic liquids (molecular liquids that become ionic in
the presence of CO2) that have lower specific heat and higher CO2 working capacities
compared to aqueous amines, resulting in potential savings in the sensible heat
required to strip CO2.
Figure 1: Uptake of CO2 by Alkanolguanidine BOL (left),
and formation of Zwitterionic CO2BOL (right)
Like aqueous amines, CO2BOLs are basic, but the base (e.g., guanidine, amidine) does
not directly react with CO2. Instead, the alcohol component reacts with CO2, forming
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
530 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
alkyl carbonic acid, and subsequently transfers a proton to the base, forming liquid alkylcarbonate. Current CO2BOL generation
combines the base and the alcohol moieties in a single molecule, lowering volatility (Figure 1).
The addition of a non-polar solvent (anti-solvent) to CO2BOLs and other switchable solvents during the solvent regeneration
destabilizes bound CO2, thus potentially lowering the temperature at which the stripper can be operated; (this is referred to as
the polarity-swing-assisted regeneration [PSAR] process). Preliminary results indicate that PSAR could reduce the regeneration
temperatures of CO2BOLs by more than 20 °C. This allows novel possibilities for heat integration, such as transferring heat from
the absorber to the stripper using heat pumps, thereby lowering steam demand for solvent regeneration. The anti-solvent can
be separated out from the CO2BOL by cooling and liquid-liquid phase separation. A schematic of the CO2BOL-PSAR process is
shown in Figure 2.
Previous generations of single-component CO2BOLs were highly viscous before CO2 absorption. The current generation of
alkanolguanidine CO2BOLs has lower viscosity before CO2 absorption.
Figure 2: CO2BOL absorption and PSAR process
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 531
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
The solvent and process parameters identified to date are provided in Table 1.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 171.14 171.14
Normal Boiling Point °C 262 (decomposes >200) 262 (decomposes >200)
Normal Freezing Point °C <0 <0
Vapor Pressure @ 15 °C 0.179 (37 °C) (DBU) 0.001
bar 0.001
(100 °C)
Manufacturing Cost for Solvent $/kg $35 $10
Working Solution
Concentration 1 (anhydrous) 1 (anhydrous)
kg/kg
0.91 (hydrated) 0.91 (hydrated)
Specific Gravity (15 °C/15 °C) - 1.03 1.03
Specific Heat Capacity @ STP kJ/kg-K 1.9 1.9
Viscosity @ STP 1.9 (CO2-free solvent) 1.9 (CO2-free solvent)
cP
50 (lean solvent) 11 (lean solvent)
Absorption
Pressure 1 (near atmospheric, 1 (near atmospheric,
bar 0.15 bar CO2 partial 0.15 bar CO2 partial
pressure) pressure)
Temperature
°C 40 40
Equilibrium CO2 Loading 0.5 (at 0.15 bar CO2 partial 0.5 (at 0.15 bar CO2 partial
mol/mol
pressure) pressure)
Heat of Absorption -80 (anhydrous) -80 (anhydrous)
kJ/mol CO2
-90 (hydrated) -90 (hydrated)
Solution Viscosity cP 356 50
Desorption
Pressure bar 2 2
Temperature °C 103.8 103.8
Equilibrium CO2 Loading mol/mol 0.25 0.25
Heat of Desorption kJ/mol CO2 -80 (anhydrous) -80 (anhydrous)
-90 (hydrated) -90 (hydrated)
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure %/%/bar — — —
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Molecular Design and Optimization
The objective of this project was to expand DOE’s Office of Fossil Energy’s (FE) capabilities for molecular design and optimization
of transformational solvent systems, starting with PNNL’s CO2BOLs solvent platform as a model for this activity. Key program
metrics include identification of a viable candidate with a CO2-loaded viscosity below 50 cP and at a cost no greater than $10/kg,
and to learn why viscosity increases occur in water-lean solvents and how to minimize viscosity increases. To achieve this, PNNL
has developed a novel physical property prediction model that can accurately reproduce laboratory-measured material
properties. Previously synthesized and characterized CO2BOL derivatives from PNNL’s completed programs were used to
establish the molecular model. A concurrent molecular design effort was started to produce libraries of new compounds with
reduced viscosity by introducing design motifs based on organic chemistry principles. Once the molecular model was
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
532 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
completed, molecules in the library were simulated to determine which compounds showed reduced viscosity, and, more
importantly, why they were less viscous. Modeled compounds are compared against synthesized compounds for validation and
refinement (Figure 3). Once design principles were discovered, these new structural motifs were introduced into subsequent
molecular designs to achieve reductions in rich-solvent viscosity.
To date, the reduced model has been developed with 91 percent accuracy compared to full-scale simulations. The model has
identified hydrogen bonding and electrostatic (specifically dipole-dipole between molecules) interactions as the most critical
design elements for low-viscosity CO2BOLs, and from this knowledge we have designed and simulated hundreds of molecules,
with tens of candidate molecules that are projected to be less viscous than the previous derivative. The reduced model and the
knowledge gained from this study can be used to improve transformational solvent systems across FE’s solvent portfolio.
!!
!
First!100!
! Model!Validation:!
Compounds!
! Direct!Comparisons!
Identified! and!Empirical!Fits!
!
!
!
Molecular!Modeling!Outputs!
!
• !Ring!size! Up!to!13!Compounds!
Experimental!Measures!!
• !Solvation!of!charge! DownCselected!and! (as$a$function$of$CO2$loading)$
Synthesized! • Viscosity!
• !Hydrogen!bonding!
• Heat!of!reaction!(CO2)!
• !Intermolecular!contacts!
• Water!uptake!
! • Heat!capacity!
! • CO2!capacity!(VLE!curve)!
! • Gas!diffusion!(inert!gas)!
! • Surface!tension!
Initial!Predictions!
! • Viscosity! • Vapor!pressure!(up!to!100!˚C)!
!
• Heat!of!reaction!(CO2)!
!
!
Figure!2.!!Molecular!Modeling!Predictions!vs.!Experimental!Measures!
Figure 3: Molecular modeling prediction vs. experimental measures
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process dependent
(e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly 0.132 atm or
0.130 bar.
Concentration – The mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 533
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The chemical reaction for the CO2 capture process with a representative CO2BOL is
shown in Figure 1.
Solvent Contaminant Resistance – Tests of CO2BOL reactivity with hydrogen chloride (HCl), sulfur oxide (SOx) and nitrogen oxide
(NOx) will be conducted. In general, CO2BOLs form heat-stable salts (HSS) with sulfur dioxide (SO2), NOx, and HCl. The solvent can
be recovered from the HSS using caustic wash or with ion exchange resins. Levels of HSS formation are expected to be similar to
that of MEA. Minimal adverse impacts due to arsenic and mercury in the flue gas are expected.
Solvent Foaming Tendency – Foaming tendency has not been observed in prior formulations during bench-scale testing.
Foaming of future derivatives remains unknown.
Flue-Gas Pretreatment Requirements – Water management with any of the alkanolguanidine-based CO2BOLs is different from
that with MEA.CO2BOL solvents are designed to minimize water uptake by the solvent, as the presence of water increases solution
viscosity and increases the energy required to regenerate the CO2BOL. As such, CO2BOL formulations are favored energetically
to run with a 5 wt% steady-state loading of water. To achieve this loading target, the process requires a small refrigeration unit
upstream of the absorber to condense out water. Other flue-gas pretreatment requirements (for acid-gas contaminants) are
expected to be similar to those with MEA.
Solvent Makeup Requirements – Until a formal lifetime analysis can be made, the estimated makeup rate of CO2BOLs will depend
on the anticipated thermal and chemical degradations. Currently, evaporative losses are projected to be 40 kg per annum.
Waste Streams Generated – CO2BOLs have lower vapor pressure than MEA, and post-absorber CO2BOL emissions would be at
lower levels (estimated at 0.7 parts per billion [ppb]). Other major waste streams may include stripper wastes and reclaimer
wastes.
Proposed Module Design – Unless noted, the following should be assumed for flue gas leaving the flue gas desulfurization (FGD)
(wet basis): feed pressure 1.014 bar, temperature 57 °C, and composition as shown in the table below.
Composition
Pressure Temperature vol% ppmv
bara °C CO2 H2O N2 O2 Ar SOx NOx
1.014 57 13.17 17.25 66.44 2.34 0.80 42 74
technology advantages
Solvent Platform
• The lower solvent specific heat and water content leads to smaller parasitic load than current solvents (MEA).
• The lower solvent evaporative losses and thermal degradation may lead to lower cost of CO2 capture.
• The rates of liquid-phase mass-transfer kinetics with CO2BOLs are comparable to those of current solvents (MEA and
piperazine), albeit at higher solution viscosity.
• PSAR may enable low-temperature CO2BOL regeneration, reducing the pressure of low-pressure steam used for
regeneration, thereby increasing net power production and reducing parasitic loads.
• Heat integration possibilities with PSAR and CO2BOLs may have minimal impact on steam plant cycles, facilitating retrofits
for existing plants.
Molecular Design and Optimization
• The current PNNL-developed reduced molecular model can predict solvent thermodynamic and kinetic behavior, providing
projections of solution viscosity and heats of reaction. This model enables rapid screening of advanced water-lean solvent
platforms for development, as compared to conventional computationally intensive molecular dynamics simulations.
• The PNNL model has identified hydrogen bonding and electronic stacking as the two most critical contributors to viscosity
in water-lean solvent platforms such as CO2BOLs, enabling rapid optimization of solvent chemistry.
• The PNNL model is translatable to other solvent platforms across DOE’s portfolio.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
534 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
R&D challenges
Solvent Platform
• The estimated cost of manufacturing the current-generation CO2BOL solvent is high, leading to high operation costs.
• Water absorption by the CO2BOL requires the amount of water in the flue gas to be reduced significantly by refrigeration to
avoid water buildup in the solvent recirculation loop. However, these nominal capital costs and auxiliary electric loads are
recovered in the net power gains by the PSAR.
Molecular Design and Optimization
• The challenge is to make targets from molecular predictions at a cost of $10/kg.
status
The project was completed on September 30, 2017. PNNL results indicated that PSAR could reduce the regeneration
temperatures of CO2BOLs by more than 20 °C, allowing novel possibilities for heat integration thereby lowering steam demand
for solvent regeneration. PNNL also determined that the reduced model has been developed with 91 percent accuracy compared
to full-scale simulations. The reduced model and the knowledge gained from this study can be used to improve transformational
solvent systems across FE’s solvent portfolio.
available reports/technical papers/presentations
Heldebrant, D., “Accelerating the Development of ‘Transformational’ Solvents for CO2 Separations,” 2017 NETL CO2 Capture
Technology Project Review Meeting, Pittsburgh, PA. https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/4-
Thursday/2D-Heldebrant2-PNNL-Transformational-Solvents.pdf
Heldebrant, D., “Accelerating the Development of Transformational Solvent Systems for CO2 Separations,” June 20, 2017,
Morgantown, WV. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/PNNL-FWP-
65872-Project-Update-June-2017.pdf
Heldebrant, D., Final Report, “CO2-Binding Organic Liquids, Enhanced CO2 Capture Process with a Polarity-Swing-Assisted
Regeneration,” August 31, 2014. http://www.osti.gov/scitech/servlets/purl/1151840.
“CO2-Binding Organic Liquids, Enhanced CO2 Capture Process with a Polarity-Swing-Assisted Regeneration,” 2014 CO2 Capture
Technology Meeting, Pittsburgh, PA. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/D-
Heldebrant-PNNL-CO2-Binding-Organic-Liquids.pdf.
“CO2-Binding Organic Liquids, Enhanced CO2 Capture Process with a Polarity-Swing-Assisted Regeneration,” 2013 CO2 Capture
Technology Meeting, Pittsburgh, PA. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/D-Heldebrant-
Battelle--Organic-Liquids-with-PSA-Regen.pdf.
“CO2-Binding Organic Liquids, Enhanced CO2 Capture Process with a Polarity-Swing-Assisted Regeneration,” 2012 CO2 Capture
Technology Meeting, July 2012, Pittsburgh, PA. http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/co2-
binding-organic-liquids-gas-capture-july2012.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
535
Appendix: Post-Combustion Solvent Technologies
Large Pilot-Scale Carbon technology maturity:
Dioxide (CO2) Capture Project
Large Pilot-Scale (10-MWe),
Actual Flue Gas
Using Aminosilicone Solvent project focus:
Aminosilicone Solvent
primary project goals participant:
GE Global Research
GE Global Research developed a plan to define a 10-MW e large pilot-scale project
for post-combustion carbon dioxide (CO2) capture using their novel aminosilicone- project number:
based solvent, minimizing and quantifying risks associated with technical success,
cost, and schedule. The information from this Phase I project can be used to inform FE0026498
the experimental design, budget, and schedule for a Phase II pilot test project.
predecessor projects:
FE0013755
technical goals FE0007502
NT0005310
• Evaluate and select a site for the 10-MW e large pilot plant.
• Qualify a supplier for the aminosilicone solvent. NETL project manager:
• Develop a technology gap analysis, a screening-level design and cost Steven Mascaro
estimate. [email protected]
• Prepare an environmental, health, and safety assessment.
principal investigator:
• Complete a techno-economic analysis for the CO2 capture system.
Philip DiPietro
GE Global Research
technical content [email protected]
GE Global Research, in Phase I of this large-pilot project, developed a project plan partners:
for large-scale (10-MW e) testing of their aminosilicone-based solvent CO2 capture N/A
process. In prior project FE0013755, GE Global Research designed, constructed,
and operated a 0.5-MW e slipstream post-combustion CO2 capture pilot-scale start date:
process using this solvent at the NCCC Pilot Solvent Test Unit (PSTU), as shown
10.01.2015
in Figure 1. The process is based on the use of the aminosilicone-based solvent
which was developed on the bench-scale in previous US DOE funded projects
(DE-FE0007502 and DE-NT0005310). Specifically, the solvent system is percent complete:
composed of a mixture of GAP-1m and triethylene glycol (TEG). The carbamate 100%
formed upon CO2 absorption does not precipitate out in this solvent mixture. The
solvent has a much lower volatility than monoethanolamine (MEA), which
simplifies the desorption process and decreases the energy required for CO 2
desorption. The solvent can be regenerated at elevated pressures, resulting in
lower compression costs. The solvent also shows higher CO 2 capacity, high
thermal stability, and low corrosivity.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
536 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 1: Pilot-scale system at NCCC
Testing on the 0.5-MW e pilot-scale system using coal-fired flue gas provided data, including mass transfer parameters,
kinetic parameters, heat transfer parameters, solvent stability, effects of flue gas contaminants, and recommended
operating conditions, to update process models and to perform a techno-economic assessment and determine a scale-
up strategy.
Two different desorption concepts were evaluated. The first, as shown above in Figure 1, used a continuous stirred tank
reactor (CSTR) for desorption. The benefits of this concept include lower capital cost, simple operation, single stage
desorption, and a small footprint. Adding water recycle can lower thermal degradation, decrease wastewater, and reduce
solvent loss.
The other concept evaluated, shown in Figure 2, used a steam stripper column (SSC). This is a multistage desorption
process resulting in a lower desorption temperature.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
537
Appendix: Post-Combustion Solvent Technologies
Figure 2: Process design with steam stripper
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
538 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight 322.67 (GAP-1m)/150.17 322.67 (GAP-1m)/150.17
mol-1
(TEG) (TEG)
Normal Boiling Point °C 310 (GAP-1m)/287 (TEG) 310 (GAP-1m)/287 (TEG)
Normal Freezing Point °C -85 (GAP-1m)/-7 °C (TEG) -85 (GAP-1m)/-7 °C (TEG)
Vapor Pressure @ 15°C 0.005 bar @ 140 °C (TEG) 0.005 bar @ 140 °C (TEG)
bar 0.037 bar @ 140 °C (GAP- 0.037 bar @ 140 °C (GAP-
1m) 1m)
Manufacturing Cost for Solvent $/kg — —
Working Solution
Concentration kg/kg 60/40 GAP-1m/TEG 60/40 GAP-1m/TEG
Specific Gravity (15°C/15°C) - 0.913 (GAP-1m)/1.124 (TEG) 0.913 (GAP-1m)/1.124 (TEG)
Specific Heat Capacity @ STP kJ/kg-K 2.319 (60/40 GAP-1m/TEG) 2.319 (60/40 GAP-1m/TEG)
Viscosity @ STP cP 4.37 (GAP-1m)/49 (TEG) 4.37 (GAP-1m)/49 (TEG)
Absorption
Pressure bar 0 (gauge) 0 (gauge)
Temperature °C 40-60 C 40-60 C
Equilibrium CO2 Loading mol/mol 0.78 (CO2)/1 (GAP-1m) 0.78 (CO2)/1 (GAP-1m)
Heat of Absorption kJ/mol CO2 99.7 (60/40 GAP-1m in TEG) 99.7 (60/40 GAP-1m in TEG)
Solution Viscosity cP 431 (60/40 GAP-1m in TEG) 431 (60/40 GAP-1m in TEG)
Desorption
Pressure bar 2 (gauge) 2 (gauge)
Temperature °C 140 C 140 C
Equilibrium CO2 Loading mol/mol 0.25 (CO2)/1 (GAP-1) 0.25 (CO2)/1 (GAP-1)
Heat of Desorption kJ/mol CO2 99.7 (60/40 GAP-1m in TEG) 99.7 (60/40 GAP-1m in TEG)
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 99.7 (60/40 GAP-1m in TEG)
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 3
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
539
Appendix: Post-Combustion Solvent Technologies
to a CO2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120 °C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO 2. Note that for a typical pulverized coal (PC) power plant, the
total pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial
pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOx NOx
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – The reaction of the GAP class of aminosilicones with CO2 is shown in Figure
2. The aminosilicone in this study is a mixture of GAP molecules where the average value of the subscript (x) shown in
Figure 2 is one. This solvent is designated GAP-1. GAP-1 is combined with TEG in a 60/40 (by weight) mixture to inhibit
the solidification that occurs when the neat solvent (GAP-1) reacts with CO2.
Figure 2: Reaction of GAP class of aminosilicones with CO2 to form GAP carbamate
Solvent Contaminant Resistance – As with MEA, aminosilicones will react irreversibly with sulfur dioxide (SO 2) to form
heat- stable salts (HSS). Solvent makeup will be required to replace aminosilicone lost to reaction with SO 2.
Solvent Foaming Tendency – None observed.
Flue Gas Pretreatment Requirements – In a full-scale system, the flue gas pretreatment requirements are identical to
those of an MEA-based process, including a selective catalytic reduction reactor, particulate removal, and flue gas
desulfurizer (FGD).
Solvent Make-Up Requirements – In addition to the solvent makeup required due to reaction of aminosilicone with SO 2,
additional solvent makeup will be required due to thermal decomposition. However, it has been demonstrated that GAP-
1 is significantly more thermally stable than MEA, as discussed below.
Waste Streams Generated – A waste stream of HSS from the reaction of SO2 with aminosilicone will be generated.
Process Design Concept – The process flow diagram for the aminosilicone-based, bench-scale CO2-capture system is
shown in Figure 3.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
540 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 3: The process flow diagram for the bench-scale system
technology advantages
• Lower volatility.
o Simplified separations.
o Less energy wasted vaporizing solvent and/or water.
o Lower airborne release rates.
• Lower heat capacity.
• Reduced corrosion.
• Potential for decreased issues with aerosol formation.
R&D challenges
• Completing design to integrate the process into the host site.
status
This project was completed. GE qualified a major chemical manufacturer as the GAP-1 solvent supplier. A 100-kg solvent
sample was received and tested on the bench-scale, meeting purity and performance specifications. The phase I project
effort identified Technology Centre Mongstad as a host site, and designed and estimated the cost for retrofit to
accommodate the GE solvent at the TCM plant. The techno-economic analysis indicated a CO2 removal cost using the
steam stripper for desorption as $42/tCO2 (entitlement) and $48/tCO2 (with degradation, at ~15 percent/year solvent
makeup). The CO2 removal cost using the CSTR desorber was higher, with the cost dominated by the solvent make-up
costs. Due to a schedule slip in the testing at NCCC (predecessor project FE0013755), GE decided not to submit a Phase
II application.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
541
Appendix: Post-Combustion Solvent Technologies
available reports/technical papers/presentations
Hancu, D., “Pilot-Scale Silicone Process for Low-Cost CO2 Capture,” Final Project Review Presentation, October 2017.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0026498-Final-Project-
Status.pdf
DiPietro, P., “Large Pilot-Scale CO2 Capture Project Using Aminosilicone Solvent,” 2016 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/2-Tuesday/P-DiPietro-GE-CO2-Capture-
using-Aminosilicone-Solvent.pdf
DiPietro, P., “Large Pilot-Scale CO2 Capture Project Using Aminosilicone Solvent,” Project Kick-Off Meeting
Presentation, Pittsburgh, PA, November 2015.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0026498-Kickoff-
Presentation.pdf
Wood, B., “Pilot-Scale Silicone Process for Low-Cost CO2 Capture,” 2016 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, August 2016. http://netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/1-Monday/B-
Wood-GE-Silicone-Process-for-CO2-Capture.pdf
Wood, B., “Pilot-Scale Silicone Process for Low-Cost CO2 Capture,” 2015 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, June 2015. http://netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/B-Wood-GE-Pilot-
Silicone-Process.pdf
Wood, B., “Pilot-Scale Silicone Process for Low-Cost CO2 Capture,” 2014 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File Library/Events/2014/2014 NETL CO2 Capture/B-Wood-GE-
Pilot-Scale-Silicone-Process.pdf.
Final Report, “Bench-Scale Silicone Process for Low-Cost CO2 Capture,” December 2013.
http://www.osti.gov/scitech/servlets/purl/1133118.
Wood, B., “Bench-Scale Silicone Process for Low-Cost CO2 Capture,” 2013 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/B-Wood-GE-Bench-
Scale-Silicone-Process.pdf.
Wood, B., “Bench-Scale Silicone Process for Low-Cost CO2 Capture,” 2012 NETL CO2 Capture Technology Meeting,
July 2012. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/bench-scale-silicone-process-low-cost-
july2012.pdf.
Wood, B., “Bench-Scale Silicone Process for Low-Cost CO2 Capture,” Project Kick-Off Meeting Presentation,
Pittsburgh, PA, November 22, 2011. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/bench-scale-
silicone-process-low-cost-kickoff-nov2011.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
542 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Development and technology maturity:
Pilot-Scale, Actual Flue Gas
Demonstration of Waste Heat Slipstream
Integration with Solvent project focus:
Process for More Efficient CO2
waste Heat Integration
Removal from Coal-Fired Flue participant:
Southern Company Services
Gas project number:
FE0007525
primary project goals
predecessor projects:
Southern Company Services developed viable heat integration methods for the N/A
capture of carbon dioxide (CO 2 ) produced from pulverized coal (PC) combustion. The
project quantified energy efficiency improvements to an existing amine-based CO 2 NETL project manager:
capture process by utilizing a waste heat recovery, high-efficiency system (HES) and Bruce Lani
evaluated the technical and economic feasibility of full-scale implementation of this [email protected]
technology.
principal investigator:
technical goals Nick Irvin
Southern Company Services
[email protected]
• Reduction of the amount of extraction steam required for sensible heat load in the
solvent regeneration system by providing process stream heating through waste partners:
heat streams.
Mitsubishi Heavy Industries,
• Heating of boiler feed water through waste heat to reduce extraction steam America, Inc., AECOM
demands on the low-pressure (LP) turbine.
• Increasing LP steam available for power generation or CO 2 regeneration. start date:
10.01.2011
technical content
percent complete:
Southern Company Services developed viable heat integration methods for the 100%
capture and sequestration of CO 2 produced from PC combustion. A waste heat
recovery technology, HES, was integrated with an existing 25-megawatt electric (MW e )
amine-based CO 2 capture process, (MHI’s Kansai Mitsubishi Carbon Dioxide Recovery
(KM-CDR™) process), at Plant Barry to evaluate improvements in the energy efficiency
of the CO 2 capture process. Pilot-scale testing also provided operational experience to
determine the stability of the integrated HES/CO 2 capture process, particularly with use
of a high-sulfur flue gas. An advanced level of heat integration between the power
plant and the CO 2 capture facility is demonstrated by using waste heat to provide
process heating to the CO 2 absorber process condensate and boiler feed-water,
reducing the extraction steam requirements, making more low pressure steam
available for CO 2 regeneration or power generation. The heat integration approach
involves the incorporation of a CO 2 cooler within the carbon capture and storage (CCS)
plant and a low temperature flue gas cooler (HES) installed downstream of the power
plant’s air-preheater. The CO 2 cooler is a standard heat exchanger that recovers waste
heat from the outlet of the stripper in the CO 2 capture facility and the HES is a form of
regenerative heat exchange that extracts waste heat from the flue gas exiting the
plant’s air-preheater. The HES technology provides other benefits to the host plant,
including reduced water usage in the flue gas desulfurization (FGD) due to lower flue
gas temperatures, better electrostatic precipitator (ESP) performance due to lower ash
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
543
Appendix: Post-Combustion Solvent Technologies
resistivity, and enhanced removal of sulfur trioxide (SO 3 ) and trace metals from the flue gas in existing systems. These
improvements have the added benefit of reducing both amine solvent loss and accumulation of metals, thereby reducing
operating costs of the solvent capture process.
Figure 1: Heat integration of power plant and CCS, including HES
technology advantages
• Costs driven by flue gas compression. The HES provides the efficient use of traditionally wasted heat in coal-fired flue gas
and captured CO 2 .
• Water usage and parasitic energy loss in carbon capture and storage (CCS) is reduced by the technology.
• The HES accommodates more efficient removal of SO 3 and heavy metals in the ESP by reducing the flue gas temperature
and resistivity of fly ash.
• This technology could prove to be a vital method of controlling water usage in FGD due to lower flue gas inlet temperature.
• Potential to simplify the boiler/steam turbine cycles and reduce the number of heat exchange systems in base plant, leading
to reduced capital cost.
R&D challenges
• Developing and demonstrating control schemes that maintain proper heat balance in the steam cycle and carbon capture
plant.
• Lowering flue gas temperature after the air-preheater can be problematic due to metal corrosion potential as a result of acid
gas condensation; developing specific operating parameters and controls to manage the threat is a specific challenge.
• Uncertainty on the reliability of the system with higher sulfur fuels (>1 percent).
status
Operation and testing of the KM-CDR™ CO 2 capture process was completed at the host PC power plant, Plant Barry, with heat
integration, confirming an improvement in energy efficiency and cost of electricity. Testing also showed removal of SO 3 to less
than 0.05 ppm and removal of other trace metal impurities, confirming an improvement in ESP performance, as well as a
reduction in water consumption. The HES was operated for 913 hours for the long-term durability test and showed no damage
to tubes or soot blowers and no ash deposition on tube walls.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
544 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
available reports/technical papers/presentations
Honjo, S., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from
Coal-Fired Flue Gas,” presented at the 2017 NETL CO 2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2017.
https://www.netl.doe.gov/File%20Library/Events/2017/co2%20capture/2-Tuesday/S-Honjo-MHIA-Waste-Heat-Integration.pdf
“Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from Coal-Fired
Flue Gas,” Project Closeout Meeting presentation, May 2017.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/DE--FE0007525-Southern-Company-HES-
Closeout-Meeting.pdf
Thomas, J., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from
Coal-Fired Flue Gas,” presented at the 2016 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/2-Tuesday/J-Thomas-SouthernCo-Waste-Heat-
Integration.pdf
Thomas, J., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from
Coal-Fired Flue Gas,” presented at the 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/J-Thomas-Southern-Waste-Heat-Integration-with-
Solvent.pdf
Wall. T., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from
Coal-Fired Flue Gas,” presented at the 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
https://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/T-Wall-Southern-Waste-Heat-Integration-
With-Solvent-Process.pdf
Wall, T., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient CO 2 Removal from
Coal-Fired Flue Gas,” presented at the 2013 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2013.
https://www.netl.doe.gov/File%20Library/Events/2013/Co2%20Capture/T-Wall-SouthernCo-Waste-Heat-Integration.pdf
Dombrowski, K. and Wu, T., “Development and Demonstration of Waste Heat Integration with Solvent Process for More Efficient
CO 2 Removal from Coal-Fired Flue Gas,” presented at the 2012 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
https://www.netl.doe.gov/File%20Library/Events/2012/CO2%20Capture%20Meeting/K-Dombrowski-URS-Waste-Heat-Integration.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
545
Appendix: Post-Combustion Solvent Technologies
Advanced Solvent-Based technology maturity:
Large-Pilot, Actual Flue Gas
Carbon Capture Technology (equivalent to 25 Mwe)
Development project focus:
Amine-Based Solvent and
Process Improvements
primary project goals
participant:
Southern Company Services evaluated the technical and economic feasibility of adding Southern Company Services
an integrated stripper/reboiler, particulate matter management, and a new solvent to
the existing 25-megawatt electric (MW e )-scale, amine-based Kansai Mitsubishi Carbon project number:
Dioxide Recovery Process (KM CDR Process™) at Southern Company's Plant Barry.
FE0026590
technical goals predecessor projects:
N/A
• Perform preliminary techno-economic analysis, preliminary design, and technical
gap analysis for a large-scale pilot plant project. NETL project manager:
• Define a project plan to include baseline, parametric, and long-term testing. Steven Mascaro
[email protected]
• Evaluate technical and economic feasibility of full-scale installation of further
improvements to the KM CDR Process™, including a built-in reboiler, particulate
matter management, and a new solvent. principal investigator:
john Carroll
Southern Company Services
technical content [email protected]
The KM CDR Process™ at Plant Barry (Figure 1) is a fully-integrated carbon capture and partners:
storage (CCS) plant and has achieved 90 percent CO 2 capture at a production rate of 500 Mitsubishi Heavy Industries
metric tons per day. The large-scale pilot plant uses the proprietary KS-1™ solvent, which America; AECOM
shows several benefits relative to monoethanolamine (MEA)-based processes. In this
project, the key technical challenges of high-steam consumption, solvent performance start date:
degradation, and process equipment footprint were investigated by Southern Company
10.01.2015
Services by: (1) evaluating a built-in reboiler, (2) evaluating the reduced operating and
capital costs associated with reduction or elimination of mechanical filtration of
particulate matter, and (3) conducting a new solvent test plan (referred to as NSL) to
percent complete:
demonstrate a new solvent (termed New Solvent A), which is expected to reduce 100%
regeneration steam as well as raw material costs. This Phase I of the project was to
evaluate the technical and economic feasibility of full-scale installation of these
improvements to the KM CDR Process™. Phase II, which was not awarded, would have
covered the engineering, construction, and testing at the pilot plant.
The built-in reboiler would replace the regenerator reboiler and stripper with an
integrated unit as shown in Figure 2. It would use a welded-plate heat exchanger,
designed for high condensation or evaporation duty, installed in the column, reducing
capital and operating cost and footprint.
Particulate matter management would determine if solvent purification can be eliminated. By
turning off the solvent purification system to mimic removal of the flue gas filtering process,
allowing particulate matter levels in the solvent to build, the maximum allowable particulate
matter concentration at which the solvent performance degrades can be determined.
A new improved amine solvent, Advanced Solvent A developed by Mitsubishi Heavy
Industries America (MHIA), was proposed to replace their KS-1TM amine solvent. This
solvent offers reduced steam consumption compared to both the KS-1™ and MEA
solvents.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
546 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 1: KM CDR Process™ at Plant Barry
Figure 2: (L) Conventional reboiler and stripper; (R) proposed integrated built-in reboiler
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
547
Appendix: Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 proprietary data proprietary data
Normal Boiling Point °C proprietary data proprietary data
Normal Freezing Point °C proprietary data proprietary data
Vapor Pressure @ 15 °C Bar proprietary data proprietary data
Manufacturing Cost for Solvent $/kg proprietary data proprietary data
Working Solution
Concentration kg/kg proprietary data proprietary data
Specific Gravity (15 °C/15 °C) - proprietary data proprietary data
Specific Heat Capacity @ STP kJ/kg-K proprietary data proprietary data
Viscosity @ STP cP proprietary data proprietary data
Absorption
Pressure Bar proprietary data proprietary data
Temperature °C proprietary data proprietary data
Equilibrium CO 2 Loading mol/mol proprietary data proprietary data
Heat of Absorption kJ/mol CO 2 proprietary data proprietary data
Solution Viscosity cP proprietary data proprietary data
Desorption
Pressure Bar proprietary data proprietary data
Temperature °C proprietary data proprietary data
Equilibrium CO 2 Loading mol/mol proprietary data proprietary data
Heat of Desorption kJ/mol CO 2 proprietary data proprietary data
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr proprietary data
CO 2 Recovery, Purity, and Pressure % / % / bar proprietary data
Absorber Pressure Drop Bar proprietary data
Estimated Absorber/Stripper Cost of __$__
proprietary data
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO 2 -free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
548 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
(e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the solution. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly
0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO 2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – CO 2 is captured by chemical absorption.
Solvent Contaminant Resistance – New Solvent A is highly resistant to contaminant compared to conventional solvent MEA.
Solvent Foaming Tendency – New Solvent A has low foaming tendency compared to conventional solvent MEA.
Flue Gas Pretreatment Requirements – Flue gas cooling and SO x removal unit may be required depending on flue gas
conditions.
Solvent Make-Up Requirements – Solvent makeup rate depends on the impurities level in the flue gas but is generally lower
than conventional solvent MEA.
Waste Streams Generated – Solvent reclaiming waste is the main waste stream generated.
Process Design Concept – KM CDR ProcessTM is equipped with proprietary amine emission reduction system, energy-saving
system, and amine purification system, which maximize the capture efficiency while minimizing the energy consumption and
environmental impact.
Proposed Module Design –Not applied.
technology advantages
• New Solvent A has potential to reduce steam regeneration requirements by 5 percent from their KS-1TM amine solvent and
by 37 percent from MEA.
• Reduced capital and operating cost and footprint for the built-in reboiler.
R&D challenges
• Determining maximum allowable particulate matter concentration at which solvent performance degrades.
• Matching or reducing heat transfer efficiency and steam consumption for the built-in reboiler compared to non-integrated
reboiler.
• Minimizing corrosion, scaling, and impurity buildup from testing.
• Integration of process updates with operations at Plant Barry.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
549
Appendix: Post-Combustion Solvent Technologies
status
Phase I has been completed. A preliminary techno-economic analysis of the KM CDR Process™ indicated a cost of CO 2 capture of
$58.8/tonne and cost of electricity (COE) of 133.7mils/kW. Adding the built-in reboiler, particulate matter management, and new
solvent further improved costs to $56.0/tonne CO 2 captured and COE of 130.6 mils/kW. The project was not awarded a Phase II.
available reports/technical papers/presentations
Thomas, J., “Advanced Solvent-Based Carbon Capture Technology Development,” presented at the 2016 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/2-Tuesday/J-Thomas-SouthernCo26590-
Advanced-Solvent-Based-Capture.pdf
Thomas, J., “Demonstration of Advanced CO 2 Capture Process Improvements for Coal-Fired Flue Gas,” Project Kickoff Meeting,
Pittsburgh, PA, December 2015. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/FE0026590-Kickoff-Presentation.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
550 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Slipstream Pilot-Scale technology maturity:
Pilot-Scale, Actual Flue Gas
Demonstration of a Novel (equivalent to 1 Mwe)
Amine Based Post-Combustion project focus:
Process Technology for CO2
Slipstream Novel Amine-
Based Post-Combustion
Capture from Coal-Fired
Process
Power Plant Flue Gas
participant:
Linde, LLC
project number:
primary project goals
FE0007453
Linde is refining a post-combustion carbon dioxide (CO 2 ) capture technology
incorporating BASF’s novel amine-based solvent, with the main technical goal of
predecessor projects:
significantly reducing solvent regeneration energy requirements over conventional N/A
monoethanolamine (MEA)-based amine capture. Technology development has been
fostered by designing, building, and operating a 1-megawatt electric (MW e ) equivalent NETL project manager:
slipstream pilot plant at the National Carbon Capture Center (NCCC) to evaluate and Andrew jones
optimize performance. [email protected]
principal investigator:
technical goals
Krish Krishnamurthy
Linde
• Capture at least 90 percent of CO 2 from coal-derived flue gas while demonstrating [email protected]
significant progress toward achievement of the DOE target of less than 35 percent
increase in levelized cost of electricity (LCOE) (<$40/tonne CO 2 ). partners:
• Produce a CO 2 product with a purity of at least 99.9 percent (dry basis) with low O 2 BASF, Linde Engineering
impurity levels that can meet the requirements for CO 2 utilization applications Dresden GMbH, Selas Fluid
such as enhanced oil recovery (EOR). Processing Corporation, EPRI
• Successfully test the CO 2 capture technology at a capacity of >1.5 MW e (>15,500
lb/hr flue gas). start date:
• Validate amine emissions control methods. 12.01.2011
• Successfully test regenerator at an operating pressure of 3.4 bar absolute (bara).
percent complete:
• Validate unique design features that lower overall capital and operating costs: (1)
high-capacity packing, (2) gravity-driven interstage cooler, (3) blower positioned 100%
downstream of absorber, and (4) unique reboiler design providing low solvent
holdup and fast dynamics.
• Reduce energy requirements ~27 percent relative to that of baseline MEA capture
(2.65 GJ/tonne CO 2 vs. 3.61 GJ/tonne CO 2 ). Achieve specific regeneration energy
of 2.65 GJ/tonne CO 2 (with additional heat integration concepts to further
reduction to 2.3 GJ/tonne CO 2 ).
• Demonstrate solvent stability by showing a very low accumulation of heat stable
salts (HSS) over the entire duration of parametric and long-term continuous testing
(4,109 hours of testing with flue gas).
• Complete techno-economic assessment of a 550-MW e power plant integrated
with the Linde-BASF post-combustion capture plant incorporating BASF’s OASE®
blue aqueous amine-based solvent, and leveraging Linde’s innovative process
features to increase energy efficiency, improve emissions performance, and reduce
plant footprint.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
551
Appendix: Post-Combustion Solvent Technologies
technical content
Linde’s technology uses BASF’s OASE® blue solvent, which has been developed to address the key drawbacks in the large-scale
application of MEA for flue gas carbon capture, including: (1) high specific energy for rich solvent regeneration/CO 2 recovery, (2)
lack of solvent stability toward thermal and oxidative degradation, (3) increased solvent corrosiveness with increased CO 2
loading, and (4) lack of solvent tolerance to impurities from coal combustion products. The specific proprietary solvent was
selected by: (1) screening approximately 400 chemical substances using vapor-liquid equilibrium measurements to determine
approximate cyclic capacities, (2) laboratory measurements of the key thermodynamic and kinetic properties of the 70 screened
candidates and their mixtures to identify approximately 15 targets, (3) testing of the targets to determine optimum circulation
rate and specific energy consumption in a laboratory-scale mini-plant to identify the leading candidates, and (4) pilot testing of
three candidates with real power plant flue gas to identify the optimum solvent for the flue gas application. CO 2 recovery from
the solvent is carried out by using low-pressure steam, typically from the power plant steam cycle. Testing using a 0.45-MW e pilot
plant utilizing lignite-fired power plant flue gas has shown that the OASE® blue solvent is stable and little degradation was
observed over 5,000 hours, whereas the reference MEA solvent started to degrade appreciably under same conditions after 2,000
hours.
Linde’s post-combustion CO 2 capture process using BASF OASE® blue solvent technology has several distinct characteristics.
Firstly, the direct-contact cooler, CO 2 absorber, and water wash are integrated into a single column with high-performance
structured packing for increased capacity (smaller absorber diameter) and an advanced material of construction to minimize
capital costs. Secondly, the absorber also has an inter-stage solvent cooler operating on gravity flow, eliminating the capital and
operating expenses of a solvent pump. The flue gas blower is located downstream of the absorber to minimize its size (due to
the reduced volume of flue gas handled by the blower). Further, the stripping column can be operated at higher pressures (up
to 3.4 bara) than that of a MEA stripper, lowering compression costs. Finally, optional process heat integration allows steam,
which is raised by heat exchange with flue gas upstream of the flue gas desulfurization (FGD) unit, to be used at an intermediate
point in the desorber, and the use of back-pressure steam turbines allows the recovery of part of the energy of the intermediate-
pressure (IP), low-pressure (LP) crossover steam.
Figure 1: Linde-BASF post-combustion capture plant process concept
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
552 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Techno-Economic Study Cases and Results
Three conceptual cases of pulverized coal combustion power plants with 90 percent CO 2 capture accomplished using the Linde-
BASF technology were modeled to quantify expected costs and process efficiencies resulting from the improved solvent and the
energy-saving process features noted above.
Linde-BASF LB1
The LB1 design employs high-performance structured packing, gravity-drain absorber intercooler, emission control system in
absorber wash sections, blower downstream of absorber, novel stripper reboiler design, and elevated regeneration pressure
(3.33 bar absolute). Modeling suggests this combination of features would result in a specific regeneration energy of 2.61 GJ/MT
CO 2 . The Wilsonville NCCC pilot plant is based on the LB1 design.
Linde-BASF SIH
The SIH design employs advanced stripper interstage heater design that improves heat recovery from CO 2 -lean solution leaving
stripper. Modeling suggests this combination of features would result in a specific regeneration energy of 2.30 GJ/MT CO 2 .
Linde-BASF LB1-CREB
The LB1-CREB design employs novel cold CO 2 -rich solution bypass exchanger and secondary CO 2 -lean/CO 2 -rich heat exchanger
that optimizes heat recovery from hot CO 2 product vapor leaving stripper and hot CO 2 -lean solution. Modeling suggests this
combination of features would result in a specific regeneration energy of 2.10 GJ/MT CO 2 .
Figure 2 show the overall power plant efficiencies for these cases, indicating incremental improvements over the baseline power
plant case using the Linde technology, compared to conventional amine-based CO 2 capture (DOE NETL Bituminous Baseline
Case 12).
Figure 2: Comparison of PCC plant case efficiencies from techno-economic analysis
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
553
Appendix: Post-Combustion Solvent Technologies
The cost of CO 2 captured was estimated to be as follows:
• DOE NETL Case 12 (baseline) $56.49/MT CO 2
• Linde-BASF LB1 $41.85/MT CO 2
• Linde-BASF SIH $40.66/MT CO 2
• Linde-BASF LB1-CREB $39.90/MT CO 2
One major reason the cost of CO 2 captured is significantly reduced in moving from Case 12 to LB1 is due to the higher inlet CO 2
gas pressure for CO 2 compression (48 psia for LB1 vs. 24 psia for Case 12) afforded by elevated regenerator pressure, which
reduces downstream compression energy and capital costs. Additionally, as power plant efficiency increases, the flow rate of
CO 2 produced decreases due to a reduced coal flow rate needed for the same power production. This leads to increasingly
smaller incremental reductions in cost of CO 2 captured for each Linde-BASF process improvement.
Figure 3 shows the cost breakdowns for the cases relative to the baseline DOE NETL Case 12.
Figure 3: Cost of electricity comparisons from techno-economic analysis
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
554 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 proprietary —
Normal Boiling Point °C proprietary —
Normal Freezing Point °C proprietary —
Vapor Pressure @ 15 °C bar proprietary —
Manufacturing Cost for Solvent $/kg proprietary —
Working Solution
Concentration kg/kg proprietary —
Specific Gravity (15 °C/15 °C) - proprietary —
Specific Heat Capacity @ STP kJ/kg-K proprietary —
Viscosity @ STP cP proprietary —
Absorption
Pressure bar ≈1 atm ≈1 atm
Temperature °C 30–70 30–60
Equilibrium CO 2 Loading mol/mol proprietary —
Heat of Absorption kJ/mol CO 2 proprietary —
Solution Viscosity cP proprietary —
Desorption
Pressure bar 1.6–2.5 1.6–3.4
Temperature °C 124–132 124–140
Equilibrium CO 2 Loading mol/mol proprietary —
Heat of Desorption kJ/mol CO 2 proprietary —
Proposed Module Design (for 550-MW e PCC Plant) (for equipment developers)
Flue Gas Flowrate kg/hr LB1 Case: 2,718,270 SIH Case: 2,674,784
CO 2 Recovery, Purity, and Pressure 90%, 99.98% (dry 90%, 99.98% (dry),
%/%/bar
basis), 3.4 bara 3.4 bara
Absorber Pressure Drop bar 0.1
Estimated Absorber/Stripper Cost of __$__
proprietary
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO 2 -free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
555
Appendix: Post-Combustion Solvent Technologies
(e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the solution. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO 2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted otherwise, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – CO 2 in the flue gas chemically binds to the OASE blue® aqueous amine-based solvent
via an exothermic absorption step and this chemical bond is broken in the endothermic desorption step via heat provided by
steam in the reboiler of the regenerator column, generating pure CO 2 .
Solvent Contaminant Resistance – The OASE blue® solvent is highly resistant against many contaminants in the flue gas as shown
in both parametric and long-term continuous tests (see EPRI report [“BASF-Linde Post Combustion Carbon Capture…”] for
additional information).
Solvent Foaming Tendency – During the pilot plant operation, although anti-foaming injection was included in the design, its
use was not found necessary.
Flue Gas Pretreatment Requirements – The pretreatment requirement includes reducing sulfur oxide (SO x ) in the flue gas to 2–
5 parts per million (ppm) in order to limit solvent degradation and is implemented in a direct contact cooler in conjunction with
flue gas cooling, typically by adding appropriate amount of sodium hydroxide corresponding to the SO x present in the flue gas.
Solvent Make-Up Requirements – The OASE blue® solvent make-up rate is determined by the sum of the amine losses in the
treated gas leaving the absorber column and the rate of solvent degradation during operation over time. Low make-up rates
were observed during long-term testing well below an operationally manageable threshold (see Final Testing Report
[“Slipstream Pilot Plant Demonstration…”] on page 22). During the parametric testing, higher amine losses were observed and
this was attributed to the lack of baghouse filter in the power plant resulting in a high density of fine aerosol particles in the flue
gas that caused carryover of amine with the CO 2 -depleted gas.
Waste Streams Generated – The main waste liquid stream is from the direct contact cooler where SO x is removed; this stream is
typically handled in the power plant waste water treatment facility. A small amount of solid waste is removed using carbon filters
that are replaced at regular intervals. Since the degradation observed in the pilot testing is small, no solvent reclamation unit is
envisioned in the large scale.
Process Design Concept – See Figure 1 above.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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556 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
technology advantages
• Significant reduction in regeneration steam consumption (24–40 percent lower), electrical power (14–26 percent lower), and
cooling water duty (26–43 percent lower) compared to a reference MEA plant.
• Higher plant efficiency due to a combination of advanced solvent and process improvements, including integrated
absorber, down-stream gas blower, higher desorber pressure, and inter-stage gravity-flow cooler.
• Aggregate capital, O&M, fuel, and other cost reductions result in lower COE (15 percent less than the MEA-based DOE NETL
reference case).
• The Linde-BASF technology is readily scalable to large capacities with a single-train system, offering the potential to further
reduce costs by utilizing economies of scale.
• BASF is a producer of the solvent in addition to being the technology owner, thereby enabling application at scale by
avoiding issues related to solvent manufacturing for large-scale commercial plants.
R&D challenges
• Proving the process enhancements at the 1-MW e plant and at larger scale.
• Validating the basis for scale up of the advanced process features and the large, single-train capability.
status
The Linde-BASF technology has been selected by DOE for Phase 1 of a large pilot plant demonstration opportunity. Linde has
teamed with the University of Illinois in proposing Phase 2 work, identifying the Abbott coal fired power plant as the intended
host site for the large pilot, which if selected and executed is expected to advance the technology to near-commercial readiness.
available reports/technical papers/presentations
“Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology for CO 2 Capture from Coal-Fired
Power Plant Flue Gas,” Final Report, February 2017.
Final Techno-Economic Analysis of 550 MW e Supercritical PC Power Plant CO 2 Capture with Linde-BASF Advanced PCC Technology,”
January 2017.
“Slipstream Pilot Plant Demonstration of a Amine-Based Post-Combustion Capture Technology for CO 2 Capture from Coal-Fired
Power Plant Flue Gas,” Final Project Review Meeting Presentation by Krish R. Krishnamurthy & Devin Bostick, Linde LLC,
Pittsburgh, PA, January 2017.
“Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Process Technology for CO 2 Capture from Coal-
Fired Power Plant Flue Gas,” presented by Krish R. Krishnamurthy, Linde LLC, 2016 NETL CO 2 Capture Technology Project Review
Meeting, Pittsburgh, PA, August 2016.
“Development and Scale-Up of an Advanced Aqueous Amine-Based Post-Combustion CO 2 Capture Utilizing BASF's OASE® Blue
Technology,” presented by Krish R. Krishnamurthy, Linde LLC, 2016 Carbon Capture, Utilization & Storage Conference, Tysons,
VA, June 2016.
“Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Process Technology for CO 2 Capture from Coal-
Fired Power Plant Flue Gas, presented by Krish R. Krishnamurthy, Linde LLC, 2015 CO 2 Capture Technology Meeting, Pittsburgh,
PA, June 2015.
“Pilot plant demonstration of an advanced amine-based post-combustion capture technology for CO 2 capture from power plant flue
gases,” presentation at the 12th Greenhouse Gas Control Technologies (GHGT-12) Conference, October 2014.
Krishnamurthy, K., “Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Process Technology for CO 2
Capture from Coal-Fired Power Plant Flue Gas,” 2014 CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
557
Appendix: Post-Combustion Solvent Technologies
Krishnamurthy, K., “Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Process Technology for CO 2
Capture from Coal-Fired Power Plant Flue Gas,” 2013 CO 2 Capture Technology Meeting, Pittsburgh, PA.
“Techno-Economic Analysis of 550 MWe Subcritical PC Power Plant with CO 2 Capture,” Topical Report of initial techno-economic
analysis, May 2012.
“Techno-Economic Analysis of 550 MWe Subcritical PC Power Plant with CO 2 Capture,” presentation given at NETL by S. Jovanovic
& K. Krishnamurthy, Pittsburgh, PA, May 2012.
“Slipstream Pilot-Scale Demonstration of a Novel Amine-Based Post-Combustion Process Technology for CO 2 Capture from Coal-
Fired Power Plant Flue Gas,” Project Kick-Off Meeting Presentation, November 2011.
“Slipstream Pilot Plant Demo of an Amine-Based Post-Combustion Capture Technology for CO 2 Capture from Coal-Fired Power Plant
Flue Gas,” presented by Krish R. Krishnamurthy, Linde LLC, 2011 Fall Technical Subcommittee Meeting, Pittsburgh, PA, October
31, 2011.
Krishnamurthy, K.R., “Slipstream Pilot Plant Demo of an Amine-Based Post-Combustion Capture Technology for CO2 Capture from a
Coal-Fired Power Plant Flue Gas,” presented at the 2012 NETL CO 2 Capture Technology Meeting, July 2012, Pittsburgh, PA.
“BASF-Linde Post Combustion Carbon Capture Pilot Plant at the National Carbon Capture Center, 2016 Test Campaign Results,
EPRI, February 2017.
“Slipstream Pilot Plant Demonstration of an Amine-Based Post-Combustion Capture Technology for CO 2 Capture from Coal-
Fired Power Plant Flue Gas,” Final Testing Report to NCCC, February 2017.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
558 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Improvement of GE Power’s technology maturity:
Bench-Scale, Simulated Flue
Chilled Ammonia Process Gas
Large Pilot with the Use of project focus:
Membrane Technology
Chilled Ammonia Process
Improvements
participant:
primary project goals GE Power
GE Power developed several concepts for improving their existing solvent-based project number:
Chilled Ammonia Process (CAP) for capturing carbon dioxide (CO 2 ) from coal-fired
FE0026589
power plants by incorporating commercially available membrane technologies to
reduce energy and capital costs. Three concepts were investigated at bench-scale to
determine feasibility of testing with a large pilot CO 2 validation facility at Technology predecessor projects:
Centre Mongstad (TCM). N/A
NETL project manager:
technical goals Steven Mascaro
[email protected]
• Implement several improvement concepts utilizing membrane technology at an
existing CAP large-scale pilot plant to lower the overall cost of CAP CO 2 capture principal investigator:
technology.
David Muraskin
• Leverage CAP experience in collaboration with TCM, the host site, which operates GE Power
an existing CAP large pilot facility (~15 MW e equivalent) in Norway. [email protected]
• Complete a techno-economic assessment (TEA) and technology gap analysis of .com
membrane concepts for the CAP at a full-scale 550-MW power generation facility.
partners:
• Develop key project risks.
ElectroSep™; General
Electric Power and water;
technical content Georgia Institute of
Technology; Technology
GE Power teamed with ElectroSep™, General Electric Power and Water, and Georgia Centre Mongstad
Institute of Technology, to investigate concepts for improving an existing solvent-
based CAP pilot plant using liquid-liquid bipolar and reverse osmosis membrane start date:
systems to reduce energy and capital costs. GE Power’s CAP uses an ammonia-based 10.01.2015
solvent for the absorption of CO 2 from flue gas at low temperature. Ammonia is an
energy-efficient reagent that is stable, not susceptible to contaminants in flue gas, and percent complete:
is replenished in low consumption rates. The CAP has been tested at large pilot scale 100%
(20 MW e ) and is prepared for large scale demonstration in 2020. The main features of
the CAP technology are:
• The flue gas leaving the CAP has no solvent degradation byproducts and the
solvent can tolerate higher amounts of residual acid gases (SO x , NO x , etc.) in
the incoming flue gas.
• The CAP technology can utilize cooler ambient conditions to lower the energy
consumption of the process.
• The reactions within the CO 2 absorption process are reversible with
regeneration of the solvent at elevated pressure allowing for reduced CO 2
compression.
• The CAP reagent is anhydrous ammonia—a low cost, commodity chemical
that is readily available.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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Appendix: Post-Combustion Solvent Technologies
• The byproduct is an aqueous ammonium sulfate stream that can be used commercially as fertilizer.
Three concepts for improving the CAP CO 2 capture technology using commercially available membrane systems were
previously investigated at the bench-scale level for eliminating CAP liquid ammonium sulfate effluent stream and reducing
CAP energy demand. GE Power plans to modify the CAP large pilot facility at the TCM in Norway for the implementation of
these membrane systems once they are validated at bench-scale.
The first concept involves eliminating ammonium sulfate byproduct and reducing the consumption of ammonia and sulfuric
acid reagents. In the CAP plant, as flue gas enters the conditioning section, residual SO x in the direct contact column (DCC)
reacts with ammonia to form ammonium sulfate byproduct. In the direct contact heating (DCH) column, residual ammonia in
the treated flue gas from the absorption/water wash section is reduced to form ammonium sulfate using a sulfuric acid rinse.
The ammonium sulfate byproduct generated in both unit operations is then transported as a concentrated liquid solution or
processed on-site using crystallization technology to form a fertilizer, which requires high operating and capital costs. In this
concept, a bipolar membrane electrodialysis (ED) unit converts the byproduct to sulfuric acid and anhydrous ammonia (process
reagents). Figure 1 illustrates the ion exchange process through a bipolar membrane ED unit and Figure 2 shows an ED unit
implemented into the CAP plant. Through electrodialysis, ions are transported through cation and anion exchange membranes
from one solution to another under the influence of an electrical driving force. The ammonium sulfate bleed stream is
dissociated into acidic and basic ionic species. Bipolar membranes consisting of an anion exchange membrane and a cation
exchange membrane bonded together dissociate water into hydrogen and hydroxyl ions for combining with the ionic species,
forming sulfuric acid and ammonia. Eliminating the ammonium sulfate byproduct stream is beneficial for power plants that are
not able to use the byproduct as commercial fertilizer and reducing process reagent consumption solves the problems of on-
site storage for substantial amounts of reagents.
Figure 1: Bipolar membrane electrodialysis
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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560 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
Figure 2: Bipolar membrane electrodialysis for byproduct elimination and reagent recovery
The second concept involves reducing the ammonia stripper energy. In the CAP plant, ammonia in the flue gas leaving the CO 2
absorber is first captured in a water wash vessel and then regenerated in an ammonia recovery stripper by heating the rich
solution with saturated steam. In this concept, as shown in Figure 3, a reverse osmosis membrane separator is used to increase the
ammonia concentration in the feed to the ammonia stripper, resulting in reduced feed flow rate, which minimizes stripper duty.
As a result, stripper and heat exchanger sizes are reduced as well as steam energy demand. Also, the improvement in stripper
performance potentially allows the CO 2 absorber to operate at a higher temperature resulting in lower refrigeration duty.
Figure 3: Reverse osmosis membrane for ammonia stripper energy reduction
The third concept involves reducing the CO 2 regeneration energy by recovering absorbent. In the CAP plant, a large amount of
circulation flow between the CO 2 absorber and the CO 2 regenerator is required due to low CO 2 loading, which leads to high
capital and operating costs of the plant. In this concept, as shown in Figure 4, a reverse osmosis membrane separator is used to
recover the water and some portion of the ionic absorbent that passes through the CO 2 wash column after leaving the
regenerator. The wash water with recovered ammonium is sent to the absorber for CO 2 capture, while the remaining carbon-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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561
Appendix: Post-Combustion Solvent Technologies
containing ionic species that does not permeate through the membranes is returned to the CO 2 wash section to capture
ammonia. This process allows for operation of the regenerator at lower pressure and higher ammonia emissions. In the current
plant, the CO 2 is regenerated at high pressure, which reduces the ammonia content in the CO 2 product and minimizes the
downstream compressor duty. However, this requires relatively high-pressure steam, which affects the power production
capability of the power plant. Operating the regenerator at lower pressure allows for use of lower quality steam, which reduces
the energy losses associated with high pressure steam utilization, but also increases the amount of ammonia emission from the
CO 2 regenerator. This excess ammonia is captured in the CO 2 wash section and then processed in the reverse osmosis
membrane system as described above.
Figure 4: Reverse osmosis membrane for increased ammonium recovery from CO 2 wash
Each of these membrane systems were tested previously at laboratory-scale and bench-scale using process streams consistent
with those within the CAP plant. A bench-scale electrodialysis test apparatus consisting of ion specific membranes with a total
surface area of 0.152 m2 was used to assess the first concept at ElectroSep. A sulfuric acid product tank was used to accumulate
the sulfuric acid produced by the electrodialysis stack and confirmed an increase in sulfuric acid concentration, indicating that
the initial membrane selection is feasible. Through testing of the commercial reverse osmosis membranes at Georgia Institute
of Technology, it was determined that a higher osmotic pressure is needed; however, higher pressure membranes are not
robust and are associated with high operating and capital costs. An alternate concept was developed utilizing a low-pressure
reverse osmosis membrane design that is expected to improve costs by eliminating the stripper and steam consumption. The
development program was revised to allow for further testing of this new concept at bench-scale and a decision was made to
not proceed with modifications to the large pilot plant.
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture of
gases found in de-sulfurized flue gas.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
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562 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube,
and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination
of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO 2 -rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
technology advantages
• Uses ammonia—a low-cost, stable, readily available chemical—as a reagent.
• Uses commercially available membranes that can be scaled up using conventional methods.
• The incorporation of bipolar membrane technology eliminates the CAP byproduct stream (ammonium sulfate) and
associated disposal/processing costs as well as recovers reagents (ammonia and sulfuric acid).
• The incorporation of reverse osmosis membrane technology minimizes the CAP regenerator steam consumption and
reduces the stripper and associated heat exchanger sizes by ~50 percent.
R&D challenges
• Utilizing lower pressure membranes for reverse osmosis concept.
status
Bipolar membrane electrodialysis for the CAP is prepared for large pilot-scale testing based on the successful completion of
bench-scale testing at ElectroSep, Inc. Bench-scale testing of the reverse osmosis concept determined that the low-pressure
membrane rejection rate is insufficient, and therefore, modification of the initial process scheme is required along with bench-
scale testing to validate the new process before proceeding to large pilot-scale testing. A preliminary techno-economic analysis
was completed based on the bench-scale tests, showing an improvement in power plant steam cycle efficiency and a small
reduction in cost of electricity (COE) from the DOE baseline case. The COE improvement was not sufficient to justify further
development of the original reverse osmosis concept. Bench-scale testing along with an economic assessment for the alternate
concept using low pressure reverse osmosis membranes is required to allow consideration of the membrane technology for CAP
improvements.
available reports/technical papers/presentations
Muraskin, David, “Improvement of GE Power’s Chilled Ammonia Process using Membrane Technology,” Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/2-Tuesday/D-Muraskin-GE-Alstom-Chilled-
Ammonia-Large-Pilot.pdf
“Improvement of Alstom’s Chilled Ammonia Process using Membrane Technology,” Project kickoff meeting presentation,
October 28, 2015. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0026589-
Kickoff-Presentation.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
563
Appendix: Post-Combustion Solvent Technologies
Novel Flow Sheet for Low technology maturity:
Energy CO2 Capture Enabled
Bench-Scale, Actual Flue
Gas
by Biocatalyst Delivery System project focus:
Carbonic Anhydrase
Catalyzed Advanced
primary project goals Carbonate and Non-
Volatile Salt Solution
Akermin developed an advanced biocatalyst enabled solvent system for lower (“Solvents”)
cost carbon dioxide (CO2) capture. The project focused on the development of
encapsulated carbonic anhydrase (CA) biocatalyst technology. The project participant:
combines an improved biocatalyst delivery system (BDS), a new solvent, and
Akermin, Inc.
process improvements tested in a modified bench-scale system incorporating
these new advancements.
project number:
FE0012862
technical goals
predecessor projects:
• Demonstrate a second-generation biocatalyst that has lower production costs, FE0004228
is more readily scaled up, and enables on-stream catalyst replacement.
• Optimize production of the BDS. NETL project manager:
• Demonstrate consistent long-term performance in lab-scale closed loop Andrew Jones
reactor. [email protected]
• Design and modify bench-scale test unit to incorporate the next-generation
BDS and to accommodate the novel process improvements. principal investigator:
• Optimize the process flow sheet to utilize low grade steam for solution Alex Zaks
regeneration and to achieve parasitic power less than 220-kWh/t CO2. Akermin, Inc.
[email protected]
• Evaluate performance of advanced AKM24 solvent.
• Complete field testing with the bench-scale test unit at the National Carbon partners:
Capture Center (NCCC) using coal-derived flue gas.
Worley Parsons; Novozymes
• Demonstrate on-stream biocatalyst maintenance.
• Perform techno-economic assessment and engineering study to demonstrate start date:
viability of the new technology, targeting at least 30 percent reduction in cost
10.01.2013
of CO2 capture.
percent complete:
technical content 100%
Akermin is developing a low-energy, enzyme-catalyzed solvent system for CO2
capture and testing in a bench-scale unit to continue advancing the technology
that was previously developed under project DE-FE0004228. The novel system
combines the next-generation BDS and a non-volatile salt solution (AKM24
“solvent”). Updates to an existing 500 standard liters per minute (SLPM) bench-
scale test unit incorporated the process and solvent advancements. The process
scheme is shown in Figure 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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564 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
Figure 1: Akermin’s CO2 capture process
The technology uses a next-generation BDS, in which, the CA enzyme is immobilized within proprietary polymeric
microparticles. CA accelerates hydration of CO2 to bicarbonate to enhance the performance of the solvent for CO 2
capture. The microparticles have high surface area to enable higher mass transfer rates and provide a protective
environment for the enzymes against inactivation by temperature, solvent and shear forces. The catalyst can be delivered
by two potential concepts: (1) by recirculation in the absorber only, which requires particle separation, or (2) by continuous
circulation in the absorber and stripper, which would not require particle separation, but would require lower temperature
stripping to avoid denaturation of the enzyme-based biocatalyst. By incorporating the non-volatile salt solution that has
significantly lower regeneration energy combined with using lower temperature steam from the power plant, the result is
significant reductions in parasitic power requirements and also lower capital costs for the power plant and integrated CO2
capture system. Since AKM24 operates with higher CO 2 loading capacity, lower circulation rates can be realized. The
modified bench-unit was operated with actual coal-derived flue gas at the NCCC to evaluate performance and validate
process modeling performance estimates.
The solvent and process parameters are provided in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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Appendix: Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 not disclosed not disclosed
Normal Boiling Point °C 107 107
Normal Freezing Point °C -8 -8
Vapor Pressure @ 15 °C bar non-volatile non-volatile
Manufacturing Cost for Solvent $/kg not disclosed not disclosed
Working Solution
Concentration kg/kg not disclosed not disclosed
Specific Gravity (15 °C/15 °C) — 1.18 1.18
Specific Heat Capacity @ STP kJ/kg-K 3.33 3.33
Viscosity @ STP cP 3.98 33.98
Absorption
Pressure bar 1.07 1.07
Temperature °C 50 50
Equilibrium CO2 Loading mol/mol 0.80 0.80
Heat of Absorption kJ/mol CO2 52 52
Solution Viscosity cP 2.01 2.01
Desorption
Pressure bar 1.07 1.07
Temperature °C 107 107
Equilibrium CO2 Loading mol/mol 0.40 0.40
Heat of Desorption kJ/mol CO2 70 70
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 40
CO2 Recovery, Purity, and Pressure %/%/bar 90 >99 1.05
Absorber Pressure Drop bar <0.02
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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Appendix: Post-Combustion Solvent Technologies
dependent (e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler
temperature of 120 °C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized (PC) power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure
of CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOx NOx
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Chemical/Physical Solvent Mechanism – The reaction of CO2 with water (H2O) in the presence of CA and base (B) is
as follows:
H2O + CO2 <--> HCO3- + H (slow without catalyst)
H+ + B <--> BH+ (fast)
H2O + CO2 + B <--> BH+ + HCO3- (overall reaction)
The presence of CA increases the rate of conversion of CO 2 to bicarbonate (improving the slow step above), but does
not affect the equilibrium properties of the solvent. The rate of hydration of CO 2 (i.e., the reaction with H2O) in the absence
of the enzyme is exceedingly slow; however, the enzyme provides dramatic acceleration of the reaction (kcat
≈1/microsecond) and is limited only by diffusion.
Solvent Contaminant Resistance – Studies with K2CO3 and CA in solution indicate that the enzyme is not inhibited by
sulfate, sulfite, nitrite, nitrate, or chloride ions in solution at levels expected for coal flue gas. Divalent metal ions (e.g.,
mercury [Hg2+], lead [Pb2+]) inhibit the activity of soluble CA, because the active site in the enzyme itself contains a
divalent metal ion (mainly zinc). However, the low solubility of their hydroxide and carbonate salts in carbonate solutions
and the stabilizing role of the immobilization system alleviate some of the decrease in CA activity.
Solvent Foaming Tendency – The presence of soluble enzyme can contribute to foaming, especially in the stripper,
whereas the tendency to foam is mitigated by using immobilized enzyme. Previous work has used small quantities of
anti-foam.
Flue Gas Pretreatment Requirements – Standard sulfur oxides (SOx), nitrogen oxides (NOx), and mercury control
systems that meet local air emission requirements will be sufficient.
Solvent Make-Up Requirements – The capture of acid gases, such as sulfur dioxide (SO2) and nitrogen dioxide (NO2),
will reduce carrying capacity over time. Initial tests indicated the loss of capacity to be on the order of 2 percent per year
or less. K2CO3 is non-volatile and has excellent oxidative stability (an inorganic salt solution). Akermin’s new solvent
(AKM24) is based on a non-volatile salt solution; therefore, it is expected to have similar benefits.
Waste Streams Generated – In the first-generation technology, the deactivated packing would need to be replaced
(recycled) to maintain CA activity on an ongoing basis. Notably, the second-generation BDS provides for on-stream
biocatalyst maintenance as a microparticle, which reduces the volume and cost of solid waste management.
Process Design Concept – Figure 1 presents the basic process flow sheet.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
567
Appendix: Post-Combustion Solvent Technologies
technology advantages
• Advanced solvent in the presence of Akermin’s BDS has high CO 2 absorption rates and higher capacity relative to
first generation. It also has significantly lower regeneration energy compared to amine-based solvents.
• Solvent is non-volatile, oxidative stable, and environmentally benign.
• Advanced solvent uses lower-grade steam with lower regeneration temperatures than amine solvents; resulting in
lower auxiliary power requirements, more power generated, lower unit capital costs, and lower CO 2 capture costs.
R&D challenges
• Scaling up and manufacturing of the immobilized biocatalyst batches that consistently achieve the critical
performance metrics (cost, efficiency, ease of integration with BDS, etc.).
• Determining the optimal catalyst recirculation option.
• Demonstrating an effective BDS in the lab- and bench-scale test units to achieve stable and consistent long-term
performance.
status
Akermin has produced and tested multiple biocatalyst batches on the kilogram scale. They have demonstrated an
average 90 percent CO2 capture over extended testing in the lab-scale closed loop reactor. An enzyme kinetic model
was built in Aspen and validated with test data. The 500 SLPM bench unit located at the NCCC was modified and
commissioned in June 2016, and testing was initiated. The project ended in July 2016, prior to the planned September
30, 2016, end date, due to unexpected circumstances.
available reports/technical papers/presentations
Zaks, A., “Novel Flow Sheet for Low Energy CO2 Capture Enabled by Biocatalyst Delivery System,” presented at the
Budget Period 1 Review Meeting, Pittsburgh, PA, July 2015.
https://netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0012862-BP1-Review-
Meeting-07-15-2015.pdf.
Zaks, A., “Novel Flow Sheet for Low Energy CO2 Capture Enabled by Biocatalyst Delivery System,” presented at the
2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/A-Zaks-Akermin-Biocatalyst-Delivery-
System.pdf.
Zaks, A., “Low Energy CO2 Capture Enabled by Biocatalyst Delivery System,” 12th Greenhouse Gas Control
Technologies (GHGT-12) Conference Presentation, October 2014. http://www.netl.doe.gov/File
Library/Research/Coal/carbon capture/post-combustion/FE0012862-GHGT-12-Presentation-10-07-14.pdf.
Reardon, J., “Novel Flow Sheet for Low Energy CO2 Capture Enabled by Biocatalyst Delivery System,” presented at
the 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File
Library/Events/2014/2014 NETL CO2 Capture/J-Reardon-Akermin-Novel-Flow-Sheet-For-Low-Energy-CO2-
Capture.pdf.
Novel Flow Sheet for Low Energy CO2 Capture Enabled by Biocatalyst Delivery System,” Project Kick-Off Meeting
Presentation, November 22, 2013. http://www.netl.doe.gov/File Library/Research/Coal/ewr/CO2/FE0012862-Kick-Off-
Meeting-Presentation-11-22-13.pdf.
Zaks, Alex, and Reardon, J., Final Report, “Advanced Low Energy Enzyme Catalyzed Solvent for CO 2 Capture,” 2013.
http://www.osti.gov/scitech/servlets/purl/1121752.
“Advanced Low Energy Enzyme Catalyzed Solvent for CO 2 Capture,” Final Project Review Presentation, November
2013. http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0004228-
Akermin-Close-Out-Mtg-Presentation-11-22-13.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
568 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Reardon, J., “Advanced Low Energy Enzyme Catalyzed Solvent for CO 2 Capture,” presented at the 2013 NETL Annual
CO2 Capture Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/J-Reardon-Akermin-Enzyme-Catalyzed-Solvent-
for-CO2.pdf
Reardon, J., et al., “Enzyme-Catalyzed Process for Low-Cost CO2 Separation and Capture,” presented at the 2012
MEGA Conference, Baltimore, MD, August, 2012.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/enzyme-catalyzed-process-aug2012.pdf.
Zaks, A., “Advanced Enzyme-Catalyzed CO2 Capture in Low-Energy Solvents,” presented at the 2012 NETL Annual
CO2 Capture Technology Meeting, July, 2012, Pittsburgh, PA.
http://www.netl.doe.gov/File%20Library/research/coal/cross-cutting%20research/advanced%20materials/advanced-
low-energy-enzyme-catalyzed-solvent-july2012.pdf.
Zaks, A., “Advanced Low Energy Enzyme Catalyzed Solvent for CO 2 Capture,” presented at the 2011 NETL Annual
CO2 Capture Technology Meeting, August, 2011, Pittsburgh, PA.
http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/23Aug11-Zaks-Akermin-Enzyme-Catalyzed-
Solvent.pdf.
Gifford, P., “Advanced Low Energy Enzyme Catalyzed Solvent for CO 2 Capture,” Presented at the 2010 NETL Annual
CO2 Capture Technology Meeting, September, 2010, Pittsburgh, PA.
http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/Paul-Gifford---Akermin-Inc.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 569
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Carbon Absorber Retrofit technology maturity:
Equipment (CARE)
Pilot-Scale, Actual Flue Gas
Slipstream
project focus:
primary project goals Carbon Absorber Retrofit
Equipment
Neumann Systems Group, Inc. (NSG) has designed, constructed, and tested a 0.5-MW
scale patented NeuStream® absorber at the Colorado Springs Utilities (CSU) Martin participant:
Drake #7 power plant. The absorber employs nozzle technology proven during a
Nuemann Systems Group
previously completed 20-MW NeuStream-S flue gas desulfurization (FGD) pilot project,
as well as a 6-m piperazine (PZ) solvent, which is an efficient solvent for capturing carbon
dioxide (CO2). The goal of the project is to show that the absorber system is capable of
project number:
significantly reducing the process equipment footprint and the CO2 capture system cost. FE0007528
Due to an unrelated turbine fire at the Martin Drake plant in May of 2014, the project scope predecessor projects:
was revised to relocate the system to NSG’s facility, where a natural gas steam boiler will
provide the flue gas and stripping heat. Stripped CO2 was recycled to increase the incoming N/A
CO2 concentration to ≈13 percent to simulate flue gas from a coal-fired boiler.
NETL project manager:
Andy O’Palko
technical goals [email protected]
• Design a 0.5-MWe slipstream CO2 scrubber to minimize parasitic power through principal investigator:
efficient design. Eric Klein
• Demonstrate a 2-month steady-state operation with a three-stage absorber and a Neumann Systems Group
multistage stripper. [email protected]
• Demonstrate 90 percent CO2 capture efficiency utilizing the best available solvent.
• Show unit traceability/scalability to commercial scale.
partners:
Colorado Springs Utilities,
UNDEERC, Industrial
technical content Constructor Managers,
University of Texas
The NSG Carbon Absorber Retrofit Equipment (CARE) project includes design,
construction, and testing of a 0.5-MW NeuStream® CO2 capture system, based on NSG’s start date:
patented flat jet, modular absorber technology. The NeuStream® absorber uses a proven 01.02.2012
technology with an array of flat jets and an advanced solvent (6 m PZ) to capture CO2. The
CARE absorber design is based on modeling (computational fluid dynamics [CFD] and
percent complete:
Aspen Plus™) and analysis of carbon capture data from slipstream experiments, where
experimental specific surface areas of 440 m2/m3 have been achieved. The CARE system 100%
slipstream test includes compact NeuStream® modules, as well as sulfur oxide (SOx)
scrubbing and amine washing equipment that also utilizes the NeuStream® flat jet
technology.
The SOx scrubbing equipment uses compact modular NeuStream® technology and can be
adjusted to residual SOx level (1–30 parts per million [ppm]) prior to CO2 capture. The
CARE project employs slipstream nitrogen oxide (NOx) removal; a four-stage, 0.5-MWe
NeuStream® high-performance absorber unit for scrubbing; a novel stripper design that
reduces heat waste; and a flue gas heat-recovery method to offset a portion of steam usage.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
570 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 1: The system layout of the 0.5-MW NeuStream®-C demonstrator system
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 86.14 86.14
Normal Boiling Point °C 146 146
Normal Freezing Point °C 106 106
Vapor Pressure @ 15 °C bar <0.001 <0.001
Manufacturing Cost for Solvent $/kg — —
Working Solution
Concentration kg/kg 34% 34%
Specific Gravity (15 °C/15 °C) — 0.99 (50 °C) 0.99 (50 °C)
Specific Heat Capacity @ STP kJ/kg-K 3.6 (50 °C) 3.6 (50 °C)
Viscosity @ STP cP 3.6 cP at 50 °C 3.6 cP at 50 °C
Absorption
Pressure** bar 0.101 0.101
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.38 0.38
Heat of Absorption kJ/mol CO2 73 73
Solution Viscosity cP 4.7 4.7
Desorption
Pressure*** bar 2/4 2/4
Temperature °C 150 150
Equilibrium CO2 Loading mol/mol 0.28 0.28
Heat of Desorption kJ/mol CO2 73 73
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,370
CO2 Recovery, Purity, and Pressure %/%/bar 90 >95 4/8
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
*unloaded PZ solution is a solid at 15 °C; **CO2 partial pressure in the flue gas at Drake plant; ***CO2 partial pressure exiting stripper
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 571
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atmosphere [atm]).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2 absorption
(e.g., the amine monoethanolamine (MEA) in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost for
new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the absorption/desorption process
(e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs at
the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent (e.g., an
MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C). Measured data at
other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal (PC) power plant, the total pressure of the
flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly 0.132
atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
vol% ppmv
Pressure Temperature CO2 H2O N2 O2 Ar SOx NOx
14.7 psia 135 °F 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The absorption of CO2 into concentrated PZ follows a carbamate mechanism, which is
typical of primary and secondary amines. The overall chemical reaction of PZ with CO2 is
2PZ + CO2 PZH+ + PZCOO,
while the full aqueous reaction pathway is [3]
2H2O H3O+ + OH-
2H2O + CO2 HCO3- + H3O+
-
HCO3- + H2O CO32 + H3O+
PZH+ + H2O PZ + H3O+
PZ + HCO3- PZCOO- + H2O
HPZCOO + H2O PZCOO- + H3O+
PZCOO- + HCO3- PZ(COO)22- + H2O.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
572 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Solvent Contaminant Resistance – 6-m PZ is thermally stable at 150 °C with negligible oxidative degradation. The total amine loss
is estimated to be 0.4 percent/week when stripping at 150 °C. At 135 °C, the reported thermal degradation of PZ is 0.07 percent as
compared to 8.1 percent in the case of an MEA solvent.[4] The main degradation products of PZ are nitrates (0.13 mM/hr) and
ethylenediamine (0.09 mM/hr).
Flue Gas Pretreatment Requirements – The flue gas is passed through a NeuStream® NOx- and SOx-removal system before being
fed to the CARE system. The SOx concentration is kept below 10 ppm using two stages of NeuStream® FGD absorbers. The polishing
scrubber for SOx removal has a high volumetric mass-transfer coefficient and 90 percent removal efficiency. The polishing scrubber
also cools the flue gas from 57 °C to ≈32 °C by contacting the flue gas with cold sorbent. This helps maintain water balance while
also reducing the volumetric flow rate through the CO2 absorber and counteracting some of the heat from the exothermic CO2
absorption reaction, reducing the PZ solvent temperature and decreasing the equilibrium vapor pressure, both of which help to reduce
the size of the CO2 absorber.
Waste Streams Generated ––Solid waste streams are generated by the reclaimer, which removes heat stable salts formed by NOx and
SO2 absorption, and by the inline filters. Fugitive liquid amine emissions will be controlled by incorporating seamless valves, rupture
disks, closed-loop ventilation systems, pumps with dual mechanical seals, minimum welds, and correct gasket material selection.
Amine slip is minimized through the use of an amine water wash absorber unit, also based on NeuStream® technology. The FGD
unit generates a gypsum by-product suitable for landfill.
Process Design Concept – Process flow diagram is shown in Figure 2 below.
Figure 2: Process flow diagram of CARE system
Proposed Module Design – The heart of the NeuStream® system is NSG’s patented, high specific surface area NeuStream® flat jet
nozzle technology (shown in Figure 3) engineered into modular, scalable, and efficient cross-flow gas liquid contactor (absorber)
units. The modular absorber units are arranged in parallel into full scale systems. Several areas of innovation make this gas-liquid
contactor extremely effective for absorbing CO2 from flue gas. First, a high specific surface area (400–800 m-1) absorption zone is
achieved over a large volume from an array of flat jets driven by low liquid-side pressure (<34 kPa). Secondly, the flat jets are
aerodynamically shaped, which allows for a high gas flow parallel to the jets while maintaining a low gas-side pressure drop (0.25
kPa/m). Packaging of the NeuStream® absorber takes advantage of the high specific surface area and high gas velocities (typically
5 m/s for CO2 capture) to reduce the footprint of the system by up to 90 percent and booster fan power requirements by up to 70
percent when compared to conventional packed towers.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 573
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Side view View along gas flow
Gas flow Gas flow
(cross flow)
Figure 3: NeuStream® flat jet technology
The system layout is shown above in Figure 1 and the process flow diagram is shown above in Figure 2. Ozone is introduced upstream
of a forced draft to oxidize NOX to more soluble components. The fan moves the flue gas through a heat exchanger to heat the
slipstream flow back up to a representative temperature (350 °F). The flue gas then passes through a second heat exchanger, which
heats loaded solvent and reduces steam usage in the regeneration subsystem. The flue gas then passes through a NeuStream® FGD
system to reduce the SOx concentration to 15 ppm and the NOx by 80–90 percent. A polishing/direct contact cooler (DCC)
NeuStream® scrubber is used to further reduce the SOx to 1 ppm, and to cool the flue gas to <35 °C. After the polishing/DDC
scrubber, the gas passes through a four-unit NeuStream® CO2 absorber (shown in Figure 4), where each unit has three stages. This
12-stage absorber reduces the CO2 by 90 percent prior to contacting the flue gas with a NeuStream® amine wash, which cleans the
amine slip from the gas before reintroducing it into the plants main flue gas stream. Due to space constraints, only 3 of the 4 absorber
units were relocated to NSG’s facility following the unrelated turbine fire at the Drake plant, such that the expected capture efficiency
at design gas flow rates would decrease from 90 percent to ≈75 percent and the gas flow would need to be de-rated in order to realize
90 percent CO2 capture.
Figure 4: Solid model of one of four NeuStream® CO2 absorber stages utilized in Project CARE
(Cross-sectional area scales with system size, but length remains unchanged.)
The regeneration system contains all typical components, such as cross heat exchangers, solvent cooler exchanger, rich pump,
reclaimer, and condenser. A custom-designed stripper vessel is utilized to lower steam usage during operation. Additionally,
approximately 10 percent of the rich flow is directed to a lower-pressure flash vessel to desorb the CO2 from the solvent using only
heat provided by the flue gas.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
574 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
technology advantages
• The NeuStream® CO2 capture technology integrates a highly-efficient, compact absorber design with an advanced solvent,
leading to substantial (≈90 percent) reduction in absorber volume as well as significant savings in both capital and operating
costs compared to conventional systems.
• The high surface areas of the NeuStream® flat jets and low-pressure drop in the absorber lower the capital cost of the absorber
considerably, leading to significant reductions in the increase in levelized cost of electricity (LCOE) over MEA.
• The NeuStream® technology is adaptable to a wide range of solvents encompassing a large spectrum of properties such as
surface tension, viscosity and mass transfer rates.
• The NeuStream® flat jets are engineered into modular absorber units, which are arranged in parallel to meet the flue gas flow
rate requirements for specific applications, facilitating rapid, low-risk scale-up of the technology.
• The NeuStream® technology incorporates PZ regeneration at high pressures, leading to lower CO2 compression power
requirements.
• The CARE system utilizes an alternative NOx-removal strategy to demonstrate the viability of this option over selective catalytic
reductions (SCRs).
• The CARE system utilizes a flue gas heat-recovery strategy to reduce the steam usage in the regeneration subsystem.
• A novel stripper design developed by NSG with Dr. Rochelle and Dr. Chen at the University of Texas is incorporated into the
CARE system to minimize steam usage.
R&D challenges
• Ensuring optimal distribution of gas in the absorber and avoiding gas bypassing the jets in large-scale absorbers may be an issue,
which is addressed via CFD modeling.
• Results from tests on the design verification stand indicate that the specific surface area is not fully preserved with increasing jet
length; this may lead to larger absorbers, increasing capital costs. It is possible this decrease is due to the wall effects that become
more prevalent at longer jet lengths in the design verification test stand.
status
NSG designed, built and tested a 0.5-MW NeuStream® CO2 capture system using flue gas from a natural gas boiler. The system
exhibited 90 percent capture at the CSU’s Martin Drake PC power plant, regenerated CO2 purity was measured to be 98.6 percent.
The NeuStream® absorbers tested support a 90 percent reduction in absorber volume compared to packed towers and with an absorber
parasitic power of less than 1 percent when configured for operation with a 550-MW coal plant. Figure 5 shows a size comparison
between a 110-MW (net) NeuStream® CO2 absorber and a commercial 110-MW (net) CO2 absorber, which was recently
commissioned at SaskPower’s Boundary Dam Unit #3.[5] As can be seen, NeuStream® technology provides a significant size
advantage over conventional CO2 capture technology, resulting in a volume reduction of 82 percent for the 160-MW Boundary Dam
application. The preliminary techno-economic analysis predicted a cost of CO2 capture at $25.73/tonne, with a corresponding COE
increase of 40 percent. Project complete as of December 31, 2015.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 575
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 5: CO2 absorber size comparison: 110 MW (net) NeuStream® vs. CanSolv’s 110 MW (net) SaskPower Boundary Dam Unit #3 Project
(Includes flue gas desulfurization, CO2, and amine wash absorbers.)
available reports/technical papers/presentations
“Carbon Absorber Retrofit Equipment (CARE) Final Scientific/Technical Report,” December 2015.
https://netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0007528-Neumann-Final-Report.pdf.
“Progress Update on the Carbon Dioxide Absorber Retrofit Equipment (CARE) Program,” 2014 NETL CO2 Capture Technology
Meeting, July 2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/A-Awtry-NSG-
Progress-Update-On-NSGs-CARE.pdf.
“Status of the Carbon Dioxide Absorber Retrofit Equipment (CARE) Program,” 2013 NETL CO2 Capture Technology Meeting, July
2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/A-Awtry-NSG-Status-of-the-CARE-Program.pdf
Brasseur, J., and Awtry, A., “Compact Absorber Retrofit Equipment (CARE),” presented at the 2012 NETL CO2 Capture Technology
Meeting, July 2012, Pittsburgh, PA. http://www.netl.doe.gov/publications/proceedings/12/CO2capture/presentations/2-Tuesday/2-
Brasseur-NeumannSG.pdf.
Awtry, A., Klein, E., and Brasseur, J., “NeuStream®-C: Carbon Capture Progress Update,” Air Quality IX, Arlington, VA, 2013.
Awtry, A., Klein, E., and Brasseur, J., “NeuStream®-C: Carbon Capture Progress Update,” Power-Gen XXV, Orlando, FL, 2013.
references
Dugas, Ross E., “CO2 Absorption, Desorption, and Diffusion in Aqueous Piperazine and Monoethanolamine,” PhD Thesis, University
[1]
of Texas, 2009.
Van Wagener, David H., “Stripper Modeling for CO2 Removal Using Monoethanolamine and Piperazine Solvents,” PhD Thesis,
[2]
University of Texas, 2011.
Bishnoi, S., and Rochelle, G. T., “Absorption of carbon dioxide into aqueous piperazine: reaction kinetics, mass transfer and
[3]
solubility,” Chemical Engineering Science 55 (2000) 5531-5543.
Dombrowski, K, “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” DOE-NETL Contractor’s
[4]
Meeting, 2010.
Couturier, Guy and DMello, Mark, (SNC-Lavalin), “From Engineering to Procurement to Construction of the Boundary Dam Carbon
[5]
Capture System,” SaskPower CCS Consortium, 2013 Information and Planning Symposium, May 21, 2013.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
576 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Combined Pressure, technology maturity:
Temperature Contrast and
Bench-Scale, Simulated Flue
Gas
Surface-Enhanced Separation project focus:
of Carbon Dioxide for Post-
Novel Absorption/Stripper
Process
Combustion Carbon Capture participant:
William Marsh Rice University
primary project goals
project number:
FE0007532
William Marsh Rice University developed a novel process for the separation of
carbon dioxide (CO2) from flue gas from conventional, pulverized coal-fired power
plants. The process combines the solvent absorber and stripper columns into a predecessor projects:
single integrated unit. The combined absorber and stripper system benefited from N/A
using a high surface area ceramic foam gas-liquid contactor for enhanced mass
transfer. The project included bench-scale testing of the system. NETL project manager:
Isaac Aurelio
technical goals [email protected]
principal investigator:
• Combine absorber and stripper columns into a single, integrated process unit
to achieve significant cost savings in capital costs and to mitigate space Dr. Michael S. Wong
availability constraints. William Marsh Rice University
[email protected]
• Use a high surface area ceramic foam gas-liquid contactor for enhanced mass
transfer.
partners:
• Use vacuum stripping in combination with waste heat for regeneration of a
N/A
CO2 solvent.
• Assess the potential to functionalize the ceramic gas-liquid contactors with start date:
solid catalyst for enhanced CO2 desorption.
10.01.2011
• Evaluate the use of catalysts for CO2 desorption.
• Determine best absorbent and operating conditions for the process. percent complete:
• Develop a two-dimensional (2D) model to simulate gas and liquid flow in the 100%
capture process.
• Perform a techno-economic analysis.
technical content
The technical approach involves the integration of the absorber and stripper
sections into a single unit. Figure 1 shows a schematic of a combined absorber
and stripper unit.
In Figure 1, the region shaded in blue represents a gas-liquid contactor on the
absorption side whereas the region shaded in red represents the same on the
stripping side. The gas-liquid contactor must possess a large geometric surface
area for good gas-liquid contacting. For liquid to be transported from the
absorption to stripping side, horizontal flow of the liquid is a requirement. This can
take place in two ways, either by flow through the connected pores of a ceramic
contactor or as a liquid film moving over the surface of a contactor with a complex
three-dimensional structure.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 577
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 1: Schematic of combined pressure and temperature contrast and surface-enhanced separation of CO2
A bench-scale prototype of the gas absorption process was developed to study various aspects of fluid flow in the system.
A simulation model for the process was also developed to optimize the properties of ceramics being used and the process
operating conditions.
The expected outcomes of this project include significant reduction in the capital and operating costs of the gas absorption
process and a resulting decrease in cost of electricity (COE). The use of waste heat instead of high-quality steam provides
a significant reduction in operating costs. An integrated absorber and stripper unit substantially reduces capital costs.
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 86.14 86.14
Normal Boiling Point °C 146 146
Normal Freezing Point °C 106 106
Vapor Pressure @ 15 °C bar <0.001 <0.001
Manufacturing Cost for Solvent $/kg — —
Working Solution
Concentration kg/kg 34% 34%
Specific Gravity (15 °C/15 °C) — 0.99 (50 °C) 0.99 (50 °C)
Specific Heat Capacity @ STP kJ/kg-K 3.6 (50 °C) 3.6 (50 °C)
Viscosity @ STP cP 3.6 cP at 50 °C 3.6 cP at 50 °C
Absorption
Pressure** bar 0.101 0.101
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.38 0.38
Heat of Absorption kJ/mol CO2 73 73
Solution Viscosity cP 4.7 4.7
Desorption
Pressure*** bar 2/4 2/4
Temperature °C 150 150
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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Appendix: Post-Combustion Solvent Technologies
Equilibrium CO2 Loading mol/mol 0.28 0.28
Heat of Desorption kJ/mol CO2 73 73
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 2,370
CO2 Recovery, Purity, and Pressure % / % / bar 90 >95 4/8
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
*unloaded PZ solution is a solid at 15 °C; **CO2 partial pressure in the flue gas at Drake plant; ***CO2 partial pressure exiting stripper
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., the amine monoethanolamine (MEA) in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically
occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding
to a CO2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated
data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler
temperature of 120 °C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure;
if it is a mixture of gases, this is the partial pressure of CO2. Note that for a typical PC power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is
roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis)
should be assumed as:
Composition
Pressure Temperature vol% ppmv
14.7 psia 135 °F CO2 H2O N2 O2 Ar SOx NOx
13.17 17.25 66.44 2.34 0.80 42 74
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 579
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The absorption of CO2 into concentrated PZ follows a carbamate mechanism,
which is typical of primary and secondary amines. The overall chemical reaction of PZ with CO2 is
2PZ + CO2 PZH+ + PZCOO,
while the full aqueous reaction pathway is [3]
2H2O H3O+ + OH-
2H2O + CO2 HCO3- + H3O+
HCO3- + H2O CO32- + H3O+
PZH+ + H2O PZ + H3O+
PZ + HCO3- PZCOO- + H2O
HPZCOO + H2O PZCOO- + H3O+
PZCOO- + HCO3- PZ(COO)22- + H2O.
Solvent Contaminant Resistance –6-m PZ is thermally stable at 150 °C with negligible oxidative degradation. The total
amine loss is estimated to be 0.4 percent/week when stripping at 150 °C. At 135 °C, the reported thermal degradation of
PZ is 0.07 percent as compared to 8.1 percent in the case of an MEA solvent.[4]. The main degradation products of PZ
are nitrates (0.13 mM/hr) and ethylenediamine (0.09 mM/hr).
Flue Gas Pretreatment Requirements – The flue gas is passed through a NeuStream® nitrogen oxides (NOx)- and
sulfur oxides (SOx)- removal system before being fed to the CARE system. The SOx concentration is kept below 10 ppm
using two stages of NeuStream® FGD absorbers. The polishing scrubber for SOx removal has a high volumetric mass-
transfer coefficient and 90 percent removal efficiency. The polishing scrubber also cools the flue gas from 57 °C to ≈32
°C by contacting the flue gas with cold sorbent. This helps maintain water balance while also reducing the volumetric flow
rate through the CO2 absorber and counteracting some of the heat from the exothermic CO2 absorption reaction, reducing
the PZ solvent temperature and decreasing the equilibrium vapor pressure, both of which help to reduce the size of the
CO2 absorber.
Waste Streams Generated ––Solid waste streams are generated by the reclaimer, which removes heat stable salts
formed by NOx and SO2 absorption, and by the inline filters. Fugitive liquid amine emissions will be controlled by
incorporating seamless valves, rupture disks, closed-loop ventilation systems, pumps with dual mechanical seals,
minimum welds, and correct gasket material selection. Amine slip is minimized through the use of an amine water wash
absorber unit, also based on NeuStream® technology. The FGD unit generates a gypsum by-product suitable for landfill.
Process Design Concept – Process flow diagram is shown in Figure 2 below.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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580 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
Figure 2: Process flow diagram of care system
Proposed Module Design – The heart of the NeuStream® system is NSG’s patented, high specific surface area
NeuStream® flat jet nozzle technology (shown in Figure 3) engineered into modular, scalable, and efficient cross-flow
gas liquid contactor (absorber) units. The modular absorber units are arranged in parallel into full scale systems. Several
areas of innovation make this gas-liquid contactor extremely effective for absorbing CO2 from flue gas. First, a high
specific surface area (400–800 m-1) absorption zone is achieved over a large volume from an array of flat jets driven by
low liquid-side pressure (<34kPa). Secondly, the flat jets are aerodynamically shaped which allows for a high gas flow
parallel to the jets while maintaining a low gas-side pressure drop (0.25 kPa/m). Packaging of the NeuStream® absorber
takes advantage of the high specific surface area and high gas velocities (typically 5 m/s for CO2 capture) to reduce the
footprint of the system by up to 90 percent and booster fan power requirements by up to 70 percent when compared to
conventional packed towers.
Side view View along gas flow
Gas flow Gas flow
(cross flow)
Figure 3: NeuStream® flat jet technology
The system layout is shown above in Figure 1 and the process flow diagram is shown above in Figure 2. Ozone is
introduced upstream of a forced draft to oxidize NOx to more soluble components. The fan moves the flue gas through a
heat exchanger to heat the slipstream flow back up to a representative temperature (350 °F). The flue gas then passes
through a second heat exchanger, which heats loaded solvent and reduces steam usage in the regeneration subsystem.
The flue gas then passes through a NeuStream® FGD system to reduce the SOx concentration to 15 ppm and the NOx
by 80–90 percent. A polishing/direct contact cooler (DCC) NeuStream® scrubber is used to further reduce the SOx to 1
ppm, and to cool the flue gas to <35 °C. After the polishing/DDC scrubber, the gas passes through a four-unit
NeuStream® CO2 absorber (shown in Figure 4), where each unit has three stages. This 12-stage absorber reduces the
CO2 by 90 percent prior to contacting the flue gas with a NeuStream® amine wash, which cleans the amine slip from the
gas before reintroducing it into the plants main flue gas stream. Due to space constraints, only 3 of the 4 absorber units
were relocated to NSG’s facility following the unrelated turbine fire at the Drake plant. The expected capture efficiency at
design gas flow rates would decrease from 90 percent to ≈75 percent and the gas flow would to be de-rated in order to
realize 90 percent CO2 capture.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 581
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 4: Solid model of one of four NeuStream® CO2 absorber stages utilized in project CARE
(cross-sectional area scales with system size, but length remains unchanged)
The regeneration system contains all typical components, such as cross heat exchangers, solvent cooler exchanger, rich
pump, reclaimer, and condenser. A custom-designed stripper vessel is utilized to lower steam usage during operation.
Additionally, approximately 10 percent of the rich flow is directed to a lower-pressure flash vessel to desorb the CO2 from
the solvent using only heat provided by the flue gas.
technology advantages
• The NeuStream® CO2 capture technology integrates a highly-efficient, compact absorber design with an advanced
solvent, leading to substantial (≈90 percent) reduction in absorber volume as well as significant savings in both capital
and operating costs compared to conventional systems.
• The high surface areas of the NeuStream® flat jets and low-pressure drop in the absorber lower the capital cost of
the absorber considerably, leading to significant reductions in the increase in levelized cost of electricity (LCOE) over
MEA.
• The NeuStream® technology is adaptable to a wide range of solvents encompassing a large spectrum of properties
such as surface tension, viscosity and mass transfer rates.
• The NeuStream® flat jets are engineered into modular absorber units which are arranged in parallel to meet the flue
gas flow rate requirements for specific applications, facilitating rapid, low-risk scale-up of the technology.
• The NeuStream® technology incorporates PZ regeneration at high pressures, leading to lower CO2 compression
power requirements.
• The CARE system utilizes an alternative NOx-removal strategy to demonstrate the viability of this option over
selective catalytic reductions (SCRs).
• The CARE system utilizes a flue gas heat-recovery strategy to reduce the steam usage in the regeneration
subsystem.
• A novel stripper design developed by NSG with Dr. Rochelle and Dr. Chen at the University of Texas is incorporated
into the CARE system to minimize steam usage.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
582 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
R&D challenges
• Ensuring optimal distribution of gas in the absorber and avoiding gas bypassing the jets in large-scale absorbers
may be an issue which is addressed via computational fluid dynamics (CFD) modeling.
• Results from tests on the design verification stand indicate that the specific surface area is not fully preserved with
increasing jet length; this may lead to larger absorbers, increasing capital costs. It is possible this decrease is due to
the wall effects that become more prevalent at longer jet lengths in the design verification test stand.
status
NSG designed, built and tested a 0.5-megawatt (MW) NeuStream® CO2 capture system using flue gas from a natural
gas boiler. The system exhibited 90 percent capture at the CSU’s Martin Drake PC power plant, regenerated CO2 purity
was measured to be 98.6 percent. The NeuStream® absorbers tested support a 90 percent reduction in absorber volume
compared to packed towers and with an absorber parasitic power of less than 1 percent when configured for operation
with a 550-MW coal plant. Figure 5 shows a size comparison between a 110-MW (net) NeuStream® CO2 absorber and
a commercial 110-MW (net) CO2 absorber which was recently commissioned at SaskPower’s Boundary Dam Unit #3.[5]
As can be seen, NeuStream® technology provides a significant size advantage over conventional CO2 capture
technology, resulting in a volume reduction of 82percent for the 160-MW Boundary Dam application. The preliminary
techno-economic analysis predicted a cost of CO2 capture at $25.73/tonne, with a corresponding COE increase of 40
percent. The project was complete as of December 31, 2015.
Figure 5: CO2 Absorber size comparison: 110-MW (net) NeuStream® vs. CanSolv’s 110-MW (net) SaskPower Boundary Dam Unit #3 project
(includes flue gas desulfurization, CO2 and amine wash absorbers)
available reports/technical papers/presentations
“Carbon Absorber Retrofit Equipment (CARE) Final Scientific/Technical Report, December 2015.
https://netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0007528-Neumann-Final-
Report.pdf.
“Progress Update on the Carbon Dioxide Absorber Retrofit Equipment (CARE) Program,” 2014 NETL CO2 Capture
Technology Meeting, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/A-Awtry-NSG-Progress-Update-
On-NSGs-CARE.pdf.
“Status of the Carbon Dioxide Absorber Retrofit Equipment (CARE) Program,” 2013 NETL CO2 Capture Technology
Meeting, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/A-Awtry-NSG-Status-of-the-
CARE-Program.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 583
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Brasseur, J., and Awtry, A., “Compact Absorber Retrofit Equipment (CARE),” presented at the 2012 NETL CO2 Capture
Technology Meeting, July 2012, Pittsburgh, PA.
http://www.netl.doe.gov/publications/proceedings/12/CO2capture/presentations/2-Tuesday/2-Brasseur-NeumannSG.pdf.
Awtry, A., Klein, E., and Brasseur, J., “NeuStream®-C: Carbon Capture Progress Update”, Air Quality IX, Arlington, VA,
2013.
Awtry, A., Klein, E., and Brasseur, J., “NeuStream®-C: Carbon Capture Progress Update”, Power-Gen XXV, Orlando, FL,
2013.
references
Dugas, Ross E., “CO2 Absorption, Desorption, and Diffusion in Aqueous Piperazine and Monoethanolamine,” PhD Thesis,
[1]
University of Texas, 2009.
Van Wagener, David H., “Stripper Modeling for CO2 Removal Using Monoethanolamine and Piperazine Solvents,” PhD
[2]
Thesis, University of Texas, 2011.
Bishnoi, S., and Rochelle, G. T., “Absorption of carbon dioxide into aqueous piperazine: reaction kinetics, mass transfer
[3]
and solubility,” Chemical Engineering Science 55 (2000) 5531-5543.
Dombrowski, K, “Evaluation of Concentrated Piperazine for CO2 Capture from Coal-Fired Flue Gas,” DOE-NETL
[4]
Contractor’s Meeting, 2010.
Couturier, Guy and DMello, Mark, (SNC-Lavalin), “From Engineering to Procurement to Construction of the Boundary
[5]
Dam Carbon Capture System”, SaskPower CCS Consortium, 2013 Information and Planning Symposium, May 21, 2013.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Development of a Novel Gas technology maturity:
Pressurized Stripping-Based
Bench-Scale, Real Flue Gas
project focus:
Technology for CO2 Capture Gas-Pressurized Stripping
from Post-Combustion Flue participant:
Gases Carbon Capture Scientific
project number:
primary project goals FE0007567
Carbon Capture Scientific has performed bench-scale development, testing, and
predecessor projects:
computer simulations of a novel solvent-based carbon dioxide (CO2) capture N/A
technology, known as gas-pressurized stripping (GPS) process. The GPS
technology has the potential to significantly reduce the energy penalty NETL project manager:
associated with solvent regeneration and compression by operating the Andrew Jones
regeneration step at higher pressures, which in-turn reduces the compression [email protected]
requirements for CO2 storage.
principal investigator:
technical goals Shiaoguo (Scott) Chen
Carbon Capture Scientific,
• Computer simulation to predict GPS column performance under different LLC
scottchen@carboncapturescie
operating conditions.
ntific.com
• Lab-scale tests of individual process units to document experimental results
and obtain necessary information to progress the technology to the next partners:
level.
CONSOL Energy, Inc.,
• Experimental investigation of selected solvents to minimize the economic Nexant, Inc., Western
risk of the proposed technology.
Kentucky University
• Design, build, and operate a bench-scale GPS unit capable of processing
about 500 standard liters of actual coal-derived flue gas per minute (SLPM) start date:
at the National Carbon Capture Center (NCCC).
10.01.2011
• Derive a techno-economic analysis (TEA) of the GPS process on a
pulverized coal plant compared to a baseline pulverized coal plant. percent complete:
100%
technical content
The project conducted lab-scale individual process unit tests and integrated
continuous bench-scale GPS system tests using actual coal-derived flue gas at
the NCCC. The overall objective was to reduce the energy consumption and
capital cost of the CO2 capture process.
Computer simulation tasks investigated the GPS column behavior under different
operating conditions, optimizing the column design and operating conditions,
leading to a capital cost increase less than five percent over the baseline
monoethanolamine (MEA) case. Solvent related tasks collected information on
the solvent operating cost when a modified, commercially-available solvent is
used in the GPS process. Experiment related tasks with the major individual
units obtained information needed for the bench-scale unit design, and the
integrated continuous bench-scale GPS system tests using actual coal-derived
flue gas at the NCCC provided all the necessary information for the next level
pilot-scale process and engineering design along with the GPS system
performance data. Testing at the NCCC demonstrated that the GPS process can
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
585
Appendix: Post-Combustion Solvent Technologies
achieve 90 percent CO2 removal from typical coal-derived flue gas. The GPS process can produce high-pressure CO2
product with required purity. Finally, the GPS process has an energy consumption much lower than that of the DOE
MEA baseline case. A TEA of the GPS process was derived, showing that a GPS-based pulverized coal (PC) plant has
net power production of 647 MW, greater than the MEA baseline study. This increase is attributed to the lower steam
requirement and smaller CO2 compression auxiliary power consumption. The TEA also found that the 20-year levelized
cost of electricity for a supercritical PC plant with GPS-based PCC is 52 percent more than the baseline supercritical
PC plant without CO2 capture but 23 percent lower than the baseline supercritical PC plant with MEA. Figure 1 is a
flowchart for the GPS process. Figure 2 shows the GPS-based skid developed and tested at the NCCC. Table 1 lists
the process parameters relevant to the GPS process.
Clean CO2 Product
Flue Gas Makeup
Amine
Cooling
Hot Rich
Solution
Lean
Solution
Cooling
Heating
Absorption Stripping
Column Column
Cooling Heating
Cross Heat
Exchanger
Raw Flue Stripping
Gas Gas
Rich Solution Hot
Lean Solution
Figure 1: GPS-based absorption/stripping process
Figure 2: GPS-based skid used for bench-scale slipstream testing at NCCC
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
586 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D Value Target R&D Value
Molecular Weight mol-1 112.4 112.4
Normal Boiling Point °C 226.8 226.8
Normal Freezing Point °C 4.4 4.4
Vapor Pressure @ 15 °C bar <1.3E-05 <1.3E-05
Manufacturing Cost for Solvent $/kg 3 3
Working Solution
Concentration kg/kg — —
Specific Gravity (15 °C/15 °C) — 1.06 1.06
Specific Heat Capacity @ STP kJ/kg-K ca. 3 ca. 3
Viscosity @ STP cP N/A
Absorption
Pressure bar 1.01 1.01
Temperature °C 40 40
Equilibrium CO2 Loading mol/mol 0.41 0.49
Heat of Absorption kJ/mol CO2 59.6 59.6
Solution Viscosity cP 6.2 4
Desorption
Pressure bar 6 6
Temperature °C 120 120
Equilibrium CO2 Loading mol/mol 0.19 0.19
Heat of Desorption kJ/mol CO2 58.5 58.5
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 40
CO2 Recovery, Purity, and Pressure %%/bar 90% >95% 6 bar
Absorber Pressure Drop bar 0.05
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced
CO2 absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated
manufacturing cost for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the
absorption/desorption process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which
typically occurs at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure
(corresponding to a CO2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are
preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which
typically occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
587
Appendix: Post-Combustion Solvent Technologies
are process-dependent (e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a
reboiler temperature of 120 °C). Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO 2, this is the total
pressure; if it is a mixture of gases, this is the partial pressure of CO 2. Note that for a typical PC power plant, the total
pressure of the flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial
pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – Pressurized stripping is a process applicable to different types of solvents.
Chemistry of the GPS-based absorption/stripping process depends on the solvent used in the process. In the proposed
research, a modified commercially-available amine solvent will be used. Therefore, the chemistry of the amine-based
CO2 capture process will apply to the GPS-based process.
The reaction kinetics of the GPS-based process also depends on the solvent selected. With the solvent currently
selected, it is believed that the reaction kinetics of the modified commercially available solvent will perform better than
the baseline monoethanolamine (MEA) process.
Solvent Contaminant Resistance – Since the selected solvent is an amine-based solvent, it will share common
issues that other amine-based solvents have. Sulfur oxide (SO x) and nitrogen oxide (NOx) could be the major
contaminants in flue gas, which will be detrimental to all amine-based solvents, including the solvent used in this
process. Similar to other amine-based solvents, pretreatment of flue gas will be required to minimize amine
degradations.
Solvent Foaming Tendency – The solvent is a commercially available solvent, with different strength. The solvent
forming tendency should be manageable based on industrial experience.
Flue Gas Pretreatment Requirements – Similar to other amine-based solvents, pretreatment of flue gas will be
required to minimize amine degradations.
Solvent Makeup Requirements – Solvent stability study has demonstrated that this commercially-available solvent
will have solvent makeup rate of 1 kg solvent/tonne CO 2.
Waste Streams Generated – Waste stream of the GPS-based process is also similar to other amine-based
absorption/stripping processes. The main waste material is amine degradation products.
Process Design Concept – Flowsheet/block flow diagram of the GPS process is shown in Figure 1. It is clear that the
GPS process is virtually the same as a conventional absorption/stripping process except the two unique innovations:
(1) using two side heat exchangers to replace a bottom reboiler, and (2) introducing a stripping gas (N 2 or other inert
gas) into the GPS column from the bottom. This process configuration will reduce stripping heat significantly.
Proposed Module Design – Unless noted, flue gas feed pressure is 1.014 bara, temperature is 57 °C, and
composition leaving the flue gas desulfurization (FGD) unit (wet basis) should be assumed:
Composition
Pressure Temperature vol% ppmv
bara °C CO2 H2O N2 O2 Ar SOx NOx
1.014 57 13.17 17.25 66.44 2.34 0.80 42 74
technology advantages
• The use of off-the-shelf process equipment will accelerate process development.
• The use of absorption/stripping technology would be suitable for low-cost, large-scale applications.
• The higher stripper operating pressure reduces the stripping heat requirement and subsequent compression work.
As a result, GPS process offers higher energy efficiency.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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588 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
• The GPS technology is flexible in terms of operating pressures and temperatures, and is applicable to different
types of solvents.
R&D challenges
The major challenge of the GPS-based process is its capital cost. The optimal GPS-based process has almost the
same capital cost as the baseline process. New process equipment, which can significantly reduce capital cost, is
needed to commercialize the GPS technology.
status
The project was completed on September 30, 2015. Carbon Capture Scientific and their partners determined that a
combination of experimental, computer simulation, and techno-economic analysis was effective to identify optimal
process configurations and operating conditions for the GPS technology and that the GPS-based post-combustion
capture process is energy-efficient and cost-effective compared with the benchmark MEA process. Integrating the GPS
process into a 550-MW e PC-fired power plant will increase cost of electricity approximately 23 percent less than that for
the benchmark MEA process.
available reports/technical papers/presentations
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” Final Scientific/Technical Report, October 2015.
https://www.osti.gov/scitech/servlets/purl/1233208.
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” Project Closeout Meeting, Pittsburgh, PA, December 2015.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0007567-Final-
Review-Presentation-12-18-2015.pdf.
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” 2015 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/S-Chen-CCS-Gas-Pressurized-
Stripping.pdf.
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/S-Chen-CCS-Development-
Of-A-Novel-Gas-Pressurized-Stripping.pdf.
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” 2013 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/S-Chen-CCS-Novel-GPS-Based-
Technology.pdf.
Shiaoguo (Scott) Chen, “Preliminary Technical and Economic Feasibility Study–Topical Report,” October 2012.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/FE0007567-Topical-Report-10-30-12.pdf.
Shiaoguo (Scott) Chen, “Development of a Novel Gas Pressurized Stripping (GPS)-Based Technology for CO2 Capture
from Post-Combustion Flue Gases,” 2012 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/development-novel-gas-pressurized-stripping-
july2012.pdf.
“Development of a Novel Gas Pressurized Stripping Process-Based Technology for CO2 Capture,” Project Kick-Off
Meeting Presentation, November 2011. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/development-
novel-gas-pressurized-stripping-kickoff-nov2011.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
589
Appendix: Post-Combustion Solvent Technologies
Low-Energy Solvents for CO2 technology maturity:
Bench-Scale, Simulated Flue
Capture Enabled by a Gas
Combination of Enzymes and project focus:
Vacuum Regeneration
Solvent + Enzyme and
vacuum Regeneration
Technology
primary project goals participant:
Novozymes
Novozymes, together with the project partners, designed, built, and tested an
integrated bench-scale system that combines the attributes of an enzyme catalyst project number:
(carbonic anhydrase [CA]) with low-enthalpy absorption liquids and vacuum
FE0007741
regeneration in a solvent-based carbon dioxide (CO 2 ) capture process, and evaluated a
novel ultrasonically enhanced regeneration concept.
predecessor projects:
N/A
technical goals
NETL project manager:
• Conduct preliminary evaluation of the potential for ultrasonic regeneration to Andrew jones
deliver a lean-loading equivalent to the lean loading predicted with vacuum [email protected]
stripping at 70 °C.
• Optimize enzyme-promoted potassium carbonate (K 2 CO 3 )-based solvent for principal investigator:
maximum CO 2 absorption rate. Dr. Sonja Salmon
• Demonstrate enzyme robustness for meeting targeted bench-scale test Novozymes
conditions.
• Design and build an integrated bench-scale unit incorporating the vacuum partners:
regeneration component to validate stripping performance at 70–80 °C. University of Kentucky CAER;
Pacific Northwest National
• Demonstrate system performance and benefits based on completion of 500 hours
Laboratory; Doosan
of testing.
• Complete a full technology assessment of the process and potential for meeting start date:
reductions in net parasitic load compared to conventional technology for post-
10.01.2011
combustion CO 2 capture.
percent complete:
technical content 100%
Novozymes, together with the project partners, designed, built, and tested an
integrated bench-scale system that combines the attributes of the bio-renewable
enzyme carbonic anhydrase (CA) with low-enthalpy aqueous potassium carbonate-
based solvent and vacuum regeneration. Preliminary evaluation of a novel
ultrasonically enhanced regeneration system was also made. The objective was to
develop a CO 2 capture process with improved efficiency and economics when
compared with existing CO 2 technologies.
The application of CA accelerates inter-conversion between dissolved CO 2 and
bicarbonate ion, which is the rate-limiting step for absorption and desorption in low
enthalpy of reaction solutions that rely on reactive absorption of CO 2 . The mechanism
for CO 2 absorption and desorption when using potassium carbonate solvent is:
CO 2 + H 2 O + K 2 CO 3 ↔ 2 KHCO 3
The use of low enthalpy CO 2 absorption solvents offers the opportunity to regenerate
the solvent at lower temperatures relative to existing CO 2 scrubber technologies. The
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Appendix: Post-Combustion Solvent Technologies
system was evaluated with respect to energy requirement and enzyme effects in a process where the enzyme is dissolved and
recirculates through the absorber and reduced-temperature stripper. A replenishment program to compensate for active
enzyme loss while maintaining system performance was also evaluated.
One method of achieving low temperature stripping is to apply vacuum to decrease the solvent boiling point to ≈70–80 °C, and
provide driving force for the regeneration. Process simulations of this approach have been made indicating that the use of low-
enthalpy solvents, which could require low-pressure steam during the regeneration cycle, together with vacuum has the
potential to require 43 percent less parasitic power from a coal-fired power plant compared to NETL Case 10 MEA scrubbing
technology. It is recognized that application of vacuum would have a corresponding compression penalty downstream of the
CO 2 capture unit. Therefore, the aim of the evaluation was to demonstrate the feasibility of the vacuum approach by a
combination of bench-scale system testing and corresponding projections of feasibility at 550-megawatt electric (MW e ) scale.
Figure 1: Bench-scale process schematic
In another method of low temperature stripping, application of ultrasonic energy transforms dissolved CO 2 into gas bubbles,
thereby increasing the overall driving force of the solvent regeneration reaction. This is shown in Figure 2, where the effects of
sonication can be seen on the loaded solvent. The ultrasonic effect known as rectified diffusion where expanding bubbles allow
for a biased transfer of dissolved gas into the bubble from solution, could have the potential to yield lean solvent CO 2 loading
equivalent to vacuum stripping. Several different configurations of the prototype ultrasonic regenerator were evaluated,
including combination with vacuum and novel incorporation of a hydrocyclone to enhance gas-liquid separation. The
magnitude of measured CO 2 release was within the range of temperature-dependent release, meaning that application of
ultrasonics could provide thermal regeneration effects. However, additional work would be required to validate whether rectified
diffusion could replace the vacuum requirement at low stripping temperatures.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
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Appendix: Post-Combustion Solvent Technologies
Figure 2: Ultrasonic regeneration batch tests for loaded solvent at 70 °C – (L) no sonication; (R) with sonication
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 138.21 138.21
Normal Boiling Point °C — —
Normal Freezing Point °C — —
Vapor Pressure @ 15 °C bar — —
Manufacturing Cost for Solvent $/kg 1.3 <1.3
Working Solution
Concentration kg/kg 0.23 0.23
Specific Gravity (15 °C/15 °C) - 1.21 1.21
Specific Heat Capacity @ STP kJ/kg-K ~3.4a ~3.4a
Viscosity @ STP cP ~1.4 ~1.4
Absorption
Pressure bar 1 1
Temperature °C 30–40 30–50
Equilibrium CO 2 Loading mol/mol 0.55 0.67
Heat of Absorption kJ/mol CO 2 27 27
Solution Viscosity cP ~1.4 ~1.4
Desorption
Pressure bar 0.35 0.35
Temperature °C 77 70–80
Equilibrium CO 2 Loading mol/mol 0.35 0.30
Heat of Desorption kJ/mol CO 2 27 27
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr —
CO 2 Recovery, Purity, and Pressure % / % / bar — — —
Absorber Pressure Drop bar —
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Notes: Working solution additionally contains CA enzyme catalyst.
Technical Data: Properties of Potassium Carbonate. Armand Products Company.
a
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
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Appendix: Post-Combustion Solvent Technologies
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO 2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO 2 -free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent
(e.g., an MEA-based absorption system has a typical CO 2 partial pressure of 1.8 bar and a reboiler temperature of 120°C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the solution. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO 2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization
(FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism –
1. CO 2(g) ↔ CO 2(aq) (gas-liquid physical mass transfer)
2. CO 2(aq) + HO- ↔ HCO 3 -
3. HCO 3 - + HO- ↔ CO 3 = + H 2 O (pK a = 10.3)
4. CO 2(aq) + H 2 O ↔ H 2 CO 3
5. H 2 CO 3 + HO- ↔ HCO 3 - + H 2 O (pK a = 6.4)
6. H 2 O ↔ H+ + HO-
For the solvent system in the proposed operating range (pH 9-11), Reaction 2 and reactions 4 together with 5 are responsible for
the absorption of CO 2 into the liquid phase as bicarbonate. CA enzyme catalyzes Reaction 6 in the enzyme active site to produce
a zinc-hydroxide nucleophile that reacts with CO 2 to produce and release bicarbonate according to Reaction 2. The proton
produced during Reaction 6 is transferred from the active site to the reaction medium where the proton is neutralized by the
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
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593
Appendix: Post-Combustion Solvent Technologies
alkalinity and buffering capacity of the medium. The transfer of proton away from the active site has been determined in the
literature as the rate limiting step for CA catalysis.
The kinetics of CO 2 absorption in CA enzyme/K 2 CO 3 solution were measured using the wetted-wall column technique. The
current enzyme/K 2 CO 3 solvent supports a mass transfer rate ≥50 percent the rate of benchmark 30 percent MEA.
Solvent Contaminant Resistance – Publications by Akermin, Inc. (DE-FE0004228 and DE-FE0012862) and the University of Illinois
(DE-FC26-08NT0005498) demonstrate the robustness of enzyme-promoted K 2 CO 3 solvents to typical flue gas contaminants at
lab scale.
Solvent Foaming Tendency – Based on bench-scale tests, solvent foaming can be mitigated by antifoam, as necessary.
Flue Gas Pretreatment Requirements – No special requirements expected beyond conventional pretreatment for particulate,
sulfur oxide (SO x ), and nitrogen oxide (NO x ) removal.
Solvent Make-Up Requirements – Preliminary feasibility study assumed a K 2 CO 3 makeup rate of 0.1 ton/day and continuous
enzyme reclamation from 0.05 percent lean solvent slipstream. However, lower than targeted enzyme longevity in the bench
scale test resulted in significant cost impact of solvent makeup requirements in the final TEA.
Waste Streams Generated – Waste stream consists of K 2 CO 3 salts and biodegradable enzyme, which could be used as compost,
fertilizer or boiler fuel.
Process Design Concept – Bench-scale process schematic is shown in Figure 1.
technology advantages
• The energy required for solvent regeneration is provided by low-pressure steam and vacuum.
• Enzyme helps overcome the inherently slow reaction rates of the K 2 CO 3 based solvent, which have previously made its use
for atmospheric CO 2 capture prohibitive. Enzyme-enhanced rates of CO 2 absorption compared to aqueous K 2 CO 3 without
CA could lead to capital cost savings.
• By providing enzyme in dissolved form, conventional liquid handling approaches can be used to adjust enzyme dose and
replenishment rates to achieve optimal system performance.
• K 2 CO 3 has chemical handling advantages due to negligible vapor pressure, no flash point, no odor, no degradation, good
safety and environmental profile, and ready availability.
R&D challenges
• Scale-up of the vacuum and ultrasonic regeneration systems from lab- to bench-scale (10–30 standard liters/minute [SLPM]
gas, 0.1–0.30 LPM solvent) to provide sufficient lean loading to support 90 percent capture.
• Ultrasonic test system showed tendency towards rapid CO 2 re-dissolution of generated gases and foaming phenomena,
which pointed to the need for specialized gas removal in the continuous system. Further work is needed to verify predicted
ultrasonic advantages.
• Enzyme dose required to achieve and maintain 90 percent capture.
• Accurate scale up of bench scale data to full scale predictions using process models.
• Practicality of vacuum equipment to handle CO 2 gas flow at 550-MW e scale.
• Utilization of a very low pressure (VLP) turbine for extracting the solvent regeneration steam at 8 psia (and 85 °C).
status
This project was completed on June 30, 2015. A novel flow-through ultrasonic regenerator was designed and tested, confirming
that CO 2 was released, however the release values were below the equilibrium projections. The highest ultrasonic results were
explainable by the localized temperature increases in the liquid caused by the ultrasonic energy alone, therefore the remainder
of the project focused on the use of vacuum regeneration. The fully integrated bench-scale system including vacuum
regeneration was designed and fabricated, with parametric and alternative solvent testing completed. Overall, the system was
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
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Appendix: Post-Combustion Solvent Technologies
operated successfully for an accumulated 500 hours of operation with vacuum conditions. An average of 84 percent CO 2 capture
efficiency was attained during the period using enzyme replenishment. The presence of enzyme caused foaming in the stripper,
which was controlled via antifoam addition. There was a faster decay rate of the enzyme activity at longer residence time at
elevated temperatures in the cycle. TEA studies of the system indicated higher COE, higher cost of CO 2 captured, and slightly
lower energy requirement compared to DOE Case 10 (Econamine solvent process), with the difference in costs primarily due to
higher variable costs.
available reports/technical papers/presentations
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Vacuum
Regeneration,” Novozymes North America, Inc., 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June
2015. http://netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0007741-Final-Project-Meeting-09-
23-15.pdf
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Vacuum
Regeneration,” Novozymes North America, Inc., 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June
2015. http://netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/S-Salmon-Novozymes-Low-Energy-Solvents.pdf
House, A., “Low-Energy Solvents for CO 2 Capture Enabled by a Combination of Enzymes and Vacuum Regeneration,” AIChE
2014 Meeting, Atlanta, GA, November 17, 2014. http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/FE0007741-AIChE-2014-Presentation-11-17-2014.pdf.
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Vacuum
Regeneration,” Novozymes North America, Inc., 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/S-Salmon-Novozymes-Low-Energy-
Solvents.pdf.
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Vacuum
Regeneration,” Novozymes North America, Inc., 2013 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/S-Salmon-Novozymes-Low-Energy-Solvents.pdf.
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Ultrasonics,” Project
Review Meeting, October 2012. http://www.netl.doe.gov/File Library/Research/Coal/ewr/CO2/DE-FE0007741-netl-project-review-
bp1-Oct2012_FINAL.pdf.
Salmon, S., “Lab-Scale Assessment of a Post-Combustion Carbon Dioxide Capture Process Enabled by a Combination of
Enzymes and Ultrasonics,” 2012 Pittsburgh Coal Conference, Pittsburgh, PA, October
2012. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/ipcc-oct2012-session11-salmon.pdf.
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Ultrasonics,” 2012
NETL CO 2 Capture Technology Meeting, Pittsburgh, PA. July 2012. http://www.netl.doe.gov/File
Library/Research/Coal/ewr/CO2/enzymes-ultrasonics-july2012.pdf.
Salmon, S., “Low-Energy Solvents for Carbon Dioxide Capture Enabled by a Combination of Enzymes and Ultrasonics,” Project
Kick-Off Meeting, November 2011. http://www.netl.doe.gov/File Library/Research/Coal/ewr/CO2/enzymes-ultrasonics-kickoff-
nov2011.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 595
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Appendix: Post-Combustion Solvent Technologies
DEVELOPMENT OF AN ENERGY-
EFFICIENT, ENVIRONMENTALLY
FRIENDLY SOLVENT FOR THE CAPTURE technology maturity:
OF CO2 Bench-Scale, Simulated
and Actual Flue Gas
primary project goals project focus:
Optimized Solvent
This Babcock & Wilcox Power Generation Group, Inc., (B&W) project focuses on Formulation
identifying concentrated piperazine (PZ)-based solvent formulations that improve overall
solvent and system performance. participant:
Babcock & Wilcox
technical goals
project number:
• Improve system operability and reliability. FE0007716
• Minimize environmental impacts.
NETL project manager:
• Reduce corrosion potential.
Bruce Lani
• Maximize solvent durability.
[email protected]
technical content principal investigator:
George Farthing
B&W is characterizing and optimizing the formulation of a novel solvent for the capture of Babcock & Wilcox
carbon dioxide (CO2) at coal-fired utility plants. The solvent of interest has been identified [email protected]
through a 5-year solvent development program conducted at B&W. The solvent formulations
of interest comprise concentrated solutions of a cyclic diamine, PZ. Testing at B&W indicates partners:
that blends of concentrated PZ with other compounds have the potential to perform
substantially better than PZ itself. The objective is to lower the total cost of solvent-based CO2 University of Cincinnati,
capture systems by identifying formulations that improve overall solvent and system First Energy
performance.
performance period:
10/1/11 – 4/30/14
Figure 1: B&W 7-Ton/Day Pilot Facility
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
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596 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Solvent Technologies
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism – The CO2-reactive species (there may be other non-reactive species) in the solvent
formulation may include amines, carbonates, or amino acid salts in combination with concentrated PZ. Amine solvents are grouped
according to their molecular structure. Carbonate and amine reactions with CO2 can be summarized as follows:
Carbonates: CO3 = + CO2 + H2O ↔ 2 HCO3-
Hindered and tertiary amines: CO2 + R3N + H2O ↔ HCO3- + R3NH+
Primary and secondary amines: CO2 + 2R2NH ↔ R2NCOO- + R2NH2+
Solvent Contaminant Resistance – Amine solvents chemically degrade in a variety of ways (thermal degradation due to exposure to
the high temperatures of the regeneration process, oxidative degradation due the presence of oxygen in the flue gas, carbamate
polymerization, etc.). Degradation reactions can be accelerated by the presence of degradation or corrosion products and heat-
stable salts, and through the catalytic effects of various metals (possibly originating with the coal fly ash). Minimizing solvent
degradation and the attendant production of potentially hazardous chemical species is a central objective of this project.
Flue Gas Pretreatment Requirements – Flue gas supplied to the CO2 capture system must be cooled to approximately 40°C and
relatively free of contaminants. Concentrations of sulfur dioxide (SO2) and nitrogen dioxide (NO2) must be less than about 10 parts
per million (ppm)—preferably around 1 ppm.
Solvent Makeup Requirements – Solvent makeup is required to offset solvent losses due to volatility, degradation, the formation of
heat stable salts, etc. PZ-based solvents are expected to minimize such losses due to the lower volatility and better resistance to
thermal degradation exhibited by PZ relative to solvents such as monoethanolamine (MEA). This project is focused on minimizing
solvent losses in the system.
Waste Streams Generated – Waste streams generated by the process will be similar to those generated by convention amine
processes, including reclaimer waste solids, spent carbon and particulate filter cake from solvent filtration equipment, and
potentially waste water. It is an objective of this project to minimize the environmental impact of these streams through careful
selection of the solvent formulation and operating conditions.
Process Design Concept – The CO2 capture process, illustrated in Figure 2, comprises a relatively conventional
absorption/stripping process.
Figure 2: Schematic of Solvent-Based CO2 Capture Process
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 597
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Appendix: Post-Combustion Solvent Technologies
technology advantages
Piperazine, used alone, has demonstrated high rates of absorption and low regeneration energy. Recent testing at B&W indicates that
blends of concentrated PZ with other organic compounds may perform substantially better than PZ alone.
R&D challenges
• Selection of a solvent formulation involves compromises that seek to optimally balance competing effects. Using limited and
potentially non-representative data generated in laboratory-scale equipment is extremely challenging. Previous solvent
development work supports correlation of laboratory results with pilot-scale performance estimation to optimize solvent
formulation.
• Goals include improved system operability and reliability, minimizing environmental impacts, reducing corrosion potential,
and maximizing solvent durability.
results to date/accomplishments
• A list of candidate solvent formulations was developed and refined. This work comprised evaluations regarding overall solvent
performance criteria, identification of primary active components, and verification of wet chemistry analytical techniques for
CO2 loading and alkalinity.
• Several modeling approaches were identified. Tools considered include equilibrium models, semi-empirical rate-based models,
and rigorous rate-based models. Tools for the prediction of process economics were also evaluated.
• Characterization tests in B&W’s wetted-wall column (WWC) were completed on a baseline concentrated PZ solvent and 12
candidate solvent formulations. The liquid film mass transfer coefficient (kg), as well as equilibrium partial pressure of CO2
(PCO2*), were obtained from each WWC test. Other parameters, such as heat of absorption and CO2 working capacity, were
also derived from these experimental data. Preliminary solvent formulation performance was then estimated with in-house,
semi-empirical models.
• Solvent volatility and solubility testing was performed on several candidate formulations of concentrated PZ solutions
containing salts of amino acids, carbonates, and other amines. Also evaluated were organic additives designed to improve the
solubility of PZ and its carbamates. In addition, it was found necessary to characterize candidate formulations with respect to
their viscosities in order to ensure good mass transfer performance and acceptable operability.
• Installation of the bench-scale continuous solvent degradation system (CSDS) was completed. The CSDS will enable
comprehensive investigations of proposed solvent formulation degradation under representative operating conditions. It is
intended to simulate key features of industrial CO2 capture processes, including cyclical absorption and regeneration process
conditions. The CSDS is designed for continuous, unattended operation for tests lasting 100 to 1,000 hours or more.
next steps
This project ended on April 30, 2013.
available reports/technical papers/presentations
Final Report, “Optimized Solvent for Energy-Efficient, Environmentally Friendly Capture of CO2 at Coal-Fired Power Plants,”
June 2014. http://www.osti.gov/scitech/servlets/purl/1136527.
Farthing, G., “Optimized Solvent for Energy-Efficient, Environmentally Friendly Capture of CO2 at Coal-Fired Power Plants,”
presented at the 2012 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
598 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
BENCH-SCALE DEVELOPMENT OF A
HOT CARBONATE ABSORPTION
PROCESS WITH CRYSTALLIZATION- technology maturity:
ENABLED HIGH-PRESSURE STRIPPING Laboratory-Scale,
Simulated Flue Gas
FOR POST-COMBUSTION CO2 CAPTURE project focus:
Hot Carbonate Absorption
primary project goals with Crystallization-
Enabled High-Pressure
The University of Illinois at Urbana-Champaign (UIUC) is performing a proof-of-concept Stripping
study that will generate process engineering and scaleup data to optimize the Hot
Carbonate Absorption Process (Hot-CAP) with crystallization-enabled, high-pressure participant:
stripping technology. The study seeks to demonstrate its capability to achieve the U.S.
Department of Energy (DOE) goals of at least 90 percent carbon dioxide (CO2) removal University of Illinois at
from coal-fired power plant flue gas with less than a 35 percent increase in the cost of Urbana-Champaign
electricity (COE), helping to advance the process to pilot-scale level within 3 years.
project number:
technical goals FE0004360
NETL project manager:
• Perform laboratory- and bench-scale tests to measure thermodynamic and reaction
engineering data that will be used to evaluate technical feasibility and cost- Andrew Jones
effectiveness, performance of scaleup, and commercial competitiveness of the Hot- [email protected]
CAP with monoethanolamine (MEA)-based processes and other emerging post-
combustion CO2 capture technologies. principal investigator:
• Perform a combination of experimental, modeling, process simulation, and technical Yongqi Lu
and economic analysis studies. University of Illinois at
Urbana-Champaign
[email protected]
technical content
partners:
UIUC and Carbon Capture Scientific, LLC are investigating a Hot-CAP to overcome the
energy use disadvantage of MEA-based processes. A preliminary technical-economic Carbon Capture
evaluation shows that the energy use of the Hot-CAP is about 40 percent less than that of Scientific, LLC
its MEA counterpart, and the process has the potential to meet or exceed DOE’s technical
and cost goals of greater than or equal to 90 percent CO2 removal and less than or equal to performance period:
a 35 percent increase in the COE. 1/1/11 – 3/31/14
The Hot-CAP is an absorption-based, post-combustion CO2 technology that uses a
carbonate salt (K2CO3 or Na2CO3) as a solvent. The process integrates a high-temperature
(70–80 °C) CO2 absorption column, a slurry-based high-pressure (up to 40 atm) CO2
stripping column, a crystallization unit to separate bicarbonate and recover the carbonate
solvent, and a reclaimer to recover CaSO4 as the byproduct of the sulfur dioxide (SO2)
removal.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 599
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Project objectives include performing a proof-of-concept study aimed at generating process engineering and scaleup data to help
advance the Hot-CAP technology to pilot-scale demonstration level. The project tasks employ lab- and bench-scale test facilities to
measure thermodynamic and reaction engineering data that can help evaluate technical feasibility and cost-effectiveness,
performance of scaleup, and commercial competitiveness of the Hot-CAP compared to the MEA-based processes and other
emerging post-combustion CO2 capture technologies.
To meet project objectives, lab- and bench-scale tests include measurement of the kinetics and phase equilibrium data associated with
the major reactions and unit operations in the Hot-CAP, including CO2 absorption, bicarbonate crystallization, sulfate recovery, and CO2
stripping. The results from the lab- and bench-scale studies support development of a process flow diagram, equipment and process
simulations, and a techno-economic study for a conceptual 550-MWe high-sulfur coal-fired power plant retrofitted with the Hot-CAP.
Figure 1: Hot Carbonate Absorption Process with High-Pressure Stripping Enabled by Crystallization (Hot-CAP)—Process Flow Diagram
TABLE 1: PROCESS PARAMETERS FOR CARBONATE SALT SOLVENT
(based on 40 wt% [K2CO3 equivalent] K 2CO3 /KHCO 3 solution)
Units Current R&D Value Target R&D Value
Pure Solvent
Molecular Weight mol-1 138 g/mol N/A
105–115 (depending on %
Normal Boiling Point °C K2CO3 to KHCO3 conversion, N/A
i.e., CO2 loading)
Normal Freezing Point °C <0 (estimated) N/A
Vapor Pressure at 15 °C bar N/A (not volatile) N/A
Manufacturing Cost for Solvent $/kg 0.4–1.0 (dry, pure K2CO3) 0.8
Working Solution
Concentration kg/kg 0.4 0.4
Specific Gravity (15 °C/15 °C) — 1.42 N/A
Specific Heat Capacity at STP kJ/kg-K 2.72 N/A
Viscosity at STP cP 5.1 N/A
Absorption (Rich Solution at Bottom)
Pressure (CO2 partial) bar 0.09 (1.32 psia) <0.1
Temperature °C 60–80 60–80
Equilibrium CO2 Loading mol/mol 0.4–0.45 0.4–0.45
Heat of Absorption kJ/kg CO2 609 609
Solution Viscosity cP 1.5 N/A
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
600 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
TABLE 1: PROCESS PARAMETERS FOR CARBONATE SALT SOLVENT
(based on 40wt% [K 2 CO3 equivalent] K 2 CO3 /KHCO 3 solution)
Units Current R&D Value Target R&D Value
Desorption (Lean Solution at Bottom)
Pressure (CO2 partial) bar 0.3-1.7 (4-12 total pressure) >0.6 (>6 total pressure and
CO2/H2O>3:1)
Temperature °C 140–200 <200
Equilibrium CO2 Loading mol/mol 0.20-0.40 (60 wt% slurry 0.20-0.40
concentration)
600–1,500 (including heat
Heat of Desorption kJ/kg CO2
of crystallization)
<1,500
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr 1,600,000
CO2 Recovery, Purity, and Pressure %/%/bar 90%, 99%, 10 bar
Absorber Pressure Drop bar 0.07 (structured packing)
Definitions:
STP – Standard Temperature and Pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost for
new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the absorption/desorption process
(e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs at
the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent (e.g., an
MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C). Measured data at
other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly
0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 601
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism –
The overall reaction for CO2 absorption into potassium carbonate solution at 70–80 °C is:
K2CO3 + CO2 + H2O = 2KHCO3
The CO2-rich solution from the absorber is cooled to 30–35 °C to crystallize KHCO3:
KHCO3 (aq) = KHCO3(s)
The overall reaction for CO2 stripping using KHCO3 slurry at 140–200 °C is:
2KHCO3 = K2CO3 + CO2 + H2O
Solvent Contaminant Resistance – K2CO3 reacts with the flue gas contaminants (e.g., SO2, nitrogen oxide [NOx], and hydrogen
chloride [HCl]), to form K2SO4, KNO3, and KCl, respectively, resulting in solvent losses if the salts are not reclaimed.
Solvent Foaming Tendency – K2CO3/KHCO3 solution itself does not have a foaming problem. If an organic promoter is used,
foaming may occur for the K2CO3/KHCO3 + promoter solution. However, the foaming tendency is expected to be less severe than
the conventional amine-based processes because the promoter concentration is generally low.
Flue Gas Pretreatment Requirements – If an organic promoter is used, pretreatment of the flue gas is required to reduce the
concentration of SO2 to below 30 parts per million by volume (ppmv). If an inorganic promoter or a catalyst is used, flue gas
pretreatment can be eliminated by a K2SO4 reclamation process under development in this project.
Solvent Makeup Requirements – Stoichiometric loss of K2CO3 due to reactions with acidic gases in the flue gas (SO2, NOx, etc.) is
estimated 1.46 kg K2CO3/tonne CO2 captured based on the assumed 42 ppmv SO2 and 74 ppmv NOx in the flue gas exiting a wet
flue gas desulfurization (FGD) unit.
If an organic promoter is used, the promoter has tendency to degrade. Since the promoter concentration is low and most of the
promoter does not enter the Hot-CAP stripping column, nominal losses due to promoter degradation is estimated to be less
than10 percent of that in the conventional MEA-based processes.
Waste Streams Generated – Waste streams include sludge of inorganic salts (e.g., sulfate, nitrate, chloride, etc.) as a result of
K2CO3/KHCO3 reactions with acid gases in the flue gas and liquid blowdown from the process to avoid accumulation of chlorine,
metals, etc.
Process Design Concept – Shown in Figure 2 below.
Figure 2: Process Design Concept
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
602 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
technology advantages
• High stripping pressure, which equates to low compression work and low stripping heat (high CO2/H2O ratio).
• Low sensible heat as a result of higher working capacity and lower Cp (1/2) compared with MEA.
• Low heat of absorption: 7–17 kcal/mol CO2 (crystallization heat included) versus 21 kcal/mol for MEA.
• Increased absorption rate by employing high K2CO3 concentration and high absorption temperature.
• FGD may be eliminated.
• No degradation of the carbonate solution and low degradation of the promoter.
• Low-cost solvent.
• Less corrosiveness.
R&D challenges
• Identifying favorable process conditions and promoters/catalysts for achieving fast absorption kinetics in carbonate solution.
• Identifying process conditions and solution properties for achieving a fast crystallization rate and a desirable crystal size for
solid separation.
• Identifying process conditions for potassium bicarbonate slurry to achieve stripping pressure ≥6 bar.
• Identifying process conditions for >95 percent SO2 removal and continuous reclamation of the sulfate.
• Identifying risk mitigation strategies to prevent fouling on surfaces of heat exchangers and crystallizers due to bicarbonate
crystallization.
results to date/accomplishments
• Three inorganic catalysts and five amine and three amino acid salt promoters were evaluated using a batch-stirred tank reactor.
• A bench-scale, packed-bed column was designed and fabricated to investigate the kinetics, mass transfer, and hydrodynamic
performance of CO2 absorption. Absorption column tests revealed that CO2 removal efficiency by 40 wt% K2CO3/KHCO3
solution promoted by either of two selected promoters at 70 °C was higher than that of the counterpart 5M MEA solution at
50 °C at the CO2 loading levels typical of the two processes.
• Absorption column tests also showed that KHCO3 precipitation could occur when the CO2 loading reached a level equivalent
to 40–45 percent of K2CO3 conversion. However, the accumulation of precipitates in the solution did not result in a
pronounced decrease in CO2 removal efficiency.
• Mixed suspension-mixed product removal (MSMPR) crystallization tests revealed that pure KHCO3 crystals could be obtained
and the crystallization of KHCO3 was kinetically fast and a residence time of as few as 15 minutes was sufficient to obtain
large crystal particles (>80 µm) required for efficient solid-liquid separation.
• Vapor Liquid Equilibrium (VLE) measurements for concentrated KHCO3/K2CO3 aqueous systems with high levels of K2CO3
conversion at temperatures of 140–200 °C revealed the thermodynamic feasibility of high-pressure stripping (achieving both a
high total pressure and a low H2O/CO2 pressure ratio).
• Parametric tests of reclaiming the potassium sulfate desulfurization byproduct were performed and results provided guidance
for developing a modified process concept for the combined SO2 removal and CO2 capture. The feasibility of the modified
process was preliminarily demonstrated. A bench-scale, packed-bed stripping column with a temperature rating of 200 °C and
pressure rating of 500 pounds per square inch absolute (psia) was fabricated and installed at the UIUC laboratory.
• Parametric testing of high-pressure CO2 stripping with concentrated bicarbonate-dominant slurries at high temperatures
(≥140 °C) in the bench-scale stripping column demonstrated lower heat use than with MEA. For example, it was observed that
compared with the 5 M MEA solution at 120 °C, the heat duty for CO2 stripping at 160 °C from the 30 to 50 wt%
KHCO3/K2CO3 feed solutions with the CO2 loading equivalent to 80 percent of carbonate conversation was two-to-three times
lower.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 603
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
• In addition to the experimental studies, the technical challenges pertinent to fouling of slurry-handling equipment and the
design of the crystallizer and stripper were addressed through consultation with vendors and engineering analyses.
• A techno-economic analysis for the baseline Hot-CAP integrated with a 550-MWe power plant showed that the net power
produced in the PC + Hot-CAP is 609 MWe, greater than the PC + MEA (550 MWe). The LCOE (levelized cost of electricity)
increase for the Hot-CAP, including CO2 transportation and storage, incurs a 60 percent increase over the base PC plant
without CO2 capture. The LCOE increase caused by the Hot-CAP is 29 percent lower than that for MEA.
next steps
This project ended on March 31, 2014.
available reports/technical papers/presentations
Shihan Zhang, Xinhuai Ye, Yongqi Lu. Development of a Potassium Carbonate-based Absorption Process with Crystallization-
enabled High-pressure Stripping for CO2 Capture: Vapor–liquid Equilibrium Behavior and CO2 Stripping Performance of
Carbonate/Bicarbonate Aqueous Systems. Energy Procedia 2014, 63: 665-675.
Final Report, “Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High-Pressure
Stripping for Post-Combustion CO2 Capture,” April 2014.
Final Project Review Presentation, May 2014.
Lu, Y., O’Brien K.; and Chen, S., “Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled
High Pressure Stripping for Post-Combustion CO2 Capture,” presented at the Project Review Meeting, Pittsburgh, PA, February 15,
2013. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/HotCAP-review-meeting-021513.pdf.
Lu, Y., “Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High Pressure Stripping
for Post-Combustion CO2 Capture,” 2012 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
http://www.netl.doe.gov/publications/proceedings/12/co2capture/presentations/2-Tuesday/Y%20Lu-ISGS-Hot%20CAP.pdf.
Lu, Y., “Bench-Scale Development of a Hot Carbonate Absorption Process with Crystallization-Enabled High Pressure Stripping
for Post-Combustion CO2 Capture,” 2011 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2011.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
604 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 605
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
606 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 607
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
608 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 609
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
610 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 611
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
612 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 613
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
614 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 615
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
616 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 617
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
618 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 619
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
620 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 621
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
622 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 623
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
DEVELOPMENT OF CHEMICAL
ADDITIVES FOR CO2 CAPTURE COST
REDUCTION technology maturity:
Bench-Scale, Simulated
primary project goals Flue Gas
project focus:
Lawrence Berkeley National Laboratory (LBNL) is investigating a novel mixed solvent
system that integrates amine-based, potassium-based, and ammonia-based solvents to Chemical Additives for
provide benefits of three systems while avoiding many of their drawbacks. CO2 Capture
participant:
technical goals
Lawrence Berkeley
• Develop chemical additives for solvent systems to reduce the cost of post-combustion National Laboratory
capture of carbon dioxide (CO2).
project number:
• Determine the optimal process configuration and operating condition for the transfer
of CO2 in amine solvent to potassium carbonate (K2CO3), and then to an ammonium FWP-ED33EE
species, resulting in the production of NH4HCO3.
NETL project manager:
Elaine Everitt
technical content [email protected]
The new solvent system uses a novel solvent transfer approach after the capture of CO2 principal investigator:
from flue gas. Using this approach, the energy demand and the capital cost of solvent
regeneration are expected to be significantly reduced compared to the monoethanolamine Shih-Ger (Ted) Chang
(MEA) system. LBNL
[email protected]
An aqueous solution of amine is used as an absorbent to facilitate favorable CO2
absorption kinetics. The amine is chosen such that the CO2 absorbed in an absorber can be partners:
readily transferred to potassium carbonate (K2CO3) in a recirculation tank to produce
KHCO3 solids. Subsequently, KHCO3 solids enter into a regenerator by gravitation, where N/A
it reacts with an ammonia catalyst to regenerate K2CO3 for reuse and generate a
concentrated CO2 stream suitable for sequestration. performance period:
6/1/08 – 5/31/13
The approach contains the benefits of three solvent systems: amine, K2CO3 and ammonia
systems. The benefits are: (1) amine’s fast CO2 absorption kinetics; (2) K2CO3 and
ammonium species’ low reagent cost, high chemical stability, and small heat capacity; and
(3) ammonium bicarbonate’s low decomposition temperature, fast decomposition kinetics,
and amenable for high-pressure CO2 production. The employment of solids significantly .
reduces the sensible and latent heat consumed by water in solvent regeneration. The low
decomposition temperature of ammonium bicarbonate enables waste heat and/or low-
quality steam to be used for the production of concentrated CO2 gas.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
624 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
TABLE 1: PROCESS PARAMETERS
Units Current R&D Value Target R&D Value
Pure Solvent
Molecular Weight mol-1 100–212 100–212
Normal Boiling Point °C 165–252 165–252
Normal Freezing Point °C (-50)–28 (-50)–28
Vapor Pressure at 15 °C bar 0–0.0013 0–0.0013
Manufacturing Cost for Solvent $/kg 30–250 30–250
Working Solution
Concentration kg/kg 0.3–0.6 0.3–0.6
Specific Gravity (15 °C/15 °C) - 0.9–1.7 0.9–1.7
Specific Heat Capacity at STP kJ/kg-K 3–4 3–4
Viscosity at STP cP 20–40 20–40
Absorption
Pressure bar 1.01 1–1.5
Temperature °C 40–70 30–80
Equilibrium CO2 Loading mol/mol 0.7–0.9 0.7–0.9
Heat of Absorption kJ/mol CO2 65–75 65–75
Solution Viscosity cP 10–15 10–15
Desorption
Pressure bar 2.7 1–75
Temperature °C 80–120 80–300
Equilibrium CO2 Loading mol/mol 0.4–0.6 0.4–0.6
Heat of Desorption kJ/mol CO2 85–92 85–92
Proposed Module Design (for equipment developers)
Flue Gas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar 90%, 99%, 75 bar
Absorber Pressure Drop bar
Definitions:
STP – Standard Temperature and Pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., the amine MEA in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost for
new solvents, or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the absorption/desorption process
(e.g., the liquid mixture of MEA and water).
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs at
the bottom of the absorption column. These may be assumed to be 1 atm total flue gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 625
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent (e.g., an
MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C). Measured data at
other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly
0.132 atm or 0.130 bar.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism –
Absorber: Amine + CO2 ↔ Amine-CO2
Recirculation tank: Amine-CO2 + K2CO3 + H2O ↔ Amine + 2 KHCO3↓
Regenerator: 2 KHCO3 + (NH4+) → K2CO3 + H2O + CO2↑ + (NH4+)
Solvent Contaminant Resistance – Sulfur dioxide (SO2) has little impact to the amine. The amine is regenerated by chemical rather
than thermal methods. The amine employed should be much more resistant to oxygen (O2) and nitrogen oxides (NOx) than MEA.
Nevertheless, the reaction kinetics and products of O2 and NOx with amine need to be investigated.
Solvent Foaming Tendency – Solvent foaming was not observed in laboratory experiments.
Flue Gas Pretreatment Requirements – Flue gas from coal-fired power plants equipped with conventional pollution control systems
does not require additional pretreatment. Residual SO2 after dissolution can be separated from the liquid stream as K2SO3/K2SO4
precipitates. The formation of heat-stable salts with amine should not be an issue, as amine is regenerated by chemical rather than
thermal methods involving steam.
Solvent Makeup Requirements – Amine is confined in the low-temperature absorber and recirculation tank loop. As a result, the
thermal degradation, chemical degradation (due to the reactions with flue gas trace constituents), and emission loss (due to the
volatility) are expected to be insignificant compared to the benchmark MEA process. Absorber is not expected to exhibit a plugging
problem resulting in operation breakdown and reagent loss as KHCO3 solid is produced in the recirculation tank located above the
K2CO3 regeneration tank (i.e., the stripper). A long-term integration test that lasts a significant number of hours will be needed to
determine the amine’s makeup requirements. KHCO3 and K2CO3 are stable chemicals and do not degrade under high-temperature
operation in the regenerator.
Waste Streams Generated – Waste streams from the absorber/recirculation tank low-temperature loop may contain trace amount of
fly ash, dissolved NOx, and amine degradation products. Waste streams from the stripper are expected to contain K2SO3 and K2SO4,
if SO2 polishing is not equipped ahead of the CO2 capture system.
Process Design Concept – Shown in Figure 1 below.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
626 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
Figure 1: Process Design Concept
Proposed Module Design – Unless noted, flue gas feed pressure is 1.014 bar, temperature is 57 °C, and composition leaving the
flue gas desulfurization (FGD) unit (wet basis) should be assumed:
Composition (% vol) Composition (ppmv)
CO2 H2 O N2 O2 Ar SOx NOx
13.17 17.25 66.44 2.34 0.8 42 74
technology advantages
• Possession of high-CO2 absorption kinetics, resulting in an acceptable absorber capital cost.
• Reduction of processing water, resulting in reduced solvent regeneration energy demands.
• Employment of low-heat capacity KHCO3/K2CO3, resulting in reduced sensible heat demands.
• Reduction of reagent loss and equipment corrosion, resulting in reduced operation costs.
• Reduction of emission as KHCO3 can be treated at high temperature without any emissions of heat degradable harmful
products.
• Reduction of CO2 compression ratio, resulting in reduced CO2 compression energy and compressor capital costs.
R&D challenges
• Development of a new system for the transfer of KHCO3 solid from the recirculation tank to the stripper by the gravitation
method and with pressurized steam.
• Determination of the optimal operation condition to regenerate K2CO3 and to produce high pressure CO2 gas for enhanced oil
recovery (EOR) or methanol production.
results to date/accomplishments
• Evaluated more than 50 amines and amino acid salts for CO2 absorption amenable for the new solvent regeneration approach.
• Compared relative CO2 absorption efficiencies of various lean amines regenerated by chemical methods.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 627
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Solvent Technologies
• Investigated conditions required for phase separation and determined phase diagrams following chemical regeneration of lean
amine in the recirculation tank in attempt to understand its chemical and physical behaviors.
• Elucidated the kinetics and mechanisms of CO2 absorption and chemical regeneration involved in the new solvent system.
• Constructed a stripper system equipped with a calorimeter for the determination of K2CO3 regeneration rates and energy
demands. Preliminary results indicated that K2CO3 regeneration energy demand was 2,079 kJ/kg CO2 at steady-state
conditions, which is approximately 40 percent less than that of MEA.
• Performed a semi-continuous integration test encompassing CO2 absorption in the absorber, amine regeneration in the
recirculation tank, and K2CO3 regeneration and CO2 production in the stripper.
• Performed mass and water balances, and developed a stream table of the bench-scale new solvent system.
next steps
Project completed May 31, 2013.
available reports/technical papers/presentations
“Developing Chemical Additives for Aqueous Ammonia to Reduce CO2 Capture Cost,” presented at the Annual NETL CO2
Capture Technology for Existing Plants Meeting, Pittsburgh, PA, March 2009.
“Development of Chemical Additives for CO2 Capture Cost Reduction,” presented at the 2010 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, September 2010.
http://www.netl.doe.gov/publications/proceedings/10/CO2capture/presentations/monday/Ted%20Chang-LBNL.pdf.
“Development of Chemical Additives for CO2 Capture Cost Reduction,” presented at the 2011 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, August 2011. http://www.netl.doe.gov/publications/proceedings/11/CO2capture/presentations/2-
Tuesday/23Aug11-Chang-LBNL-Additives%20for%20Reducing%20CO2%20Capture%20Costs.pdf.
“Development of Chemical Additives for CO2 Capture Cost Reduction,” presented at the 2012 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, August 2012. http://www.netl.doe.gov/publications/proceedings/12/CO2capture/presentations/2-
Tuesday/T%20Chang-LBNL-Additives.pdf.
“Development of Chemical Additives for CO2 Capture Cost Reduction,” presented at the 2013 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/events/2013/CO2%20capture/Y-Li-LBNL-Additives-
for-Reducing-CO2-Capture-Costs.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SOLVENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
628 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 629
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
630 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 631
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
632 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 633
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
634 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 635
Appendix: Post-Combustion Solvent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
636 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Solvent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 637
Appendix: Post-Combustion Solvent Technologies
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NATIONAL ENERGY TECHNOLOGY LABORATORY
638 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
POST-COMBUSTION
SORBENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
639
Appendix: Post-Combustion Sorbent Technologies
Pilot-Scale Evaluation of an technology maturity:
Bench-Scale, Actual Flue
Advanced Carbon Sorbent- Gas
Based Process for Post- project focus:
Combustion Carbon Capture
Novel Solid Sorbent
participant:
SRI International
primary project goals
project number:
SRI International operated a bench-scale test unit for post-combustion carbon dioxide
FE0013123
(CO 2 ) capture to demonstrate their process using a novel low-cost, low-energy, and
high-capacity carbon sorbent in a single column integrating both the absorber and
desorber. SRI also designed a 0.5-megawatt electric (MW e ) pilot-scale test unit.
predecessor projects:
NT0005578
technical goals NETL project manager:
Andrew jones
• Operate SRI’s 40-kilowatt electric (kW e ) sorbent test unit on actual flue gas at the [email protected]
National Carbon Capture Center (NCCC) to provide data for initial techno-
economic assessment and for pilot plant design. principal investigator:
• Design 0.5-MW e slipstream pilot plant for post-combustion CO 2 capture using Marc Hornbostel
the novel sorbent. SRI International
• Complete preliminary techno-economic assessment and environment, [email protected]
health, and safety (EH&S) assessment based on data from testing.
partners:
• Develop sorbent formulation and method of manufacture.
ATMI, Inc.; Linde, LLC;
Electric Power Research
technical content Institute
SRI International tested their process for post combustion CO 2 capture on the bench- start date:
scale using their novel carbon sorbent. The technology is based on the sorbent 10.01.2013
developed in a previously funded DOE project NT0005578. This novel sorbent,
manufactured by ATMI, Inc., is composed of carbon microbeads, as shown in Figure 1. percent complete:
These microbeads show excellent CO 2 capacity and selectivity, fast
100%
adsorption/desorption kinetics, and good resistance to agglomeration and attrition,
allowing for reductions in both capital and operating expenses. Reduced steam
regeneration requirements in the process can reduce the parasitic power load.
Figure 1: Graphic displays of novel carbon pellets sorbent
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
640 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Figure 2 depicts the proposed sorbent system for an existing coal-fired power plant. Flue gas first enters an existing flue gas
desulfurization (FGD) system where most of the sulfur content is removed. The gas is then cooled before entering the
continuous falling-bead sorbent reactor which integrates the adsorber and stripper in a single vertical column, providing a low
pressure drop for gas flow and minimizing physical handling of the high capacity carbon sorbent (0.05–0.08 kg of CO 2 per kg of
sorbent). As the gas stream passes over the lean sorbent, CO 2 is removed from the gas and adsorbed by the sorbent. The
loaded sorbent cascades down the separation column and is heated by low-pressure steam, causing the sorbent to release the
adsorbed CO 2 . The CO 2 is siphoned off to a compressor where it can be prepared for sequestration. The sorbent is then dried,
cooled, and sent back into the separation column for reuse and the cycle begins again.
Figure 2: Sorbent system
SRI also designed a 0.5-MW e pilot-scale system based on this technology. The system includes a heat exchanger for recovering
sensible heat from the hot, regenerated sorbent for use to preheat the sorbent from the adsorber. The system is designed for a
nominal flue gas flow of 70 cubic feet per minute (cfm) and a CO 2 capture capacity of approximately 1 ton/day.
The sorbent and process parameters are provided in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
641
Appendix: Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,100 1,100
Bulk Density kg/m3 700 700
Average Particle Diameter mm 0.2 0.2
Particle Void Fraction m3/m3 0.45 0.45
Packing Density m2/m3 1.1 x 109 1.1 x 109
Solid Heat Capacity @ STP kJ/kg-K 1.0 1.0
Crush Strength kg f — —
Manufacturing Cost for Sorbent $/kg proprietary proprietary
Adsorption
Pressure bar 1 1
Temperature °C 20 20
Equilibrium Loading g mol CO 2 /kg 4 4
Heat of Adsorption kJ/mol CO 2 27 27
Desorption
Pressure bar 1 1
Temperature °C 100 100
Equilibrium CO 2 Loading g mol CO 2 /kg 0.96 0.96
Heat of Desorption kJ/mol CO 2 27 27
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — continuous, moving bed
Flue Gas Flowrate kg/hr 1,860
CO 2 Recovery, Purity, and Pressure % / % / bar 90 95 1
Adsorber Pressure Drop bar 0.005
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a
CO 2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly
0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
642 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – Rapid physical adsorption and desorption rates: The adsorption of CO 2 occurs on the
micropores of the sorbent with low activation energy (<5 kJ/mole), allowing rapid equilibrium. Similarly, the adsorbed CO 2 is
desorbed rapidly at the regeneration temperature (≈100 °C), and the sorbent performance can be predicted by equilibrium
models.
Sorbent Contaminant Resistance – The sorbent is pure carbon and generally resistant to many contaminants. The sulfur
dioxide (SO 2 ) needs to be reduced to <10 parts per million (ppm) levels, preferably to 1 ppm level. Nitrogen oxides (NO x ) can
be present at ≈50 ppm levels. Fly-ash particles in flue gas downstream of an electrostatic precipitator do not appear to interfere
with CO 2 adsorption.
Sorbent Attrition and Thermal/Hydrothermal Stability – The sorbent granules are hard and attrition-resistant. No observable
attrition was noticed in a recent field test conducted over 7,000 cycles of adsorption and regeneration. The sorbent has a high
hydro-thermal stability and direct heating with steam can be used for CO 2 desorption. The sorbent regenerated at the elevated
temperature can be cooled by evaporative cooling of moisture adsorbed on the sorbent.
Flue Gas Pretreatment Requirements – Reduce SO 2 levels to <5 ppm. The flue gas needs to be cooled to ≈25 °C.
Sorbent Makeup Requirements – Preliminary data suggest multi-year lifetime for sorbent makeup.
Waste Streams Generated – The sorbent particles are hard and attrition-resistant, and no fine sorbent particles are generated
during operation. Steam condensate from the dehydrator may need to be treated before cycling back to the steam boiler.
Process Design Concept – The module will be located between FGD and flue gas chimney.
technology advantages
• Low cost carbon sorbent.
• Low activation energy and rapid cycling for adsorption/desorption.
• Reduced capital and operating costs.
• The sorbent has a high capacity for CO 2 adsorption (20 wt% at 1 atm CO 2 ) and good selectivity for CO 2 over other flue gas
components (CO 2 -N 2 separation factor >20).
• Low heat capacity minimizes thermal energy required to heat the sorbent to regeneration temperature.
• Carbon sorbent particles have excellent attrition resistance, minimal dust generation, and high resistance to
agglomeration.
• High hydrothermal stability: Direct heating with steam can be used for CO 2 desorption. The sorbent regenerated at the
elevated temperature can be cooled by evaporative cooling of moisture adsorbed on the sorbent.
• High thermal conductivity: The thermal conductivity of 0.8 W/m-K enables rapid thermal equilibrium between the surface
and interior of the microbeads.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
643
Appendix: Post-Combustion Sorbent Technologies
• The sorbent is essentially hydrophobic, indicating little interaction between the condensed water and the sorbent. The
thermal energy required to desorb the condensed water is significantly less than that required to evaporate water from
oxide surfaces such as those found in molecular sieves (zeolites), alumina, and silica.
• Continuous, falling microbead sorbent reactor geometry integrates the adsorber and stripper in a single vertical column.
o Low pressure drop for gas flow.
o Minimal physical handling of solvent.
R&D challenges
• Other elements of the flue gas, such as sulfur oxides (SO x ), may compete with CO 2 in being adsorbed by the sorbent,
reducing the amount of CO 2 that is adsorbed as the gas passes through the reactor.
status
The project was completed on June 30, 2016. SRI completed approximately 250 hours of testing on their 40-kW e bench-scale
unit using actual flue gas at the NCCC. The project achieved CO 2 purity of 93 percent and CO 2 capture efficiency of 67 percent.
SRI indicated that 90 percent capture is achievable by decreasing the sorbent temperature and increasing the adsorber height.
A basic engineering design package was completed for the 0.5-MW e pilot unit.
available reports/technical papers/presentations
Krishnan, G. “Pilot-Scale Evaluation of an Advanced Carbon Sorbent-Based Process for Post-Combustion Carbon Capture,”
presented at Project Review Meeting, Pittsburgh, PA, June 2016.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0013123-Project-Review-
Presentation-06-21-2016.pdf
Hornbostel, M. “Pilot-Scale Evaluation of an Advanced Carbon Sorbent-Based Process for Post-Combustion Carbon Capture,”
presented at 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/M-Hornbostel-SRI-Pilot-Advanced-Sorbent-
Process.pdf
Krishnan, G. “Pilot-Scale Evaluation of an Advanced Carbon Sorbent-Based Process for Post-Combustion Carbon Capture,”
Project Review Meeting, Pittsburgh, PA, October 2014.
http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0013123-Project-Review-
Presentation-10-28-2014.pdf
Krishnan, G. “Pilot-Scale Evaluation of an Advanced Carbon Sorbent-Based Process for Post-Combustion Carbon Capture,”
presented at the 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/G-Krishnan-SRI-Pilot-Scale-Evaluation.pdf
Krishnan, G., “Development of Novel Carbon Sorbents for CO 2 Capture,” Final Technical Report, March 2014.
http://www.osti.gov/scitech/servlets/purl/1132602.
Krishnan, G. “Pilot-Scale Evaluation of an Advanced Carbon Sorbent-Based Process for Post-Combustion Carbon Capture”,
presented at Project Kickoff Meeting, Pittsburgh, PA, December 2013.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/FE0013123-Kickoff-Presentation-12-04-2013.pdf
Krishnan, G. “Development of Advanced Carbon Sorbents for CO 2 Capture,” presented at the 2013 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO 2 %20Capture/G-
Krishnan-SRI-Advanced-Carbon-Sorbents.pdf.
Krishnan, G. “Development of Advanced Carbon Sorbents for CO 2 Capture,” presented at the 2012 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2012. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO 2 /development-of-
advanced-carbon-sorbents-july2012.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
644 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Hornbostel, M. “Development of Novel Carbon Sorbents for CO 2 Capture,” presented at the 2011 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, August 2011.
http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/22Aug11-Hornbostel-SRI-Novel-Carbon-Sorbents.pdf.
Krishnan, G. “Development of Novel Carbon Sorbents for CO 2 Capture,” presented at the 2010 NETL CO 2 Capture Technology
Meeting, Pittsburgh, PA, September 2010.
http://www.netl.doe.gov/publications/proceedings/10/CO 2 capture/presentations/monday/Gopala%20Krishnan-NT0005578.pdf.
Krishnan, G, “Development of Novel Carbon Sorbents for CO 2 Capture – Project Overview,” presented at the Annual NETL CO 2
Capture Technology for Existing Plants R&D Meeting, Pittsburgh, PA, March 2009.
http://www.netl.doe.gov/publications/proceedings/09/CO 2 /pdfs/5578%20SRI%20carbon%20sorbent%20%28Hornbostel%29%20m
ar09.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
645
Appendix: Post-Combustion Sorbent Technologies
Bench-Scale Development technology maturity:
Bench-Scale, Simulated Flue
and Testing of Aerogel Gas
Sorbents for CO2 Capture project focus:
Advanced Aerogel Sorbents
primary project goals participant:
Aspen Aerogels, Inc.
Aspen Aerogels designed an innovative aerogel sorbent for carbon dioxide (CO 2 )
capture with improved CO 2 capacity, high adsorption/desorption cyclic stability, and project number:
resistance to contaminants in the flue gas, improving the performance and economics
of CO 2 capture. FE0013127
predecessor projects:
technical goals SC0004289
• Optimize Amine Functionalized Aerogel (AFA) to maximize CO 2 adsorption, NETL project manager:
decrease regeneration temperature, maintain kinetics for fluidized bed operation, Isaac Aurelio
and maintain high cyclic-adsorption stability. [email protected]
• Develop pellet- and bead-forming processes.
• Develop a sulfur oxide (SO x )-resistant coating to minimize aerogel degradation principal investigator:
due to flue gas contaminants. Redouane Begag
• Develop optimum AFA pellet/binder (SO x coating) formulations. Aspen Aerogels, Inc.
[email protected]
• Develop aerogel production process.
• Test and evaluate aerogel sorbent technology at the bench-scale to determine CO 2 partners:
capture performance and optimize operating conditions. University of Akron; ADA
• Complete a techno-economic analysis of the system. Environmental Solutions,
Longtail Consulting, LLC
technical content start date:
10.01.2013
Aspen Aerogels has designed an AFA sorbent for CO 2 capture with improved CO 2
capacity, high adsorption/desorption cyclic stability, and resistance to contaminants in
percent complete:
the flue gas to achieve an overall reduction in total carbon capture cost. The AFA
contains amine groups bonded to an aerogel backbone. AFA benefits include high 100%
surface area, high porosity, hydrophobicity to enhance CO 2 adsorption selectivity, low
specific heat for lower energy regeneration, and high temperature stability. The unique,
specific aerogel structural morphology is shown in Figure 1, along with the AFA beads,
shown in Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
646 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Figure 1: Structural morphology of an aerogel
Figure 2: AFA sorbent in bead form
This project maximized those benefits via bench-scale evaluation of the aerogel sorbents. Optimization of the initial sorbent
formulations aimed to increase CO 2 loading capacity, improve resistance to flue gas contaminants, maintain kinetics for fluidized
bed operation, and maintain high cyclic stability. Initial testing on aerogel powders provided performance data to determine
optimal formulations. For use in larger scale applications, the use of AFA pellets or beads is necessary instead of powders. The
AFA pellets are formed by adding binder to the aerogel powder. Further development optimized the process of aerogel bead
fabrication. Bead performance was compared to AFA pellet performance, with not only the optimization of CO 2 capacity, cycle
life, and stability to contaminants, but also for parameters important to high performance in a fluidized bed, including particle
size, density, attrition index, and crush strength. Bench-scale cold-flow fluidized bed testing on the final AFA formulations
provided hydrodynamic properties and heat transfer coefficients.
Upon testing, both the AFA bead and pellet forms demonstrated comparable CO 2 capture performance. Pellets showed superior
stability during long term CO 2 capture testing. The pellet form was chosen moving forward primarily due to scale-up production
capabilities of the aerogel at Aspen and the pelletization capabilities at the University of Akron for future large-scale production.
Opportunities to improve the sorbent in terms of advancing the production process include: (1) reducing the mass of the pellet
binder to increase the CO 2 mass loading by using lightweight aerogel beads, needing minimal binder as coating for SO 2
resistance, and (2) lowering density of AFA and using the bead form to reduce capital costs and sorbent circulation rate, directly
tied to sorbent costs due to attrition.
The sorbent and process parameters are provided in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
647
Appendix: Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,150 1,200–1,300
Bulk Density kg/m3 250-800 ≈1,000
Average Particle Diameter mm 0.2–1.0 0.3–0.6
Particle Void Fraction m3/m3 0.56
Packing Density m2/m3 not measured
Solid Heat Capacity @ STP kJ/kg-K ≈1.3 0.7
Crush Strength kg f 3.8–6.4
Manufacturing Cost for Sorbent $/kg N/A 7- 10
Adsorption
Pressure bar 0.8 (in Colorado) 1.0
Temperature °C 40 <70
Equilibrium Loading g mol CO 2 /kg 100-200 >250
Heat of Adsorption kJ/mol CO 2 55-62 60
Desorption
Pressure bar 0.8 (in Colorado) 1.0
Temperature °C 100-120 <130
Equilibrium CO 2 Loading* g mol CO 2 /kg 20–100 <100
Heat of Desorption kJ/mol CO 2 55–62 —
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — —
Flue Gas Flowrate kg/hr —
CO 2 Recovery, Purity, and Pressure % / % / bar — — —
Adsorber Pressure Drop bar —
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
*Under 100 percent CO 2
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs
at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent.
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The primary mechanism of CO 2 capture on AFA sorbents occurs by chemisorption.
The homogenous distribution of amine grafted on the high surface area aerogel structure facilitates mass transfer of CO 2 to and
from receptor sites. Adsorption/desorption of CO 2 occurs by temperature swing, between 40 °C and 100–120 °C.
Sorbent Contaminant Resistance – Development of a series SO 2 resistant coatings was initiated. Preliminary studies of the
performance of the coatings were carried out. These coatings reduced the effect of SO 2 poisoning on the AFA sorbent and
increased the stability of the sorbent in the presence of SO 2 . The effectiveness of the newly developed coatings shows a CO 2
capacity reduction of only 4 percent after 20-cycle exposure to 40 ppm SO 2 in simulated flue gas, versus 55–61 percent reduction
with no coating on the sorbent.
Sorbent Attrition and Thermal/Hydrothermal Stability – Selected AFA pellets were subjected to ASTM D5757 (Standard Test
Method for Determination of Attrition and Abrasion of Powdered Catalysts by Air Jets), to measure the attrition index (AI). The
initial sizes of the tested pellets are above 500 µm. AI is lower for AFA pellets relative to a reference of fluidized catalytic cracker
(FCC). The attrition index was higher for < 20 micron particles at 300 ft/s than the reference FCC sample. The AI index indicates
that the sorbent is suitable for a fluidized bed process where it will not only encounter mechanical attrition from the fluidized
bed at relatively low velocities, but it will also be subject to high gas velocity cyclones needed to separate the sorbent from the
gas flow.
Flue Gas Pretreatment Requirements – Protecting sorbents from SO 2 poisoning and generating high-purity CO 2 from the
process are two unavoidable tasks for CO 2 Capture and Sequestration (CCS). The economic feasibility considerations are also
important to the scale-up and commercialization of the CO 2 capture process. SO 2 -resistant coating was verified effective to
reduce the SO 2 poisoning of the AFA sorbent pellets. However, it was determined that a SO 2 polishing scrubber was needed
prior to the CO 2 capture process, based on the maximum SO 2 concentration that the AFA sorbent can tolerate.
As for temperature of the flue gas entering the adsorber, for example for an adsorption temperature of 40 °C, some cooling was
required due to inevitable gas heating in the blower (to overcome the pressure drop of the sorbent bed in the adsorber).
Sorbent Makeup Requirements – This has not yet been determined.
Waste Streams Generated – None known.
Process Design Concept – The solid sorbent capture case utilizing AFA sorbent was modeled using ADA-ES’s general process
design reported in their 1 MW pilot testing report 1 (Figure 3). However, individual reactors were specifically designed and sized
for use with Aspen Aerogel’s sorbent (AFA).
1
Sjostrom, S. (2016). Evaluation of Solid Sorbents as a Retrofit Technology for CO2 Capture. ADA-ES, Inc. U.S. Department of Energy
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Figure 3: ADA-ES solid sorbent CO2 capture process flow diagram
technology advantages
• AFA sorbent has high CO 2 capacity and long life, reducing equipment size requirements and process costs.
• High sorbent selectivity allows for reduced sorbent cycling times, which allows for reductions in sorbent quantity, reactor
size, and cost.
• Low specific heat results in low energy regeneration.
• High moisture resistance.
• High temperature stability.
• Reduced delta T for adsorption/desorption.
R&D challenges
• Optimizing pellet formulation to balance properties for optimum performance, including CO 2 capacity, attrition and SO x
resistance, thermal conductivity to improve kinetics, as well as selecting the optimal particle size and density for use in a
fluidized bed.
• Optimizing pellet and bead fabrication to match performance of the aerogel powder.
• Reducing attrition.
• Overcoming the issue of reduced CO 2 capacity for AFA beads due to some amine leaching out during the fabrication process.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
status
The project was completed on December 31, 2016. Aspen Aerogels tested bead and pellet formulations of the AFA, with both
showing comparable CO 2 capture performance, with total CO 2 capacity between 11–14 wt%, CO 2 working capacity between
6.0–6.5 wt%, and cyclic stability over 500 cycles in a fixed bed. The AFA production and pelletization processes were scaled up,
with 30 kg of pelletized sorbent prepared. The pellet form was chosen for scale-up and testing based primarily on the
pelletization capabilities at the University of Akron for future large-scale production. The pelletized AFA sorbent was tested on
the bench-scale in a cold-flow fluidized bed and showed good fluidization could be attained at bed velocity of 1.5 ft/s and pellet
density of 1150 kg/m3.
available reports/technical papers/presentations
Begag, R., et al. “Bench-Scale Development and Testing of Aerogel Sorbents,” presented at the 2016 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/R-Begag-Aspen-Testing-of-
Aerogel-Sorbents.pdf
Begag, R., et al. “Bench-Scale Development and Testing of Aerogel Sorbents,” presented at the 2015 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, June 2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/R-
Begag-AAI-Aerogel-Sorbents.pdf
Begag, R., et al. “Bench-Scale Development and Testing of Aerogel Sorbents,” presented at the 2014 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File Library/Events/2014/2014 NETL CO2 Capture/G-
Gould-AAI-Bench-Scale-Development.pdf
Begag, R., et al. “Development and Testing of Aerogel Sorbents for CO 2 Capture,” presented at BP1 Review Meeting, July
2014. http://www.netl.doe.gov/File Library/Research/Coal/carbon capture/post-combustion/BP1-NETL-presentation-Final-Rev-2-
nonproprietary.pdf
Begag, R., et al. “Bench-Scale Development and Testing of Aerogel Sorbent for CO 2 Capture,” presented at Project Kick-Off
Meeting, Pittsburgh, PA, November 8, 2013. http://www.netl.doe.gov/File Library/Research/Coal/ewr/CO2/Aspen-Aerogels-NETL-
DOE--Kick-Off-Final-Non-proprietary.pdf
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Appendix: Post-Combustion Sorbent Technologies
NRG CO2NCEPT – Confirmation technology maturity:
of Novel Cost-Effective
Conceptual Design of Pilot-
Scale, Actual Flue Gas
Emerging Post-Combustion
Slipstream (equivalent to 10
MWe or greater)
Technology project focus:
Temperature Swing
Adsorption with Structured
primary project goals Sorbent
NRG Energy proposed to develop a post-combustion carbon dioxide capture participant:
project utilizing the Inventys VeloxoTherm TM technology utilizing a structured NRG Energy, Inc.
adsorbent in a rotary bed adsorber using rapid cycle temperature swing
adsorption. The project would have included developing the scope,
project number:
configuration, and design basis of a pilot-scale system.
FE0026581
technical goals predecessor projects:
N/A
• Develop the scope, configuration, and design basis for a pilot plant using the
VeloxoThermTM process sized for a 10-megawatt electric (MW e) or greater NETL project manager:
slipstream of flue gas from an NRG coal plant.
Bruce Lani
• Determine optimal size and host site location at one of NRG’s coal plants. [email protected]
• Complete a techno-economic analysis and identify technology gaps.
principal investigator:
David Greeson
technical content
NRG Energy, Inc.
[email protected]
NRG Energy was working to establish the technical and economic feasibility of
the Inventys VeloxoTherm TM post-combustion carbon dioxide (CO2) capture partners:
process. VeloxoTherm TM is an intensified temperature swing adsorption process
using a proprietary combination of structure sorbent and process design using a Inventys
rotary adsorption machine, as depicted in Figure 1.
start date:
The structured sorbents provide high surface area along with mass and heat
10.01.2015
transfer kinetics allowing for low pressure drop, immobilization with no
fluidization, and high surface area. The VeloxoTherm TM process is based on
rotary air preheaters, which have been used in process industries. The process percent complete:
implements a cycle design without the need of discrete vessels, multiple large 100%
switching valves, and complicated interconnecting piping and ducting. The
VeloxoTherm TM technology has previously been validated for capturing CO2 from
a natural gas-fired boiler. The current project is aimed at determining the size,
scope, configuration, and design basis for a pilot plant using a slipstream of flue
gas from one of NRG Energy’s coal plants.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Figure 1: Inventys VeloxoThermTM rotary adsorption machine concept
Definitions:
STP – Standard Temperature and Pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated
manufacturing cost for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which
typically occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure
(corresponding to a CO2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are
preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which
typically occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper
are process-dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total
pressure; if it is a mixture of gases, this is the partial pressure of CO 2. Note that for a typical pulverized coal (PC) power
plant, the total pressure of the flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore,
the partial pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in
either continuous, cyclic, or semi-regenerative operation.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas
desulfurization (FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO2 H2O N2 O2 Ar SOx NOx
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
technology advantages
• Technology proven at 0.5 MW e pilot scale using natural gas feed.
• Structured adsorbents have high surface area per reactor volume and low pressure drop.
• Structured adsorbents allow for high heat and mass transport due to short diffusion paths within structured
materials.
• High heat retention due to anisotropic heat transfer properties.
• Laminate design allows degrees of freedom for adjusting void fraction, packing densities, and hydrodynamics.
• Rapid cycle temperature swing adsorption (TSA) with structured adsorbents shows good resistance to sulfur oxides
(SOx) and other flue gas contaminants.
R&D challenges
• Risk of scale up to a large-scale rotary adsorption machine.
o Maintaining flow distribution.
o Size of adsorbent beds.
o Scale-up of gas seal design.
o Rotor imbalances/process asymmetry.
• Developing the technology for a coal-based flue gas feed.
status
During the initial phase of the project NRG and Inventys conducted a six-week test exposing the adsorbent to flue gas
from one of NRG coal-fired boilers and determined that further work was needed to improve the economics before a
large scale pilot demonstration could be attempted. Consequently, the project was wrapped up September 30, 2016.
NRG completed conceptual design of a 15 m diameter large scale pilot rotary adsorption machine, along with a
preliminary EH&S risk assessment and technology gap analysis. Increased structured adsorbent bed density and use
of a vacuum-assisted regeneration strategy was determined to be necessary to achieve process performance targets
for the coal flue gas TSA cycle.
available reports/technical papers/presentations
Armpriester, A. and Stevenson, M. “NRG CO2NCEPT – Confirmation of Novel Cost-Effective Emerging Post-
Combustion Technology,” presented at the 2016 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/2-Tuesday/A-Armpriester-NRG-
CO2NCEPT.pdf
Armpriester, A. “NRG CO2NCEPT – Confirmation of Novel Cost-Effective Emerging Post-Combustion Technology,”
presented at the Project Kickoff Meeting, Pittsburgh, PA, November 2015.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0026581-NRG-
Inventys-DOE-Kickoff-Meeting.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Bench-Scale Development technology maturity:
Bench-Scale, Simulated Flue
and Testing of Rapid Pressure Gas
Swing Adsorption for Carbon project focus:
Dioxide Capture
Rapid Pressure Swing
Adsorption
participant:
primary project goals w.R. Grace and Co.
W.R. Grace developed a rapid pressure swing adsorption (rPSA) process to evaluate project number:
concept cost and performance benefits by testing a bench-scale system using a low-
FE0007639
cost, structured adsorbent with low-pressure drop, high mass-transfer rates, high
capacity, and high availability that will enable large feed throughputs.
predecessor projects:
N/A
technical goals
NETL project manager:
• Develop an attrition-resistant and low-pressure drop structured adsorbent based Bruce Lani
on a commercial zeolite that is compatible with the high velocities associated [email protected]
with rapid PSA operation.
• Design, develop, and test a bench-scale rapid PSA process using the structured principal investigator:
adsorbent to deliver efficient and cost-effective separation of carbon dioxide james A. Ritter
(CO 2 ) from flue gas. University of South Carolina
[email protected]
technical content partners:
University of South Carolina;
W.R. Grace worked to develop a rapid PSA process with a much shorter cycle time
Catacel Corporation;
compared to conventional PSA, which could potentially reduce the cycle time from
Battelle Memorial Institute
300 seconds (conventional PSA cycle) to 30 seconds or less. This would increase the
feed throughput, and thus decrease the size of the columns by a factor of 10 or more,
start date:
significantly reducing both the capital and operating costs, as well as the plant
footprint. Pressure swing adsorption is attractive because it requires only electricity 10.01.2011
and not any of the power plant’s steam.
percent complete:
The key challenge to the success of this concept is two-fold: (1) an attrition-resistant 100%
and low-pressure drop structured adsorbent must be developed based on
commercial zeolite that is compatible with the high velocities associated with rapid
PSA operation; and (2) a rapid PSA cycle configuration must be developed in concert
with the structured adsorbent so that the resulting rapid PSA process achieves
necessary cost and performance metrics.
One advantage of a rapid PSA process over other CO 2 adsorption processes is
simplified heat management. The rapid cycle times minimize temperature swings.
Thus, the columns will heat up only slightly during adsorption and cool down only
slightly during desorption, approaching nearly isothermal operation, which is optimal.
Management of water will provide some operational challenges. Degradation of the
PSA process performance in the presence of water is well documented. It is
anticipated that for a rapid PSA CO 2 removal process, up to 95 percent of the water in
the flue gas will need to be removed using commercial desiccant technology. This will
increase capital and operating costs; however, any increases are more than offset by
cost savings in other parts of the process.
The structured adsorbent to be developed will consist of zeolite crystals coated on a
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
metal support. This process has been successfully demonstrated using metal foil, as shown in Figure 1.
Figure 1: Edge view of zeolite-coated metal substrate at 400x magnification (left); edge view of zeolite-coated metal substrate at 800x
magnification indicating washcoat is 35–40 µm thick (center); top view of zeolite-coated metal foil substrate at 4,000x magnification (right)
Corrugated cores have been fabricated (Figure 2) to serve as the metal substrate for testing the rapid PSA process. These cores
were tested to evaluate pressure drop, and coated with zeolite crystals for process testing.
Figure 2: Side view of 1.5” x 6” x 289 psi corrugated cores
In addition, a dynamic volumetric frequency response (DVFR) apparatus (Figure 3) that is being used to characterize adsorbate
mass-transfer rates in various adsorbents at cycle times up to 10 Hz, as well as a single-column rapid pressure swing adsorption
(S-C rPSA) system (Figure 4), is being used to study the effect of cycle time on the mass-transfer rates at step times as short as
0.25 seconds.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Figure 3: Photograph DVFR apparatus
Figure 4: Photograph of S-C rPSA system
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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Appendix: Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS1
Sorbent Units Current R&D value Target R&D value
True Density @ STP2 kg/m3 1,090 2,518
Bulk Density3 kg/m3 688 400
Average Particle Diameter4 mm 5.0 0.100
Particle Void Fraction m3/m3 0.47 0.47
Packing Density m2/m3 750 6,070
Solid Heat Capacity @ STP2 kJ/kg-K 0.92 0.82
Crush Strength5 kg f 3.6 N/A
Manufacturing Cost for Sorbent $/kg 20 37.4
Adsorption6
Pressure7 bar 1.2/1.14 1.2/1.14
Temperature °C 50 50
Equilibrium Loading8 g mol CO 2 /kg 4.18 4.18
Heat of Adsorption kJ/mol CO 2 37.5–46.0 37.5–46.0
Desorption
Pressure7 bar 0.05/0.00085 0.05/0.00085
Temperature °C 50 50
Equilibrium CO 2 Loading9 g mol CO 2 /kg 0.14 0.14
Heat of Desorption kJ/mol CO 2 37.5–46.0 37.5–46.0
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — fixed bed/cyclic
Flue Gas Flowrate kg/hr 2.32 × 106
CO2 Recovery, Purity, and Pressure % / % / bar 90 95 1.38
Adsorber Pressure Drop bar 0.15
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
1. For the Current R&D Value, the calculation is based on 5-mm 13X beads. For the Target R&D Value, the calculation is based on a 52-micron thick stainless steel support
containing a 100-micron thick zeolite crystal coating at each side.
2. The Target R&D Value includes the stainless steel support.
3. The Target R&D Value corresponds to mass of adsorbent (zeolite) per volume of bed.
4. The Target R&D Value corresponds to coating thickness.
5. The structured support for the target will be unaffected by PSA dynamic stresses.
6. The adsorption step is considered as the Heavy Reflux step, which follows the feed step in the PSA cycle and is highly enriched in CO 2 and obtained from another
desorption step in the PSA cycle.
7. First value is total pressure; second value is partial pressure of CO 2 .
8. The value corresponds to conditions of the heavy product gas.
9. The value corresponds to conditions of the light product gas.
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a
CO 2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The relative thermodynamic adsorption selectivity toward CO 2 over other gases such
nitrogen (N 2 ), oxygen (O 2 ), and argon (Ar) on a commercial zeolite at partial pressures of CO 2 at around or below 1.0 bar.
Sorbent Contaminant Resistance – The effect of the contaminant sulfur dioxide (SO 2 ) is not clear yet; tests are planned. It is
expected, however, that the 42 parts per million (ppm) in the fresh flue gas will be significantly reduced at the condensing heat
exchanger that will be located upstream of the PSA unit. It is not expected that the zeolite will be irreversibly affected by
nitrogen oxides (NO x ).
Sorbent Attrition and Thermal/Hydrothermal Stability – The sorbent will be deposited on the surface of a metal structured
support; thus, thermal or mechanical stresses present in pelletized/beaded systems will not be observed.
Flue Gas Pretreatment Requirements – The flue gas requires a blower to bring the pressure up to 120 kPa and then a
condensing heat exchanger followed by a dryer to bring the content of water to less than 0.1 vol% prior to entering the PSA
unit.
Sorbent Makeup Requirements – There are no sorbent makeup requirements in PSA units. The structured adsorbent is
expected to last at least 5 years and possibly 10 years before it needs to be replaced. This is common in commercial PSA
systems.
Waste Streams Generated – There are no waste streams generated in the flowsheet. All potential waste streams are recycled
and used in the process somewhere. For example, the condensing heat exchanger will produce about 460,000 lb/h of
condensed water that is recycled back as makeup water for the flue gas desulfurization (FGD) unit. It may contain up to
1,125 mg/L of dissolved SO2 and no other contaminants. In addition, about 3.69 x 106 lb/h of N 2 -rich product at about 80 °C is
vented into the air. This stream will contain, by volume, about 1.8 percent CO 2 , 4.0 percent H 2 O, 3.3 percent O 2 , 1.09 percent
Ar, and balance N 2 .
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
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Appendix: Post-Combustion Sorbent Technologies
technology advantages
• Established large-scale technology for other applications.
• Requires no steam or water, only electricity.
• Tolerant to trace contaminants; possibly with use of guard or layered beds.
• Zeolite adsorbent is commercial and widely available.
• Increase in cost of electricity (COE) lower than other capture technologies.
• If research and development (R&D) is successful, beds could be installed under a parking lot.
R&D challenges
• Energy-intensive (but better than current amines).
• Reducing bed size; larger bed implies large pressure drop, requiring more power.
• Minimizing pressure drop, mass transfer issues, and adsorbent attrition.
status
The project has ended. Three 6-inch Catacel core structures were successfully coated with a 50 µm thick layer of Zeolite
crystals, with a density of 240 kg/m3. One-bed and three-bed bench-scale PSA apparatuses were constructed. Testing of the
structured adsorbent began using these units. The dynamic adsorption process simulator was validated with experimental
data from the testing.
available reports/technical papers/presentations
Ritter, J. “Bench-Scale Development and Testing of Rapid PSA for CO 2 Capture,” presented at the 2015 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, June 2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/J-
Ritter-USCarolina-Rapid-PSA.pdf
Ritter, J. “Bench-Scale Development and Testing of Rapid PSA for CO 2 Capture,” presented at the 2014 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO 2 %20Capture/J-Ritter-USCarolina-Rapid-Pressure-
Swing-Adsorption.pdf
Ritter, J. “Bench-Scale Development and Testing of Rapid PSA for CO 2 Capture,” presented at the 2013 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO 2 %20Capture/J-Ritter-
USC-Rapid-Pressure-Swing-Adsorption.pdf
Ritter, J. “Bench-Scale Development and Testing of Rapid PSA for CO 2 Capture,” presented at the 2012 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2012. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/rapid-pressure-
swing-adsorption-july2012.pdf
Ritter, J. “Bench-Scale Development and Testing of Rapid PSA for CO 2 Capture,” presented at the Project Kickoff Meeting,
Pittsburgh, PA, May 2012. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/rapid-pressure-swing-adsorption-kickoff-
july2012.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
660 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Optimizing the Costs of Solid technology maturity:
Bench-Scale Testing at
Sorbent-Based CO2 Capture Simulated Full-Scale Process
Conditions
Process through Heat project focus:
Integration Cross-Heat Exchanger for
Sorbent-Based CO2 Capture
primary project goals participant:
ADA-ES, Inc.
ADA Environmental Solutions (ADA-ES) investigated heat recovery for a temperature-
swing-adsorption (TSA) capture process, including the use of a cross-heat exchanger project number:
to recover sensible heat from the sorbent leaving the regenerator. Recovering heat
FE0012914
generated by the sorbent during the capture process reduces the energy penalty and
overall cost for carbon dioxide (CO 2 ) capture.
predecessor projects:
FE0004343
technical goals NT0005649
• Evaluate options to reduce the plant heat rate and levelized cost of electricity NETL project manager:
(LCOE) associated with the ADAsorbTM process through heat integration with the Bruce Lani
plant and use of a cross-heat exchanger. [email protected]
• Optimize approach temperature and cross-heat exchanger design.
• Assess two different sorbents with preliminary design and techno-economics.
principal investigator:
Sharon Sjostrom
• Assess two cross-heat exchanger designs with laboratory testing, preliminary
ADA-ES, Inc.
design and techno-economics.
[email protected]
technical content partners:
Solex Thermal Science;
ADA-ES, along with partners Solex Thermal Science, Technip Stone and Webster Lehigh University–Energy
Process Technologies, and the Energy Research Center at Lehigh University, Research Center; Technip
optimized its promising dry sorbent-based post-combustion capture process—the Stone and webster Process
ADAsorb™ process—developed under another DOE-funded project (DE-FE0004343), Technologies
by evaluating heat integration opportunities as well as working to develop an overall
optimized process. In prior project DE-NT0005649, ADA-ES evaluated multiple solid start date:
sorbents at the lab- and bench-scale. In prior project DE-FE0004343, ADA-ES 10.01.2013
evaluated the ADAsorbTM process at the 1 megawatt electric (MW e ) pilot-scale. The
ADAsorbTM process is shown in Figure 1. The concepts, however, will be applicable to percent complete:
other TSA processes. The optimization study includes a sensitivity analysis across a
100%
range of sorbent properties to identify cost and energy demand trends so that the
general conclusions can be applied to most sorbent-based CO 2 capture processes.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
661
Appendix: Post-Combustion Sorbent Technologies
Figure 1: ADAsorbTM process overview
Cross-heat exchangers are standard features of solvent-based processes; large-scale heat exchangers appropriate for solids in
this application currently do not exist. Although the fundamental components for solids-based heat exchangers are
commercially available, the design details and integration approach are being developed and optimized to ensure that the
additional equipment capital costs do not outweigh benefits associated with reduced overall energy penalty. Figure 2 is a
concept drawing for the cross-heat exchanger.
Figure 2: Cross-heat exchanger concept
The team evaluated heat integration opportunities and optimizing the process by:
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
662 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
• Bench-scale testing the heat exchanger concept with a single sorbent to collect the data required for scale-up
modeling and the subsequent computational modeling.
• Modeling using ASPEN Plus and custom tools to determine the optimal operating conditions for the heat exchanger in
a moving-bed and fluidized bed arrangements integrated into the overall CO 2 capture process to minimize capital and
operating cost.
• Process modeling to assess the viability of heat integration options (with the power plant and the CO 2 compressors).
• Optimization of the flue gas moisture level.
• Adsorber and regenerator design assessment to reduce pressure drop.
The sorbent and process properties are provided in Table 1.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 646 646
Bulk Density kg/m3 453 453
Average Particle Diameter mm 0.18 0.18
Particle Void Fraction m3/m3 0.418 0.418
Packing Density m2/m3 N/A N/A
Solid Heat Capacity @ STP kJ/kg-K 1.05 1.05
Crush Strength kg f 2.2 2.2.
Manufacturing Cost for Sorbent $/kg 150 10
Adsorption
Pressure bar 1 1
Temperature °C 40 40
Equilibrium Loading g mol CO 2 /kg 2.4 7.2
Heat of Adsorption kJ/mol CO 2 -60 -60
Desorption
Pressure bar 1 1
Temperature °C 120 <100
Equilibrium CO 2 Loading g mol CO 2 /kg 0.8 0.6
Heat of Desorption kJ/mol CO 2 60 60
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — fluidized bed, temperature swing adsorption
Flue Gas Flowrate kg/hr 3,500
CO 2 Recovery, Purity, and Pressure % / % / bar 90 85(CO 2 )/15(H 2 O) ambient
Adsorber Pressure Drop bar 0.55
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
663
Appendix: Post-Combustion Sorbent Technologies
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a
CO 2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization
(FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The sorbent selected for this project is an ion exchange resin with a primary benzyl
amine that removes CO 2 in a TSA process. It is important to note that other supported amine sorbents with similar enthalpy of
adsorption and physical properties could also be used in the same process without major equipment changes.
One of the most important sorbent properties for post-combustion CO 2 capture is the CO 2 working capacity. Isotherms were
generated using experimental data and the Langmuir isotherm model, which are provided in Figure 3. To calculate the CO 2
working capacity of this sorbent, the adsorption conditions are assumed to be 40 °C and pCO 2 (partial pressure of carbon
dioxide) = 0.15 bar, while the regeneration conditions are assumed to be 120 °C and 0.81 bar (note that the CO 2 in the
regenerator exhaust will be slightly diluted with desorbing moisture). Using the isotherms provided in Figure 3, the CO 2
loading under adsorption conditions is approximately 10.5 g CO 2 /100 g fresh sorbent, while the CO 2 loading under the
regeneration conditions is approximately 3.5 g CO 2 /100 g fresh sorbent; the CO 2 working capacity is approximately 7 g
CO 2 /100 g fresh sorbent, which is nearly an 80 percent improvement versus the working capacity of aqueous
monoethanolamine provided in the 2010 version of the DOE baseline report.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
664 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Figure 3: Sorbent isotherms
Sorbent Contaminant Resistance – Amines will react with sulfur dioxide (SO 2 ) in the flue gas. The selected sorbent will react
with SO 2 and, as a result, the overall working capacity for CO 2 will decrease. However, this is a reversible reaction and the
sorbent can be regenerated to recover CO 2 capture effectiveness.
Sorbent Attrition and Thermal/Hydrothermal Stability – Based on laboratory testing, the selected sorbent is expected to have
low mechanical attrition. Comparisons to fluid catalytic cracking (FCC) catalyst attrition are favorable. The moisture uptake on
the sorbent is important because it results in an increase in the regenerator heat duty due to the enthalpy of
vaporization/condensation (assuming that the water (H 2 O) is physically adsorbed). In addition, in the regenerator, the released
H 2 O will necessitate the addition of condensers to separate the H 2 O from the CO 2 exhaust. This sorbent demonstrates a small
(≈0.9 g H 2 O/100 g fresh sorbent under expected 1-MW e pilot operating conditions) H 2 O working capacity.
Flue Gas Pretreatment Requirements – A secondary scrubber has been incorporated into the pilot design to reduce the flue
gas SO 2 . An assessment of the cost-benefit of scrubbing SO 2 versus regenerating the sorbent that has reacted with SO 2 to
recover CO 2 capture effectiveness must be conducted to determine the commercial process design and operating details.
Additional work has examined the possibility of regenerating sorbents contaminated by acid gases such as SO 2 so that the
sorbents may be reused in the process.
Sorbent Makeup Requirements – Current estimates used in cost projections are to replace the sorbent nominally once per year.
Further testing is required, including pilot testing to refine the makeup requirements.
Waste Streams Generated – Waste streams will include spent sorbent, flue gas scrubber blow-down, and flue gas cooler
condensate.
Process Design Concept – Flowsheet/block flow diagram included above.
Proposed Module Design – The CO 2 capture module will be located downstream of the plant’s existing SO 2 scrubber. The gas
stream from which CO 2 will be removed is representative of that from a coal-fired power plant with nominal conditions of
pCO 2 = 0.13 bar and T = 55 °C. The adsorber is designed to operate isothermally at 40 °C. The exhaust pressure for regeneration
is approximately ambient pressure. The minimum superficial velocity of the flue gas will be limited to 1.2 m/s (4.0 ft/s) to
minimize the number and footprint of reactors, and thus capital costs. Pneumatic conveying will be utilized for all required
material conveying to increase reliability, decrease operations and maintenance (O&M) costs, and increase technology
acceptance. Because the sorbent and flue gas are contacted in a system that approaches counter-current flow, CO 2 working
capacity can be maximized. In addition, the heat transfer has been optimized through the use of bubbling fluidized beds. The
optimal mixing that is characteristic of bubbling fluidized beds also translates into effective gas/solids contacting. The design
of the system employed established methods and principles used for gas-solid systems, including gas distribution, in-bed heat
transfer, risers, standpipes, cyclones, and diplegs. Large-scale, two-stage fluidized beds have been used commercially for FCC
processes. However, not all aspects of the design are commercially available.
In addition, the cross-heat exchanger module will consist of a further module based upon two concepts. The first concept is a
moving bed plate and frame heat exchanger which transfers sensible heat from the hot CO 2 lean sorbent to cold CO 2 rich
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
665
Appendix: Post-Combustion Sorbent Technologies
sorbent via a working fluid within the plates. As the sorbent flows between the plates heat is either transferred from hot
sorbent to cool plates and the working fluid in the plates or cool sorbent flows past plates being warmed by the hot heat
transfer fluid circulating within the plates.
The second concept uses a fluidized bed system with heat exchanger coils to extract heat from the hot CO 2 lean sorbent and
transfer heat to the cold CO 2 rich sorbent. This system is analogous to a shell and tube heat exchanger where the fluidized
sorbent in a vessel flows past coils with a heat transfer fluid circulating through the coils. The sensible heat of the hot CO 2 lean
sorbent is then rejected to the heat transfer fluid in the coils which then is used in another exchanger to heat the cool CO 2 rich
sorbent before it enters the regenerator.
technology advantages
• Sensible heat recovery.
• Reduced adsorber pressure drop.
o Sorbent is currently cooled in top adsorber bed.
o Reduced cooling requirements, smaller bed, reduced flue gas blower power, and reduced thermal
regeneration input and cooling duty.
• Reduced regenerator pressure drop.
o Sorbent enters regenerator at higher temperature.
o Less heat transfer surface required.
R&D challenges
• Benefits of heat recovery must outweigh the increase in capital costs.
• The addition of a cross-heat exchanger may increase the footprint of the existing capture unit.
o For many existing power plants, overall site footprint may be a limiting factor.
• A heat exchanger will necessitate more sorbent residence time and increase the amount of sorbent required for the
process.
• Sorbent cycling time flexibility will be limited by heat exchange requirements.
status
The project ended on December 31, 2015. Two cross-heat exchanger designs—moving bed and fluidized bed—were
evaluated for use between the adsorber and regenerator. The initial assessment indicated that the fluidized bed concept was
not a practical approach due to the prohibitively high additional electric load associated with fluidization. The techno-
economic assessment indicated that addition of a cross-heat exchanger and heat integration significantly improved net unit
heat rate, but the additional equipment costs required almost always outweighed the performance improvement. Sorbent BN
with the cross-heat exchanger had lower cost of electricity (COE) than for the case without. Sorbent OJ with cross-heat
exchanger alone lowered the COE by 0.2 percent, however it showed thermodynamic benefits over the other sorbent. The
lowest cost sorbent OJ case had a 15 percent lower COE than the lowest cost sorbent BN case.
available reports/technical papers/presentations
Sjostrom, S. “Optimizing the Costs of Solid Sorbent-Based CO 2 Capture Process through Heat Integration,” presented at Project
Closeout Meeting, Pittsburgh, PA, March 2016. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/7017-DOE-Closeout-DE-FE0012914-Final.pdf
Sjostrom, S. “Optimizing the Costs of Solid Sorbent-Based CO 2 Capture Process through Heat Integration,” presented at 2015
NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/S-Sjostrom-2-ADA-Solid-Sorbents-with-Heat-
Integration.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
666 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Sjostrom, S. and Morris, W. “Optimizing the Costs of Solid Sorbent-Based CO 2 Capture Process through Heat Integration,”
presented at 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/S-Sjostrom-ADA-Optimizing-the-Costs-of-
Solid-Sorbent-Based-CO2.pdf.
Sjostrom, S. “Optimizing the Costs of Solid Sorbent-Based CO 2 Capture Process through Heat Integration,” Project Kick Off
Meeting, Pittsburgh, PA, November 2013. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/NETL-ADA-Heat-
Integration-Project-Kickoff-Meeting.pdf.
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” presented at the project closeout
meeting, Pittsburgh, PA, June 2016. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/7013-Closeout-Final-0004343.pdf
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” presented at the 2015 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, June 2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/S-
Sjostrom-ADA-Solid-Sorbents.pdf
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” presented at the 2014 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO 2 %20Capture/S-Sjostrom-ADA-Evaluation-of-Solid-
Sorbents.pdf.
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” presented at the 2013 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/S-
Sjostrom-ADA-Solid-Sorbents-as-Retrofit-Technology.pdf.
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” presented at the 2011 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, August 2011.
https://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/22Aug11-Starns-ADAES-Solid-Sorbents-Retrofit.pdf
Sjostrom, S.; Krutka, H.; Starns, T.; and Campbell, T., “Pilot Test Results of Post-Combustion CO 2 Capture Using Solid Sorbents,”
Energy Procedia, 2011, 4, 1584-1592.
Sjostrom, S., and Krutka, H., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture,” Fuel, 2010, 89, 1298-1306.
http://www.sciencedirect.com/science/article/pii/S0016236109005286.
Sjostrom, S., “Evaluation of Solid Sorbents as a Retrofit Technology for CO 2 Capture from Coal-Fired Power Plants,” presented at
the 2010 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, September 2010.
http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/Sharon-Sjostrom---ADA-Environmental-Solutions.pdf.
Sjostrom, S., “Solid Sorbents as a Retrofit CO 2 Capture Technology: Viability Review and Pilot Testing,” presented at the Tenth
Annual Conference on Carbon Capture and Sequestration, Pittsburgh, PA, May 2011.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/solid-sorbents-retrofit-may2011.pdf
ADA-ES Inc., “Evaluation of Solid Sorbents as Retrofit Technology for CO 2 Capture from Coal-Fired Power Plant,” presented at
the Annual NETL CO 2 Capture Technology for Existing Plants R&D Meeting, Pittsburgh, PA, March 2009.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/evaluation-of-solid-sorbents-nt0005649-mar2009.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
667
Appendix: Post-Combustion Sorbent Technologies
Bench-Scale Development of technology maturity:
Bench-Scale, Simulated Flue
an Advanced Solid Sorbent- Gas
Based CO2 Capture Process project focus:
for Coal-Fired Power Plants
Advanced Solid Sorbents
and Processes for CO2
Capture
primary project goals participant:
RTI International
RTI International addressed the technical and economic hurdles to developing a
sorbent-based carbon dioxide (CO 2 ) capture process by transitioning a promising project number:
sorbent chemistry, based on molecular basket sorbent (MBS) materials, to a low-cost
FE0007707
sorbent suitable for use in a fluidized-bed process and developing a scalable circulating
fluidized, moving-bed reactor (FMBR) process arrangement.
predecessor projects:
N/A
technical goals
NETL project manager:
• Improve the thermal and chemical stability of the base polyethyleneimine (PEI) Bruce Lani
reactant while transitioning the current fixed-bed form MBS material into a [email protected]
fluidizable form.
• Collect critical process engineering data using a bench-scale test unit to allow for principal investigator:
a detailed design of a CO 2 capture prototype system based on improved MBS Thomas Nelson
materials. RTI International
• Improve reactor design, optimize operability, and optimize heat integration [email protected]
strategies for the FMBR system.
partners:
• Scale-up advanced MBS materials production for use in the CO 2 capture prototype
system. Pennsylvania State
University; Masdar New
• Demonstrate the technical and economic feasibility of a commercial embodiment
ventures; Masdar Institute
of the MBS-based CO 2 capture process through a detailed technology feasibility
study.
start date:
10.01.2011
technical content
percent complete:
The project team developed an advanced sorbent process that utilizes a polymeric 100%
amine-based CO 2 sorbent developed by Pennsylvania State University (PSU) under a
previous project (DE-FE-0000458) to capture CO 2 from coal-fired power plant flue gas.
This molecular basket sorbent consists of a high-surface area support, such as silica,
impregnated with branched PEI polymer, as exhibited in Figure 1.
The branched polymer contains primary, secondary, and tertiary amine sites that
adsorb CO 2 . Carbon dioxide absorption is favored between 50 and 90 °C (122 and
194 °F), with a heat of reaction of ΔHabs = 66 kJ/mol- CO 2 (645 Btu/lb- CO 2 ). At
temperatures greater than 110 °C (230 °F), the reverse reactions predominate and the
sorbent releases CO 2 .
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
668 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Post-Combustion Sorbent Technologies
Figure 1: Molecular basket sorbent concept
This advanced sorbent CO 2 capture process operates as a cyclic adsorption-regeneration thermal swing process where the solid
sorbent is continuously circulated between two FMBRs—a CO 2 adsorber and a sorbent regenerator. A basic block flow diagram
of this process, installed within a pulverized coal (PC)-fired power plant, is provided in Figure 2.
Figure 2: Block flow diagram of advanced solid sorbent CO 2 capture process
Carbon dioxide-rich flue gas from the PC power plant goes through a caustic scrubbing system to remove strong acid gases prior
to entering the CO 2 adsorber. The CO 2 adsorber is designed as an FMBR. Within the adsorber, flue gas comes in contact with lean
sorbent that is fed to the adsorber from the sorbent regenerator. The sorbent selectively removes CO 2 and generates heat due
to the heat of reaction for CO 2 removal. In order to control the sorbent bed temperature, cooling water is used to cool the sorbent
through indirect contact. Treated flue gas exits the CO 2 adsorber and enters a baghouse filter for removal of particulates,
primarily attrited sorbent particles. Following particulate removal, the flue gas is then directed to the stack and vented.
The CO 2 -rich sorbent exits the adsorber and is transported to the sorbent regenerator. The sorbent regenerator design and
operation is similar to the CO 2 adsorber, except that the sorbent bed is indirectly heated with condensing steam in order to strip
the sorbent of the adsorbed CO 2 . The regenerated sorbent produces a concentrated CO 2 gas stream that is swept out of the
sorbent regenerator with a CO 2 sweep gas. The concentrated CO 2 gas stream is then sent to a dehydration and compression
unit, and the sorbent is transferred through a sorbent cooling unit and on to the CO 2 adsorber for continued CO 2 removal. Fresh
sorbent is added to this stream to make up for attrited sorbent and diminished sorbent performance.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
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COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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Appendix: Post-Combustion Sorbent Technologies
RTI led an effort to conduct process evaluations in a bench-scale, single-stage, fluidized-bed unit capable of sustained CO 2
capture and sorbent regeneration, followed by the design and fabrication of a bench-scale, continuous-flow CO 2 capture
prototype system. This system is integrated and commissioned at RTI’s Energy Technology Development Facility (ETDF) using
simulated flue gas.
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 N/A N/A
Bulk Density kg/m3 ≈500 ≈1,000
Average Particle Diameter mm ≈0.1 0.05 to 0.2
Particle Void Fraction m3/m3 not measured TBD
Packing Density m2/m3 not measured TBD
Solid Heat Capacity @ STP kJ/kg-K 1.53 1.1 to 1.5
Crush Strength kg f N/A N/A
Manufacturing Cost for Sorbent $/kg N/A <10
Adsorption
Pressure bar 1.01 1.01
Temperature °C 75 60 to 90
Equilibrium Loading g mol CO 2 /kg 2.27 3.18
Heat of Desorption kJ/mol CO 2 66 60 to 70
Desorption
Pressure bar 1.01 1.01
Temperature °C 100 >110
Equilibrium CO 2 Loading g mol CO 2 /kg 0.68 0.45
Heat of Desorption kJ/mol CO 2 78 70 to 80
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — —
Flue Gas Flowrate kg/hr —
CO 2 Recovery, Purity, and Pressure % / % / bar — — —
Adsorber Pressure Drop bar —
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs
at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent.
Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
670 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the FGD (wet basis) should be
assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – see Figure 1.
Sorbent Contaminant Resistance – Most, if not all materials used for CO 2 capture, including aqueous amine solvents, alkaline
and alkali-based solvents and sorbents, and the amine-based sorbents being developed in this project, have a high affinity for
strong acid gases, including sulfur oxide (SO x ), nitrogen oxide (NO x ), and hydrogen chloride (HCl). Considerations have been
made regarding how to implement contaminant control within the overall CO 2 capture system. Resistance to trace metal
contaminants is unknown at this point.
Sorbent Attrition and Thermal/Hydrothermal Stability – Sorbent attrition will be a function of the process operating
environment and physical strength of the sorbent. These will be measured and observed during larger-scale testing campaigns.
The base PEI reagent suffers from performance instability at temperatures greater than 110 °C. One of the focuses of this project
is to improve the sorbent performance stability.
Flue Gas Pretreatment Requirements – Most likely, the flue gas will require a scrubbing of acid gases prior to entering the CO 2
adsorber containing the sorbent being developed in this project.
Sorbent Makeup Requirements – Continuous sorbent makeup will be required during operation of a commercial system in order
to replenish sorbent lost to attrition, entrainment, and deactivation by reaction with contaminants.
Waste Streams Generated – As a whole, the process generates few waste streams. It is expected that a continuous purge of
sorbent will be required to maintain a desired level of CO 2 removal within the sorbent bed. In addition, sorbent will be lost from
the process through attrition and entrainment. The sorbent can either be treated and reused, or disposed of following minimal
treatment.
Process Design Concept – See Figure 2.
technology advantages
• Potential for reduced parasitic loads and lower capital and operating costs than conventional technology.
• High CO 2 loading capacity.
• Relatively low heat of absorption with no heat of vaporization penalty.
• Reactor design offers superior gas-solid heat and mass transfer characteristics.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
671
Appendix: Post-Combustion Sorbent Technologies
• Counter current gas-solids flow maximizes CO 2 driving force.
• Required process equipment exists and is used industrially.
R&D challenges
• Heat management / temperature control.
• Solids handling / solids circulation control.
• Sorbent attrition resistance.
• Stability of sorbent performance.
• Heat management and novel heat integration strategies are critical to reduce parasitic power losses.
status
The project was completed on December 31, 2015. RTI has produced a fluidizable form of a high capacity sorbent and has
optimized and scaled up sorbent production to 135 kg scale. The multi-stage fluidized bed bench-scale test unit with a flue gas
processing capacity of 13 standard cubic feet per minute (scfm) was operated with several hundred hours of parametric and
long-term performance testing, identifying optimal operating conditions and achieving 90 percent CO 2 capture using a
simulated flue gas. The sorbent maintained CO 2 working capacity between 4 and 7 wt% during 100+ hours of continuous testing.
The techno-economic analysis indicated an estimated cost of CO 2 capture for a conceptual commercial layout of the process to
be approximately $45.0/tonne CO 2 .
available reports/technical papers/presentations
Nelson, T., et al. “Advanced Solid Sorbents and Process Designs for Post-Combustion CO 2 Capture,” presented at the 2016 NETL
CO 2 Capture Technology Meeting, Pittsburgh, PA, August
2016. https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/4-Thursday/T-Nelson-RTI-Solid-Sorbent-Based-
CO2-Capture.pdf
Nelson, T., et al. “Bench-Scale Development of an Advanced Solid Sorbent-Based CO 2 Capture Process for Coal-Fired Power
Plants,” Final Scientific/Technical Report, June
2016. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/fe0007707-final-report.pdf
Nelson, T., et al. “Advanced Solid Sorbents and Process Designs for Post-Combustion CO 2 Capture,” presented at the 2015 NETL
CO 2 Capture Technology Meeting, Pittsburgh, PA, June
2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/T-Nelson-RTI-Advanced-Solid-Sorbents.pdf
Nelson, T., et al. “Advanced Solid Sorbents and Process Designs for Post-Combustion CO 2 Capture,” presented at the 2014 NETL
CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/T-Nelson-RTI-Advanced-Solid-
Sorbents-and-Process-Designs.pdf.
Nelson, T., et al. “Advanced Solid Sorbents and Process Designs for Post-Combustion CO 2 Capture,” presented at the 2013 NETL
CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/T-Nelson-RTI-Advanced-Solid-Sorbents.pdf.
Nelson, T., et al. “Advanced Solid Sorbents and Process Designs for Post-Combustion CO 2 Capture,” presented at the 2012 NETL
CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2012. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/advanced-solid-sorbents-process-designs-july2012.pdf
Nelson, T., et al. “Advanced Solid Sorbent CO 2 Capture,” presented at the Project Kickoff Meeting, Pittsburgh, PA, December
2011. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/novel-solid-sorbents-kickoff-dec2011.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
672 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Low-Cost High-Capacity technology maturity:
Bench-Scale, Actual Flue
Regenerable Sorbent for Gas
Carbon Dioxide Capture from project focus:
Existing Coal-Fired Power
Low-Cost, High-Capacity
Regenerable Sorbent
Plants participant:
TDA Research, Inc.
primary project goals project number:
FE0007580
TDA Research, Inc. (TDA) developed a low-cost, high-capacity carbon dioxide (CO 2 )
adsorbent to demonstrate its technical and economic viability through sorbent
predecessor projects:
evaluation and optimization, development of sorbent production techniques, and
bench-scale testing of the process using actual flue gas. N/A
NETL project manager:
technical goals Andrew O’Palko
[email protected]
• Optimize sorbent chemical composition.
• Optimize physical properties and mechanical integrity of the sorbent to meet the principal investigator:
specific requirements of the process. Gokhan Alptekin
• Design and test performance on moving-bed and fixed-bed units. TDA Research, Inc.
[email protected]
• Identify optimum operating conditions and process parameters for design
calculations.
partners:
• Assess the economic viability of the new carbon capture process.
Babcock & wilcox; Gas
Technology Institute;
technical content University of California, Irvine
TDA developed a low-cost, high-capacity CO 2 adsorbent and demonstrated its start date:
technical and economic viability for post-combustion CO 2 capture for existing 10.01.2011
pulverized coal (PC)-fired power plants. The sorbent consists of a carbon material
modified with surface functional groups that remove CO 2 via physical adsorption. It percent complete:
exhibits a much higher affinity to adsorb CO 2 than nitrogen, water, or oxygen, 100%
enabling effective CO 2 separation from the flue gas. The sorbent binds CO 2 more
strongly than common adsorbents, providing the chemical potential needed to
remove the CO 2 . However, because CO 2 does not form a true covalent bond with the
surface sites, regeneration can be carried out with only a small energy input. The heat
input to regenerate the sorbent is only 4.9 kcal/mol of CO 2 , which is much lower than
that for chemical absorbents (e.g., 29.9 kcal/mol CO 2 for sodium carbonate) or amine-
based solvents (e.g., 14.2 kcal/mol CO 2 for monoethanolamine [MEA]).
Initial sorbent testing under conditions simulating the environment downstream of a
wet flue gas desulfurization unit showed stable CO 2 capacity for more than 220 cycles
with no sign of degradation (Figure 1).
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
673
Appendix: Post-Combustion Sorbent Technologies
Figure 1: Capacity testing under multiple VSA cycles—capacity maintained over 770 cycles
(T = 22 °C; half-cycle time = 4–8 min.; P ads = 16 psia; P des = 1 psia; simulated flue gas, 17 vol% CO 2 , H 2 O = 1.2 vol%)
The presence of acid gases, such as sulfur dioxide (SO 2 ) and nitrogen oxide (NO x ), and water (H 2 O) vapor up to 15 vol% caused
no adverse effect on the CO 2 capacity (Figure 2).
Figure 2: Capacity analysis in presence of SO 2 and water
(adsorption T = 62 °C, 15.2 percent CO 2 , 2.8 percent O 2 , bal. N 2 , sat. with H 2 O, 300 ppmv SO 2 )
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
674 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Both a moving-bed and fixed-bed vacuum swing adsorption unit were designed for proof-of-concept testing. The 4-bed
vacuum swing adsorption (VSA) system is shown in Figure 3.
Figure 3: 4-bed VSA prototype
The regeneration of the sorbent and the recovery of CO 2 and its pressurization can then be achieved by several approaches,
including temperature swing and vacuum swing. Figure 4 shows a schematic diagram of the process. The sorbent and process
parameters are shown in Table 1.
Figure 4: TSA process schematic
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
675
Appendix: Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 — —
Bulk Density kg/m3 — —
Average Particle Diameter mm — —
Particle Void Fraction m3/m3 — —
Packing Density m2/m3 — —
Solid Heat Capacity @ STP kJ/kg-K 0.93 0.93
Crush Strength kg f — —
Manufacturing Cost for Sorbent $/kg — —
Adsorption
Pressure bar 1.02 1.02
Temperature °C 70 58
Equilibrium Loading g mol CO 2 /kg 0.3 0.4
Heat of Adsorption kJ/mol CO 2 -20.5 -20.5
Desorption
Pressure bar 0.204 0.15–0.2
Temperature °C 70 58
Equilibrium CO 2 Loading g mol CO 2 /kg — —
Heat of Desorption kJ/mol CO 2 — —
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — —
Flue Gas Flowrate kg/hr —
CO 2 Recovery, Purity, and Pressure %/%/bar — — —
Adsorber Pressure Drop bar —
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically
occurs at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a
CO 2 partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically
occurs at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-
dependent. Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical PC power plant, the total pressure of the flue gas is
about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132 atm or
0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
676 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization
(FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
technology advantages
• The sorbent competitively adsorbs CO 2 over water.
• The heat of adsorption of CO 2 is low (much lower than amine-based solvents; comparable to that of Selexol).
• The net energy loss in sorbent regeneration is expected to be lower than amine scrubbers.
R&D challenges
• Mechanical integrity of the sorbent material at the conditions of use must be demonstrated.
• The gas-solid contactor design must be proven with full capabilities to be demonstrated.
status
The project was completed on September 30, 2015. Proof-of-concept testing was completed on both a moving-bed and a
fixed-bed VSA unit. B&W estimated the total plant cost for the moving-bed system as approximately $424 million (2011 basis)
and a total plant cost for the fixed-bed system to be approximately $276 million. A 4-bed VSA system was tested for over 750
hours on a 4-standard cubic feet per minute (scfm) slipstream of actual flue gas at Gas Technology Institute’s Combustion
Facility, showing stable performance and achieving >90 percent CO 2 capture.
available reports/technical papers/presentations
Alptekin, G., Jayaraman, A., and Copeland, R., “Post-Combustion CO 2 Capture System for Existing Coal-Fired Power Plant,”
presented at the 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/G-Alptekin-TDA-New-Sorbent-Process.pdf.
Alptekin, G., Jayaraman, A., and Copeland, R., “Post-Combustion CO 2 Capture System for Existing Coal-Fired Power Plant,”
presented at the 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/G-Alptekin-TDA-A-New-Sorbent-For-Post-
Combustion.pdf.
Alptekin, G., Jayaraman, A., and Copeland, R., “Post-Combustion CO 2 Capture System for Existing Coal-Fired Power Plant,”
presented at the 2013 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/G-Alptekin-TDA-New-Sorbent-for-Post-Combustion.pdf.
Alptekin, G., Jayaraman, A., and Copeland, R., “Post-Combustion CO 2 Capture System for Existing Coal-fired Power Plant,”
presented at the 2012 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/new-sorbent-for-post-combustion-july2012.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
677
Appendix: Post-Combustion Sorbent Technologies
Alptekin, G., “Post-Combustion CO 2 Capture System for Existing Coal-fired Power Plant,” presented at the Project Kickoff
Meeting, Pittsburgh, PA, December 2011. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/low-cost-high-
capacity-regenerable-sorbent-dec2011.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
678 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Rapid Temperature Swing technology maturity:
Bench-Scale, Simulated Flue
Adsorption Using Gas
Polymeric/Supported Amine project focus:
Hollow Fiber Materials
Rapid Temperature Swing
Adsorption
participant:
primary project goals Georgia Tech Research
Corporation
Georgia Tech Research Corporation developed a rapid temperature swing adsorption
(RTSA) carbon dioxide (CO 2 ) process and evaluated the cost and performance benefits project number:
of this novel hybrid capture approach via bench-scale testing of a module containing
FE0007804
polymeric/supported amine hollow fibers, which are loaded with supported
adsorbents and surround an impermeable lumen layer that allows for cooling and
heating. predecessor projects:
N/A
technical goals NETL project manager:
Bruce Lani
• Produce polymeric hollow fiber contactors loaded with amine adsorbent [email protected]
particles for post-combustion (CO 2 capture.
• Develop a computational model of the fiber module and validate it in parallel principal investigator:
with the experimental program. Christopher w. jones
• Assess adsorption/desorption and heat-exchange performance of hollow fiber Georgia Tech
modules using simulated clean and simulated dirty flue gas. [email protected]
h.edu
technical content partners:
Trimeric Corporation;
Supported amine adsorbents have many promising properties with regard to CO 2 Algenol Biofuels; Southern
capture from post-combustion flue gas. However, most previous studies of supported Company Services; GE
amine materials focus only on CO 2 adsorption, ignoring desorption. In addition, Energy
essentially all published studies describe the use of supported amine materials in fixed
beds. This process configuration is difficult to use at practical scales due to heat start date:
integration challenges. This is especially important for supported amines; whose heats 10.01.2011
of adsorption are among the highest of known CO 2 adsorbents (50–80 kJ/mol), but
which enables large swings in capacity with temperature. Thus, practical process
percent complete:
designs for amine sorbents must include effective heat transfer.
100%
Recently, the use of novel polymeric hollow fiber contactors loaded with CO 2
adsorbents has been introduced as a scalable process configuration for CO 2 capture. In
this approach, polymeric hollow fibers, similar to those used for commercial-scale
membrane gas separation, are prepared and loaded with large volumes of solid CO 2
adsorbing materials. However, unlike those used for membrane applications, these
hollow fibers have several unique aspects. First, high volumes of adsorbent materials
are included, typically 60–75 percent by volume. Second, the polymeric phase is
designed to have many large voids, allowing rapid mass transfer to the sorbent
particles. Third, a dense lumen layer is installed in the fiber bore to largely shutdown
transport from the shell side of the fibers to the bore. This design yields fibrous
structures that are ideally suited for application as combined sorption and heat transfer
modules in an RTSA process. Total cycle times are in the order of 3 minutes.
In the amine-hollow-fiber RTSA process, flue gases flow over the shell of the fibers while
cooling water flows through the bore. Given the small diameter of the fibers, the fibers
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
679
Appendix: Post-Combustion Sorbent Technologies
and adsorbents can be maintained in nearly isothermal conditions, with the cooling fluid providing an effective reservoir for heat
of adsorption (Figure 1). At the appropriate time, the flue gas can be rerouted to another bed and the fibers can be switched to
desorption mode by passing hot water through the fiber bore, driving off the CO 2 .
Figure 1: Sorption (top) and desorption (bottom) modes in hollow fiber sorbents
This RTSA approach was previously demonstrated using cellulose acetate fibers and zeolite 13X as the adsorbent in the fibers.
Zeolite 13X is not an ideal sorbent for wet post-combustion CO 2 capture streams, but supported amines may be well suited for
the task.
The hollow fiber architecture has three key attributes: (1) it provides the adsorption surface area needed to handle large volumes
of flue gas, (2) it enables efficient heat transfer needed to handle the high heat of adsorption of supported amines, and (3) it is
readily scalable given the current commercial capability to produce large surface area hollow fibers on an industrial scale.
The RTSA process based on hollow fibers containing supported amine adsorbents represents a novel new process configuration
for post-combustion CO 2 capture. In a commercial process, multiple hollow fiber modules would be used, and modules would
cycle synergistically between adsorption and desorption modes in a continuous process, as shown in Figure 2.
Figure 2: Potential RTSA process configuration
The sorbent and process parameters are shown in Table 1.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
680 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
TABLE 1: SORBENT PROCESS PARAMETERS
Sorbent Units Current R&D value Target R&D value
True Density @ STP kg/m3 1,100 1,100
Bulk Density kg/m3 1,100 1,100
Average Particle Diameter mm 1.2 1.0
Particle Void Fraction (void fraction of fiber bed) m3/m3 0.4–0.5 0.28–0.3
Packing Density (packing density of fiber bed) m2/m3 1,000 1,600
Solid Heat Capacity @ STP kJ/kg-K 1,800 3,000
Crush Strength kg f 1.140 1.140
Manufacturing Cost for Sorbent $/kg unknown unknown
Manufacturing Cost for Fiber Module (includes $/kg unknown $10/m2 or $25–$35/kg
hardware, fibers, sorbent)
Adsorption
Pressure (partial pressure of CO 2 ) bar 0.159 0.13
Temperature °C 55 35
Equilibrium Loading g mol CO 2 /kg fiber 0.84 1.0–1.5
Heat of Adsorption kJ/mol CO 2 59 55–65
Desorption
Pressure bar 0.2 1.0
Temperature °C 120 90
Equilibrium CO 2 Loading g mol CO 2 /kg fiber 0.34 0.1
Heat of Desorption kJ/mol CO 2 59 55–65
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — shell and tube
kg/hr 200 sccm (lab), ≈2,900 0.5 (lab), ≈2,900
Flue Gas Flowrate
(full scale, per module) (full scale, per module)
91%/96 mol%/0.2 bar 90%/95 mol%/1 bar or
CO 2 Recovery, Purity, and Pressure % / % / bar
(0.19 bar partial pressure) 80 mol% at 5.5 bar
Adsorber Pressure Drop bar <0.1 <0.15
Estimated Adsorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO 2 -free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost
for new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs
at the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO 2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent.
Measured data at other conditions are preferable to estimated data.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
681
Appendix: Post-Combustion Sorbent Technologies
Pressure – The pressure of CO 2 in equilibrium with the sorbent. If the vapor phase is pure CO 2 , this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO 2 . Note that for a typical pulverized (PC) power plant, the total pressure of the
flue gas is about 1 atm and the concentration of CO 2 is about 13.2 percent. Therefore, the partial pressure of CO 2 is roughly 0.132
atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO 2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization (FGD)
(wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO X NO X
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Chemical/Physical Sorbent Mechanism – The underlying mechanism is primary and secondary amines reacting with CO 2 to
produce carbamates or (bi)carbonates, depending on the nature of the amines, amine loading, and humidity level. Under most
conditions, a mixture of species is formed on the adsorbent surface.
Sorbent Contaminant Resistance – Thus far, the solid supported amines developed for this project have displayed excellent
oxidative stability, stability in humid conditions (5–90 percent relative humidity [RH]), and resistance to nitric oxide. The active
amine fillers are poisoned by high concentrations of sulfur oxide (SO x , 200 parts per million [ppm]), and extensive sulfur removal
is needed.
Sorbent Attrition and Thermal/Hydrothermal Stability – Due to the sorbents being “protected” within the walls of the hollow
fiber sorbents, the Georgia Institute of Technology has yet to experience any mechanical issues (such as attrition) in their studies.
The fibers themselves are quite temperature-resistant, but the amines have a realistic upper temperature limit of ≈130 °C. The
amines contained within the fiber walls exhibit higher CO 2 uptake capacities in the presence of water; moreover, the fibers
themselves have been continuously cycled between 35°C and 120°C without damage to the fiber structure. These suggest that
the materials are hydrothermally stable within the operating ranges of the RTSA process.
Flue Gas Pretreatment Requirements – Current analysis indicates that flue gas cooling to approximately 35 °C is required for
low-cost CO 2 capture. Experimental work suggests that partial dehydration of the flue gas may prolong fiber lifetimes (i.e.,
90 percent RH vs. 100 percent RH). Finally, further wet FGD may be required for additional SO x removal for optimum long-term
performance of the amines.
Sorbent Makeup Requirements – Analyses investigating the amine loss rates are needed. It has been demonstrated that
deactivated amines can be removed when required, and fresh amines redeposited in the fibers, allowing fiber recycling and
reuse.
Waste Streams Generated – Spent fiber sorbents represent the only process waste stream. Currently, the fibers are assumed to
last 3 years before replacement is required. With appropriate flue gas scrubbing, such lifetime may be achievable.
Process Design Concept – See Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
682 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
technology advantages
• Deleterious thermal effects typically associated with packed-bed sorption can be mitigated and higher sorption
efficiencies can be achieved by utilizing the hollow fiber morphology to supply cooling agents in the bore of the fiber
during adsorption.
• The thin porous walls of the fiber sorbent allow for rapid heat and mass transfer equilibration, thereby allowing for more
rapid thermal cycles and thus reducing device volume.
• Pressure drops through these beds will be correspondingly lower than those of packed or fluidized solid sorbent beds,
which will reduce draft fan costs.
• Heat transfer fluids in the bore of the fibers can be as simple as hot water and cold water, providing an environmentally
friendly overall process.
• Rapid heat transfer enables potential recovery of heat of adsorption and reuse of sensible heat of the bed. This affords
heat integration both within the capture process and may facilitate heat integration with the boiler feed water preheat.
This can dramatically reduce the overall parasitic thermal load of the RTSA process.
R&D challenges
• High heat of adsorption, with heat management improved by contactor design.
• Deactivation of sorbents upon exposure to SO x and exposure to saturated humidity and temperature.
• Low-working capacity in more conventional contactors.
• Efficient heat integration with power plant.
• Long-term operation of complete cycles with bore-side heating and cooling.
• Manufacturing cost estimates of fibers have significant uncertainty.
• Design of efficient multibed cycles to improve recovery and purity.
• Adaptive scheduling and control to manage slow degradation over many cycles and variability between modules.
status
The project was completed on March 31, 2015. Georgia Tech has developed a post-spinning amine infusion method to create and
recharge sorbents. A dual layer spinning method was developed for constructing a barrier lumen layer in the fiber bore, which allows
the fiber to be used as an adsorbing shell-in-tube heat exchanger. Testing has been completed on hollow fiber RTSA modules. Heat
integration in the RTSA process has allowed for up to 70 percent recovery of the heat of adsorption and the RTSA cycle time has
been reduced to 3 minutes. A detailed process model of the cyclic pressure temperature swing adsorption module was developed
and validated against experimental data. The process model was integrated with costing models for the overall process that
included compression and flue gas conditioning. The CO 2 capture cost was estimated to be $44.8/tonne CO 2 .
available reports/technical papers/presentations
Swernath, S. et al., “Optimization and Technoeconomic Analysis of Rapid Temperature Swing Adsorption Process for Carbon
Capture from Coal-Fired Power Plant” Proceedings of the 8th International Conference on Foundations of Computer Aided Process
Design. 2015;34:633-638.
Kalyanaraman, J. et al., “Bayesian estimation of parametric uncertainties, quantification and reduction using optimal design of
experiments for CO 2 adsorption on amine sorbents” Computers in Chemical Engineering. 2015;81:376-388.
Fan. Y. et al., “Stability of amine-based hollow fiber CO 2 adsorbents in the presence of NO and SO 2 ” Fuel. 2015;160:153-164.
Lively, R., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fiber Materials,”
presented at the 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June
2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/R-Lively-GIT-RTSA-Using-Polymeric-
Supported-Hollow-Fiber.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
683
Appendix: Post-Combustion Sorbent Technologies
Jones, C., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fiber Materials,”
presented at the Project Close-out Meeting, Pittsburgh, PA, April
2015. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/Ga-Tech-7804-closeout-
presentation.pdf
Labreche Y. et al. Direct dual layer spinning of aminosilica/Torlon (R) hollow fiber sorbents with a lumen layer for CO 2
separation by rapid temperature swing adsorption. Journal of Applied Polymer Science. 2015;132:4185.
http://onlinelibrary.wiley.com/wol1/doi/10.1002/app.41845/full
Rezaei, F. et al. Shaping amine-based solid CO 2 adsorbents: Effects of pelletization pressure on the physical and chemical
properties. Microporous and Mesoporous Materials. 2014:34-42.
https://www.sciencedirect.com/science/article/pii/S1387181114006404
Fan, Y. et al. CO 2 Sorption Performance of Composite Polymer/Aminosilica Hollow Fiber Sorbents: An Experimental and
Modeling Study. Industrial & Engineering Chemistry Research. 2015;54:1783-1795. https://pubs.acs.org/doi/abs/10.1021/ie504603h
Kalyanaraman J, Fan Y, Lively RP, Koros WJ, Jones CW, Realff MJ, et al. Modeling and experimental validation of carbon dioxide
sorption on hollow fibers loaded with silica-supported poly(ethylenimine). Chemical Engineering Journal. 2015;259:737-751.
https://www.sciencedirect.com/science/article/pii/S1385894714010778
Labreche Y. et al. Poly(amide-imide)/Silica Supported PEI Hollow Fiber Sorbents for Post-Combustion CO 2 Capture by RTSA. ACS
Applied Materials & Interfaces. 2014;6:19336-19346. https://pubs.acs.org/doi/abs/10.1021/am400636c
Rezaei, F. et al. Stability of Supported Amine Adsorbents to SO 2 and NOx in Post-Combustion CO 2 Capture. 2. Multicomponent
Adsorption. Industrial & Engineering Chemistry Research. 2014;53:12103-12110. https://pubs.acs.org/doi/abs/10.1021/ie502024z
Fan, Y. et al. Evaluation of CO 2 adsorption dynamics of polymer/silica supported poly(ethylenimine) hollow fiber sorbents in
rapid temperature swing adsorption. International Journal of Greenhouse Gas Control. 2014;21:61-71.
https://www.sciencedirect.com/science/article/pii/S1750583613004246
Fan, Y. et al. Dynamic CO 2 Adsorption Performance of Internally Cooled Silica-Supported Poly(ethylenimine) Hollow Fiber
Sorbents. AIChE Journal 2014;60:3878-3887. http://onlinelibrary.wiley.com/wol1/doi/10.1002/aic.14615/full
Rezaei. F. et al. Modeling of rapid temperature swing adsorption using hollow fiber sorbents. Chemical Engineering Science.
2013;113:62-76. https://www.sciencedirect.com/science/article/pii/S000925091400150X
Jones, C., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fibers,” presented
at the 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/C-Jones-GIT-Rapid-Temperature-
Swing-Adsorption.pdf.
Rezaei, F. et al. Stability of Supported Amine Adsorbents to SO 2 and NO x in Post-Combustion CO 2 Capture. 1. Single-
Component Adsorption. Industrial & Engineering Chemistry Research. 2013;52:12192-12201.
https://pubs.acs.org/doi/abs/10.1021/ie4019116
Rezaei, F. et al. Aminosilane-Grafted Polymer/Silica Hollow Fiber Adsorbents for CO 2 Capture from Flue Gas. ACS Applied
Materials & Interfaces. 2013;5:3921-3931. https://pubs.acs.org/doi/abs/10.1021/am400636c
Labreche, Y. et al. Post-spinning infusion of poly(ethyleneimine) into polymer/silica hollow fiber sorbents for carbon dioxide
capture. Chemical Engineering Journal. 2013;221:166-175. https://www.sciencedirect.com/science/article/pii/S1385894713001320
Jones, C., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fibers,” presented
at the 2013 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/C-Jones-GTech-Rapid-TSA-using-Amine-Hollow-
Fibers.pdf.
Realff, M., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fibers,” presented
at the 2012 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July
2012. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/rapid-temperature-swing-adsorption-july2012.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
684 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Jones, C., et al., “Rapid Temperature Swing Adsorption Using Polymer/Supported Amine Composite Hollow Fibers,” Presented
at the Project Kickoff Meeting, Pittsburgh, PA, November
2011. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/rapid-temperature-swing-adsorption-kickoff-nov2011.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 685
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
EVALUATION OF CARBON DIOXIDE
CAPTURE FROM EXISTING COAL-FIRED
PLANTS BY HYBRID SORPTION USING technology maturity:
SOLID SORBENTS Bench-Scale, Actual Flue
Gas
primary project goals project focus:
Solid Sorbent-Based CO2
The University of North Dakota (UND) and Envergex LLC are developing a solid sorbent Capture
technology—Capture from Existing Coal-Fired Plants by Hybrid Sorption
(CACHYS™)—that is based on the following principles: participant:
• Reduction of energy for sorbent regeneration. University of North
• Utilization of novel process chemistry. Dakota
• Contactor conditions that minimize sorbent-CO2 heat of reaction and promote fast project number:
CO2 capture.
FE0007603
• Low-cost method of heat management.
• Low-cost, carbon-based sorbent impregnated with an alkali carbonate salt and an NETL project manager:
active promoter.
Andrew Jones
[email protected]
technical goals
principal investigator:
• Sorbent selection and formulation, as well as the determination of heat of sorption, Steven A. Benson
sorbent capacity (CO2 loading), and sorbent physical properties for process design University of North
definition. Dakota
• Conduct lab-scale, fixed-bed tests to investigate adsorption and desorption kinetics, [email protected]
working capacity, heats of adsorption and desorption and a relative measure of
attrition during multiple cycles. partners:
• Establish the optimum process conditions (e.g., temperatures, pressures, and Industrial Commission of
residence times), preferred sorbent compositions, and bench-scale equipment design North Dakota
(e.g., size, energy duties, and material feed rates). Envergex LLC
• Design, build, and operate a bench-scale CACHYS™ adsorption and desorption Barr Engineering
system designed for a flue gas flow rate of 30 actual cubic feet per minute (acfm) Solex Thermal Science
obtained as a slipstream from a sub-bituminous coal-fired stoker boiler at the UND
campus steam plant.
Incorporated
ALLETE Incorporated
SaskPower
technical content
performance period:
The project was intent on developing key information for the CACHYS™ process - sorbent 10/1/11 – 12/31/14
performance, energy for sorbent regeneration, physical properties of the sorbent, the
integration of process components, sizing of equipment, and overall capital and operational
cost of the integrated CACHYS™ system. The bench-scale CACHYS™ test unit includes a
flue gas conditioning system to remove particulate matter and sulfur dioxide via a fabric
filter and a wet packed-bed scrubber using sodium hydroxide solution, respectively. Two
circulating fluidized beds are employed for CO2 adsorption. The Solex Thermal regenerator
system consists of three functional units capable of operating at elevated pressure—the
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
686 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
preheater, the regenerator, and the cooler. Sorbent transferred from the adsorber system is heated to the desired regeneration
temperature in the preheater and transferred to the regenerator unit where the CO2 is desorbed from the sorbent. The sorbent then
transfers to the cooler, where the temperature of the sorbent is returned to the adsorption temperature. The sorbent is then transferred
back to the adsorber system via pneumatic conveyance.
Figure 1: CACHYS™ Sorption Process
TABLE 1: ADSORPTION-BASED POST-COMBUSTION CO2/N2 SEPARATIONS
Units Current R&D Value Target R&D Value
S or bent
True Density at STP kg/m3 1,800–2,200 1,800–2,200
Bulk Density kg/m3 400–700 400–700
Average Particle Diameter mm 0.1–1 0.1–1
Particle Void Fraction m3/m3
Packing Density m2/m3 230 230
Solid Heat Capacity at STP kJ/kg-K 1.2 1.2
Crush Strength kgf
Manufacturing Cost for Sorbent $/kg 1.65 1.00
A b s o r p ti o n
Pressure (partial of CO2) bar 0.1 0.1
Temperature °C 50–80 50–80
Equilibrium CO2 Loading g mol CO2/kg 2.1 2.1
Heat of Absorption kJ/mol CO2 30–80 30–80
Desorption
Pressure (partial of CO2) bar 1.9 1.9
Temperature °C 140–160 140–160
Equilibrium CO2 Loading mol/mol 0.5 0.5
30–80
Heat of Desorption kJ/mol CO2 30–80
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — fluidized bed
Flue Gas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar 90%, 95–99%
Adsorber Pressure Drop bar
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 687
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
Definitions:
STP – Standard Temperature and Pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost for
new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs at
the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40°C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent.
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical pulverized coal (PC) power plant, the total pressure of
the flue gas is about 1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly
0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
technology advantages
• Low heat of sorption.
• Increased sorption kinetics.
• Low-cost sorbent.
• Commercially-available and easily-scalable equipment.
R&D challenges
• Confirmation of energetics.
• Sorbent integrity.
• Sorbent handling.
• Achievement of 90% CO2 capture.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
688 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Sorbent Technologies
results to date/accomplishments
• Performed laboratory-scale testing that showed heat of desorption was 30–80 kJ/mol CO2, depending on process conditions.
Sorbent CO2 working capacity ranged from 70–100 g/kg sorbent. Both metrics exceeded the target levels.
• 100-cycle tests demonstrated excellent chemical stability and no detectable loss in capacity.
• The CACHYS™ bench-scale test facility was constructed at UND’s coal-fired steam plant. The system captures CO2 from 30
acfm of flue gas with a sorbent throughput of 200-400 lb/hr.
• Bench-scale parametric testing resulted in a maximum CO2 capture of 85 percent and demonstrated the significant benefits of
hybrid sorption compared to standard carbonate sorption: Much higher capture and reaction rates (≈2–3X) and excellent
control of exothermic heat of adsorption.
• Continuous and integrated bench-scale testing demonstrated sustainable (5–7 hours) capture of 70–80 percent with 4 percent
CO2 in flue gas and 40–60 percent with 8 percent CO2 in flue gas. A 15-hour continuous test with stable operations was
completed.
• Based on the testing data gathered over the course of the project, a final technical and economic feasibility study was
completed. Results indicate a modest improvement over the benchmark MEA process and progress towards the DOE goals.
next steps
This project ended December 31, 2014.
available reports/technical papers/presentations
Benson, S., et al., “Evaluation of CO2 Capture from Existing Coal-fired Plants by Hybrid Sorption Using Solid Sorbents,”
presented at the 2014 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/S-Benson-UNDakota-S-Srinivasachar-
Envergex-Evaluation-of-CO2.pdf.
Presentation at the Thirteenth Annual Conference on Carbon Capture, Utilization, and Storage, Pittsburgh, PA, April 28–May 1,
2014. http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/2014-CCUS-Presentation-
7603.pdf.
Benson, S., et al., “Evaluation of CO2 Capture from Existing Coal-fired Plants by Hybrid Sorption Using Solid Sorbents,”
presented at the 2013 NETL CO2 Capture Technology Meeting, Pittsburgh, Pennsylvania, July 2013,
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/S-Benson-UND-Hybrid-Sorption-Using-Solid-
Sorbents.pdf.
Benson, S., et al., “Evaluation of CO2 Capture from Existing Coal-fired Plants by Hybrid Sorption Using Solid Sorbents,”
presented at the 2012 NETL CO2 Capture Technology Meeting, Pittsburgh, PA, July 2012.
Preliminary Carbon Dioxide Capture Technical and Economic Feasibility Study—Topical Report (November 2012).
Project Review Meeting Presentation (September 2012). http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/und-
CO2-capture-budget-period1.pdf.
Evaluation of CO2 Capture from Existing Coal-Fired Power Plants by Hybrid Sorption Using Solid Sorbents (CACHYS™) Project
Kick-Off Meeting Presentation, November 21, 2011. http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/und-CO2-
capture-budget-period1.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 689
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
690 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 691
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
692 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 693
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
694 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 695
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
696 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 697
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
698 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 699
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
700 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 701
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
702 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Sorbent Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 703
Appendix: Post-Combustion Sorbent Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
704 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
POST-COMBUSTION
MEMBRANE TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
705
Appendix: Post-Combustion Membrane Technologies
Novel Inorganic/Polymer technology maturity:
Pilot-Scale, Actual Flue Gas
Composite Membranes for project focus:
CO2 Capture Inorganic/Polymer
Composite Membranes
primary project goals participant:
Ohio State University
Ohio State University developed an inorganic/polymer composite membrane
consisting of a thin, selective inorganic-containing layer embedded in a polymer project number:
structure. The project developed the new membrane design to improve system
performance through laboratory, bench-scale, and pilot-scale testing, and developed a FE0007632
continuous manufacturing process to decrease costs.
predecessor projects:
N/A
technical goals
NETL project manager:
• Develop membrane synthesis process that incorporates a thin, selective inorganic- josé Figueroa
containing layer embedded in a polymer structure. [email protected]
Membranes were developed and down-selected to achieve the Department of
Energy (DOE) target of <$40/tonne carbon dioxide (CO 2 ) captured for 2025 (for principal investigator:
a CO 2 /nitrogen [N 2 ] selectivity of >100 and a CO 2 permeance of >800 gas Dr. winston Ho
permeation units [GPU]). Ohio State University
Continuous fabrication of the proposed hybrid membrane morphology was [email protected]
performed with the use of a continuous membrane fabrication machine.
• Conduct membrane characterization via bench-scale testing. partners:
Functional hybrid membranes were synthesized for incorporation into three Gradient Technology, TriSep
prototype membrane modules for parametric and continuous testing with Corporation, American
simulated or actual flue gas. Electric Power (AEP)
• Complete system and cost analysis of the membrane system. start date:
10.01.2011
technical content
percent complete:
Ohio State University developed a cost-effective design and manufacturing process for 100%
new membrane modules that capture CO 2 from flue gas. In one approach, the
membranes are comprised of a thin, selective inorganic particle-containing layer
embedded in a polymer structure so that it can be made in a continuous manufacturing
process. In another approach, a continuous zeolite membrane is rapidly synthesized on a
polymer support. Figures 1 and 2 show the two hybrid membrane concepts studied in
this project. The membrane of the first approach was incorporated in spiral-wound
modules for testing with simulated and actual coal-fired flue gas. Preliminary cost
calculations showed that a single-stage membrane process is economically unfavorable,
primarily because of the low concentration of CO 2 (≈14 percent) in the flue gas stream. A
two-stage process is more economical, but requires plant operation with a CO 2 -enriched
recycle stream. An important cost driver in current carbon capture membrane
technologies is the energy requirement for maintaining the driving force for the
membrane separation. The flue gas must be kept at atmospheric pressure and the
concentrated CO 2 stream kept under vacuum (approximately 3 pounds per square inch
[psi]) conditions. Preliminary calculations showed that the carbon capture energy
requirement can be sufficiently reduced in a two-stage process. In the first stage, CO 2 is
removed from flue gas by evacuation; in the second stage, remaining CO 2 is removed
using an air-sweep such that the 90 percent capture target is met.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
706 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
Figure 1: Membrane concept with selective amine polymer layer on zeolite nanoparticles embedded in polymer support
Figure 2: Membrane concept with polymer caulking layer on selective zeolite membrane grown on polymer support
Figure 3: Process concept for two-stage membrane system
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
707
Appendix: Post-Combustion Membrane Technologies
The entrance sweep flow is the same as the combustion air used in the current plant; the now CO 2 -enriched stream is
subsequently used for combustion. The 95 percent pure CO 2 , captured in the first stage, is then compressed to 15 MPa (≈2,200
psi). DOE’s cost targets can be met with a membrane that has a selectivity ≈170, a permeance of 1,100 GPU, and full stability
against flue gas contaminants. This combination cannot be achieved with fully polymeric membranes. Fully inorganic, micro-
porous membranes are sufficiently selective and stable, but generally too expensive due to high manufacturing costs. The focus
of this project was a design that combines favorable inorganic membrane selectivity with the cost-effectiveness resulting from
the manufacture of a composite membrane in continuous mode. The micro-porous membranes are aluminosilicates. Fully
inorganic structures have CO 2 /N 2 selectivities of >200, and permeances of <3,000 gas GPU. The latter can be improved by
reducing membrane thickness, in combination with defect abatement with a thin polydimethylsiloxane (PDMS) layer. Two types
of inorganic selective layers including alumina and zeolite Y (zeolite Y has a silica-to-alumina ratio of their framework of three or
greater) were investigated. Membrane fabrication with growth of zeolite Y (ZY) into a continuous layer offers better selectivity,
lower processing cost, and is easier to scale-up than membrane fabrication with rapid modification of the top aluminum oxide
layer to form a microporous layer. A zeolite Y/polymer composite membrane was down-selected for further studies. Zeolite Y
layers can be grown from solutions at 95 °C; however, the zeolite Y layer requires long growth time, which was reduced to 1 hour
via application of a novel zeolite synthesis approach. The membrane system can be deposited on available polyethersulfone
supports, which are fabricated into 14-inch supports with a continuous fabrication machine.
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — zeolites and/or amine-containing polymer
Materials of Fabrication for Support Layer — polyethersulfone or polysulfone on non-woven fabric
Nominal Thickness of Selective Layer nm 150–250 150–250
Membrane Geometry — flat sheet spiral-wound sheet
Max Trans-Membrane Pressure bar can be 0.2–50 0.2–1.5
Hours Tested without Significant Degradation — 200 hours 200 hours
Manufacturing Cost for Membrane Material $/m2 20 20
Membrane Performance
Temperature °C 57 °C and 102 °C 57 °C
CO 2 Pressure Normalized Flux GPU or equivalent 800 GPU >800 GPU
CO 2 /H 2 O Selectivity — not determined not determined
α = 140–800 for
CO 2 /N 2 Selectivity — 20 CO 2 /80 N 2 with α >100 for flue gas conditions
p tot = 101 kPa
CO 2 /SO 2 Selectivity — not determined not determined
Type of Measurement — mixed gas mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — countercurrent
Packing Density m2/m3 about 1800
Shell-Side Fluid — air sweep
Flue Gas Flowrate kg/hr about 0.2
CO 2 Recovery, Purity, and Pressure %/%/bar >90%, >95%, 0.2–1.2 bar
Pressure Drops Shell/Tube Side bar about 0.05/0.05
Estimated Module Cost of Manufacturing and __$__
—
Installation kg/hr
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
708 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm mercury (Hg). For non-linear materials, the
dimensional units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa (SI units).
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture of
gases found in desulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube,
and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination
of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO 2 -rich) or retentate (flue gas) stream.
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Flue Gas Assumptions – Unless noted, flue gas pressure, temperature, and composition leaving the flue gas desulfurization
(FGD) (wet basis) should be assumed as:
Composition
Pressure Temperature vol% ppmv
psia °F CO 2 H2O N2 O2 Ar SO x NO x
14.7 135 13.17 17.25 66.44 2.34 0.80 42 74
Other Parameter Descriptions:
Membrane Permeation Mechanism – Surface adsorption and diffusion and molecular sieving for the zeolite selective layer;
solution-diffusion for the polymer cover layer; facilitated transport for amine-containing selective layer.
Contaminant Resistance – Fully resistant polymer and inorganic materials.
Flue Gas Pretreatment Requirements – Removal of particulates, possibly dehydration.
Membrane Replacement Requirements – Estimated approximately 4 years.
Waste Streams Generated – N 2 with water (H 2 O), about 1 percent CO 2 and minor impurities.
Process Design Concept – See Figure 3.
technology advantages
High CO 2 /N 2 selectivity and cost-effective separation principle.
R&D challenges
Synthesis and scale-up of sufficiently selective and permeable membranes.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
709
Appendix: Post-Combustion Membrane Technologies
status
The project was completed on December 31, 2015, resulting in the development of a pilot-scale continuous casting machine for
the fabrication of 14-inch polymer substrates and the development of a pilot-scale continuous membrane fabrication machine
for the deposition of zeolite particles on polymer substrates using a vacuum-assisted dip coating method, followed by coating
of the amine-containing polymer cover layer on the zeolite/polymer substrates. The pilot-scale amine-containing composite
membranes were rolled into spiral-wound modules and implemented in a two-stage CO 2 capture process. These membrane
modules were tested with real flue gas at the National Carbon Capture Center (NCCC), achieving >800 GPU of CO 2 permeance
and >150 CO 2 /N 2 selectivity. A process for rapid (1 hour) zeolite membrane growth, involving a continuous zeolite layer grown
within polymer support, was also developed.
available reports/technical papers/presentations
Ho, W., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” Final project review meeting presentation, Pittsburgh,
PA, February 2016. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/FE0007632-Project-
Meeting-Final-public-release-2-26-16.pdf.
Ho, W. “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” presented at the 2015 NETL CO 2 Capture Technology
Meeting, Pittsburgh, PA, June 2015. https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/W-Ho-OSU-
Inorganic-Polymer-Composite-Membranes.pdf.
Ho, W., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” presented at the Continuation Application Status
Meeting, Pittsburgh, PA, August 2014. https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-
combustion/FE0007632-Continuation-Application-Status-Mtg-public-release-8-11-14.pdf.
Ho, W., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” presented at the 2014 NETL CO 2 Capture Technology
Meeting, Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/W-Ho-
OSU-Inorganic-Polymer-Composite-Membranes.pdf.
Ho, W., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” presented at the 2013 NETL CO 2 Capture Technology
Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/W-Ho-OSU-Inorganic-
Polymer-Composite-Membranes.pdf.
Verweij, H., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” presented at the 2012 NETL CO 2 Capture
Technology Meeting, Pittsburgh, PA, July 2012. https://www.netl.doe.gov/File%20Library/events/2012/co2%20capture%20meeting/H-
Verweij-OSU-Composite-Membranes.pdf.
Verweij, H., “Novel Inorganic/Polymer Composite Membranes for CO 2 Capture,” project kickoff meeting presentation, December
2011. https://www.netl.doe.gov/File%20Library/Research/Coal/ewr/co2/NETL-kick-off.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
710 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
BENCH-SCALE, HIGH-PERFORMANCE,
THIN FILM COMPOSITE HOLLOW FIBER
MEMBRANE FOR POST-COMBUSTION technology maturity:
CARBON DIOXIDE CAPTURE Bench-Scale, Simulated
Flue Gas
primary project goals project focus:
Composite Hollow Fiber
General Electric Global Research (GE) is developing high-performance, thin film polymer Membranes
composite hollow fiber membranes and advanced processes for economical post-
combustion carbon dioxide (CO2) capture. The project includes bench-scale testing to tune participant:
the properties of a novel phosphazene polymer membrane and decrease costs through
General Electric Global
development of innovative fabrication techniques.
Research Center
technical goals project number:
FE0007514
• Optimize phosphazene polymer and coating solution: Synthesize phosphazene
polymer, optimize separation performance, and develop processable coating NETL project manager:
solutions.
Isaac Aurelio
• Fabricate hollow fiber support layer: Produce highly porous, robust hollow fiber [email protected]
supports with controlled surface porosity from commercially available materials.
• Fabricate composite coated hollow fiber membranes: Develop processes to apply thin principal investigator:
layer coatings on hollow fiber supports and elucidate fundamental polymer Paul Glaser
properties.
General Electric
• Test membranes at bench-scale under flue gas conditions: Exposure and performance [email protected]
test materials and membranes under flue-gas conditions.
• Conduct process evaluation and module design: Conduct technical and economical partners:
process evaluation and module design and fabrication.
Idaho National
Laboratory,
technical content Western Research
Institute,
GE and partners are developing a high-performance, thin film polymer composite hollow Georgia Institute of
fiber membrane and advanced process for economical post-combustion CO2 capture. The Technology
project utilizes novel phosphazenepolymeric materials to produce an economical and
scalable composite hollow fiber membrane module. performance period:
The membrane will be optimized at bench-scale, including tuning the properties of the 10/1/11 – 12/31/14
phosphazene polymer in a coating solution and fabricating highly engineered porous
hollow fiber supports. The project will also define the processes for coating the fiber
support to manufacture thin, defect-free composite hollow fiber membranes.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 711
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
Figure 1: GE Test Rig – Flat Sheet and Hollow Fiber Membranes
The physical, chemical, and mechanical stability of the materials (individual and composite) to flue gas components will be
evaluated using exposure and performance tests. Membrane fouling and cleanability studies will define long-term performance.
GE and the Georgia Institute of Technology (Georgia Tech) will work together on developing processes to apply the thin layer
coating formulations onto the hollow fiber supports. GE will leverage the knowledge gained from using its flat sheet film coating
apparatus to enable development of the continuous dip process for coating of hollow fiber membrane supports. Georgia Tech will
use the in situ process developed to coat porous cellulose acetate hollow fibers with defect-free layers as a benchmark, which will
be further adapted to obtain thin, defect-free coated layers. Both the continuous dip coating and batch in situ processes will be
optimized to provide economical and scalable coated composite hollow fiber membranes.
Figure 2: Georgia Tech Hollow Fiber Fabrication Line
Working with Idaho National Laboratory, Georgia Tech will characterize phosphazene material properties in films cast on porous
polymer supports to elucidate polymer properties including aging, membrane fouling, and cleanability. The characterization
techniques will enable a better understanding of polymer and composite membrane performance. Membrane performance
validation testing under flue-gas conditions will be performed at Western Research Institute’s coal combustion test facility. Module
design and technical and economic feasibility analyses will be conducted to evaluate the overall performance and impact of the
process on the cost of electricity.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
712 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
TABLE 1: PROCESS PARAMETERS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer — phosphazene
Materials of Fabrication for Support Layer — polymer
Nominal Thickness of Selective Layer µm 1–10 <1
Membrane Geometry — flat sheet/hollow fiber hollow fiber
Max Trans-Membrane Pressure bar 2–5 up to 10
200 (flat sheet)
Hours Tested Without Significant Degradation — 100 (hollow fiber)
100–1,000
Manufacturing Cost for Membrane Material $/m2 — —
Membrane Performance
Temperature °C 30 and 65 30 and 60
50–275 Barrer (flat sheet 30 °C)
1,000–2,500 GPU
CO2 Pressure Normalized Flux GPU or equivalent 100–425 Barrer (flat sheet 65 °C)
(hollow fibers)
up to 70 GPU (hollow fibers 35 °C)
CO2/H2O Selectivity — 8–10 8–10
15–20 (65 °C) flat sheet
CO2/N2 Selectivity — 30–40 (30 °C) flat sheet 30–40
10–35 (35 °C) hollow fibers
CO2/SO2 Selectivity — not tested non tested
Type of Measurement — mixed gas mixed gas
Proposed Module Design (for equipment developers)
Flow Arrangement — countercurrent
Packing Density m2/m3 >1,000
Shell-Side Fluid — retentate
Flue Gas Flowrate kg/hr <1
CO2 Recovery, Purity, and Pressure %/%/bar >90%, 60–80%, 0.2–1 bar
Pressure Drops Shell/Tube Side bar 1–4
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cmHg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture of gases
found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 713
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Solution-diffusion mechanism.
Contaminant Resistance – Phosphazene-based membranes have been tested to be resistant to contaminant species such as oxygen
(O2), nitrogen oxide (NOx), sulfur dioxide (SO2), and moisture present in coal flue gas.
Flue Gas Pretreatment Requirements – Fly ash particulate removal.
Membrane Replacement Requirements – Membranes found to be stable with up to 200 hours of testing. Long-term stability tests
are currently in progress.
Waste Streams Generated – Acidic water condensate stream.
technology advantages
• Surface property optimization to reduce fly ash adhesion.
• Highly scalable, low-cost hollow fiber support platform.
• Ease of cleaning should provide longer membrane life.
• Phosphazene polymer with high permeability and selectivity.
R&D challenges
• Fouling potential from fly ash/particulates.
• Permeability and selectivity at 60 °C lower than anticipated.
• Large membrane area requirements and process integration.
results to date/accomplishments
• Synthesized phosphazene polymer, characterized separations performance under realistic flue gas conditions, and developed
hollow fiber support coating solutions.
• Developed engineered, high-porosity, hollow fiber supports.
• Built/upgraded bench-scale membrane coating and testing facilities.
• Completed initial process technical and economic feasibility study.
• Fabricated phosphazene coated defect-free hollow fiber membranes.
• Membrane performance studies conducted showed stability over >100 hours of testing.
next steps
• Optimize phosphazene polymer coatability on hollow fiber supports.
• Optimize the continuous dip and batch coating processes to provide economical and scalable coated composite hollow fiber
membranes.
• Continue testing of coated composite hollow fiber membranes at bench scale under flue gas conditions.
• Conduct final technical and economic feasibility analyses and an environmental, health, and safety assessment.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
714 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
available reports/technical papers/presentations
Bhandari, D., et al., “Composite Hollow Fiber Membranes for Post Combustion CO2 Capture,” presented at the 2014 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/D-Ajit-Bhandari-GE-Composite-
Hollow-Fiber-Membranes.pdf.
Bhandari, D., et al., “Composite Hollow Fiber Membranes for Post Combustion CO2 Capture,” presented at the 2013 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/DBhandari-GEGR-2013-CO2-NETL-Conference.pdf.
Bhandari, D., et al., “Composite Hollow Fiber Membranes for Post Combustion CO2 Capture,” presented at the 2013 North
American Membrane Society Meeting, Boise, ID, June 2013.
http://www.netl.doe.gov/File%20Library/Research/Coal/ewr/CO2/GEGR-2013-CO2-NAMS-Conference.pdf.
Bhandari, D., et al., “Composite Hollow Fiber Membranes for Post Combustion CO2 Capture,” presented at the 2012 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2012.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 715
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
LOW-PRESSURE MEMBRANE
CONTACTORS FOR CO2 CAPTURE
technology maturity:
primary project goals
Bench-Scale, Simulated
Membrane Technology and Research (MTR) is developing a new type of membrane
and Actual Flue Gas
contactor (or mega-module) to decrease capture costs, energy use, and system footprint
through bench-scale testing of a module with a membrane area that is 100 m2, 5 times project focus:
larger than that of current modules used for carbon dioxide (CO2) capture. Low-Pressure Membrane
Contactors (mega-
technical goals module)
participant:
• Develop a module design to reduce energy cost by lowering module pressure drop.
Membrane Technology and
• Develop a module design with a large membrane area.
Research, Inc.
• Develop a module design to reduce manifold complexity, footprint, and cost.
project number:
technical content FE0007553
MTR is developing a new type of membrane contactor (or mega-module) to separate CO2 NETL project manager:
from power plant flue gas. This module membrane area is 100 m2, which is 4–5 times Morgan Mosser
larger than that of current modules used for CO2 capture. The countercurrent sweep [email protected]
module is crucial to the MTR-developed CO2 removal from flue gas process, as this
membrane module permits the use of air as a sweep gas, which increases the CO2 flux principal investigator:
through the membrane without requiring additional compression energy. This means the
CO2 concentration in the flue gas is increased at a minimal energy cost.
Richard Baker
Membrane Technology and
Research, Inc.
[email protected]
partners:
University of Toledo
performance period:
10/1/11 – 9/30/14
Figure 1: Two-Stage Membrane CO2 Capture Process
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
716 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
TABLE 1: PROCESS PARAMETERS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer proprietary polymer
Materials of Fabrication for Support Layer proprietary polymer
Nominal Thickness of Selective Layer µm <1 <1
Membrane Geometry plate-and-frame plate-and-frame
Max Trans-Membrane Pressure bar 70 70
Hours Tested Without Significant Degradation 500 500
Manufacturing Cost for Membrane Material $/m2 100 10
Membrane Performance
Temperature °C 30 30
CO2 Pressure Normalized Flux GPU or equivalent 1,500 >2,500
CO2/H2O Selectivity — 0.5 0.5
CO2/N2 Selectivity — 50 50
CO2/SO2 Selectivity — 0.5 0.5
Type of Measurement — pure gas pure gas
Proposed Module Design (for equipment developers)
Flow Arrangement — cross-flow
Packing Density m2/m3 1,000
Shell-Side Fluid — N/A
Flue Gas Flowrate kg/hr 5,000
CO2 Recovery, Purity, and Pressure %/%/bar 90%, >96%, 140 bar
Pressure Drops Shell/Tube Side bar feed: 0.1; sweep:0.2
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; target permeance and selectivities should be for mixture of gases
found in de-sulfurized flue gas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (CO2-rich) or retentate (flue gas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 717
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
Other Parameter Descriptions:
Contaminant Resistance – The membranes are known to be unaffected by water (H2O), oxygen (O2), and sulfur dioxide (SO2). The
effect of trace contaminants, such as mercury, arsenic, etc., is unknown and is being examined in the ongoing field demonstration at
the National Carbon Capture Center (NCCC) in Wilsonville, AL, under a different U.S. Department of Energy National Energy
Technology Laboratory (DOE/NETL)-sponsored project (DE-FE0005795).
Flue Gas Pretreatment Requirements – Currently, pretreatment requirements are unknown. The current demonstration tests at
NCCC treat post-flue gas desulfurization (FGD) flue gas and will help determine the need for gas treatment prior to entering the
membrane system. The greatest concern of species present in flue gas is that particulate matter will foul the membranes, reducing
module lifetimes. Particulate filters that can achieve an order of magnitude better ash removal than a standard bag house, and are
used today to treat refinery and gasification streams, may be needed.
Waste Streams Generated – The membrane process will recover >95 percent of the H2O in flue gas as liquid. The quality of this
H2O and its potential to be reused in the plant will be studied in future work.
technology advantages
• In flue gas applications, the novel countercurrent sweep module recycles CO2 to the boiler with an air sweep, which increases
the CO2 concentration in the flue gas with minimal energy input.
• The recycle of CO2 to the boiler increases the concentration of CO2 in the flue gas, which could make the CO2 capture process
easier for technologies other than membranes.
• The novel countercurrent sweep module design has low-pressured drop, which reduces the energy costs.
• Mega-modules (500 m2 or larger) reduce the manifolding complexity, footprint, and cost of the membrane system.
R&D challenges
• The novel sweep plate and framed design will need to overcome several issues, including sweep-side pressure drop, poor
utilization of the membrane area due to module geometry, and non-uniform flow patterns.
• Spacer design and selection needs to maximize packing density and mechanical support while minimizing pressure drop.
• Scaleup issues associated with building membrane modules 10–20 times larger than conventional modules.
results to date/accomplishments
• Completed design and fabrication of various 20-m2 prototype membrane modules.
• Completed pressure drop and CO2 separation performance testing of various 20-m2 prototype membrane modules with bench-
scale lab test system
• Completed design and construction of larger lab test system, sized for parametric studies of 100-m2 membrane modules.
• Conducted CFD simulations of various sweep module designs that incorporate pressure drop, velocity profiles, and mass
transfer.
• A large sweep module test unit was designed and assembled at MTR for all pure-gas, pressure drop, and CO2 separation
performance testing of 100 m2 modules. The pressure drop through the plate-and-frame module is more than 10-fold lower
than that through the best modified spiral module, significantly lower than the project target of 1.5 psi, and demonstrate
substantial energy savings for the membrane capture process.
• A CFD comparative analysis of crossflow and countercurrent sweep membrane modules demonstrated that
countercurrent/sweep modules require 35 percent less membrane area than crossflow modules to remove the same amount of
CO2, but the pressure drop through crossflow modules was lower.
• A 500-m2 sweep membrane module skid was designed and fabricated for field testing. A pressure vessel with five 100-m2
membrane modules can be run individually or as a group. The skid was designed for integration into the existing MTR 20-tpd
CO2 capture pilot test unit for testing at NCCC in Wilsonville, AL. The 500-m2 sweep module skid is to be tested at NCCC in
early 2015.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
718 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Membrane Technologies
• A detailed performance and economic analysis of the MTR membrane CO2 capture process with low-pressure sweep modules
was performed. The methodology used by MTR to evaluate the membrane process is consistent with Case 10 of the 2010 DOE
report: Econamine was used to capture 90 percent of the flue gas CO2. The “all membrane” case demonstrates savings over the
Econamine CO2 capture process, but the cost is still higher than the DOE target of $40/tonne CO2 captured.
next steps
This project ended on September 30, 2014.
available reports/technical papers/presentations
Baker, R., et.al, “Low-Pressure Membrane Contactors for CO2 Capture,” presented at the 2014 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/R-
Baker-MTR-Low-Pressure-Membrane-Contactors.pdf.
Baker, R., et.al, “Low-Pressure Membrane Contactors for CO2 Capture,” presented at the 2013 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/R-Baker-MTR-Low-
Pressure-Membrane-Contactors.pdf.
Baker, R., et.al, “Low-Pressure Membrane Contactors for CO2 Capture,” presented at the 2012 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2012.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 719
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
720 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 721
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
722 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 723
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
724 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 725
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
726 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 727
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
728 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 729
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
730 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 731
Appendix: Post-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
732 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Post-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 733
Appendix: Post-Combustion Membrane Technologies
this page intentionally left blank
NATIONAL ENERGY TECHNOLOGY LABORATORY
734 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
POST-COMBUSTION
NOVEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
735
Appendix: Post-Combustion Novel Concepts
Supersonic Post-Combustion technology maturity:
Bench-Scale, Simulated Flue
Inertial CO2 Extraction System Gas
project focus:
primary project goals Supersonic Inertial CO2
Extraction System
Orbital ATK, Inc. (OA) developed an inertial carbon dioxide (CO 2 ) extraction system
(ICES) that converts CO 2 from flue gas to solid CO 2 (dry ice) using supersonic expansion participant:
followed by inertial separation. The project included bench-scale testing of the system Orbital ATK, Inc.
with simulated flue gas.
project number:
technical goals FE0013122
• Demonstrate ICES at bench-scale including condensation, migration, CO 2 removal, predecessor projects:
and diffusion of the CO 2 -depleted flue gas to atmospheric pressure. N/A
• Develop approach to obtain condensed CO 2 particle size required for effective
migration and separation. NETL project manager:
• Demonstrate pressure recovery efficiency of system consistent with economic Andrew O’Palko
goals. [email protected]
• Demonstrate CO 2 capture efficiency. principal investigator:
Dr. vladimir Balepin
technical content Alliant Techsystems
Operations LLC
Orbital ATK, Inc. designed an inertial CO 2 extraction system (ICES) that aims to achieve [email protected]
an overall reduction in total carbon capture cost for post-combustion CO 2 capture. The
ICES system, shown in Figure 1, is derived from aerospace applications and is based on partners:
supersonic inertial separation technology. Compressed flue gas is directed to a ACENT Laboratories LLC;
converging-diverging nozzle and undergoes supersonic expansion (high velocity, low Electric Power Research
pressure and temperature), which results in CO 2 desublimation. Turning the supersonic Institute; Ohio State
flow in the curved flow path causes inertial separation of the dense, solid CO 2 particles, University, New York State
which are collected in a CO 2 -rich stream through a duct in the wall into a cyclone Energy Research and
separator where the CO 2 solids are collected. The CO 2 -depleted stream is diffused and Development Authority,
sent to the stack. worleyParsons Group, Inc.
Factors for improved performance of the ICES system included controlling and start date:
increasing CO 2 particle size to increase migration and capture, pre-cooling of the flue
10.01.2013
gas to enable subsonic condensation and promote heterogeneous nucleation for
larger particles, and efficient pressure recovery. The compact design, along with
efficiencies in CO 2 capture, reduces costs of the carbon capture system. An initial
percent complete:
techno-economic assessment by Worley Parsons estimated a $41.80/tonne CO 2 100%
captured for an ICES plant, with cost savings coming from lower capital costs (smaller
equipment), lower operating costs (no moving parts, chemicals or media), and
improved capture efficiency compared to a typical amine solvent-based plant.
However, further studies found that more compression is required due to lower
pressure recovery than predicted and, therefore, a cost of >$50/tonne CO 2 captured is
anticipated. ICES is expected to have comparatively favorable economics for
applications requiring less capture and/or applications with lower CO 2 concentration
since compression costs scale with these parameters.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
736 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
Figure 1: ICES system
Lab-scale testing of the system in a previous project has shown that CO 2 particles of >2.5 µm is required to ensure efficient inertial
migration. Initial test results also proved that CO 2 only condenses on solid or liquid media in the flow (heterogeneous
condensation). This led to the conclusion that solid CO 2 seeding is the most viable path to 90 percent CO 2 capture by causing
flue gas CO 2 to condense on particles that are already >2.5 µm. Preliminary testing on a bench-scale apparatus (Figure 2) using
a liquid throttle to inject CO 2 of a controlled particle size in the duct demonstrated >50 percent capture of solid CO 2 and indicated
a higher amount of CO 2 captured with a lower inlet temperature. An approach was developed to recirculate a fraction of the
collected liquid CO 2 back to the inlet to achieve additional cooling at the inlet along with the creation of large “seeded” particles
to promote heterogeneous nucleation capable of migration. However, compression requirements would further increase with
this method since more energy would be needed to accelerate the added mass of the recycled CO 2 to high speed. Based on
thermodynamic analyses, a method for pre-cooling of the flue gas using captured CO 2 as a “cold sink” was determined to be the
best approach. This pre-cooling enables subsonic condensation of a small quantity of CO 2 (and trace water) resulting in “in situ”
seeding without the need to recirculate solid CO 2 . Testing of a subsonic ICES system with pre-cooling by liquid nitrogen showed
that a significant amount of CO 2 condensed into large CO 2 particles with an average size of 30–40 µm.
Figure 2: Bench-scale ICES test apparatus illuminated with laser sheet
Scaling the technology for use in a full-scale power plant involves combining multiple ICES units for increased capacity. The
compactness of the group of ICES units, as shown in the proposed plant configuration in Figure 3, leads to substantial reductions
in the footprint capture plant compared to a similar capacity capture plant using amine solvent capture technology (8,000 m2 vs.
20–30,000 m2). Stacking the ICES nozzles and compressors further reduces the footprint.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
737
Appendix: Post-Combustion Novel Concepts
Figure 3: ICES plant layout and footprint
Definitions:
Inertial Separation – Method that uses a rapid change in air direction and principles of inertia to separate particulate from an air
stream.
Heterogeneous nucleation – Process that occurs in the formation of a crystal from a solution, liquid, or vapor, in which
particles become arranged in a pattern characteristic of a crystalline solid, forming a site upon which additional particles are
deposited as the crystal grows.
technology advantages
• No moving parts, chemicals/additives, or consumable media.
• No refrigeration expense—low temperatures from supersonic expansion.
• Inexpensive construction based on sheet metal and concrete.
• Small equipment footprint.
• “Cold sink” available from accumulated solid CO 2 .
• Costs driven by flue gas compression.
R&D challenges
• Development of optimized supersonic contour to maximize particle size and migration and minimize pressure losses.
• Minimization of slip gas that is removed with solid CO 2 .
• CO 2 purity—condensable flue gas impurities removed along with CO 2 .
• Solid CO 2 processing.
• Optimization of flow path pressure recovery.
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
738 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
status
Testing of a bench-scale capture duct/diffuser system achieved ≥50 percent CO 2 capture. Testing of a subsonic ICES test article
demonstrated large CO 2 particle formation through partial subsonic condensation enabled by pre-cooling of the flue gas. The
pre-cooling approach addresses the increase in compression requirements that evolved from thermodynamic modeling efforts.
Future work will continue optimization of the ICES for a range of CO 2 concentrations and/or CO 2 capture levels to identify the
most favorable operating conditions.
available reports/technical papers/presentations
“Supersonic Post-Combustion Inertial CO 2 Extraction System,” Final Report, April 2017.
https://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/Final-Report-ATK-FE0013122-April-
2017.pdf
Castrogiovanni, A., Balepin, V., Robertson, A., Calayag, B., “Supersonic Post-Combustion Inertial CO 2 Extraction System,” presented at
the 2016 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, August 2016.
https://www.netl.doe.gov/File%20Library/Events/2016/c02%20cap%20review/3-Wednesday/T-Castrogiovanni-ACENT-Supersonic-
Inertial-CO2-Extraction.pdf
Balepin, V., Castrogiovanni, A., Robertson, A., Tyll, J., “Supersonic Post-Combustion Inertial CO 2 Extraction System,” presented at the
2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
https://www.netl.doe.gov/File%20Library/Events/2015/co2captureproceedings/A-Castrogiovanni-AL-Supersonic-CO2-Extraction.pdf
Balepin, V., Castrogiovanni, A., Robertson, A., Calayag, B., “Supersonic Post-Combustion Inertial CO 2 Extraction System,” presented at
the 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/A-Castrogiovanni-ATK-Supersonic-Post-
Combustion.pdf
“Supersonic Post-Combustion Inertial CO 2 Extraction System,” Kickoff Presentation, November 2013.
http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/post-combustion/11-14-2013-NETL-ICES-Kickoff-
Nonproprietary.pdf
CARBON CAPTURE TECHNOLOGY SHEETS POST-COMBUSTION NOvEL CONCEPTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 739
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
NOVEL CONCEPTS FOR THE
COMPRESSION OF LARGE VOLUMES
OF CO2 technology maturity:
Pilot-Scale, 90 tonnes/hr
primary project goals
project focus:
Southwest Research Institute (SwRI) is developing novel compression technology Evaluation of
concepts to reduce carbon dioxide (CO2) compression power requirements by 10 percent Compression Efficiency
compared to conventional compressor designs. The basic concept is a semi-isothermal Improvements
compression process where the CO2 is continually cooled using an internal cooling jacket
rather than using conventional interstage cooling. The project includes thermodynamic participant:
testing (Phase I), prototype testing (Phase II), and a full-scale demonstration of a
multistage, internally cooled diaphragm pilot test (Phase III).
Southwest Research
Institute
technical goals project number:
FC26-05NT42650
Phase III
• Design and construct a pilot-scale demonstration of a multistage internally cooled NETL project manager:
compressor diaphragm design. Travis Shultz
• Complete a comprehensive thermodynamic and cost analysis of both pulverized coal [email protected]
(PC) and integrated gasification combined cycle (IGCC) plant incorporating the new
compression technology. principal investigator:
• Design a multistage diaphragm and test loop. Jeffery Moore
• Design, fabricate, and test a third-generation cooled diaphragm and test in a single- Southwest Research
stage test rig. Institute
[email protected]
technical content partners:
Dresser-Rand
In the cooled diaphragm concept, the gas is continually cooled after each stage in the flow
path through the compressor. A cooling jacket insert is used in the diaphragm of each
stage to provide continuous cooling. Figure 1 shows a conceptual design for an internally performance period:
cooled compressor. The flow of the CO2 is shown in red, while the cooling liquid is 9/28/2005 – 6/30/2014
shown in blue.
SwRI examined a number of different compression options to find the ones that would
consume the least amount of power. Figure 2 shows how two hypothetical compression
processes can achieve the same pressure, but still consume different quantities of power.
The isothermal compression, even at 60 percent efficiency, requires less power than the
isentropic compression at 100 percent efficiency. Therefore, efficiency alone cannot be
used as a figure of merit for the compression process.
Figure 3 shows the pressure/enthalpy curves for six of the options examined by SwRI.
While liquefaction and pumping is a viable option and may be superior to a pure
compression route in cold climates, the semi-isothermal compression proved to be
superior when all of the heat exchanger performance and other losses were taken into
account.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
NATIONAL ENERGY TECHNOLOGY LABORATORY
740 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
Figure 1: Design for an Internally Cooled Compressor
Figure 2: Example of Path Dependency of Compression Power
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 741
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
Figure 3: Required Compression Power for the Investigated Technology Options
Table 1 presents a description of the compression and cooling technology options and the resultant power requirements for the U.S.
Department of Energy (DOE) 550-megawatt (MW) PC reference power plant with carbon capture using an amine process
(≈1.3 million lb/hr CO2 stream, Ramezan 2007)
• Single stream inlet pressure/temperature = 14.8 psia/115 °F
• Discharge pressure = 2,150 psia
• Intercooler/after-cooler exit temperature = 115 °F
The following configurations were analyzed for power comparisons:
1. DOE baseline (efficiencies and refrigeration/ liquefaction cycle performance calibrated to match data in [1])
2. Back-to-back LP and HP compressors with uncooled diaphragms
3. Back-to-back LP and HP compressors with cooled diaphragms, 15 percent effectiveness, 85 °F cooling water
4. Back-to-back LP and HP compressors with cooled diaphragms, 20 percent effectiveness, 85 °F cooling water
The power calculations in this analysis include gas horsepower for compression, cooling horsepower required for liquefaction,
pumping horsepower, and gearbox power losses of 2 percent. The estimates exclude bearing and windage losses and power required
for the pumping and chilling of cooling water.
The overall compression system analysis results for the methods shown above are displayed in Table 1. A back-to-back compressor
with a cooled diaphragm is expected to achieve 10.4–11.7 percent power savings (15–20 percent effectiveness) relative to the DOE
baseline case.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
NATIONAL ENERGY TECHNOLOGY LABORATORY
742 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
TABLE 1. OVERALL COMPRESSION POWER SAVINGS ANALYSIS RESULTS
Assumed
Case Power
HX
Description Savings
Effectiveness
DOE Baseline NA 0%
D-R B2B LP and HP Uncooled Diaphragm 0% 6.6%
D-R B2B LP and HP with Cooled Diaphragm 15% 10.4%
D-R B2B LP and HP with Cooled Diaphragm 20% 11.7%
The goal of the current work was to develop and construct a pilot-scale demonstration compression plant to optimize CO2
compression, as well as perform a balance of plant measurement for total power required and savings realized by improving on the
technology developed in Phase II, but in a multi-stage version of the cooled diaphragm design. A new compressor, based on a Dresser-
Rand DATUM® D12 frame size, consisted of a six-stage, back-to-back centrifugal compressor (D12R6B) that incorporated the
cooled diaphragms. A new test loop with required coolers, valves, and piping was constructed to test this new compressor. The cooled
diaphragm, compressor, and loop design, commissioning, and testing will be discussed in this paper. The compressor impeller
selection was made for an adiabatic compressor for the design point of 15 psia (1.03 bara) to 250 psia (17.2 bara) for a mass flow of
15.1 lbm/sec (6.85 kg/s). This flow is equivalent to the CO2 produced by a 35 MW coal fired power plant. The design speed of the
compressor is 11,403 rpm and is driven by a 3 MW electric motor through a speed increasing gearbox.
The compressor package was delivered and set, leveled, and bolted to 20 sub-sole plates (Figure 4). Hand valves, control valves,
orifice plates, flow conditioners, strainers, and the cooling tower were received and installed. The heat exchangers and piping were
assembled and the cooling water supply was tested through the process heat exchangers. The completed pipe assembly is shown in
Figure 5. A venting control valve is also used to maintain the desired suction pressure to the compressor. Cooling water was provided
to the heat exchangers and compressor diaphragm via an 800 gpm evaporative cooling tower.
Figure 4. Installed Dresser-Rand Datum Compressor Package
The compressor package and pipe loop were commissioned, including oil flush, pipe alignment, shaft alignment, and mechanical
testing. All mechanical parameters of the compressor met manufacturer’s specifications.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 743
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
Figure 5. Pipe Loop Assembly Aerial View
Several compressor operating configurations were tested in order to verify compressor performance and determine the effects of the
cooled diaphragms. The adiabatic tests (with no cooling water) showed close correlation to the predicted aerodynamic performance
maps. These tests established a baseline temperature distribution and power. The liquid cooling system was commissioned and tuned
to provide the correct flow distribution to the diaphragms. The subsequent cooled diaphragm testing showed similar head-flow
characteristic curves, but slightly higher head and pressure ratio for a given flow due to the increased volume reduction caused by
lower stage discharge temperatures.
The polytropic head for varying flow rates from Test 1 is plotted in Figure 6 for the two sections. The adiabatic test points are shown
in blue, and the data points for testing with cooling water at the two different flow rates are shown in red and green. The solid black
line denotes the predicted adiabatic curve. All data are normalized with respect to the adiabatic test data at the design flow.
The measured adiabatic data were reasonably close to the predicted adiabatic curve, with polytropic head for Sections 1 and 2
measured to be slightly lower and higher than predicted near the design point, respectively. The data also showed that diaphragm
cooling changed the characteristics of the speed line slightly by increasing the volume flow capacity for each section, particularly near
the choke side of the map. This performance change is attributed to the gas volume reduction that occurred as the gas was cooled in
the diaphragm, which caused the latter stages in each section to stay out of choke and operate closer to their design point. The opposite
would be true at low flow operation allowing the flow range to be extended by shutting off cooling flow when operating near the surge
line. Since the introduction of cooling water affected the head characteristics, the speed during the cooled tests was reduced to match
identical discharge pressure as the adiabatic test in order to allow a direct comparison on power.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
NATIONAL ENERGY TECHNOLOGY LABORATORY
744 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
1.15
1.1
Section 1 Normalized Polytropic Head
1.05
0.95
0.9
Adiabatic 11403 rpm
Cooled Normal Flow 11403 rpm
0.85
Cooled High Flow 11403 rpm
Predicted 11403 rpm
0.8
0.75
0.75 0.8 0.85 0.9 0.95 1 1.05 1.1 1.15
Section 1 Normalized Inlet Flow
Figure 6. Section 1 Normalized Polytropic Head vs. Normalized Flow (Test 1)
Internal temperature measurements were taken at various points along the compressor. At each of these points, several temperature
and pressure measurements were taken at different circumferential locations. These data points were averaged to get a temperature and
pressure at each location. For both the adiabatic and cooled cases, the predicted design point temperature was plotted against the actual
design point temperature in Figure 7 for Section 1. These results indicate that the adiabatic temperature rise was slightly higher than
predicted and cooled temperatures were slightly lower than predicted but showed good agreement overall. The measured discharge
temperature was over 100 °F lower for the cooled case.
Test 2
1
Cooled Design Point
0.9 Adiabatic Design Point
Normalized Design Point Temperature, deg F
Predicted Adiabatic Design Point
Predicted Cooled Design Point
0.8
0.7
0.6
0.5
0.4
0.3
0.2
Suction Stg 1-2 RC Stg 2 IGV Stg 2-3 RC Stg 3 IGV Discharge
Station
Figure 7. Section 1 Comparison with Predicted Normalized Temperature for Design Flow Conditions
The data show that the cooled diaphragms reduce power consumption by 3–8 percent when the compressor is operated as a back-to-
back unit, with the higher power savings at high flow operating points using the high speed torquemeter for reference as shown in
Table 2. Additional performance savings could be realized by adding more stages and running the compressor at a slower speed.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 745
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
TABLE 2. HORSEPOWER PERCENT SAVINGS WITH INTERCOOLER
Adiabatic versus Cooled
Point
Diaphragm Difference (%)
1 7.99
2 6.28
3 (design PR) 3.24 (predicted 2.9%)
4 3.03
5 3.01
6 3.32
The results from Test 3 (no intercooling to simulate a straight-through compressor), as shown in Table 3, showed even higher power
savings of 9 percent at the design point when matching pressure ratio and speed. Based on the trends seen in back-to-back testing,
power savings are expected to be even higher at higher flows exceeding the 10 percent goal of this program.
TABLE 3. HORSEPOWER PERCENT SAVINGS WITH NO INTERCOOLER
Power Savings (%) Power Savings (%)
A. Matching speed and pressure ratio B. Matching flow and pressure ratio
5.64 9.00
technology advantages
• New compression process could use up to 10 percent less power compared to commercially available inline centrifugal
compressors.
• Applicable to all types of power plants, including PC, IGCC, and oxy-fuel.
• Could result in significant capital savings and reliability improvement compared to an integrally geared compressor.
• Inline compressors are scalable to large power plants, and their reliability is well proven in LNG and Ethylene service.
R&D challenges
• The wide range of CO2 output from the power plant based on required electrical output.
• Carbon dioxide compression technology must have high reliability.
• IGCC plants contain multiple CO2 streams at different pressures.
• The volume reduction during the compression can exceed 500:1.
results to date/accomplishments
• Development complete of multistage internally cooled diaphragm.
• Detailed design of Dresser-Rand DATUM compressor with multistage cooled diaphragms is complete.
• Design of a closed-loop to test back-to-back compressor is complete.
• Pilot-scale demonstration compression plant was developed and constructed.
• Measured the CO2 baseline compressor performance with and without diaphragm cooling.
• Comparative testing of adiabatic and cooled tests at equivalent inlet conditions shows that the cooled diaphragms reduce power
consumption by 3–8 percent when the compressor is operated as a back-to-back unit and over 9 percent when operated as a
straight-through compressor with no intercooler.
• The power savings, heat exchanger effectiveness, and temperature drops for the cooled diaphragm were all slightly higher than
predicted values.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
NATIONAL ENERGY TECHNOLOGY LABORATORY
746 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Post-Combustion Novel Concepts
next steps
This project ended on June 30, 2014.
available reports/technical papers/presentations
Moore, J.J.; et al., “Novel Concepts for the Compression of Large Volumes of CO2,” presented at the 2013 NETL CO2 Capture
Technology Meeting, July 2013. http://www.netl.doe.gov/File%20Library/events/2013/CO2%20capture/J-Moore-SWI-Concepts-
for-Compression-of-Large-Volumes-of-CO2.pdf.
Moore, J.J.; et al., “Advance Centrifugal Compression and Pumping for CO2 Applications,” presented at the 2012 NETL CO2
Capture Technology Meeting, July 2012. http://www.netl.doe.gov/File%20Library/Events/2012/CO2%20Capture%20Meeting/J-
Moore-SRI-CO2-Compression.pdf.
Moore, J.J.; et al., “Novel Concepts for the Compression of Large Volumes of CO2,” presented at the 2010 NETL CO2 Capture
Technology Meeting, Pittsburgh, PA, September 2010.
Moore, J.J.; et al., “Novel Concepts for the Compression of Large Volumes of CO2 – Phase II,” presented at the Annual NETL CO2
Capture Technology for Existing Plants R&D Meeting, Pittsburgh, PA, March 2009.
CARBON CAPTURE TECHNOLOGY SHEETS ADVANCED COMPRESSION
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 747
Appendix: Post-Combustion Novel Concepts
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NATIONAL ENERGY TECHNOLOGY LABORATORY
748 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
PRE-COMBUSTION
SOLVENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
749
Appendix: Pre-Combustion Solvent Technologies
CO2 Capture from IGCC Gas technology maturity:
Pilot-Scale, Actual Syngas
Streams Using the AC-ABC (equivalent to 0.15 Mwe)
Process project focus:
CO2 Capture Using AC-ABC
Process
primary project goals
participant:
SRI International (SRI)’s goal was development of a carbon dioxide (CO2) capture SRI International
technology for integrated gasification combined cycle (IGCC)-based power plants that
uses a high-capacity and low-cost aqueous solution containing ammonium carbonate project number:
(AC) that reacts with CO2 to form ammonium bicarbonate (ABC). SRI partnered with
Bechtel Hydrocarbon Technology Solutions (BHTS) to use the Bechtel Pressure Swing FE0000896
Claus (BPSC) process to remove sulfur species from the recovered CO2 stream.
predecessor projects:
N/A
technical goals
NETL project manager:
• Test the technology on a bench-scale batch reactor to validate the concept. Steven Mascaro
• Determine the optimum operating conditions for a small pilot-scale reactor. [email protected]
• Design and build a small pilot-scale reactor capable of continuous, integrated
operation. principal investigator:
• Perform pilot-scale tests to evaluate the process in a coal gasifier environment. Anoop Nagar
• Perform a technical and economic evaluation of the technology. SRI International
[email protected]
technical content
partners:
The technology is based on the use of an aqueous ammoniated solution containing AC, Bechtel Hydrocarbon
which reacts with CO2 to form ABC. Technology Solutions, Inc.;
EIG, Inc.; National Carbon
Capture Center
start date:
09.30.2009
percent complete:
100%
Figure 1: Acid gas removal in a gasification system
The concentrated ammoniated solution is used to capture CO2 and hydrogen sulfide
(H2S) from synthesis gas (syngas) at high pressure. This high-pressure separation
technique reduces the size of the CO2 stripper, the CO2 compression needs, and the
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
750 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Solvent Technologies
electric power consumption relative to capture at lower syngas pressures. Figure 1 depicts the AC-ABC acid gas removal process
in the larger context of a coal gasification and syngas cleanup system.
Figure 2 depicts the flows within the AC-ABC process, showing how acid gases are removed from the syngas in the absorber
column, and how they are recovered as a separate gas stream in the stripping column. AC is a low-cost and readily available
reagent with high net CO2 loading capacity, requiring relatively low circulation of solvent between the CO2/H2S absorber and
CO2/H2S stripper. The ammonium carbonate is highly selective to CO2 and H2S at the lower temperatures of the gas and solvent
in the absorber (solvent entering column at 85 °F), while the solubility of hydrogen (H2), carbon monoxide (CO), and methane
(CH4) in the absorber solution is extremely low, resulting in minimal losses of syngas species in the absorber. Rich solvent exiting
the absorber is regenerated in the stripping column by increasing its temperature (solution entering column at 250 °F), causing
the CO2 and H2S to evolve as a relatively pure gas stream from the stripper. The pressure is relatively constant in this cycle, with
only the temperature being varied, classifying this a temperature-swing absorption cycle for acid gas removal from syngas.
Figure 2: Schematic of the CO2 and H2S capture system
Because the AC-ABC process removes a mixture of CO2 and H2S, it is necessary to separate the H2S to enable utilization or storage
of the CO2. Accordingly, the BPSC process was chosen for this purpose downstream from the AC-ABC unit. BPSC is a high-
pressure, sub dew point Claus system which recovers H2S directly from an acid gas stream in the form of elemental molten sulfur,
using SO2 as an oxidant. In this technology, multiple sub dew point reactors are used in rotation (Lead/Lag/Regeneration) similar
to a molecular sieve dehydration unit, a pressure swing absorption unit, or a low-pressure sub dew point Claus system. BPSC
allows recovery of sulfur species as elemental sulfur while maintaining system pressure. Due to the higher pressures compared
to traditional Claus units, equipment size is reduced. Figure 3 shows the basic process scheme of the BPSC system.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
751
Appendix: Pre-Combustion Solvent Technologies
Figure 3: Schematic of the Bechtel pressure swing Claus H2S removal system
In the BPSC process, SO2 (produced by oxidizing some of the product sulfur) is introduced to the acid gases (“feed gas”) and they
are heated indirectly by steam in the “reactor feed heater”. Then the mixture is fed to the first or primary on-line reactor (“primary
reactor”), where most of the H2S, carbonyl sulfide (COS), and SO2 are converted to sulfur and adsorbed on the catalyst. The gas
flows through a cooler (“reactor intercooler”), where it is cooled by generating steam. Provisions are made to accommodate any
sulfur that may condense at this location. Any recovered sulfur drains to a sulfur pit, and the vapor goes to the next reactor
(“secondary reactor/sulfur trap”), which acts as a sulfur trap/guard bed. The product gas is returned to the facility for compression.
After about 8–12 hours online, the primary reactor is rotated to regeneration, the secondary reactor moves up to the primary
position, and the regenerated reactor is switched to the secondary reactor position. The sulfur-loaded bed is partially
regenerated by pressure let down. Flash gas passes through a sulfur condenser and is recompressed in the Regen Recycle
Compressor and Regen Gas Compressor prior to being mixed into the BPSC feed stream. There is a heating and cooling cycle
(“Regeneration Heater & Cooler”) using recycled sweep gas to complete the reactor regeneration.
In 2016, SRI International and EIG Inc. were awarded a patent on the technology for simultaneous high-efficiency capture of CO2
and H2S from pressurized gas, which is at the core of the AC-ABC Process. For further information, refer to U.S. Patent No.
9,463,416 B2, dated October 11, 2016.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
752 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Solvent Technologies
TABLE 1: SOLVENT PROCESS PARAMETERS
Pure Solvent Units Current R&D value Target R&D value
Molecular Weight mol-1 nominal 18 nominal 18
Normal Boiling Point varies with pressure: varies with pressure:
°C
100 °C at 1 atm 100 °C at 1 atm
Normal Freezing Point nominal 0 °C, varies nominal 0 °C, varies
°C
with composition with composition
Vapor Pressure @ 15°C NH3 vapor pressure varies NH3 vapor pressure varies
bar with composition and with composition and
temperature temperature
Manufacturing Cost for Solvent cost of anhydrous ammonia
$/kg —
typically $200–$400/ton
Working Solution
Concentration kg/kg 0.1 kg NH3/kg 0.15 kg NH3/kg
Specific Gravity (15 °C/15 °C) - 1.1 1.1
Specific Heat Capacity @ STP kJ/kg-K 3.5 3.5
Viscosity @ STP cP nominal 1 nominal 1
Absorption
Pressure bar 20 30
Temperature °C 25 25–40
Equilibrium CO2 Loading varies with the composition varies with the composition
mol/mol
of the solution of the solution
Heat of Absorption kJ/mol CO2 40-60
Solution Viscosity cP nominal 1 nominal 1
Desorption
Pressure bar 30 30
Temperature °C <200°C —
Equilibrium CO2 Loading mol/mol varies with the composition varies with the composition
of the solution of the solution
Heat of Desorption kJ/mol CO2 — —
Proposed Module Design (for equipment developers)
Syngas Flowrate kg/hr 225
CO2 Recovery, Purity, and Pressure % / % / bar 90% >95% 30 bar
Absorber Pressure Drop bar <1 bar
Estimated Absorber/Stripper Cost of __$__
—
Manufacturing and Installation kg/hr
Definitions:
STP – Standard temperature and pressure (15 °C, 1 atm).
Pure Solvent – Chemical agent(s), working alone or as a component of a working solution, responsible for enhanced CO2
absorption (e.g., the amine monoethanolamine [MEA] in an aqueous solution).
Manufacturing Cost for Solvent – “Current” is market price of chemical, if applicable; “Target” is estimated manufacturing cost
for new solvents or the estimated cost of bulk manufacturing for existing solvents.
Working Solution – The solute-free (i.e., CO2-free) liquid solution used as the working solvent in the absorption/desorption
process (e.g., the liquid mixture of MEA and water).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
753
Appendix: Pre-Combustion Solvent Technologies
Absorption – The conditions of interest for absorption are those that prevail at maximum solvent loading, which typically occurs
at the bottom of the absorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO2
partial pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum solvent loading, which typically occurs
at the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent
(e.g., an MEA-based absorption system has a typical CO2 partial pressure of 1.8 bar and a reboiler temperature of 120 °C).
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the solution. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2.
Concentration – Mass fraction of pure solvent in working solution.
Loading – The basis for CO2 loadings is moles of pure solvent.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Chemical/Physical Solvent Mechanism –
NH4OH + CO2 ↔ NH4HCO3
(NH4)2CO3 + CO2 + H2O ↔ 2NH4HCO3
NH4(NH2CO2) + CO2 + 2H2O ↔ 2NH4HCO3
Solvent Contaminant Resistance – The solvent is expected to be resistant to several contaminants nominally present in an IGCC
gas stream. Hydrogen sulfide reacts with the solvent, but it can be removed during the regeneration. The ammonia (NH3) in the
IGCC may negate any NH3 loss from the solvent. The resistance of the solvent to trace metals is not known yet.
Solvent Foaming Tendency – Solvent foaming tendency was not observed in the bench-scale tests.
Syngas Pretreatment Requirements – The IGCC gas stream needs to undergo a water gas shift (WGS) reaction to convert CO to
CO2 and to be cooled to a temperature of 25–50 °C.
Solvent Makeup Requirements – The AC is a readily available commodity chemical, and the makeup requirements are estimated
to be small. However, the actual amount will be determined in the field test.
Waste Streams Generated – Ammonium sulfate solution from the capture of trace residual NH3 in the gas.
Process Design Concept – See Figures 1–3.
Proposed Module Integration – Note the module location, as well as the pressure, temperature, and composition of the gas
entering the module.
Composition
Pressure Temperature vol% ppmv
psia °F CO2 CO CH4 N2 H2 Ar H2S
185 68 13.4 0.03 0.6 74.4 10.1 0.6 2000
technology advantages
• Low-cost and stable reactive solution/solvent—low ammonia loss demonstrated in testing.
• Ammoniated solution is very effective in rapid absorption of CO2 at elevated pressure—CO2 capture efficiency greater than
99 percent demonstrated in testing.
• The reactive ammoniated solution has a high CO2 loading capacity (12 percent CO2 effective loading).
• H2S can be simultaneously absorbed along with CO2 in a single absorber column—H2S capture efficiency greater than 99
percent demonstrated in testing.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
754 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Solvent Technologies
• The absorption/loss of fuel gas species like H2, CO, and CH4 was very low as shown in testing—therefore high conversion of
CO in the syngas is not required to achieve 90 percent reduction of carbon emissions.
• CO2 stripping in the AC-ABC process can be accomplished at elevated pressures in the range of 20–50 bar, resulting in a 3–
7.5 pressure ratio to compress the gas to the pipeline pressure of 150 bar pressure—i.e., the availability of regenerated CO2
at elevated pressure significantly reduces the compressor requirements for CO2 sequestration.
• The AC-ABC process does not require compressors other than the CO2 compressor.
• Both the absorber and regenerator are operated at similar elevated pressure, reducing the need for pumping solvents across
pressure boundaries.
• Hot syngas from the shift reactor can be used as the main heat source for the CO2 stripping, reducing the power output
penalty.
• The BPSC process removes H2S from the high-pressure CO2 (or syngas) stream with minimal reduction in pressure, which
reduces the power output penalty.
• The BPSC process combines the function of three units (solvent, Claus, and Claus tail gas) into one. The thermal oxidizing
unit needed for the traditional approach is not needed with BPSC, reducing total carbon footprint.
R&D challenges
• Possible sulfating problem on beds of BPSC process catalyst.
• Difficulty in measurement/quantification of sulfur produced in the BPSC process at pilot scale.
• Difficulties in engineering packing or trays to effectively control ammonia emissions from the absorber at pilot scale.
status
The project was completed in September 2016. In the culmination of project activities, a 0.15-megawatt electric (MWe) integrated
pilot plant was constructed and operated, processing 500 lb/hr of shifted syngas from an air blown gasifier at the National Carbon
Capture Center in Wilsonville, Alabama, with total testing duration of over 700 hours. This successfully demonstrated use of the
AC-ABC process for carbon dioxide and sulfur capture from actual coal-derived syngas. System availability was considered to be
favorable, even at the pilot-scale level.
The results of the techno-economic analysis (with baseline case 750-MW IGCC plant using CO2 capture using conventional Selexol
and traditional Claus plant) indicate that the increase in cost of electricity (COE) with the AC-ABC process will be ~30 percent,
and the cost of CO2 captured is projected to be less than $27/metric ton of CO2 while meeting DOE’s 90 percent CO2 capture goal.
available reports/technical papers/presentations
Nagar, A. et al., “CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” Final Report, SRI Project P19207 and P21321,
Cooperative Agreement No. DE-FE0000896, SRI International, Menlo Park, CA, 16 February 2017.
“CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” presented at the 2014 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2014.
“CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” presented at the 2013 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2013.
“CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” presented at the 2012 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2012.
“CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” presented at the 2011 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, August 2011.
“CO2 Capture from IGCC Gas Streams Using AC-ABC Process,” presented at the 2010 NETL CO2 Capture Technology Meeting,
Pittsburgh, PA, September 2010.
“CO2 Capture from IGCC Gas Streams Using the AC-ABC Process,” presented at the Pre-Combustion CO2 Capture Kick-Off
Meetings, Pittsburgh, PA, November 2009.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
755
Appendix: Pre-Combustion Solvent Technologies
“Analysis of SRI AC-ABC and Bechtel Pressure Swing Claus Technologies for Pre-Combustion Carbon Capture,” presented at the
Eleventh Annual Conference on Carbon Capture, Utilization and Sequestration, Pittsburgh, PA, May 2012.
“Bechtel Pressure Swing Claus Sulfur Recovery,” presented at the International Pittsburgh Coal Conference, Pittsburgh, PA,
September 2009.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SOLvENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
756 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
PRE-COMBUSTION
SORBENT TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 757
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
EVALUATION OF DRY SORBENT
TECHNOLOGY FOR PRE- COMBUSTION
CO2 CAPTURE technology maturity:
Bench-Scale Using
primary project goals Simulated Syngas
project focus:
URS Group and the University of Illinois at Urbana-Champaign (UIUC) are developing
dry carbon dioxide (CO2) sorbent materials, through the coupling of thermodynamic, Sorbent Development for
molecular simulation, as well as process simulation modeling with novel synthesis WGS
methods, that possess superior adsorption and regeneration properties at conditions
applicable to water gas shift (WGS) systems. If successful, this project will demonstrate participant:
that one or more sorbent materials are able to remove greater than 90 percent of the CO2
from a simulated synthesis gas (syngas) at conditions applicable to a WGS reactor, thus
URS Group, Inc.
meeting a key U.S. Department of Energy (DOE) program objective.
project number:
FE-0000465
technical goals
NETL project manager:
Specific technical objectives of this project include:
Elaine Everitt
• Determination of optimal CO2 sorbent properties and operating conditions for CO2 [email protected]
removal and regeneration and carbon monoxide conversion in a simulated syngas
using a combination of computational and experimental methods. principal investigator:
• Development of one or more sorbents that recover high-quality heat during CO2 Carl Richardson
adsorption, regenerate at elevated pressure, have minimal deactivation over multiple URS Group, Inc.
cycles, have high selectivity at high temperatures, have high adsorption capacity, and [email protected]
have acceptable thermal stability and mechanical integrity. This will result in
sorbents capable of 90 percent CO2 removal with high loading capacities and able to partners:
operate at the high temperatures and pressures typically encountered upstream of a
Illinois Clean Coal
WGS reactor. If successful, the sorbents developed in this program will augment or
replace the carbon monoxide conversion catalysts currently used in WGS reactors Institute University of
and improve overall WGS thermal efficiency. Illinois at Urbana-
• Determine the techno-economic feasibility of the sorption-enhanced WGS (SEWGS) Champaign
process for removing CO2.
performance period:
1/1/10 – 9/30/13
technical content
URS Group is leading development of a dry sorbent process configured to combine the
WGS reaction with CO2 removal for coal gasification systems. The result will be an
SEWGS technology.
A novel approach integrates the use of multiple computational models with sorbent
synthesis and characterization activities to develop sorbents with optimal CO2 removal
properties at high temperatures and pressures applicable to WGS applications. Tests
evaluate sorbent performance in simulated WGS gas mixtures at commercially relevant
conditions. Appropriate data reduction and analysis provides suitable data for a techno-
economic analysis to evaluate the feasibility and scaleup potential of the SEWGS
technology.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
758 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
Figure 1: IGCC with SEWGS vs. Conventional IGCC
Process simulation modeling and sorbent molecular and thermodynamic analyses by UIUC allow prediction of optimal sorbent
properties and identification of optimal operating temperature and pressure windows to maximize the energy efficiency of the
combined WGS and CO2 capture processes. The thermodynamic study includes developing phase equilibrium diagrams for
potential sorbents, identifying optimum operating conditions for CO2 capture, understanding impacts of syngas impurities, and
identifying promising sorbents. Molecular simulation predicts isotherms and properties, kinetics, and dynamics, and identifies
sorbents with desired properties using quantum chemistry/mechanics, force field-based molecular dynamics (MD), and reactive
dynamics (RD) simulations. Process simulation analyzes various process scenarios for heat integration between SEWGS and
integrated gasification combined cycle (IGCC) and process energy performance for individual sorbents.
The first phase testing and modeling efforts guide the synthesis of sorbents with desired pore structure and composition. Synthesis
includes use of various precursors, including calcium, magnesium, and other metal oxides, as well as zirconates, titanates, silicates,
aluminates, and adsorbent-shift catalyst hybrid. The sorbent down-selection process is guided by the decision tree shown in
Figure 2.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 759
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
Figure 2: Sorbent Development and Analysis Decision Tree
An atmospheric-pressure thermogravimetric analyzer (TGA) and high temperature and pressure reactor (HTPR) system, capable of
300 pounds per square inch gauge (psig) and 950 °C, are UIUC’s primary tools for screening sorbents for CO2 removal. A URS
HTPR provides the capability to evaluate five to seven down-selected sorbents’ adsorption performance in the presence of syngas
impurities and regeneration performance. Long-term testing is limited to a down-selection of one to two sorbents.
A preliminary engineering study of process feasibility for adsorbing and removing CO2 as part of the WGS process, and
comparison to base WGS operation and other CO2 removal strategies, is informed by the preceding laboratory test results.
Parameters under evaluation include costs of >90 percent removal (cost of electricity [COE], operation and maintenance [O&M]),
sorbent costs, anticipated lifetime (i.e., replacement rate), estimated future market costs of precursor materials, handling equipment,
sorbent regeneration costs, heat/energy integration, compression costs with SEWGS, unit footprint, and capital costs and
scalability.
TABLE 1: SOLID SORBENT PARAMETERS
Units Current R&D Value Target R&D Value
Sorbent
True Density at STP kg/m3 TBD
Bulk Density kg/m3 TBD
nano (20–70 nm) or micro meter
TBD based on the reactor
Average Particle Diameter mm (0.5–10 μm) level; particles can
design analysis
be pelletized if needed
Particle Void Fraction m3/m3
Packing Density m2/m3
Solid Heat Capacity at STP kJ/kg-K <1 <1
Crush Strength kgf
Manufacturing Cost for Solvent $/kg
Absorption
Pressure bar 30–40 40
Temperature °C 300–700 550–650
Equilibrium CO2 Loading g mol CO2/kg
Heat of Absorption kJ/mol CO2 100–200 TBD
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
NATIONAL ENERGY TECHNOLOGY LABORATORY
760 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
Desorption
Pressure bar up to 30 highest possible up to 30
°C depends on individual sorbent
TBD; optimization based on
Temperature and highest regeneration
minimal energy limit
pressure achievable
Equilibrium CO2 Loading mol/mol
Heat of Desorption kJ/mol CO2
Proposed Module Design (for equipment developers)
Flow Arrangement/Operation — temperature swing temperature swing
Flue Gas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar 90 percent, 99 percent
bar depending on sorbent
Adsorber Pressure Drop properties, to be determined TBD
during project
Definitions:
STP – Standard Temperature and Pressure (15 °C, 1 atm).
Sorbent – Adsorbate-free (i.e., CO2-free) and dry material as used in adsorption/desorption cycle.
Manufacturing Cost for Sorbent – “Current” is market price of material, if applicable; “Target” is estimated manufacturing cost for
new materials, or the estimated cost of bulk manufacturing for existing materials.
Adsorption – The conditions of interest for adsorption are those that prevail at maximum sorbent loading, which typically occurs at
the bottom of the adsorption column. These may be assumed to be 1 atm total flue-gas pressure (corresponding to a CO2 partial
pressure of 0.13 bar) and 40 °C; however, measured data at other conditions are preferable to estimated data.
Desorption – The conditions of interest for desorption are those that prevail at minimum sorbent loading, which typically occurs at
the bottom of the desorption column. Operating pressure and temperature for the desorber/stripper are process-dependent.
Measured data at other conditions are preferable to estimated data.
Pressure – The pressure of CO2 in equilibrium with the sorbent. If the vapor phase is pure CO2, this is the total pressure; if it is a
mixture of gases, this is the partial pressure of CO2. Note that for a typical PC power plant, the total pressure of the flue gas is about
1 atm and the concentration of CO2 is about 13.2 percent. Therefore, the partial pressure of CO2 is roughly 0.132 atm or 0.130 bar.
Packing Density – Ratio of the active sorbent area to the bulk sorbent volume.
Loading – The basis for CO2 loadings is mass of dry, adsorbate-free sorbent.
Flow Arrangement/Operation – Gas-solid module designs include fixed, fluidized, and moving bed, which result in either
continuous, cyclic, or semi-regenerative operation.
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
This is a research and development (R&D) program involving fairly immature technology. As such, many target R&D values will
be determined during execution of the test program and will be impacted by a number of key process parameters, including sorbent
type and cost, sorbent performance and loading capacity, sorbent lifetime, regeneration conditions and cycling parameters, and
complexity of integration of optimal adsorption and regeneration processing steps.
Sorbent Heating/Cooling Method – For sorbent regeneration, the sorbent is heated in a fluidized-bed or moving-bed configuration
with heat supplied by either hydrogen (H2) (or syngas) oxy-combustion or steam extracted from the gasification plant steam cycle.
Before entering the adsorption bed, the regenerated sorbent is cooled by exchanging heat with inlet regeneration H2/oxygen (O2) or
syngas. In the adsorption bed, a heat exchanger (such as a boiler tube bundle used in the fluidized-bed boiler) is used for recovering
heat generated from CO2 adsorption.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 761
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
Heat of Adsorption Handling – Adsorption heat is recovered during CO2 adsorption by using a heat exchanger to generate steam,
which is combined into the gasification plant’s steam cycle for electricity generation.
Heat Supply Method for Regeneration – Two methods are considered. One is to burn a small amount of the H2 or syngas using O2
to supply heat directly. Another approach is to use the steam from the gasification plant’s steam cycle if the regeneration
temperature is below 1,000 °F.
Contamination Resistance – This program will evaluate the impact of various syngas impurities on the adsorption and regeneration
performance of promising CO2 sorbents. Sorbents may not be resistant to sulfur species (hydrogen sulfide [H2S], carbon disulfide [CS2], etc).
Syngas Pretreatment Requirements – The pretreatment of H2S/CS2 is needed for sorbents with no sulfur resistance. If it is
determined that the performance of identified sorbents is inhibited by sulfur species present in the syngas, additional work will
focus on the development of sorbents materials that are resistant to sulfur; the objective will be to avoid the need for syngas
pretreatment associated with this technology.
Waste Streams Generated – Desulfurization byproducts.
technology advantages
• High carbon monoxide conversion with reduced stream addition.
• No or limited WGS catalyst use.
• High-quality adsorption heat usable for generation of high-quality steam.
• Limited gas cooling/reheating requirement downstream.
• No separate CO2 capture unit required.
• Reduced energy requirement for CO2 compression.
R&D challenges
• Sorbent pores may be plugged during adsorption, causing capacity and activity loss.
• Long-term capacity and activity stability after multiple cycles.
• Selectivity at high temperature.
• System/reactor issues, such as material transport and handling at high temperature and pressure.
results to date/accomplishments
• More than 40 sorbents were modeled and subsequently down-selected to seven candidates (magnesium oxide [MgO], calcium
oxide [CaO], lithium zirconate [Li2ZrO3], calcium zirconium oxide [CaZrO3], barium zirconate [BaZrO3], barium titanate
[BaTiO3], and barium silicate [BaSiO3]) for further development.
• Process simulations were performed for a baseline IGCC plant with WGS and a Selexol process and compared to an IGCC
with SEWGS. These showed a 0.5–2.4 percentage point increase in net thermal efficiency for the simulated plant with
SEWGS.
• Molecular simulation studies included quantum chemical (QC) calculations and MD simulations with reactive field force
• (ReaxFF). Molecular simulation was successfully applied to assess carbonation and calcination reactions (CaO).
• The impacts of sorbent structure and the sintering of calcium oxide particles with and without CO2 chemisorption, and the role
of a dopant in reducing the sintering of CaO particles, were also determined.
• More than 60 SEWGS sorbents were synthesized using mechanical alloying (MA), ultrasonic spray pyrolysis (USP), and
flame spray pyrolysis (FSP) techniques.
• CaO sorbents prepared by dry and wet ball-milled MA methods exhibited improved CO2 adsorption capacities and stabilities
over commercial CaCO3 materials. The performance of CaCO3 sorbents was improved by doping with inert MgO.
• Hollow, porous CaCO3 sorbents synthesized using the USP method were spheres of ≈1 μm with a shell thickness of 50–
100 nm. The CaO generated upon calcination of the CaCO3 exhibited a high surface area (up to 75 m2/g).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
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762 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Sorbent Technologies
• A 75:25 w/w CaO:Ca12Al14O33 (mayenite) sorbent retained 91 percent of its initial CO2 capacity after 15 cycles and 79 percent
after 50 cycles, while a USP CaO only retained 43 percent after 15 cycles.
• The surface area of nano-sized (<70 nm) CaO, ZrO2-doped CaO, MgO, MgO-doped CaO, and ZrO2-doped MgO sorbents
synthesized using the FSP method ranged between 21 and 54 m2/g. ZrO2 was found to be an effective dopant to improve the
stability of CaO-based sorbents. A ZrO2-CaO (Zr:Ca=0.2:1) sorbent maintained its capacity at 0.5 g CO2/g sorbent over 15
adsorption-desorption cycles.
• An HTPR tube reactor with quarter-inch ID and 1-foot length was also used to test sorbents at UIUC. These tests were
performed at 650 °C and CO2 partial pressures up to 4 bar adsorption conditions.
• Results from the HTPR testing showed sorbents with as high as 0.4 grams of CO2 per grams of sorbent capacity with the
ability to initially shift the WGS completely toward CO2/H2.
• A longer term experiment with a simple syngas matrix and N2/steam regeneration stream showed a USP sorbent (#199) to be
stable through 50 adsorption-regeneration cycles, though the sorbent tested had a somewhat diminished initial capacity.
next steps
This project ended on September 30, 2013.
available reports/technical papers/presentations
Richardson, Carl, URS Group et al., “Evaluation of Dry Sorbent Injection Technology for Pre-Combustion CO2 Capture,” Final
Report, 2013. http://www.osti.gov/scitech/biblio/1136521.
“Evaluation of Dry Sorbent Technology for Pre-Combustion CO2 Capture,” Carl Richardson, URS Corporation, 2013 NETL CO2
Capture Technology Meeting, Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/C-Richardson-URS-Dry-Sorbent-Technology.pdf.
Hong Lu, Yongqi Lu, Massoud Rostam-Abadi, “CO2 Sorbents for a Sorption-Enhanced Water-Gas-Shift Process in IGCC plants: A
Thermodynamic Analysis and Process Simulation Study,” International Journal of Hydrogen Energy, Volume 38, Issue 16, 30 May
2013, Pages 6663-6672. http://www.sciencedirect.com/science/article/pii/S0360319913006770.
Steen,W.; Richardson, C.; Machalek, T.; Paradis, J.; Rostam-Abadi, M.; Lu, Y.; Lu, H.; Napoli, M.; and Everitt, E., “Solid Sorbent-
Enhanced Water-Gas Shift Process for Pre-Combustion CO2 Capture,” Proceedings of the Power Plant Air Pollutant Control
“Mega” Symposium, Paper #16, Baltimore, MD, August 2012.
Evaluation of Dry Sorbent Technology for Pre-Combustion CO2 Capture; Presentation at the 2012 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, July 2012. http://www.netl.doe.gov/publications/proceedings/12/CO2capture/presentations/4-
Thursday/B%20Steen-URS-Pre-combustion%20Sorbent.pdf.
Lu, Y.; Lu, H.; Rostam-Abadi, M.; Sayyah, M.; Suslick, K.; Steen, W.; Richardson, C.; Hirschi, J.; and Napoli, M., “Evaluation of
Dry Sorbent Technology for Pre-Combustion CO2 Capture,” Proceedings of the Clearwater Clean Coal Conference—37th
International Technical Conference on Clean Coal and Fuel Systems, Clearwater, FL, June 2012.
Steen, W.; Richardson, C.; Lu, Y.; Lu, H.; and Rostam-Abadi, M., “Evaluation of Dry Sorbent Technology for Pre-Combustion
CO2 Capture,” Proceedings of the 2011 DOE-NETL CO2 Capture Technology Meeting, Pittsburgh, PA, August 2011.
http://www.netl.doe.gov/publications/proceedings/11/CO2capture/presentations/4-Thursday/25Aug11-Steen-URS-
Dry%20Sorbent%20Pre-CombustionCapture.pdf.
Richardson, C., and Lu, Y., “Evaluation of Dry Sorbent Technology,” Presentation at the 2010 NETL CO2 Capture Technology
Meeting, Pittsburgh, PA, September 2010.
http://www.netl.doe.gov/publications/proceedings/10/CO2capture/presentations/thursday/Carl%20Richardson%20-
%20FE0000465.pdf.
“Evaluation of Dry Sorbent Technology for Pre-Combustion CO2 Capture,” Pre-Combustion CO2 Capture Kick-Off Meetings,
Pittsburgh, PA, November 2009. http://www.netl.doe.gov/publications/proceedings/09/CO2capture/7-
URS%20Dry%20Sorbent%20Kickoff%20Presentatin-111309.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION SORBENTS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 763
Appendix: Pre-Combustion Sorbent Technologies
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CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
PRE-COMBUSTION
MEMBRANE TECHNOLOGIES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
765
Appendix: Pre-Combustion Membrane Technologies
Robust and Energy Efficient technology maturity:
Dual-Stage Membrane-Based
Bench-Scale, Actual Syngas
(equivalent to 0.01 MWe)
Process for Enhanced Carbon project focus:
Dioxide Recovery
Two-Stage Membrane
Separation: Carbon
Molecular Sieve Membrane
Reactor followed by Pd-
primary project goals Based Membrane
The Media and Process Technology Inc. (MPT) project objective has been to participant:
develop a dual-stage membrane-based process (DSMP) for pre-combustion Media and Process
carbon dioxide (CO2) capture in an Integrated Gasification Combined Cycle Technology, Inc.
(IGCC) power plant. The process utilizes MPT hydrogen (H2)-selective carbon
molecular sieve (CMS) membranes, in conjunction with conventional water gas
project number:
shift (WGS) reactors, in the first stage for enhanced production and bulk recovery
of H2. Following cold gas clean-up, a palladium alloy-based membrane is used in FE0013064
the second stage for efficient residual hydrogen recovery from the high-pressure
CO2 gas stream just prior to sequestration. predecessor projects:
FC26-07NT43057
technical goals
NETL project manager:
• Characterize the performance of the proposed CMS and Pd-alloy membrane Andrew Jones
[email protected]
technologies for H2-CO2 separations from simulated coal and biomass derived
syngas in laboratory scale testing.
principal investigator:
• Verify the membrane performance under extreme pressure conditions to
qualify the technology for pre-combustion capture. Paul Liu
Media and Process
• Demonstrate the performance stability of the CMS and Pd-alloy multiple tube
Technology, Inc.
membrane bundles in actual gasifier syngas in bench-scale testing at the [email protected]
National Carbon Capture Center (NCCC).
• Develop the mathematical model from the performance database obtained in partners:
lab and bench-scale work.
Technip USA Corporation,
• Perform techno-economic assessment (TEA) and environment, health, and University of Southern
safety (EH&S) analysis for the process using the performance database and California
models developed under this project.
start date:
technical content 10.01.2013
The technological approach utilizes MPT’s commercial ceramic tubular ultrafilter percent complete:
shown in Figure 1 as a support for the high performance H2 selective membranes. 100%
Ultrathin CMS and Pd-alloy layers are deposited to form composite membranes
and then packaged into high packing density multiple tube membrane elements
as illustrated. In this bundle configuration, the membranes can be operated at high
temperatures (up to 500 °C) and pressures (up to at least 1,200 pounds per square
inch gauge [psig]) to support warm syngas cleanup in pre-combustion CO2
capture.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Appendix: Pre-Combustion Membrane Technologies
MPT Tubular
Ultrafilters
CMS Layer
CMS Membrane Bundle
Pd-alloy Layer
SEM Cross Section Pd-alloy Membrane Bundle
Figure 1: MPT ceramic ultrafiltration membranes as supports for high performance H2 selective CMS and Pd-alloy membranes shown
packaged into multiple tube membrane elements
MPT’s Dual Stage Membrane Process (DSMP) is illustrated in Figure 2. In the process, the CMS and Pd-alloy membranes
are used in distinctly different roles, taking advantage of their specific performance capabilities, to deliver high H2 and
CO2 recovery from IGCC gasifier syngas. In the DSMP, the CMS membrane is deployed in a multiple step serial
arrangement with the WGS reactors in two roles, specifically, (i) to recover the bulk H2 from the gasifier off-gas and (ii) to
enhance the equilibrium conversion in WGS reactors to improve net power output. The CMS membrane is operated at
temperatures in the range of 250–300 °C and no syngas pretreatment is necessary, making them complementary to the
WGS reactors in terms of operating conditions window and reactor performance enhancement.
In the 1st Stage CMS membrane section, only about 85 percent of the H2 is recovered due to the “low” pressure (~800
psig) of the syngas and excessive carbon losses to the permeate at higher H2 recovery levels. Hence, considerable H2
remains that must be recovered to deliver adequate power output and to meet the cost of capture targets. For this
purpose, a Pd-Ag alloy membrane is used in the 2nd stage of the process. Due to the well-known deficiencies of the Pd-
based membrane, most specifically its vulnerability to sulfur poisoning and the resultant irreversible damage, it is
deployed downstream of the CO2 compressors. At this location in the process, the syngas has been processed through
the Cold Gas Cleanup Unit (CGCU) to remove various contaminants (Hg, sulfur, tar, water, etc.) as required for storage;
thus, potential membrane poisons are eliminated. Hence, the major limitation of the Pd membrane technology is avoided
while the major benefit, specifically its ultra-high (potentially infinite) selectivity of H 2-to-CO2, is brought to bear. With the
addition of this 2nd stage, >99 percent of the produced H2 is ultimately recovered.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Block Flow Diagram – Case 3a: IGCC w/CCS - Hybrid CMS/Pd Membrane System
Appendix: Pre-Combustion Membrane Technologies
CO2 Compression CO2
CMS Membrane (coupled to Sequestration
(multiple stages w/cooling)
w/WGS reactor)
5a
1. Deliver enhanced CO Tail Gas H2S Un-Shifted
conversion with reduced Recycle Sour Gas 2215 psia
Syngas
water consumption versus (from SRU) (to SRU) 800 psia 1400-2215 psia 125oC
conventional WGS. >300oC (1 or 2 MBS stages)
2. “Roughing” step to
recover the bulk H and B/C
2
reduce load on the CGCU Pd Process 2
b
3. Ideal location for CMS MBS Steam
membrane due to its 4
material and temperature Re-Heat
H2O
stability. Gas Cooler 5
b
CGCU 740 psia
~98% H2
(incl. 1-stage Cumulative
40oC
Selexol) Recovery
Un-Shifted
Syngas H2O Hg
~ 50/50
800 psia >99% CO
3a N2 Split
200-280oC Conv.
N2 Diluent/Sweep
~42% H2 A
6a
from ASU
(dry basis)
1 CMS WGS 6
MBR 6
b
385 psia
~75% H2
(w/Internal Cooling) Recovery Pd-Alloy Membrane N2 Compression 95oC
1. High selectivity yields excellent (multiple stages w/cooling)
Process residual H recovery.
2
Steam 3
2a
b
2. Ideal to achieve the CO capture
2
Gas Turbine
and purity targets.
Feed
7
~44% H2
460 psia
Figure 2: MPT Dual Stage Membrane Process for pre-combustion CO2 capture
JJM for MPT 07/13/12
By replacing the dual-stage Selexol unit of the DOE baseline design with the proposed highly efficient and robust
membrane technology, the DSMP achieves the DOE carbon capture targets, delivering 90 percent CO2 capture at 94.5
percent purity, while producing higher net power output (+3 percent, 559 MW) at reduced cost of CO2 captured (-14
percent, $33.2/tonne) in comparison with the base case.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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768 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — carbon molecular sieve (CMS)
Materials of Fabrication for Support Layer — alumina
Nominal Thickness of Selective Layer m 2–3 2–3
Membrane Geometry — tubular tubular
Maximum Trans-Membrane Pressure bar >82 bar >82 bar
>16,000 hours in lab,
Hours Tested without Significant Degradation — —
>1,000 hours at NCCC
Manufacturing Cost for Membrane Material $/m2 <1,200 <750
Membrane Performance
Temperature °C 250–300 250–300
H2 Pressure Normalized Flux GPU or equivalent 500 900
H2/H2O Selectivity — 2–4 >3
H2/CO2 Selectivity — 35 >50
H2/H2S Selectivity — >100 >100
Sulfur Tolerance ppm >10,000 >10,000
Type of Measurement — mixed gas mixed gas
Proposed Module Design
Flow Arrangement — co/counter-current or cross-flow
Packing Density m2/m3 >450
Shell-Side Fluid — permeate
Syngas Gas Flowrate kg/hr —
CO2 Recovery, Purity, and Pressure %/%/bar 90 95 >60
H2 Recovery, Purity, and Pressure %/%/bar .>80 >90 Up to 20
Pressure Drops Shell/Tube Side bar —
Estimated Module Cost of Manufacturing and __$__
kg/hr 1,500
Installation
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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769
Appendix: Pre-Combustion Membrane Technologies
TABLE 2: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D Value Target R&D Value
Materials of Fabrication for Selective Layer — palladium-alloy
Materials of Fabrication for Support Layer — alumina
Nominal Thickness of Selective Layer m 2 to 5 2 to 5
Membrane Geometry — tubular tubular
Maximum Trans-Membrane Pressure bar >82 >82
>35,000 hours lab
Hours Tested without Significant Degradation — —
150 hours at NCCC
Manufacturing Cost for Membrane Material $/m2 1,800 <1,000
Membrane Performance
Temperature °C 250 to 400 250 to 400
H2 Pressure Normalized Flux GPU or equivalent 2,000 to >5,000 1,000 to >5,000
H2/H2O Selectivity — 1,000 to >5,000 1,000 to >5,000
H2/CO2 Selectivity — 1,000 to >5,000 1,000 to >5,000
H2/H2S Selectivity — N/A N/A
Sulfur Tolerance ppm <10 <10
Type of Measurement — mixed gas. mixed gas
Proposed Module Design
Flow Arrangement — co- or counter-current
Packing Density m2/m3 450
Shell-Side Fluid — feed/retentate
Syngas Gas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar >99 93 to 94 >1,000
H2 Recovery, Purity, and Pressure %/%/bar >99 >99 1.2
Pressure Drops Shell/Tube Side bar N/A
Estimated Module Cost of Manufacturing and __$__
kg/hr 260
Installation
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this
is equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the
dimensional units reported should be based on flux measured in cm 3 (1 atm, 0 °C)/cm2/s with pressures measured in
cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for
mixture of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-
and-tube, and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some
complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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770 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
Estimated Cost – Basis is kg/hr of CO2 in CO2-rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – CMS: molecular sieving. Pd-alloy: H2 dissolution and permeation.
Contaminant Resistance –.CMS: stable in gasifier raw syngas testing conducted at NCCC. Pd-alloy: stable in gasifier
syngas with the removal of sulfur and tar species.
Syngas Pretreatment Requirements – CMS: No syngas pretreatment required. Pd-alloy: sulfur and tar-like species
removal required.
Membrane Replacement Requirements – Unknown but lifetimes of >16,000 hours for the CMS and >35,000 hours for the
Pd-alloy membranes have been demonstrated with no apparent loss in performance.
Waste Streams Generated – None.
Process Design Concept – See Figure 2.
Proposed Module Integration –
Composition
Membrane Pressure Temperature vol% ppmv
Material psia °F CO2 CO CH4 N2, Ar H2 H2O H2S
CMS 800 440–540 27.4 5.5 <1 ~1 40.8 24.5 >5,000
Pd-alloy >1,000 480–570 87.8 0.5 <1 ~3 8.4 0.17 <10
technology advantages
• The proposed DSMP matches specific capabilities and properties of the CMS (high material stability) and Pd-alloy
(high H2 selectivity) membranes to different separation requirements at separate stages in the process, enabling
efficient gas separations performance.
• The proposed DSMP delivers significant cost savings in cost of CO2 captured due to reduced capital and parasitic
compression costs relative to conventional technology. Further, since significant H2 recovery is achieved in the first
stage, the required size and cost of the cold gas cleanup unit is significantly reduced due to the nearly 50 percent
reduction in gas volume processed.
• The CMS membranes exhibited excellent performance stability in the presence of untreated gasifier syngas in testing
conducted at the NCCC. This makes them highly suitable for first-stage service in pre-combustion H2 and CO2 gas
production and separations.
• The Pd-alloy membranes were also demonstrated to be highly stable in second stage residual H2 recovery following
cold gas clean-up prior to CO2 sequestration. The high selectivity of the Pd-alloy permitted excellent residual H2
recovery to achieve CO2 capture and purity targets at higher power output and lower cost of CO2 captured.
• By limiting the Pd-alloy membrane to residual H2 recovery and fabricating it as an ultra-thin film on a ceramic support,
the Pd metal demand/consumption is significantly reduced over CO2 capture schemes that rely solely on Pd
membrane use in flat sheet geometry, thereby addressing both issues of the very high cost and limited availability of
Pd metal.
R&D challenges
• Develop the multiple tube membrane bundle suitable for the high-pressure gas processing.
• Fabricate CMS and Pd-alloy membrane bundles for bench-scale testing at the NCCC.
• Demonstrate performance stability of the multiple tube membrane bundles in actual gasifier syngas at the NCCC.
• Develop the mathematical model and confirm applicability to the proposed process in live gas testing.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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771
Appendix: Pre-Combustion Membrane Technologies
status
Multiple tube CMS and Pd-alloy membrane bundles were tested at NCCC, exposed to synthetic and actual coal gasifier
syngas for hundreds of hours, and found to be stable in this environment. Given this and their stability at elevated
temperature and pressure, the technology is expected to be viable for CO2 capture in IGCC process scenarios. Techno-
economic analysis of proposed DSMP in pre-combustion CO2 capture for an IGCC power has been completed. The TEA
shows that net power production is improved by 3 percent and the cost of CO2 captured is reduced by 14 percent over
the NETL base plant case (IGCC with dual stage Selexol CO2 capture). An EH&S assessment has been completed for
the proposed process, and based upon this assessment, there is no reason to believe that a production process and
operation meeting the EH&S satisfaction cannot be established to commercialize the proposed technology and process.
available reports/technical papers/presentations
“Robust and Energy Efficient Dual-Stage Membrane-Based Process for Enhanced CO2 Recovery,” presented by
Richard Ciora, Media and Process Technology, Inc., 2017 NETL CO2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2017.
“Robust and Energy Efficient Dual-Stage Membrane-Based Process for Enhanced CO2 Recovery,” presented by
Richard Ciora, Media and Process Technology, Inc., 2016 NETL CO 2 Capture Technology Project Review Meeting,
Pittsburgh, PA, August 2016.
“Robust and Energy Efficient Dual-Stage Membrane-Based Process for Enhanced CO2 Recovery,” presented by
Richard Ciora, Media and Process Technology, Inc., 2015 NETL CO2 Capture Technology, Pittsburgh, PA, June 2015.
“Robust and Energy Efficient Dual-Stage Membrane-Based Process for Enhanced CO2 Recovery,” presented by
Richard Ciora, Media and Process Technology, Inc., 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA,
July 2014.
“Robust and Energy Efficient Dual-Stage Membrane-Based Process for Enhanced CO2 Capture,” NETL Fact Sheet,
February 2014.
“Robust & Energy Efficient Dual-Stage Membrane-Based Process for Enhanced Carbon Dioxide Recovery,” Project
Kickoff Meeting Presentation.
Doug Parsley, Richard J. Ciora, Jr., Diane L. Flowers, John Laukaitaus, Amy Chen, Paul K.T. Liu, Jiang Yu,
Muhammad Sahimi, Alex Bonsu, Theodore T. Tsotsis, "Field evaluation of carbon molecular sieve membranes for the
separation and purification of hydrogen from coal-and biomass-derived syngas", J. Membrane Science, 450, 81 (2014)
M. Abdollah, J. Yu, H.T. Hwang, P.K.T. Liu, R.J. Ciora Jr., M. Sahimi, T. Tsotsis, “Process Intensification in Hydrogen
Production from Biomass Derived Syngas”, Ind. Eng. Chem. Res., 49, 10986, (2010).
Abdollahi, M., et al., “Hydrogen Production from Syngas, using a Catalytic Membrane Reactor,” presented at the North
American Membrane Society, Charleston, SC, June 2009.
Abdollahi, M., et al., “Integrated One-Box Process for Hydrogen Production from Syngas,” presented at the 2009
Annual Meeting, American Institute of Chemical Engineers (AIChE), November 2009.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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Appendix: Pre-Combustion Membrane Technologies
Polymer-Based Carbon technology maturity:
Bench-Scale, Simulated
Dioxide Capture Membrane Syngas (single hollow fiber
testing)
Systems project focus:
High-Temperature Polymer-
primary project goals Based Membrane
Los Alamos National Laboratory (LANL) developed and demonstrated polymer-based participant:
membrane structures, deployment platforms, and sealing technologies for attaining a Los Alamos National
combination of high selectivity, high permeability, chemical stability, and mechanical Laboratory
stability at elevated temperatures (>150 °C) and packaged in a scalable, economically
viable, high area density system amenable to incorporation into an integrated project number:
gasification combined cycle (IGCC) plant for pre-combustion carbon dioxide (CO 2 )
FwP-FE-308-13
capture.
predecessor projects:
technical goals FwP-FE-10-002
04FE13-AC24
• Minimize membrane support costs, maximize membrane flux, retain thermo-
mechanical and thermo-chemical stability characteristics, and increase the area NETL project manager:
density achievable in a commercial module design. David Lang
• Produce an asymmetric polybenzimidazole (PBI) hollow fiber comprised of a thin, [email protected]
dense, defect-minimized PBI selective layer and an open, porous underlying
support structure with morphology characteristics tailored to optimize transport principal investigator:
and mechanical property requirements (use and lifetime). Kathryn A. Berchtold
• Develop materials and methods to further mitigate defects in ultra-thin selective Los Alamos National
layers for use under process relevant conditions. Laboratory
[email protected]
• Reduce perceived technical risks of utilizing a polymeric membrane based
technology in challenging (thermal, chemical, mechanical) syngas environments.
partners:
PBI Performance Products,
technical content NETL
LANL work, from a previously funded project FWP-10-002, demonstrated that PBI and start date:
other benzimidazole-based materials show promise as membranes for pre- 10.01.2008
combustion-based capture of CO 2 . PBI is a unique polymer family that is stable to
temperatures approaching 500 °C. PBI possesses excellent chemical resistance, a high percent complete:
glass transition temperature (>460 °C), good mechanical properties, and an appropriate
100%
level of processability. The PBI-based membranes developed by LANL have
demonstrated operating temperatures significantly higher than 150 °C (up to 450 °C)
with excellent chemical, mechanical, and hydrothermal stability, and outperformed any
polymer-based membrane available commercially or reported in the literature for
separations involving hydrogen. This achievement is validated via membrane
productivity (separation factor and flux) comparisons (Figure 1). The improved
performance of this technology in an application such as IGCC-integrated capture is
further substantiated by the accessible operating temperature range (up to 400 °C),
long-term hydrothermal stability, sulfur tolerance, and overall durability of the
proposed membrane materials in these challenging pre-combustion environments.
These characteristics have been validated via extensive evaluations of LANL’s polymer-
based membrane in simulated syngas environments containing hydrogen (H 2 ), CO 2 ,
methane (CH 4 ), nitrogen (N 2 ), carbon monoxide (CO), steam (H 2 O), and hydrogen
sulfide (H 2 S), from 25 to 400 °C, and demonstration of the membrane’s thermal stability
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
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773
Appendix: Pre-Combustion Membrane Technologies
via 300-plus days in operation at 250 °C. These achievements and material/membrane property validations were largely
conducted on flat sheet and tubular platform membranes.
Figure 1: Robeson plot comparing PBI composite membrane with other polymeric membranes tested for H 2 /CO 2 separation
The line represents the 2008 upper bound and Red symbols are the corresponding experimental data from Robeson JMS 320 (2008) 390-400.
Data taken from LANL PBI: Berchtold et al., JMS 415 (2012) 265-270, Xin et al., JMS 461 (2014) 59-68 & Pesiri et al., JMS 218 (2003) 11-18;
Modified PBI: Kumbharkar et al., JMS 286 (2006) 161-169; Membrane Technology & Research (MTR) Proteus: Merkel et al., JMS 389 (2012) 441-
450; Thermally Rearranged Polybenzoxazole (TR PBO): Han et al., PCCP 14 (2012) 4365-4373 & Park et al., JMS 359 (2010) 11-24; TR-PBI: Hans et
al., JMS 357 (2010) 143-151.
Previous R&D efforts were focused on the utilization of the PBI formulations as a selective layer deposited on and supported by
a unique porous metal substrate (fabricated by Pall Corporation). Systems, economic, and commercialization analyses conducted
by NETL, LANL, and others, combined with in- and out-of-laboratory testing, established the technical viability of the technology
and indicated the strong potential for the membrane-based capture technology to meet and exceed the DOE Carbon Capture
Program goals. However, these analyses also made clear the need to cut the costs of the support material and increase the area
density realized by the ultimate module design in order to realize the desired step-change in both performance and cost of CO 2
capture associated with the use of this membrane-based capture technology. One promising option for achieving a substantial
increase in active membrane area density and mitigating the cost of a metal or inorganic material-based support is the use of a
hollow fiber membrane (HFM) platform. A HFM is the membrane configuration with the highest achievable packing density (i.e.,
the highest membrane selective area density). Commercial HFM modules have been fabricated to obtain selective area densities
as high as 30,000 m2/m3. This affords the opportunity to achieve several orders of magnitude improvement over the density
achievable with the previous polymeric-metallic membrane platform (ca. 250 m2/m3) which will reduce the size requirement of
the costly, high temperature-tolerant membrane module housings, will minimize membrane support costs through their all-
polymeric design, and will facilitate membrane flux maximization through processing facilitated selective layer thickness
minimization (Figure 2). Realization of such increases in membrane area density and flux with the materials previously developed
would lead to substantial economic and technical benefits.
Figure 2: Illustration of the transition from the technology development state at project onset (PBI-metallic composite membrane in a tubular
platform) to the technology end state (high area density all-polymeric PBI hollow fiber membrane platform)
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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774 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
The focus of recent technology development has been translation of the previously developed membrane materials chemistries
into a high area density HFM platform via commercially viable HFM manufacturing methods; developing and deploying defect
mitigation strategies for optimizing membrane performance and durability; and demonstrating the produced membranes in
simulated and actual process environments with the overarching goal of technology progression toward commercialization.
Technology advancement has now been extended to realization of polybenzimidazole (PBI)-based membrane chemistries,
structures, deployment platforms, and sealing technologies that achieve the critical combination of high permselectivity and
durability at elevated temperatures (up to 350 °C, the highest ever reported viable operating temperature of a polymer based
membrane). The work conducted as part of this development and demonstration effort includes the translation of these unique
PBI materials into a commercially viable, all polymeric HFM platform (Figure 3). Results also demonstrated that the developed
materials not only function at significantly higher temperatures than current commercially available polymeric membranes
(which are limited to <150 °C) but also provide improved performance while exhibiting long-term temperature stability, sulfur
tolerance, and overall durability in industrially relevant operating conditions. For the most detailed documentation of recent
work available, the reader is referred to the project final report for FWP-FE-308-13 (see the list of available reports below).
Figure 3: The state-of-the-art PBI HFM having ideal morphology: thin (ca. 160 nm) selective layer, macrovoid free, porous inner surface and
fiber wall, and fabricated in an environmentally benign external coagulant (water).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
775
Appendix: Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE PROCESS PARAMETERS
Materials Properties Units Current R&D value Target R&D value
Materials of Fabrication for Selective Layer — m-PBI, high T g polymer
Materials of Fabrication for Support Layer — metallic composite high T g polymer high T g polymer
Nominal Thickness of Selective Layer µm 0.6 0.2–0.5 0.1–0.5
Membrane Geometry — tubular hollow fiber hollow fiber
Max Trans-Membrane Pressure bar 301 12.51 30
Hours Tested without Significant Degradation — 8,400 (at 250 °C)2 3,000 (at ≥250 °C)2 1,000
Manufacturing Cost for Membrane Material $/m2 >100 ≤15 15
Membrane Performance
Temperature °C 250 150–350 150–350
H 2 Pressure Normalized Flux GPU or equivalent 170 200–275 250
H 2 /H 2 O Selectivity — ≈1 ≈0.3
H 2 /CO 2 Selectivity — 42 25 25–40
H 2 /H 2 S Selectivity — >1,800 >1,800 >1,800
Sulfur Tolerance ppm 10,0003 10,0003 1,000
Type of Measurement — mixed and pure mixed4 and pure mixed
Proposed Module Design (for equipment developers)
Flow Arrangement — counter counter/complex
Packing Density m2/m3 250 2,000–15,000
Shell-Side Fluid — feed/retentate
Syngas Flowrate kg/hr 210-240
CO 2 Recovery, Purity, and Pressure %/%/bar 75-90%6, HPD5,6, 50 bar6
H 2 Recovery, Purity, and Pressure %/%/bar 80-99%6,7, HPD5,7, 20 bar7
1.
Max TMP tested, not max achievable TMP.
2.
No degradation observed during testing.
3.
Max sulfur content tested with current generation HFMs was 100 ppm, not a measure of sulfur tolerance. Materials testing in other platforms indicates a tolerance to ≥10,000 ppm
4.
Typical Mixed gas conditions: simulated syngas 50.3% H 2 , 19.2% H 2 O, 29.4% CO 2 , 1.1% CO with 0, 20, & 100 ppm H 2 S.
5.
Highly process dependent (HPD).
6.
Gasifier, coal feedstock, upstream unit operation (e.g., water gas shift [WGS]), and downstream unit operation (e.g., CO 2 purification) specifications dependent.
7.
Tailored to match the turbine inlet specifications (e.g., 125 LHV Btu/ft3 and 20 bar permeate).
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is
equivalent to the membrane’s permeance.
GPU – Gas permeation unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm mercury (Hg). For non-linear materials, the
dimensional units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for mixture
of gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube,
and plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination
of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H 2 -rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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776 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
Estimated Cost – Basis is kg/hr of CO 2 in CO 2 -rich product gas; assuming targets are met.
Other Parameter Descriptions:
Membrane Permeation Mechanism – Solution diffusion where at the proposed elevated separation temperatures, permeability
is dominated by gas diffusivity in the selective layer.
Contaminant Resistance – Excellent resistance to syngas contaminants.
Syngas Pretreatment Requirements – Particulate removal.
Waste Streams Generated – Particulate removal.
Process Design Concept – Multiple location possibilities largely influenced by gasifier type (syngas pressure and quality), the
employed WGS technology, and the presence or lack thereof of a warm temperature gas cleanup for sulfur removal prior to the
capture step. For performance benchmark purposes, the membrane separation is conducted post-low temperature (250 °C) WGS.
Nitrogen from the air separation unit (ASU) is used as a membrane sweep gas, with the sweep flows specified based on the
turbine inlet heating value specification. Initial evaluations have utilized GE F-class turbine specifications and GE (Texaco) gasifier-
radiant operation.
Figure 4: Proposed design concept identifying multiple location opportunities for PBI membrane separation technology integration
Proposed Module Integration – Hollow fiber module design comprised of high-pressure, high-temperature housings and
components. The syngas will be processed at process temperature and pressure (see conditions and composition below). The
conditions of the primary separation position will be matched to those at the exit of the low-temperature WGS reactor. The
pressure drop utilized will be tailored based on the turbine inlet pressure. This process favors conditions created by gasifiers
that operate at higher pressure.
technology advantages
• Broad accessible membrane operating temperature range (150–350 °C) facilitating increased opportunity for process
integration/optimization.
• Demonstrated long-term hydrothermal stability, sulfur tolerance, and overall durability of selective layer materials.
• Membrane-based technology competitive advantages: modularity, low-maintenance operations, small footprint, low/no
waste process, and flexible design opportunities.
• CO 2 produced at higher pressure enables reduced compression costs.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
777
Appendix: Pre-Combustion Membrane Technologies
R&D challenges
• Design, control, prediction, and synthesis of tailored material morphologies in hollow fiber format.
• Realizing high-permeance, defect-free gas separation viable hollow fibers.
• Realizing sealing materials and methods compatible with the target material and process thermal, chemical, and mechanical
characteristics/environments.
status
At the project’s end, production of mechanically robust PBI hollow fibers suitable for industrial use was attained, taking
advantage of a novel continuous spinning process, defect sealing layer material and deposition method, and environmentally
benign coagulation solvent and modified commercial dope to ensure macro-void free fiber fabrication. A novel potting material
for multi-fiber module fabrication with promising properties to withstand typical syngas operating conditions and chemical
environments was developed. In fiber testing, long-term stable performance in simulated syngas containing H 2 S, steam and CO
at elevated temperatures (250–350 °C) of syngas was demonstrated.
Challenges remaining for successful industrial deployment include (1) further development and demonstration of potting
material for multi-fiber modules (current industrial materials lack hydrothermal stability, material developed in this work requires
further development and demonstration), and (2) further improvement in H 2 /CO 2 selectivity is needed to meet carbon capture
targets without relying on supplemental downstream processing/purification.
available reports/technical papers/presentations
Berchtold, K. A. and Singh, R. P., “Polymer-Based Carbon Dioxide Capture Membrane Systems,” Final Technical Report DOE/NETL FWP-FE-308-13,
2017.
“High Temperature Polymer-Based Membrane Systems for Pre-Combustion Carbon Dioxide Capture,” presented by Rajinder P. Singh & Kathryn A.
Berchtold, NETL Final Project Review Meeting, January 2017.
“High-Temperature Polymer Based CO 2 Capture Membrane Systems for Pre-Combustion CO 2 Capture,” presented by Rajinder Singh, Los Alamos
National Laboratory, 2016 NETL CO 2 Capture Technology Project Review Meeting, Pittsburgh, PA, August 2016.
Berchtold, K. A., Dudeck, K. W., Singh, R. P., and Dahe, G. J., “Polybenzimidazole hollow fiber membranes and method for making an
asymmetric hollow fiber membrane,” US 15/190,011, 2016
Radcliffe, A. J., Singh, R. P., Berchtold, K. A., and Lima, F., “Modeling and Optimization of High-Performance Polymer Membrane Reactor
Systems for Water–Gas Shift Reaction Applications,” Processes, 4 (2016) 8.
“High-Temperature Polymer Based Membrane Systems for Pre-Combustion Carbon Dioxide Capture,” presented by Kathryn A. Berchtold, Los
Alamos National Laboratory, 2015 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, June 2015.
Singh, R. P and Berchtold, K. A., “H 2 Selective Membranes for Pre-combustion Carbon Capture,” in: F.S. Morreale (Ed.) Novel Materials for
Carbon Dioxide Mitigation Technology, Elsevier, Amsterdam, 2015, pp. 177-206.
“High-Temperature Polymer Based Membrane Systems for Pre-Combustion Carbon Dioxide Capture,” presented by Kathryn A. Berchtold, Los
Alamos National Laboratory, 2014 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
Singh, R. P., Dahe, G. J., Dudeck, K. W., Welch, C. F., and Berchtold, K. A., “High Temperature Polybenzimidazole Hollow Fiber Membranes for
Hydrogen Separation and Carbon Dioxide Capture from Synthesis Gas,” Energy Procedia 63 (2014) 153-9.
Berchtold, K. A., Dudeck, K. W., Singh, R. P., Dahe, G. J., Welch, C. F., and Yang, D., “High Temperature Polymer-Based Membrane Systems for
Pre-Combustion Carbon Dioxide Capture,” in, Final Technical Report DOE/NETL FWP FE-10-002, 2013.
“High-Temperature Polymer Based Membrane Systems for Pre-Combustion Carbon Dioxide Capture,” presented by Kathryn A. Berchtold, Los
Alamos National Laboratory, 2013 NETL CO 2 Capture Technology Meeting, Pittsburgh, PA, July 2013.
Berchtold, K.A.; Singh, R.P.; Young, J.S.; and Dudeck, K.W., “Polybenzimidazole Composite Membranes for High Temperature Synthesis Gas
Separations,” Journal of Membrane Science 415-416 (2012) 265-70.
Han, S.H., and Kwon, H.J., et al., “Tuning Microcavities in Thermally Rearranged Polymer Membranes for CO 2 Capture,” Physical Chemistry
Chemical Physics 14 (2012) 4365-73.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
778 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
Stauffer, P.; Keating, G.; Middleton, R.; Viswanathan, H.; Berchtold, K.A.; Singh, R.P.; Pawar, R.; and Mancino, A., “Greening Coal: Breakthroughs
and Challenges in Carbon Capture and Storage,” Environmental Science & Technology 45 (2011) 8597-604.
Krishnan, G.D.; Steele, D.; O’Brien, K.C.; Callahan, R.; Berchtold, K.A.; and Figueroa, J.D., “Simulation of a Process to Capture CO 2 from IGCC
Syngas Using a High-Temperature PBI Membrane,” Energy Procedia 1 (2009) 4079-88.
O’Brien, K.C.; Krishnan, G.; Berchtold, K.A.; and Figueroa, J.D., et al., “Toward a Pilot-Scale Membrane System for Pre-Combustion CO 2
Separation,” Energy Procedia 1 (2009) 287-94.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 779
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
PRE-COMBUSTION CARBON DIOXIDE
CAPTURE BY A NEW DUAL-PHASE
CERAMIC-CARBONATE MEMBRANE technology maturity:
REACTOR Lab-Scale Using
Simulated Syngas
primary project goals project focus:
Dual-Phase Ceramic-
Arizona State University is developing a dual-phase, membrane-based separation device Carbonate Membrane
that will separate carbon dioxide (CO2) from typical water-gas shift (WGS) mixture feeds Reactor
and produce hydrogen (H2), which can be introduced into the combustion turbines of
integrated gasification combined cycle (IGCC) plants. participant:
Arizona State University
technical goals
project number:
• Synthesize chemically and thermally stable dual-phase, ceramic-carbonate membranes FE0000470
with CO2 selectivity (with respect to [H2], carbon monoxide [CO], or water [H2O])
larger than 500 and CO2 permeance larger than 5 × 10-7mol/m2/s/Pa. NETL project manager:
• Fabricate tubular dual-phase membranes and membrane reactor modules suitable for Elaine Everitt
WGS membrane reactor applications. [email protected]
• Identify experimental conditions for WGS in the dual-phase membrane reactor that
will produce the hydrogen stream with at least 93 percent purity and the CO2 stream principal investigator:
with at least 95 percent purity. Jerry Y.S. Lin
Arizona State University
technical content [email protected]
A membrane separation device consisting of a porous metal phase and a molten carbonate partners:
phase can conduct carbonate ions (CO32-) at a high rate. The metal-carbonate membranes None
only conduct electrons implying oxygen (O2) should be mixed with CO2 in the feed in order
to convert CO2 to CO3= ions. However, the presence of O2 can also oxidize the metallic performance period:
support and reduce its electronic conductivity, and thus CO2 permeability. The problem is
addressed by the proposed dual-phase, ceramic-carbonate membrane configuration
10/1/09 – 9/30/14
consisting of a porous ionic conducting ceramic phase and a molten carbonate phase.
At the upstream surface, CO2 reacts with oxygen ions supplied from the ceramic phase to
form CO3=, which transports through the molten carbonate phase towards the downstream
surface of the membrane. On the downstream surface, the reverse surface reaction takes
place, converting CO3= to CO2, with O= released and transported back through the ceramic
phase towards the upstream surface of the membrane. The net effect is permeation of neutral
CO2 through the membrane driven by the CO2 pressure gradient. The dual-phase membrane
will be made of continuous thin mesoporous oxygen ionic-conducting ceramic layer filled
with a molten carbonate, supported on porous stainless steel or other metal, with an
intermediate layer of sub-micron, pore-sized oxygen ionic conducting material.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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780 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Figure 1: Concept of Dual-Phase Membrane
Development of this dual-phase membrane will be divided in to two phases. Phase I work will include identifying optimum conditions
for synthesis of adequate membrane supports and the dual-phase membranes in disk geometry and studying gas permeation properties
of the membranes. The second part of the Phase I work will be focused on fabrication of the dual-phase membranes in tubular
geometries and the study of permeation, chemical, and mechanical stability of the tubular membranes relevant to their uses in
membrane reactors for WGS reaction.
Phase II work will be directed towards studying the dual-phase membrane reactor performance for WGS reaction for hydrogen
production and CO2 capture. The work includes synthesis and kinetic study of a high-temperature WGS catalyst and experimental
and modeling study of WGS reaction on the dual-phase membrane reactors. The experimental data will be compared with modeling
results to identify optimum operating conditions for WGS reaction. The project will perform an economic analysis using the dual-
phase membrane as a WGS reactor for hydrogen production and CO2 capture for an IGGC plant.
Figure 2: Proposed Membrane Reactor for WGS Reaction
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 781
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE-BASED CO2 SEPARATIONS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer — Li2/K2CO3 doped Li2/K2CO3
fast-ionic conductors
Materials of Fabrication for Support Layer — porous stainless steel
(doped ZrO2, CeO2)
Nominal Thickness of Selective Layer µm 2,000 10-200
Membrane Geometry — disk tube
Max Trans-Membrane Pressure bar 2 >6
Hours Tested Without Significant Degradation — N/A >700
Manufacturing Cost for Membrane Material $/m2 / 500
Membrane Performance
Temperature °C 700–900 700–900
CO2 Pressure Normalized Flux GPU or equivalent 600 >1,000
CO2/H2O Selectivity — 300 >500
CO2/H2 Selectivity — 300 >500
CO2/SO2 Selectivity — — >500
Type of Measurement —
Proposed Module Design (for equipment developers)
Flow Arrangement — flat disk Tube – counter-flow
Packing Density m2/m3 10 >60
Shell-Side Fluid — steam
Syngas Flowrate L(STP)/min (per tube) >0.2
CO2 Recovery, Purity, and Pressure %/%/bar 90%/99.5%/1 atm
H2 Recovery, Purity, and Pressure %/%/bar 99.9%/93%/>6 atm
Pressure Drops Shell/Tube Side bar >6
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for mixture of gases
found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
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782 DOE/NETL CARBON CAPTURE PROGRAM R&D
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Appendix: Pre-Combustion Membrane Technologies
Other Parameter Descriptions:
Membrane Permeation Mechanism – Carbon dioxide permeates through by combined transport of carbonate ions in the molten
carbonate phase and oxygen ions in the solid metal-oxide phase.
Contaminant Resistance – The membrane to be stable in 0.1–1 percent atmosphere containing hydrogen sulfide (H2S).
Proposed Module Design – Shell-tube module.
technology advantages
• WGS reaction at one temperature (above 400 °C).
• Separation of CO2 and H2 mixture in one step.
• Production of high-pressure hydrogen stream.
R&D challenges
• Failure to obtain sufficiently high CO2 permeance due to a rate-limiting surface reaction.
• Undesired surface properties of ceramic supports resulting in instability of the carbonate in the support pores.
results to date/accomplishments
• Synthesis of dual-phase membrane disks.
• Tubular membranes were prepared via pressing technique using graphite powders.
• Fabrication techniques of pressing-sintering and centrifugal casting were successfully modified to optimize support micro-
structure.
• Thin, dual-phase membranes on porous support of disk and tubular geometries were successfully fabricated.
• High CO2 selectivity and good CO2 permeance through the membranes were demonstrated.
• Separation and permeation properties of dual-phase membranes under syngas conditions was modeled and analyzed. CO2
permeation mechanism and factors affecting CO2 permeation of the dual-phase membranes have been identified.
• WGS reaction in the dual-phase membrane reactor was studied. Conditions to produce hydrogen of 93 percent purity and CO2
stream of >95 percent purity, with 90 percent CO2 capture were identified.
next steps
This project ended on September 30, 2014.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 783
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
available reports/technical papers/presentations
Lin, Jerry, Final Technical Report, “Pre-Combustion Carbon Dioxide Capture by a New Dual Phase Ceramic-Carbonate Membrane
Reactor,” http://www.osti.gov/scitech/biblio/1172599, publication date September 30, 2014.
Lin, J.Y.S., Final Project Presentation. http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/pre-
combustion/2014-12-05-Closeout-Presentation-FE0000470.pdf.
Lin, J.Y.S.; Norton, T.; Ortiz-Landeros, J.; Lu, B.; and Anderson, M; “Pre-Combustion Carbon Dioxide Capture by a New Dual-
Phase Ceramic-Carbonate Membrane Reactor,” presented at 2014 NETL CO2 Capture Technology Meeting in Pittsburgh, PA, July
2014. http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/X-Dong-ASU-Dual-Phase-
Ceramic-Carbonate-Membrane-Reactor.pdf.
Lin, J.Y.S.; Norton, T.; Dong, X; Lu, B; “Pre-Combustion Carbon Dioxide Capture by a New Dual-Phase Ceramic-Carbonate
Membrane Reactor,” presented at 2013 NETL CO2 Capture Technology Meeting in Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/T-Norton-ASU-Dual-Phase-Ceramic-Carbonate-Membrane-
Reactor.pdf.
Lu, B.; and Lin, Y.S., “Sol-Gel Synthesis and Characterization of Mesoporous Yttria Stabilized Zirconia Membranes with Graded
Pore Structure,” J. Materials Sci., 46, 7056-7066 (2011).
Norton, T.T.; and Lin, Y.S., “Transient Oxygen Permeation and Surface Catalytic Properties of Lanthanum Cobaltite Membrane
under Oxygen-Methane Gradient,” Ind. Eng. Chem. Res., 51, 12917-12925(2012).
Lin, J.Y.S.; Norton, T.; Ortiz-Landeros, J.; Lu, B.; and Wang, H., “Pre-Combustion Carbon Dioxide Capture by a New Dual-Phase
Ceramic-Carbonate Membrane Reactor,” presented at 2012 NETL CO2 Capture Technology Meeting in Pittsburgh, PA, in July 2012.
Rui, Z.B.; Anderson , M.; Li, Y.D.; and Lin, Y.S., “Ionic Conducting Ceramic and Carbonate Dual Phase Membranes for Carbon
Dioxide Separation,” J. Membrane Sci., 417-418, 174-182 (2012).
Anderson, M.; and Lin, Y.S., “Carbon Dioxide Separation and Dry Reforming of Methane for Synthesis of Syngas by a Dual- Phase
Membrane Reactor,” AIChE J., 59, 2207-2218 (2013)
Lu, B.; Lin, Y.S., “Synthesis and characterization of thin ceramic-carbonate dual-phase membranes for carbon dioxide separation”, J.
Membr. Sci., 444, 402-411 (2013)
Dong, X.; Ortiz-Landeros, J.; Lin, Y.S., “An asymmetric tubular ceramic-carbonate dual phase membrane for high temperature CO2
separation”, Chem. Commun, 49, 9654-9656 (2013)
Ortiz-Landeros, J., Norton, T.; Lin, Y.S., “Effects of support pore structure on carbon dioxide permeation of ceramic-carbonate
dual-phase membranes”, Chem. Eng. Sci., 104, 891-898 (2013)
Norton, T.T., Ortiz-Landeros, J., Lin, Y.S., “Stability of La-Sr-Co-Fe oxide-carbonate dual-phase membranes for carbon dioxide
separation at high temperatures”, Ind. Eng. Chem. Res., 53, 2432-2440 (2014)
Norton, T.T.; Lu, B.; Lin, Y.S., “Carbon dioxide permeation properties and stability of samarium-doped-ceria carbonate dual-phase
membranes”, J. Membr, Sci., 467, 244-252(2014)
Norton, T.T., Lin, Y.S., “Ceramic-carbonate dual-phase membrane with improved chemical stability for carbon dioxide separation
at high temperature”, Solid State Ionics, 263, 172-179 (2014)
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
784 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
DESIGNING AND VALIDATING
TERNARY PD-ALLOYS FOR OPTIMUM
SULFUR/CARBON RESISTANCE technology maturity:
Laboratory-Scale Using
primary project goals Simulated Syngas
project focus:
Pall Corporation is developing an economically viable hydrogen (H2)/carbon dioxide
(CO2) separation membrane system that would allow efficient capture of CO2 at high Pd-Alloys for
temperature and pressure from gasified coal in the presence of typical contaminants using Sulfur/Carbon Resistance
a ternary palladium (Pd)-alloy. Membranes were fabricated and tested in simulated coal
gasification conditions. The final objective is a membrane with high hydrogen flux and participant:
excellent resistance to syngas contaminants.
Pall Corporation
technical goals project number:
FE0001181
• Create an advanced Pd-alloy for optimum H2 separation performance using
combinatorial material methods for high-throughput screening, testing, and NETL project manager:
characterization. Jason Hissam
• Demonstrate durability under long-term testing of a pilot membrane in laboratory- [email protected]
scale.
• Understand long-term effects of the coal gasifier environment on the metallurgy of principal investigator:
the membrane components by comparing controlled diffusion studies with in-service Scott Hopkins
membranes.
Pall Corporation
[email protected]
technical content
partners:
The project developed an advanced Pd-alloy for optimum H2 separation performance to Cornell University,
demonstrate long-term durability under coal synthesis gas (syngas) conditions. Ternary Georgia Institute of
Pd-alloys with potential for favorable performance were selected based on a literature Technology,
search. This large set of ternary Pd-alloys underwent combinatorial alloy spreads on thin
Colorado School of
film support disks. These disks were tested in a syngas environment using in situ Raman
spectroscopy to measure H2 separation factor and permeability, as well as characterize Mines,
sulfur and carbon resistance of best candidate alloys. These alloys were compared to Southern Company
baseline tests of traditional Pd-gold (Au) alloy membranes.
performance period:
The best alloys were fabricated into 15-cm2 tubular membranes and tested. As with the
combinatorial disks, the 15-cm2 active area tubes were exposed to conditions 10/1/09 – 9/30/14
representative of a coal gasifier environment: high temperature and high pressure in the
presence of contaminating species. Emphasis was placed on identification and
characterization of membrane defects, surface analysis of the regions affected by the
contaminants, and assessment of the surface quality of the ceramic substrate
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 785
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Figure 1: A Co-Sputtering Chamber
Scale-up of membranes to75-cm2 was initially planned but was not conducted. The 15-cm2 active area tubes were subjected to a
100+ hour continuous testing.
Membrane Figure 2: Graph of Atom Concentration as a Function of Distance from the Gun Axis for Pt, Bi, and Pb Targets
Figure 3: A 75-cm2
Technical Targets:
• Membrane would be tolerant of up to 20 parts per million (ppm) hydrogen sulfide (H2S).
• Hydrogen flux of 200 ft3/hr/ft2 at 400 °C and 20 pounds per square inch (psi) H2 partial pressure differential.
• Total pressure differential operating capability 400 psi.
• The membrane cost must be in the range of $500/ft2.
• Permeate H2 purity should be at a level of 99.5 percent.
• The membrane must be resistant to coking with relatively low steam-to-carbon ratio.
• The system should be stable for a minimum of 3 years in service.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
786 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
TABLE 1: MEMBRANE-BASED CO2 SEPARATIONS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer — palladium-gold alloys palladium alloys
zirconia coated porous zirconia coated porous
Materials of Fabrication for Support Layer — stainless steel tubes stainless steel tubes
Nominal Thickness of Selective Layer µm 3–5 μm 3–7 μm
Membrane Geometry — shell and tube shell and tube
Max Trans-Membrane Pressure bar 400 psi at 400 °C 400 psi at 400 °C
Hours Tested Without Significant Degradation — 1,000 5,000
Manufacturing Cost for Membrane Material $/m2 1,000 500
Membrane Performance
Temperature °C 400 450
H2 Pressure Normalized Flux GPU or equivalent 170 200
H2/H2O Selectivity —
H2/CO2 Selectivity —
H2/SO2 Selectivity —
Type of Measurement —
Proposed Module Design (for equipment developers)
Flow Arrangement — outside – in
Packing Density m2/m3
Shell-Side Fluid —
Flue Gas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar
H2 Recovery, Purity, and Pressure %/%/bar
Pressure Drops Shell/Tube Side bar
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for mixture of
gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 787
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Other Parameter Descriptions:
Contaminant Resistance – Palladium-based alloy membranes should tolerate moderate levels of coal gas contaminants after
advanced hot syngas cleanup. Primary contaminants include H2S and carbon monoxide (CO). A typical hot gas cleanup process can
bring residual level of sulfur into the range of 0.5–20 parts per million volume (ppmv). After a single-stage water-gas shift (WGS)
reactor, CO can be as low as a few percent.
Waste Streams Generated – No waste streams are generated since H2 is extracted by a Pd-alloy membrane system with primarily
CO2 and water (H2O) left at high pressure. After steam is condensed, CO2 is sent for sequestration.
technology advantages
• Researchers use a proprietary process to create ultrathin, economical, Pd-alloy membranes in virtually any alloy system.
• The project applied combinatorial methods to continuous ternary alloy spreads and use a novel characterization method to
rapidly scan the alloys after syngas exposure to identify the most resistant compositions.
• A customized composite substrate from Pall was used to deposit ultrathin Pd-alloy membranes. The substrate is porous
stainless steel tubes with ceramic coating on the outside surface as a diffusion barrier; thus, membrane elements can be
assembled into the module by a conventional welding technique.
R&D challenges
• Hydrogen separation performance may not achieve target performance by membrane design alone. Supplements such as
additional gas reforming capabilities may be required either upstream or downstream of the membrane module.
• Scale-up of the Pd-alloy surface area from 15 to 75 cm2; was planned but will not be conducted under this project.
• Membrane durability during thermal cycling and its effect on stability; the stability of the ceramic coated support has been
demonstrated, but not the long-term stability with a Pd-alloy membrane in place.
results to date/accomplishments
• Identified six candidate ternary alloys that had little adsorption of sulfur and carbon after exposure.
• Added Colorado School of Mines as a subcontractor to create six ternary alloys for hydrogen permeance testing and
sulfur/carbon exposure testing.
• Made 5 cm2 membranes for exposure testing.
• Conducted preliminary tests on active area membranes.
next steps
This project ended on September 30, 2014.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
788 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
available reports/technical papers/presentations
Lewis, A., Hopkins, S.; and H. Zhao “Identifying Pd-Based Ternary Membranes for Carbon and Sulfur Applications,” 2014 NETL
CO2 Capture Technology Meeting, Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/A-Lewis-Pall-Pd-Based-Ternary-
Membranes.pdf.
Hopkins, S.; and H. Zhao. “High Throughput Design of Ternary Pd Alloys for Optimum Sulfur/Carbon Resistance in Hydrogen
Separation and Carbon Capture Membrane Systems,” presented at 2013 NETL CO2 Capture Technology Meeting in Pittsburgh,
PA, July 2013. http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/H-Zhao-Pall-Ternary-Pd-Alloys.pdf.
Hopkins, S.; and H. Zhao. “High Throughput Design of Ternary Pd Alloys for Optimum Sulfur/Carbon Resistance in Hydrogen
Separation and Carbon Capture Membrane Systems,” presented at 2012 NETL CO2 Capture Technology Meeting in Pittsburgh,
PA, July 2012.
Hopkins, S. “Designing and Validating Ternary Pd Alloys for Optimum Sulfur/Carbon Resistance,” presented at 2011 NETL CO2
Capture Technology Meeting in Pittsburgh, PA, August 2011.
Henkel, D., “Combinatorial Design of Pd Ternary Alloys for Sulfur/Carbon Tolerant Hydrogen Separation,” presented at 2010
NETL CO2 Capture Technology Meeting in Pittsburgh, PA, September 2010.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 789
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
HYDROGEN-SELECTIVE EXFOLIATED
ZEOLITE MEMBRANES
technology maturity:
primary project goals
Bench-Scale, Simulated
The University of Minnesota researchers are further developing exfoliated zeolite coating
Syngas
technology for hydrogen (H2) separation membranes, including membrane production
methodology, and determining the feasibility of integration of the membrane into a water- project focus:
gas shift (WGS) reactor model. Hydrogen-Selective
Zeolite Membranes
technical goals participant:
• Develop and optimize a membrane production method for the exfoliated zeolite
University of Minnesota
coating.
project number:
• The membrane must demonstrate high flux, high selectivity, and stable performance.
FE0001322
• Determine the feasibility of integrating these membranes in WGS reactors and
integrated gasification combined cycle (IGCC) flow sheets.
NETL project manager:
• Perform a techno-economic analysis.
Elaine Everitt
[email protected]
technical content
principal investigator:
This project will further develop a novel silica molecular sieve membrane using exfoliated Michael Tsapatsis
zeolite coatings with the potential to contribute to carbon capture by high-temperature University of Minnesota
separation of H2 from carbon dioxide (CO2) and other gases present in shifted synthesis gas [email protected]
(syngas). The project will establish procedures for the production of the required supply of
these layered silicates, first optimizing the synthesis process of the exfoliated zeolite, then partners:
the layer-by-layer coating process.
None
The pore structure of the zeolite that is currently studied (MCM-22) includes ultra-small
(potentially H2-selective) sized pores defined by six SiO4 tetrahedra (6-Member Ring pores: performance period:
6MR) along the c-axis. Therefore, c-out-of-plane oriented films are promising for H2-
separation membranes. MCM-22 has highly anisotropic plate or disk-like crystal shape, thin
10/1/09 – 9/30/14
along the c-crystallographic axis and appropriate for achieving c-oriented films. Among
available compositions, an all-silica and potentially hydrothermally stable composition has
been reported, which could enable H2-separations in applications like WGS reactors.
Membrane Microstructures Achieved Currently: MCM-22/silica composite films were
fabricated using layer-by-layer deposition towards a nanoscale realization of the selective
flake concept. The repetition of appropriate deposition cycles (i.e., particle deposition and
subsequent silica coating) led to the gradual increase of separation performance achieving
H2/nitrogen (N2) ideal selectivity as high as 120. The scanning electron microscope (SEM)
cross-section image of a five-layer membrane along with its schematic is shown in Figure 1.
The aim of the ongoing work is to improve performance using thinner flakes (exfoliated
zeolite layers).
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
790 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Figure 1: SEM Cross-Section Image of a Five-Layer Membrane Along with Schematic
The H2 permeance and selectivity to CO2 and other gases, as well as hydrothermal stability, will be determined for the developed
membrane. A series of tests will determine membrane separation performance. Performance testing configurations will include flat
alumina supports up to 220 °C; tubular membrane testing using single gases up to 600 °C; tubular membrane testing using simulated
feeds up to 600 °C; and high-temperature, high-pressure testing of tubular supports. The membrane stability will be determined in a
WGS environment. The three stability test configurations are in steam containing simulated feeds for exfoliated powders; in steam
containing simulated feeds for alumina supported films; and in steam containing simulated feeds for stainless steel supported films.
The project will also integrate the membrane into a WGS membrane reactor model, integrate the model in an IGCC flow sheet, and
perform techno-economic analysis and operability evaluation and analysis.
TABLE 1: MEMBRANE-BASED CO2 SEPARATIONS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer — MCM-22 plate like crystals exfoliated MCM-22 layers
porous alumina discs porous stainless steel tubes
Materials of Fabrication for Support Layer — (homemade) (commercial)
Nominal Thickness of Selective Layer µm
Membrane Geometry —
Max Trans-Membrane Pressure bar
Hours Tested Without Significant Degradation — 48 250
Manufacturing Cost for Membrane Material $/m2
Membrane Performance
Temperature °C 200 500
H2 Pressure Normalized Flux GPU or equivalent
H2/H2O Selectivity —
H2/CO2 Selectivity — 20 80–800
H2/H2S Selectivity —
Sulfur Tolerance
Type of Measurement —
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 791
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Proposed Module Design (for equipment developers)
Flow Arrangement —
Packing Density m2/m3
Shell-Side Fluid —
Syngas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar
H2 Recovery, Purity, and Pressure %/%/bar
Pressure Drops Shell/Tube Side bar 1–2 10
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for mixture of gases
found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
Other Parameter Descriptions:
Contaminant Resistance – These materials are crystalline silicates and the main issue is stability to steam. Other contaminants are
not expected to create problems.
Syngas Pretreatment Requirements – To be determined as project progresses.
Waste Streams Generated – To be determined as project progresses.
technology advantages
This membrane technology will form the selective film using a coating process and premade components, and will have high
selectivity, flux, and stability.
R&D challenges
• Dispersible exfoliated layers.
• Simple and efficient coatings process.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
792 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
results to date/accomplishments
• Synthesis of high aspect ratio exfoliated MCM-22 layers while preserving structure.
• Layer-by-layer coatings of exfoliated MCM-22 layers were fabricated.
• Membranes were tested for separation performance.
• Stability testing was conducted on exfoliated MCM-22 membranes in WGS environment.
• Simulation and optimization studies for IGCC-Membrane Reactor (MR) plant were performed and a techno-economic
assessment of IGCC-MR process was completed.
next steps
This project ended on September 30, 2014.
available reports/technical papers/presentations
Tsapatis, M; Daoutidis, P.; Elyassi, B.; Lima, F; Iyer, A.; Agrawal, K.; Sabnis, Sanket, Final Report, “Hydrogen Selective
Exfoliated Zeolite Membranes,” http://www.osti.gov/scitech/biblio/1178537, Publication date 09/30/2014.
Tsapatsis, M.; Daoutidis, “Hydrogen Selective Exfoliated Zeolite Membranes,” Final Project Presentation.
http://www.netl.doe.gov/File%20Library/Research/Coal/carbon%20capture/pre-combustion/2014-12-12-Final-Presentation-DOE-
CO2.pdf.
Tsapatsis, M.; Daoutidis, P.; Lima, F.; Elyassi, B. Iyer, A, “Hydrogen Selective Exfoliated Zeolite Membranes,” presented at the
2014 NETL CO2 Capture Technology Meeting in Pittsburgh, PA, July 2014.
http://www.netl.doe.gov/File%20Library/Events/2014/2014%20NETL%20CO2%20Capture/A-Iyer-UMinnesota-Zeolite-
Membranes.pdf.
Tsapatsis, M.; Daoutidis, P.; Lima, F.; Elyassi, B. Iyer, A, “ Hydrogen Selective Exfoliated Zeolite Membranes,” presented at the
2013 NETL CO2 Capture Technology Meeting in Pittsburgh, PA, July 2013.
http://www.netl.doe.gov/File%20Library/Events/2013/CO2%20Capture/A-Iyer-UMinnesota-H2-Selective-Exfoliated-Zeolite-
Membranes.pdf.
Tsapatsis, M.; Daoutidis, P.; Lima, F.; Elyassi, B. “ Hydrogen Selective Exfoliated Zeolite Membranes,” presented at the 2012
NETL CO2 Capture Technology Meeting in Pittsburgh, PA, July 2012. http://www.netl.doe.gov/File%20Library/Events/2012/
CO2%20Capture%20Meeting/F-Lima-UMn-Exfoliated-Zeolite-Membranes.pdf.
Lima, Fernando V.; Daoutidis, Prodromos; Tsapatsis, Michael; et al., “Modeling and Optimization of Membrane Reactors for
Carbon Capture in Integrated Gasification Combined Cycle Units,” Industrial & Engineering Chemistry Research, Volume: 51
Issue: 15 Pages: 5480-5489, April 18, 2012. Tsapatsis, Michael, Toward High-Throughput Zeolite Membranes, Science, Volume:
334 Issue: 6057 Pages: 767-768, November 11, 2011.
Varoon, Kumar; Zhang, Xueyi; Elyassi, Bahman; et al., “Dispersible Exfoliated Zeolite Nanosheets and Their Application as a
Selective Membrane,” Science, Volume: 333 Issue: 6052 Pages: 72-75, October 7, 2011.
Tsapatsis, M.; Daoutidis, P.; Lima, F.; Elyassi, B. “Hydrogen Selective Exfoliated Zeolite Membranes,” presented at the 2011
NETL CO2 Capture Technology Meeting in Pittsburgh, PA, August 2011. http://www.netl.doe.gov/File%20Library/Events/2011/
CO2capture/26Aug11--Lima-UMinn-H2-Selective-Zeolite-Membranes.pdf.
Tsapatsis, M.; Daoutidis, P., “Hydrogen Selective Exfoliated Zeolite Membranes,” presented at the 2010 NETL CO2 Capture
Technology Meeting in Pittsburgh, PA, September 2010.
http://www.netl.doe.gov/File%20Library/Events/2010/CO2capture/Michael- Tsapatsis-FE0001322.pdf.
Maheshwari, S.; Kumar, S.; Bates, F.S.; Penn, R.L.; Shantz, D.F.; Tsapatsis, M. Journal of the American Chemical Society 130,
1507-1516 (2008), “Layer Structure Preservation during Swelling, Pillaring and Exfoliation of a Zeolite Precursor.”
Choi, J.; Tsapatsis, M. Journal of the American Chemical Society 132(2), 448-449 (2010), “MCM-22/Silica Selective Flake
Nanocomposite Membranes for Hydrogen Separations.”
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 793
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
PRESSURE SWING ABSORPTION DEVICE
AND PROCESS FOR SEPARATING CO2
FROM SHIFTED SYNGAS AND ITS technology maturity:
CAPTURE FOR SUBSEQUENT STORAGE Laboratory-Scale Using
Simulated Syngas
primary project goals project focus:
Pressure Swing
The New Jersey Institute of Technology (NJIT) is developing, via laboratory-scale Membrane Absorption
experiments, a pressure swing membrane absorption-based (PSMAB) device using a non- Device and Process
dispersive, membrane-based gas-liquid contactor that produces hydrogen at high pressure
for integrated gasification combined cycle (IGCC), as well as a carbon dioxide (CO2) participant:
stream, between 1 and 5 atm, that contains at least 90 percent of the CO2 from a feed gas
at ≈200 °C and 300 pounds per square inch gauge (psig). New Jersey Institute of
Technology
technical goals project number:
FE0001323
• Develop, via laboratory experiments, an advanced PSMAB device and a cyclic
process to produce helium (He) (a surrogate for hydrogen) at high pressure from low- NETL project manager:
temperature, post-shift reactor synthesis gas (syngas), as well as a CO2 stream
containing at least 90 percent of the CO2 and suitable for sequestration. Steven Markovich
[email protected]
• Provide data and analysis of the cyclic process and device to facilitate subsequent
scaleup.
principal investigator:
• Develop a detailed analysis for the process and device to allow economic evaluation
for potential larger-scale use.
Dr. Kamalesh K. Sirkar
New Jersey Institute of
Technology
technical content [email protected]
In the first phase of research, an experimental setup will be developed for studying the partners:
PSMAB process. NJIT will work with Media and Process Technology, Inc., Porogen Inc.
Applied Membrane
and Applied Membrane Technologies (AMT), Inc. to develop microporous
hydrophobized ceramic tubule-based, microporous hydrophobized Polyetheretherketone Technologies,
(PEEK) hollow fiber-based and microporous Polytetrafluoroethylene (PTFE) hollow Media and Process
fiber-based absorption devices. The absorption device will be explored on a preliminary Technology,
basis for performance of PSMAB separation of a moist CO2-He gas mixture at 150– Porogen,
200 °C and 200–300 psig, simulating a low-temperature, post-shift reactor syngas stream. Techverse
performance period:
10/1/09 – 3/31/13
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
794 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Figure 1: Concentration Profile of Absorbed Species in Gas and Liquid Phases.
In Phase II, NJIT will explore, in detail, the purification and separation performance of the PSMAB process for selected absorbents
vis-à-vis purification of the feed gas stream to obtain a high-pressure, purified He stream and a low-pressure, purified CO2 stream.
Valve 3
Helium
(a) product
P
re
ss
u
re
Valve 1 Valve 2 in
Feed gas CO2 product tu
One absorption cycle
b
e
si
d
e
Valve 4 Valve 3
(b) Helium
product
Middle part
gas
Valve 5
P
re
ss
Valve 1
u
Valve 2
re
Feed gas
in
CO2 product tu
b One absorption cycle
e
si
d
Figure 2: Schematic Diagrams of (a) 3-Valve and (b) 5-Valve Pressure Swing Membrane Absorption Process and the Corresponding Pressure
e
vs. Time Profile in the Bore of the Tubule or Hollow Fiber.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 795
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Experimental setups will be developed to measure the solubility and diffusion coefficients of CO2 and He at the appropriate ranges
of temperature and pressure for selected absorbents. Researchers will develop a mathematical model of the PSMAB device and
process.
In Phase III, NJIT will generate experimental data on the solubility and diffusion coefficient for CO2 and He for the selected
absorbents. This will allow comparison of the results of simulation of the mathematical model with the observed purification and
separation in the PSAB process and device for selected absorbents. Simulations of the model will be performed to explore scale up
of the process and facilitate process evaluation. The extent of loss/deterioration of the absorbents over extended periods of
operation will be determined.
TABLE 1: LIQUID SORBENT BED PARAMETERS
Units Current R&D Value Target R&D Value
Pure Sorbent
Molecular Weight mol-1 205.26 205.26
Normal Boiling Point °C N/A N/A
Normal Freezing Point °C -6 -6
Vapor Pressure at 15 °C bar None None
Manufacturing Cost for Sorbent $/kg Not available
Working Solution
Concentration 20% PAMAM dendrimer Gen 0 in [bmim] Kg/kg 0.25 (dendrimer/[bmim][DCA])
[DCA] 1.08 at room temp.; 1.06 at 65 °C
Specific Gravity (15 °C/15 °C) g/cm3 1.092 (20 wt% dendrimer-[bmim][DCA] mixture)
at room temperature
Specific Heat Capacity at STP kJ/kg-K N/A N/A
Viscosity at STP cP 106.7 at room temp
A b s o r p ti o n
Pressure bar 13.8–17 13–20
Temperature °C 100–125 150–200
Equilibrium CO2 Loading mol/mol 0.13
Heat of Absorption kJ/mol CO2
Solution Viscosity cP 25.4 at 65 °C
Desorption
Pressure bar 0.9 1.0
Temperature °C 100–125 150–200
Equilibrium CO2 Loading mol/mol 0.019
Heat of Desorption kJ/mol CO2
Proposed Module Design (for equipment developers)
Syngas Flowrate kg/hr
H2 Recovery, Purity, and Pressure %/%/bar
Pressure Drops Shell/Tube Side bar
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
796 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
TABLE 2: MEMBRANE-CONTACTOR PARAMETERS
Units Current R&D Value Target R&D Value
Materials Properties
Materials of Fabrication for Selective Layer — fluoropolymer
Materials of Fabrication for Support Layer — ceramic, Teflon, PEEK
Nominal Thickness of Selective Layer µm
Membrane Geometry — hollow fiber, shell and tube
Max Trans-Membrane Pressure bar 20.4 bar 21 bar
Hours Tested Without Significant Degradation — 100 1,000
Manufacturing Cost for Membrane Material $/m2 100
Type of Measurement —
Proposed Module Design (for equipment developers)
Flow Arrangement —
m2/m3 ceramic: 900
Packing Density Teflon: 2,000
PEEK: 5,000
Shell-Side Fluid —
Syngas Flowrate kg/hr
CO2 Recovery, Purity, and Pressure %/%/bar N/A/85≈90.7/0.2≈1.0 90/95/1.0
H2 Recovery, Purity, and Pressure %/%/bar N/A/93≈95/5.0≈6.0 95/98/6.0–10.0
Pressure Drops Shell/Tube Side bar N/A N/A
Definitions:
Membrane Geometry – Flat discs or sheets, hollow fibers, tubes, etc.
Pressure Normalized Flux – For materials that display a linear dependence of flux on partial pressure differential, this is equivalent
to the membrane’s permeance.
GPU – Gas Permeation Unit, which is equivalent to 10-6 cm3 (1 atm, 0 °C)/cm2/s/cm Hg. For non-linear materials, the dimensional
units reported should be based on flux measured in cm3 (1 atm, 0 °C)/cm2/s with pressures measured in cm Hg.
Note: 1 GPU = 3.3464 × 10-6 kg mol/m2-s-kPa [SI units].
Type of Measurement – Either mixed or pure gas measurements; projected permeance and selectivities should be for mixture of
gases found in pre-conditioned syngas.
Flow Arrangement – Typical gas-separation module designs include spiral-wound sheets, hollow-fiber bundles, shell-and-tube, and
plate-and-frame, which result in either cocurrent, countercurrent, crossflow arrangements, or some complex combination of these.
Packing Density – Ratio of the active surface area of the membrane to the volume of the module.
Shell-Side Fluid – Either the permeate (H2-rich) or retentate (syngas) stream.
Other Parameter Descriptions:
Contaminant Resistance – Hydrogen sulfide (H2S) will not affect the ceramic substrate, nor will it affect the fluoropolymer coating
on ceramic and PEEK materials; the Teflon hollow fibers will also remain unaffected. PEEK material is also unlikely to be
affected.
Syngas Pretreatment Requirements – Syngas may need to be cooled to 100–125 °C, unless the next round of membrane modules
can withstand higher temperature on a continuous basis.
Membrane Replacement Requirements – Device has not been run long enough continuously to define the replacement time. Device
will need to run for at least 1,000–3,000 hours.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 797
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
Waste Streams Generated – Degraded absorption solvent.
Proposed Module Design – Porous hydrophobic hollow-fiber based membrane modules having very limited dead volume at the
tube-side headers and tube sheets and connections; the outside diameters of contiguous hollow fibers should not touch each other to
allow absorbent in between at the closest distance between adjacent hollow fibers
Figure 3: Schematic of Absorber Containing Ceramic Tubules or Hollow Fibers
technology advantages
• High solubility selectivity of novel selected liquid absorbents, high purification ability of the PSA process, and high gas-liquid
contacting surface area per unit device volume.
• Compact, membrane-like device.
• Will deliver highly purified hydrogen (H2) at nearly its partial pressure and temperature in the post-shifted reactor syngas feed.
• Purified CO2 stream (>90 percent CO2) will be available at 1 atm.
R&D challenges
• Continuous production of both a higher-purity He stream and a highly purified CO2 stream requires more modules and altered
module configurations. The PEEK hollow-fiber module design has to be changed to achieve higher purification. There is
considerable dead volume in the design provided to us resulting in lower CO2 concentration in the CO2-rich stream and higher
CO2 concentration in the He-rich stream.
• Absorbent leaks through microporous PTFE hollow fibers that have a plasma polymerized microporous fluorosilicone coating.
These fibers did not develop a high-enough pressure capability and need further development.
• The ceramic tubules have considerable pressure capability but have low surface area per unit volume and are therefore not
suitable with current tubule dimensions.
results to date/accomplishments
• Successful testing of PEEK membrane in lab at 250 psig and 100 °C with He/CO2 stream.
• Successful testing of ceramic membrane modules in lab at 300 psig without any leakage; extended operation at 120 °C.
• Scale-up of process and device was conducted, including implementation of improved hollow-fiber module design with regard
to inter-fiber spacing and fiber surface area in a given module.
• Absorbent liquid was characterized and degradation determined.
• Polyethylene glycol (PEG) 400 is capable of replacing the ionic liquid as the solvent especially in the presence of the
dendrimer.
• The PSMAB process was stable with time; the PEEK membrane modules performed much better than ceramic membrane
modules to separate CO2 since PEEK hollow fibers had much higher gas-liquid contacting area per unit gas volume.
• A mathematical model was developed to describe the pressure swing membrane absorption process.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
NATIONAL ENERGY TECHNOLOGY LABORATORY
798 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: Pre-Combustion Membrane Technologies
next steps
This project ended on March 31, 2013.
available reports/technical papers/presentations
Jie, X., Chau, J., Obuskovic G. and Sirkar, K. K., “Preliminary Studies of CO2 Removal from Precombustion Syngas through
Pressure Swing Membrane Absorption Process with Ionic Liquid as Absorbent,” I&EC Res., 52, 8783-8799 (2013).
Chau, J., Obuskovic, G., Jie, X., Mulukutla, T. and Sirkar, K. K., “Solubilities of CO2 and Helium in an Ionic Liquid Containing
Poly(amidoamine) Dendrimer Gen 0,” I&EC Res., 52, 10484-10494 (2013).
Chau, J., Obuskovic, G., Jie, X. and Sirkar, K.K., “Pressure Swing Membrane Absorption Process for Syngas Separation in a 3-
valve System: Modeling vs. Experiments,” J. Membrane Sci., 453, 61-70 (2014).
Jie, X., Chau, J., Obuskovic, G. and Sirkar, K.K., “Enhanced Pressure Swing Membrane Absorption Process for CO2 Removal
from Shifted Syngas with Dendrimer-Ionic Liquid Mixture as Absorbent,” I&E Chem. Res., 53(8), 3305-3320 (2014).
Sirkar, K; Jie, X; Chau, J; Obuskovic, G.; Final Technical Report, June 2013, “Pressure Swing Absorption Device and Process for
Separating CO2 from Shifted Syngas and its Capture for Subsequent Storage.” http://www.osti.gov/scitech/servlets/purl/1097081.
Sirkar, K.K., “Pressure Swing Absorption Device and Process for Separating CO2 from Shifted Syngas and its Capture for
Subsequent Storage,” presented at 2012 NETL CO2 Capture Technology Meeting, July 2012.
Chau, J.; Xingming, J.; Obuskovic, G.; and Sirkar, K.K., “Pressure Swing Absorption Device and Process for Separating CO2 from
Shifted Syngas and its Capture for Subsequent Storage,” presented at 2011 NETL CO2 Capture Technology Meeting, August 2011.
http://www.netl.doe.gov/File%20Library/research/coal/carbon%20capture/26Aug11-Sirkar-NJIT-PSA-CO2-from-Syngas.pdf.
CARBON CAPTURE TECHNOLOGY SHEETS PRE-COMBUSTION MEMBRANES
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 799
Appendix: Pre-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
800 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Pre-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 801
Appendix: Pre-Combustion Membrane Technologies
NATIONAL ENERGY TECHNOLOGY LABORATORY
802 DOE/NETL CARBON CAPTURE PROGRAM R&D
Appendix: Pre-Combustion Membrane Technologies
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 803
Appendix: Pre-Combustion Membrane Technologies
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NATIONAL ENERGY TECHNOLOGY LABORATORY
804 DOE/NETL CARBON CAPTURE PROGRAM R&D
CARBON CAPTURE TECHNOLOGY SHEETS
APPENDIX:
R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
805
Appendix: R&D Collaborations
Advancing CO2 Capture technology maturity:
Pilot Scale
Technology: Partnership For project focus:
CO2 Capture Partnership for CO2 Capture
participant:
primary project goals
University of North Dakota
The University of North Dakota Energy and Environmental Research Center (UNDEERC) Energy and Environmental
conducted pilot-scale testing to evaluate and validate a range of carbon dioxide (CO 2 ) Research Center
capture technologies to develop key technical and economic information that can be
used to examine the feasibility of capture technologies as a function of fuel type and project number:
system configuration. FC26-08NT43291
technical goals predecessor projects:
N/A
• Integrate a high-efficiency, flexible post-combustion capture system with existing
pilot-scale combustion and emission control systems to evaluate the performance NETL project manager:
of several capture techniques and technologies in flue gas streams derived from Andrew Aurelio
selected fossil fuels, biomass, and blends. [email protected]
• Conduct testing of oxy-combustion for selected fuels and blends in one or more of
UNDEERC’s existing pilot-scale units. principal investigator:
• Evaluate the performance of emerging CO 2 capture technologies under john Kay
development and identify key challenges associated with each for both pre- UNDEERC
[email protected]
combustion and post combustion platforms
• Perform systems engineering modeling to examine efficient and cost-effective partners:
integration of CO 2 capture technologies in existing and new systems.
Arthur Gallagher, Atco Power,
Black & veatch, Baker Hughes,
Cansolv Technologies, CO2
technical content Capture Project Consortium,
Constellation Power Source
UNDEERC constructed two pilot-scale systems and performed experiments on several Generation, C-Quest
advanced CO 2 capture technologies and compared them to monoethanolamine (MEA). Technologies, GE Global
Flue gas derived from one of two pilot combustors was used as the CO 2 source. The Research, Hitachi, Huntsman
pilot combustors are highly versatile; able to fire virtually any fuel and configurable with Petrochemical, Metso Power,
Midwest Generation,
all of the primary pollution control devices including electrostatic precipitators, fabric
Minnesota Power, Nebraska
filters, selective catalytic reduction for nitrogen oxide (NO x ) control, and flue gas
Public Power District, North
desulfurization. Dakota Industrial Commission,
Neumann Systems Group, PPL
Baseline testing was conducted using MEA to gather information to characterize each
Montana, Saskatchewan
of the units. The results obtained by using MEA in the CO 2 absorption system were used Power, Sulzer, TransAlta Utilities,
as a standard by which all other solvents were compared. Data collected included CO 2 and University of wyoming
removal, CO 2 purity, required regeneration heat, and effects of sulfur oxide (SO x ), NO x ,
particulate matter, and trace metals. start date:
Baseline testing of the oxy-combustion system followed similar procedures as the 05.01.2008
absorption system. The data collected can be used to identify potential challenges
concerning this technology. These challenges include effects of mercury (Hg) capture, percent complete:
flame stability, fouling, slagging, and heat-transfer issues. 100%
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
806 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: R&D Collaborations
Figure 1: UNDEERC post-combustion CO 2 capture test facility
Carbon dioxide capture technologies were selected and tested. Two flue gas pretreatment technologies were evaluated. The
Partnership for CO 2 Capture worked with Cansolv Technologies Inc. to test the operability of a benchmark solvent and an
improved formulation for sulfur dioxide (SO 2 ) removal. The testing indicated that choice of solvent should be made based on
both SO 2 removal effectiveness and energy input required for regeneration rather than on solvent operability. The second
pretreatment technology tested was a flue gas filtration technology manufactured by Tri-Mer Corporation which combines
particulate, NO X , and SO 2 control. This test showed that their capture was highly dependent on temperature, ammonia injection
rate, and amount of sorbent used. The Sorbacal sorbent SPS achieve higher levels of SO 2 removal than their SP sorbent, and the
Tri-Mer system effectively removed impurities prior to post-combustion CO 2 capture (though SO 2 levels may need additional
trimming).
Two post-combustion solvents were also tested. Korea Carbon Capture and Sequestration R&D Center’s (KCRC) Solvent-B
showed 90 percent capture with approximately 40 percent lower liquid/gas ratio and 30 percent lower regeneration energy
input than MEA at the same capture level. CO 2 Solutions Incorporated proprietary technology uses the enzyme carbonic
anhydrase as a catalyst with a salt solution. Testing showed no degradation in performance of the enzyme catalyst, no generation
of toxic waste by-products, and showed the ability to use low-grade heat for regeneration, allowing for reduction of cost of CO 2
capture.
Nine membranes for hydrogen/CO 2 separation were provided by Commonwealth Scientific and Industrial Research Organization
(CSIRO) for pre-combustion testing using syngas from EERC’s fluidized-bed gasifier with warm-gas cleanup. Membrane
performance increased with increases in temperature.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY
NATIONAL ENERGY TECHNOLOGY LABORATORY
807
Appendix: R&D Collaborations
A detailed process-modelling effort was undertaken using Aspen Plus software to develop the basis for determining cost of CO 2
capture using advanced post-combustion capture technologies and techniques including the solvents from KCRC and CO 2
Solutions. Also, three power plants were modeled using Carnegie Mellon’s Integrated Environment Control model to show the
effects that capture would have on net power production, water usage, and revenue requirements for various levels of capture.
Laboratory testing was performed to determine the feasibility of measuring residual amine and nitrosamines potentially emitted
in stack flue gases using Fourier transform infrared spectroscopy (FT-IR).
This project placed a strong emphasis on the integration of total systems so that the economic and environmental benefits of
carbon capture could be further understood and potentially implemented by utility stakeholders.
Testing of proprietary solvents was conducted on a small industrial 1 tonne/day CO 2 catch and release test system. The system
utilized real combustion flue gas generated in a pilot combustor located adjacent to the capture system with typical flue gas
conditions given in Table 1. Proprietary membrane testing was conducted utilizing UNDEERC’s gasification pilot systems. Table
2 lists the typical conditions of the syngas for membrane testing.
Table 1: Typical Flue Gas Conditions
Flue Gas Flow Composition
250 kg/hr
Pressure Temperature vol% ppmv
psia °C CO 2 H2O N2 O2 CO SO x NO x
14.7 40 15.6 11.0 80.1 4.2 25 295 200
Table 2: Typical Syngas Conditions
Syngas Flow Composition
2,200 kg/hr
Pressure Temperature vol% ppmv
psig °C CO H2 O2 N2 CO 2 CH 4 hydrocarbons H2S
309 325 2.63 37.64 0.12 11.96 47.92 2.83 0.04 4,095
technology advantages
UNDEERC has obtained experimental data for a variety of advanced CO 2 capture technologies and oxy-combustion systems.
Beyond showing a clear comparison of various approaches, this work has resulted in several improvements to solvents and
membranes. Data from this program led directly to an improved sulfur capture solvent being produced by Cansolv Technologies.
KCRC took the data obtained to focus their development pathway, focusing on a solvent which displays potential for future
performance improvement. CO 2 Solutions Incorporated utilized data generated to further develop their technology to take
advantage of waste heat availability which shows potential to reduce capture costs. Finally, CSIRO advanced their early stage
development of a membrane that shows great promise for pre-combustion CO 2 capture. These advancements are moving
concepts toward application, producing concepts and technologies that reduce the cost of CO 2 capture.
R&D challenges
Retrieving enough information on existing technologies to make appropriate selections for testing and integrating the
technologies into total systems.
status
Final report is completed.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
808 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: R&D Collaborations
available reports/technical papers/presentations
SUBTASK 2.18 – ADVANCING CO 2 CAPTURE TECHNOLOGY: PARTNERSHIP FOR CO 2 CAPTURE (PCO 2 C) PHASE III, Final Report,
J.P. Kay, at al. March 2016.https://www.osti.gov/scitech/servlets/purl/1320560
Kay, J.P.; Jensen, M.D.; Fiala, N.J., “Pilot-Scale Evaluations of Advanced Solvents for Postcombustion CO 2 Capture,” Energy
Procedia 2014, 63, 1903–1910.
Kay, J.P.; Fiala, N.J., “Comparative Evaluation of Advanced Postcombustion CO 2 Capture Technologies,” Paper presented at the
38th International Technical Conference on Clean Coal & Fuel Systems, Clearwater, FL, June 2–6, 2013.
Pavlish, B.M.; Kay, J.P.; Laumb, J.D.; Strege, J.R.; Fiala, N.J.; Stanislowski, J.J.; Snyder, A.C., “Subtask 2.5 – Partnership for CO 2
Capture – Phases I and II”, Final Report (September 1, 2010–April 30, 2013) for U.S. Department of Energy National Energy
Technology Laboratory Cooperative Agreement No. DE-FC26-08NT43291; EERC Publication 2013-EERC-08-17; Energy &
Environmental Research Center: Grand Forks, ND, August 2013.
Hildebrandt, K.; Kay, J.P., “Integration of Postcombustion CO 2 Capture into Existing Coal-Fired Power Plants,” Topical Report for
U.S. Department of Energy National Energy Technology Laboratory Cooperative Agreement No. DE-FC26-08NT43291; Energy &
Environmental Research Center: Grand Forks, ND, March 2012.
Laumb, J.D.; Stanislowski, J.J.; Kay, J.P.; Pavlish, B.M., “Evaluation of Advanced Solvents and Other Technologies for CO 2 Capture
from Fossil Fuel-Fired Systems’” Presented at the 2012 International Pittsburgh Coal Conference, Pittsburgh, PA, October 15–
18, 2012.
Pavlish, B.M.; Kay, J.P.; Stanislowski, J.J.; Laumb, J.D., “The Partnership for CO 2 Capture: Final Evaluation Results of Advanced
Solvents and Oxy-Fired Combustion Pilot-Scale Testing,” Presented at the 36th International Technical Conference on Clean
Coal & Fuel Systems, Clearwater, FL, June 5–9, 2011.
Chen, S.G.; Lu, Y.; and Rostam-Abadi, M., “Carbon Dioxide Capture and Transportation Options in the Illinois Basin,” Topical
Report October 1, 2003–September 30, 2004 for U.S. Department of Energy Contract No. DE-FC26-03NT41994.
Metz, B.; Davidson, O.; Coninik, H.; Loos, M.; and Meyer, L. “IPCC Special Report Carbon Dioxide Capture and Storage Technical
Summary,” ISBN 92-9169-119-4, September 2005.
Narula, R.; Wen, H.; and Himes, K., “Economics of Greenhouse Gas Reduction – The Power Generating Technology Options,”
Presented at the World Energy Congress, Buenos Aires, Brazil, October 2001.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 809
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: R&D Collaborations
FUTURE OF CCS TECHNOLOGY
ADOPTION AT EXISTING PC PLANTS
technology maturity:
primary project goals
Systems Analysis and
Argonne National Laboratory (ANL) is constructing scenarios that affect carbon capture
Macroeconomic Modeling
and storage (CCS) adoption as combinations of cases for the following dimensions:
electricity demand, nuclear growth, renewable energy growth, higher or lower gas price project focus:
factors, and alternative policies. Analysis of CCS
Technology Adoption
technical goals participant:
• Extension of ANL’s previous work in project FWP49539, “Evaluation of CO2
Argonne National
Capture/ Utilization/Disposal Options.” Laboratory
• Simulate oxy-combustion and amine-based processes using ASPEN.
project number:
• Expand the scenario analyses to focus on the value of coal-based CCS for existing
pulverized coal (PC) plants and for other technologies, such as coal-to-liquids with
FWP49806
CCS. continued from
• ANL will examine pathways that expedite CCS adoption, such as accelerated
FWP49539
research and development (R&D) and carbon dioxide (CO2) utilization for enhanced
oil recovery (EOR). NETL project manager:
• ANL will examine opportunities for R&D related to shale gas, such as developing José Figueroa
CCS specifically for natural gas combined cycle (NGCC) units. [email protected]
principal investigator:
technical content Donald Hanson
ANL
In a previous project (FWP49539), ANL conducted engineering assessments and [email protected]
economic evaluations on retrofitting PC boilers with oxy-combustion, and then eventually
repowering the site with integrated gasification combined cycle (IGCC). The engineering partners:
assessment for oxy-combustion was conducted with the ASPEN process model and the
economic evaluations with the AMIGA macroeconomic model. The assessment None
investigated the entire life cycle of the plant, which included the mining of the coal, coal
transportation, coal preparation, power generation, environmental controls, water use, performance period:
pipeline CO2 conditioning, and pipeline transport of CO2 for sequestration. 2/1/11 – 3/31/14
ANL also conducted ASPEN modeling for 18 different oxy-combustion and air-fired
cases. Three different power production ratings (150 MW, 300 MW, and 450 MW) were
investigated. The model included a selective catalytic reduction (SCR) system and a flue
gas desulfurization (FGD) system for flue gas cleanup.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
810 DOE/NETL CARBON CAPTURE PROGRAM R&D
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: R&D Collaborations
The analysis in the current project will demonstrate and, to the extent possible, quantify the role and benefit of R&D related to the
utilization and environmental control of fossil fuels. The impacts of R&D will be shown by comparing model results such as
deployment rates, emissions reductions, and electricity costs across various scenarios. The scenarios will capture a number of CO2
control regimes, R&D programs, and economic conditions in order to fully understand the role that R&D plays in each. With
widespread deployment of CCS under a CO2 reduction target, R&D that lowers cost of CO2 capture and increases efficiency will be
shown to have a high economic payoff.
Other topics to be analyzed with the ANL model are as follows: the value of coal-based CCS in high natural gas price scenarios;
opportunities and obstacles for R&D, on NGCC with CCS, including cost and performance parameters; the conditions under which
CO2-EOR enables faster deployment of CCS systems; the market opportunity for coal and biomass to liquid fuels and power co-
production with CCS; and impacts on PC units, especially those retrofitted with CCS, from cycling due to intermittent grid
generation from renewables.
technology advantages
The ANL model is especially designed to analyze the issues and scenarios described above.
R&D challenges
Capturing the impacts and costs of high intermittent renewable generation as it affects dispatchable coal generators, especially
those that have adopted CCS.
results to date/accomplishments
• Ran Electricity Supply and Investment Model (ESIM) for high, mid, and low gas supply scenarios to identify retirement of
existing PC power plants which do not retrofit with CCS and to identify the retrofit with CCS of other current PC plants.
• Modeled predicted increased CO2 capture and decreased CO2 emissions for the scenarios.
• Simulated the benefit of higher utilization (i.e., capacity factor) for PC plants that retrofit CCS because of rising up the loading
order (i.e., dispatch order).
• Analyzed the value of coal-based CCS in high natural gas price scenarios.
• Analyzed opportunities and obstacles for R&D, specifically regarding CCS, including cost and performance parameters.
• Analyzed market opportunity for coal and biomass to liquid fuels and power co-production with CCS.
• Analyzed impacts on PC units, especially those retrofitted with CCS, from cycling due to intermittent grid generation from
renewables.
• Concluded funding for R&D for CCS, nuclear, and biochemical technologies can help meet CO2 reduction goals.
• Concluded credits for reducing CO2 or small price on emitting CO2 will provide incentive to operate units with CCS at higher
utilization than units without capture.
• Concluded electricity prices can be moderated for consumers and businesses if revenue from a modest price on CO2 is recycled
back to help fund investments in advanced generation capacity.
next steps
This project ended on March 31, 2014.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
U.S. DEPARTMENT OF ENERGY
COMPENDIUM OF CARBON CAPTURE TECHNOLOGY 811
U.S. DEPARTMENT OF ENERGY NATIONAL ENERGY TECHNOLOGY LABORATORY
Appendix: R&D Collaborations
available reports/technical papers/presentations
Hanson, D. and Schmalzer, D, “An Adoption Scenario for Carbon Capture in Pulverized Coal Power Plants in the USA,”
Greenhouse Gases Science and Technology (3:p.303-308), 2013.
Hanson, D. “Future of CCS Technology Adoption at Existing PC Plants,” presented at CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2013. http://www.netl.doe.gov/File Library/events/2013/CO2 capture/D-Hanson-ANL-Future-of-CCS.pdf.
Hanson, D., and Schmalzer, D., “CCS Adoption Under Alternative Market Conditions,” presented at U.S. Association for Energy
Economics Conference, Austin, TX, November 2012.
Hanson, D., “Economics and Adoption of CO2 Capture for Existing PC Plants in a Power System Context,” Eleventh Annual
Conference on Carbon Capture, Utilization & Sequestration, Pittsburgh PA, May 2012.
Hanson, D., “Future of CCS Technology Adoption at Existing PC Plants,” presented at CO2 Capture Technology Meeting,
Pittsburgh, PA, July 2012.
Hanson, D.; Marano, J.; and Fout, T., “Economic Analysis of Existing Coal Plant Retrofits with CCS,” Energy, Utility, &
Environmental Conference, Phoenix AZ, January 2012.
Hanson, D., “A Market Scenario Approach to Managing Existing Power Plant Assets,” 13th Annual Electric Power Conference and
Exhibition, Rosemont, IL, May 2011.
Hanson, D., and Doctor, R., “Future of CCS Technology Adoption at Existing PC Plants,” presented at CO2 Capture Technology
Meeting, Pittsburgh, Pennsylvania, August 2011.
“ANNUAL REPORT 2009: Evaluation of CO2 Capture and Sequestration Using Oxyfuels with AMIGA Economic Modeling,”
November 23, 2009.
Doctor, R.; Hanson, D. A.; and Molburg, J. C., “Evaluation of CO2 Capture and Sequestration Using Oxyfuels with AMIGA
Economic Modeling,” presented at 2009 NETL Capture Technology Meeting, March 2009.
CARBON CAPTURE TECHNOLOGY SHEETS R&D COLLABORATIONS
NATIONAL ENERGY TECHNOLOGY LABORATORY
1450 Queen Avenue SW Program staff are also located in
Albany, OR 97321 Houston, TX and Anchorage, AK
541-967-5892
3610 Collins Ferry Road CUSTOMER SERVICE
P.O. Box 880 1-800-553-7681
Morgantown, WV 26507
304-285-4764
626 Cochrans Mill Road
www.NETL.DOE.gov
P.O. Box 10940
Pittsburgh, PA 15236
412-386-4687
CARBON CAPTURE PROGRAM R&D
2020 COMPENDIUM of CARBON CAPTURE TECHNOLOGY
05.2020–1000
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