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Techno-Economic Analysis 14butanedialproduction Single Step Bioconversion Process PDF

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408 views13 pages

Techno-Economic Analysis 14butanedialproduction Single Step Bioconversion Process PDF

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marcoesteban97
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Modeling and Analysis

Techno-economic analysis of
1,4-butanediol production by a single-­
step bioconversion process
Chinmay C. Satam , Manuel Daub, Matthew J. Realff , Georgia Institute of Technology, School of
Chemical and Biomolecular Engineering, Atlanta, GA, USA

Received October 18, 2018; revised March 12, 2019; accepted March 29, 2019
View online April 30, 2019 at Wiley Online Library (wileyonlinelibrary.com);
DOI: 10.1002/bbb.2016; Biofuels, Bioprod. Bioref. 13:1261–1273 (2019)

Abstract: 1,4-Butanediol (1,4-BDO) is one of the most important intermediate chemicals that is mainly
produced using petrochemical routes. Recently, the route to 1,4-BDO from corn-based dextrose by
single-step bioconversion has been commercialized. This paper analyzes the bio-based production
route to 1,4-­BDO and establishes the major capital and operating costs associated with production.
Bioconversion was found to be the major capital cost component while the hydraulic load from
bioconversion and other systems like membrane filtration was found to be the major operating cost
component. The process was found to be economically feasible with a minimum sales price (MSP)
of 1,4-BDO of $1.82/kg as compared to a market price of $2.5/kg. In addition, a mechanical vapor
recompression scheme for the evaporator benefitted the process, increasing energy efficiency and
therefore cost effectiveness. In general, improvements that enable the reduction of hydraulic loads lower
the MSP of 1,4-BDO. The most dramatic cost savings are seen when bioconversion titers are increased.
When the bioconversion titers are doubled to 280 g L−1, a 45% reduction in MSP is seen with respect to
the baseline process. A sensitivity analysis shows that process is sensitive to feedstock prices but not
sensitive to energy prices. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd.
Keywords: 1,4-butanediol; fermentation; membrane filtration; renewable chemicals; green chemicals;
techno-economic analysis

Introduction for about 50% of the market share in 2015.7 While a majority
of the market is located in the Asia Pacific region,7 the US

1
,4-Butanediol (1,4-BDO) is a major commodity market amounts for more than $1 billion7 in revenue at a
chemical1,2 that is used in the manufacture of plastics, 1,4-BDO sales price of $2500/MT.8 The price of this was
fibers (e.g., spandex), polyesters,1,3 polyurethanes,2–4 confirmed with an industry partner.
and pharmaceuticals.5 It is also used as a solvent3 and The first commercial route to 1,4-BDO was the Reppe
humectant.3,6 The global 1,4-BDO market is estimated to process developed by Walter Reppe. It involves the reaction
be over $6 billion7 and is estimated that it will grow to over between formaldehyde and acetylene (derived from coal
$12 billion by 2025.7 This expected growth can be attributed or petrochemicals) to produce butynediol followed by
to the increasing use of spandex in textiles, which accounted hydrogenation to butanediol.2,4,6,9,10 The process requires

Correspondence to: Matthew J. Realff, Georgia Institute of Technology, 311 Ferst Dr. NW, Atlanta, Georgia 30332.
E-mail: [email protected]

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd 1261
CC Satam, M Daub, MJ Realff Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol

careful handling of acetylene due to its explosive nature.2,10 to Novamont and BASF.16 Novamont started up the first
Mitsubishi chemicals developed an alternative process plant in late 2016,17 and by mid-2017 cumulative production
involving acetolyxation of 1,3-butadiene with acetic by the GENO BDO™ process exceeded 10 000 tons.18 Life
acid followed by hydrogenation.2 A second route from cycle analysis of a similar process for 1,4-BDO production
butadiene involved chlorination followed by hydrolysis and from wheat straw feedstock by Forte et al.9 show reduced
hydrogenation. It was developed and used by Toyo Soda environmental impact as compared to fossil based 1,4-BDO.
until the 1980s.4,10 An alternative route was developed by Another bio-based 1,4-BDO production route exists in which
Lyondell involving isomerization of propylene oxide6 to allyl succinic acid, produced by bioconversion, is converted to
alcohol and subsequent hydroformylation (licensed from 1,4-BDO in a separate reaction step. Succinic acid is another
Kuraray) to 1,4-butanediol.2 Davy Process Technology and important four-carbon compound, which is currently
BP both developed routes to 1,4-BDO from butane through produced from petrochemicals but can also be produced by
the hydrogenation of maleic anhydride.10 The Davy process fermentation. Bio-based succinic acid could potentially replace
technology route converts maleic anhydride to a diester,11 petrochemically derived maleic acid due to similar chemical
which is then hydrogenated to 1,4-BDO,6,11 whereas the BP behavior.5 The fermentation process for succinic acid was first
process directly hydrogenates maleic anhydride to 1,4- commercialized by Bioamber followed by Reverdia, Myriant,
BDO.10 Despite the availability of several routes to 1,4-BDO, Succinity (BASF/Purac).19 The Davy or BP Chemicals process
the Reppe process still accounts for a majority2,5 of the 1,4- previously discussed has been modified to produce 1,4-BDO
BDO production from non-renewable feedstocks, primarily by the hydrogenation of succinic anhydride / acid instead of
due to fewer steps and high yields.10 As the feedstocks maleic anhydride.11 Myriant20 and BioAmber21 had disclosed
for the Reppe process are mostly petroleum derived, this intentions to produce 1,4-BDO from its succinic acid by
process contributes to a significant carbon footprint. incorporating the succinic acid hydrogenation process to their
Recent years have seen a clear shift towards bio-based bio succinic acid production process.
chemicals7 such as a close analog of 1,4-BDO, namely This paper will present an analysis of the economics of the
1,3-propanediol (1,3-PDO). 1,3-Propanediol is used in production of 1,4-BDO by the single-step bioconversion
the manufacture of polyurethanes and polyester resins.3 process (‘direct route’) based on information published by
DuPont-Tate&Lyle Bioproducts was the first company to Genomatica. Since the actual configuration, performance,
commercialize bio-based 1,3-PDO successfully, including and material/energy/labor inputs of the GENO BDO™
branded products such as Susterra® and Zemea®.3 This led process are proprietary, our estimates for the direct route
to the development of fibers with at least one renewable should be regarded as conservative indicators of the GENO
component, such as DuPont’s Sorona®, which is a co-polymer BDO™ process economics; i.e., the GENO BDO™ process is
of bio-based 1,3-PDO and petroleum-derived terephthalic likely to have a lower cost than that presented here due to
acid.3,12 Sorona® finds applications in carpets and textiles.3 undisclosed improvements relative to the assumed process
The conversion of biomass to 2,3-butanediol (2,3-BDO) via design, process performance, and economic inputs of this
gasification followed by syngas fermentation was analyzed paper. The paper discusses the main process sensitivities
to be economically competitive by Benalcázar et al.13 This affecting the minimum sales price (MSP) of 1,4-BDO. Many
syngas fermentation route for production of 2,3-BDO is of the unit operations we have included in the 1,4-BDO direct
being pursued by LanzaTech.14,15 As one approach, the basic route process (e.g., bioconversion, membrane filtration, ion
process template for 1,3-PDO could be used for the bio-­ exchange, water evaporation, and distillation) are commonly
based production of 1,4-BDO as long as a suitable biological used in other bio processes for the manufacture of water-­
agent could be engineered, considering that the chemical and soluble diols (e.g., 1,3-PDO and 1,5-pentanediol). As a result,
physical properties of the two diols are similar. our analysis serves as a useful starting point in the economic
Plotkin16 notes that there have been several attempts assessment of routes for the production of other such diols.
to produce bio 1,4-BDO by direct bioconversion from Our analysis concludes that the bio-based production of
plant sugars in a single step using genetically engineered 1,4-BDO – a high-volume intermediate chemical – from
microorganisms. Samsung Electronics, LG Chem, University renewable feedstocks is already competitive on a cost
of California, Genomatica, and Showa Denko (Japan) all have basis with long-standing processes to make the chemical
successfully engineered microorganisms (mostly Escherichia from conventional, fossil fuel-based feedstocks. Indeed,
coli) to produce high concentrations of 1,4-BDO at rapid rates; Genomatica appears to have been successful in delivering
however, only Genomatica has successfully commercialized a and validating a process with top quartile economics, with
bioconversion process (GENO BDO™ process), so far licensed potential for further improvements.

1262 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

Methods 1,4-BDO direct route


Figure 1 shows the assumed sequence of unit operations for
Process modeling the 1,4-BDO direct route. We assumed a 100 kilotons per
The process model for the 1,4-BDO direct route plant is annum (KTA) 1,4-BDO capacity for our plant. Bioconversion
based on Genomatica patents and publications22–24 along with occurs in two stages, both operated under aerobic, axenic
some non-confidential input from Genomatica personnel. conditions. The first stage occurs in a seed bioconversion
The overall techno-economic analysis (TEA) model was reactor, separate from the main bioconversion reactor, to
constructed in Excel and used Matlab for more detailed increase cell concentration of the genetically modified E. coli
modeling of unit operations. The bioconversion submodel strain.1 Because the E. coli is inhibited by elevated glucose
was constructed using published Genomatica fed-batch concentration, both bioconversion reactor stages are operated
bioconversion data. Data for microfiltration were obtained in fed-batch mode with sterilized 50 wt% dextrose syrup
from Li et al.,25 while data for ultra- and nanofiltration continuously fed to avoid glucose exhaustion. The seed broth
sections were obtained from a Genomatica patent.22 For final volume is 10% by volume of the main bioconversion
the evaporation and distillation sections, Aspen Plus vapor reactor final broth volume. The seed bioconversion proceeds
pressure (PLXANT) data and NRTL models with their for 30 h after which the seed broth is transferred to the
respective component parameters were used. Feed to the main bioconversion reactor, which contains bioconversion
fermenters was based on Cargill’s 95% refined liquid dextrose medium of the same composition as the initial seed medium.
syrup26 as detailed in Table 1. In this analysis we have ignored The starting main bioconversion reactor volume after seed
the presence of sugars other than dextrose and it is assumed transfer is 60% of the final volume. The bioconversion reactor
that they will behave in a very similar way to dextrose. exhaust gases contain some volatile organic compounds,
Liquid handling costs (pumps and valves) are not included. principally ethanol, which are substantially removed by
The installation factors that we have considered for process scrubbing with water in an external column (not shown).
equipment are conservative enough that the costs of pumps The main bioconversion proceeds for 37 h and dextrose
associated with them can be absorbed in these. Operating feed is stopped near the end so that glucose is exhausted to
costs of pumping liquids are assumed to be negligible. We maximize product yield and minimize impurities. The final
have also not included storage costs for feedstocks and bioconversion broth composition is shown in Table 2.
products. The exception to this is the inclusion of pumping At the conclusion of the main bioconversion, the broth
costs in the filtration sections. Utility and wastewater costs are is heated to 60 °C for 5 min to kill the E. coli cells, and then
based on industry partner or literature sources and we have microfiltered (m/f) at that temperature to remove the spent
not modeled utility production or wastewater treatment units cells. The m/f retentate is then washed with process water by
in our analysis. countercurrent diafiltration to recover most of the 1,4-­BDO
A 30-year plant lifetime was assumed for this process based remaining in that fraction. The combined permeate from m/f
on assumptions by Humbird et al.27 A Lang factor of 5.03 and diafiltration then undergoes ultrafiltration (u/f) to remove
was used. Both the plant lifetime and the Lang factor are proteins and other macromolecules that were produced
consistent with the methodology of Ou et al.28 during bioconversion. The u/f retentate also undergoes a
diafiltration recovery step. Finally, the combined permeate
from u/f and diafiltration undergoes nanofiltration (n/f) to
Table 1. Composition of dextrose syrup.26 remove most residual sugars as well as multi-valent cations.
Mass% (dry basis) The retentate from n/f undergoes a diafiltration recovery step
Carbohydrate profile to recover 1,4-BDO. The n/f filtered broth then undergoes
Dextrose 95.0 cation and anion exchange to remove residual cations (like
Maltose 3.0 NH4+, Na+, K+) and anions (Cl−, acetate, glutamate).
Maltotriose 0.5
The ion-exchanged broth (the composition of which
is given in Table 2) is evaporated under vacuum to
Higher saccharides 1.5
remove water and low boiling organics. The vapor from
Chemical and physical properties
the evaporator is simultaneously scrubbed with cold
Total solids 70.5–71.5%
process water to recover any 1,4-BDO in the vapor. This
Moisture 28.5–29.5%
scrubbed vapor is then compressed in a mechanical vapor
Sulfated ash 0.05% max
recompressor (MVR), exchanges heat with incoming filtered
Sulfur dioxide 2 ppm max
broth, and is condensed as a result. This recompression

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016 1263
CC Satam, M Daub, MJ Realff Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol

Diluted Dextrose
Ammonia
Cation Anion
Exchange Exchange

Microfiltration Ultrafiltration Nanofiltration


Air

Bioconversion
Reactor Salts/
Cells Proteins Dextrose

Water
MVR
Compressor
BDO
Water Internal
BDO Scrubber

MVR
Exchanger

GBL
BDO Water
Column Column
Evaporator

Ethanol -Water
Mix

Figure 1. Schematic of a 1,4-BDO direct route production plant.

system saves energy and reduces the hydraulic load on the prices from the base year are updated using Marshall & Swift
distillation columns, thus reducing 1,4-BDO purification (M&S) indicex for the third quarter of the year 2016 (with
costs. It has been assumed that the condensed ethanol-­ value of 1586.3). For all other equipment the total installed
water mixture is disposed as wastewater, but this stream costs are based on the cost correlations and methodology
could potentially be recycled to the bioconversion medium, outlined in Woods,32 where the Chemical Engineering Plant
significantly reducing process water consumption and Cost Index (CEPCI) for the year 2016 is 556.8. For specific
wastewater volume but potentially increasing ethanol equipment such as fermenters and filtration systems, the free
concentration in the bioconversion if used untreated. The on board (FOB) costs were estimated with input from an
concentrated 1,4-BDO-rich mixture after evaporation is industrial partner, as the units were well outside the range of
next passed through a series of two distillation columns: cost correlations for such systems in textbooks or made of
the first column to remove residual water and other low material types not represented in them. The cost correlations
boiling impurities at the column top; and the second column for bioconversion reactor FOB costs (including estimates for
under vacuum to remove high boiling impurities, resulting known size, power coefficient, and installation factors) were
in 99.99 wt% 1,4-BDO product in the overhead stream. The obtained from an industrial partner as depicted in Eqn (1):
impure gamma butyrolactone (GBL) product is very low
n
volume and is contaminated with other byproducts; hence it  size 
FOB cost  FOB cost  known size   
is burnt for fuel value. Temperatures in the reboilers of both  known size 
    (1)
columns are kept below 160 °C to avoid sugar decomposition.
Here, n is the power coefficient that describes how
Economic analysis equipment costs scale with a value of 0.64 (as recommended
The total installed equipment cost is calculated from the sizes by our industrial partner). The FOB cost of a 500 m3 stainless
obtained from the MATLAB submodels. For pumps, vessels, steel, jacketed, pressure-rated bioconversion reactor was
heat exchangers, and compressors, the equipment installation estimated to be 1.4 MM$. The FOB costs for the fermenters
cost is calculated according to the methodology outlined in were multiplied by an installation factor of 3.0 to convert
Douglas,29 which is based on Guthrie correlations.30,31 The FOB costs to total installed cost (TIC). In the case of filtration

1264 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

Table 2. Composition of main bioconversion Table 3. Ratio factors for determining TPI,28 the
reactor final broth and post-ion exchange broth. TPEC is nominally 100 and numbers represent %
Component Bioconversion Post ion of TPEC.
reactor outlet exchange Direct costs
concentration concentration Total purchased equipment cost (TPEC) 100
(g L−1) (g L−1)
Purchased equipment installation 39
Glucose 0.25 0.02
Instrumentation and controls (installed) 26
1,4-BDO 140.0 69.7
Piping (installed) 31
Ethanol 4.43 2.1
Electrical systems (installed) 10
Acetate 3.61 —
Buildings (including services) 29
4-Hydroybutanoate 3.78 —
Yard improvements 12
Gamma butyrolactone 0.09 0.04
(GBL) Service facilities (installed) 55
2-Pyrrolidone 0.01 0.003 Total installed cost (TIC) 302

2-(4′-Hydroxybutoxy)-THF 0.33 0.2 Indirect costs

Glutamate 0.05 — Engineering and supervision 32

Cell mass (dry weight) 14.4 — Construction expenses 34

Extracellular proteins 0.84 0.02 Legal expenses 4

Sulfate 0.250 — Contractor’s fee 19

Phosphate 0.053 — Contingency 37

Citrate 0.010 — Total indirect cost 126

Sodium 0.055 — Fixed capital investment (TIC indirect plant costs) 428

Ammonium 1.721 — Working capital (15% of total capital investment) 75

Potassium 0.194 — Total project investment (fixed capital 503


investment + working capital)
Magnesium 0.007 —
Calcium 0.008 —
Table 5 gives the unit costs of the main raw materials and
systems, the FOB costs were obtained as costs per unit area, utilities used to determine operating costs and thus the MSP.
which when multiplied by the filtration area gave the FOB The cost of US dextrose depends on the cost of corn and of
cost for the system. Polymeric membranes were used for the processing that corn to dextrose syrup. Assuming corn at
purposes of the design with membrane lifetimes of 5 years $3.00 per bushel, a dextrose price of $260/metric ton (MT)
and a membrane replacement cost per unit area considered was chosen for this study. Average annual US industrial
every year which, was included in our cost estimate as natural gas prices have varied from 3.4 to 5.4 $/MMBTU,40
advised by the industrial partner. These were then converted while average annual US industrial electricity prices have
to TIC using the methodology outlined in Woods.32 varied from 6.7 to 7.1 cents kWh over the past 7 years.41
Total project investment (TPI) cost is based on cost factors An industrial natural gas price of $4.17/MMBTU for
shown in Table 3 with a Lang factor of 5.03, both of which December 2016 was used from the US Energy Information
are adapted from Ou et al.28 Operating costs are based on the Administration (EIA) website,40 while the average industrial
outputs of MATLAB submodels and Excel calculations for the US electricity price for October 2016 of 6.72 cents kWh was
same. The Excel model of the 1,4-BDO direct route plant also used from the same source.41 The unit cost of wastewater
used a discounted cash flow rate of return (DCFROR) sheet biological oxygen demand (BOD) was provided by our
based on the NREL DCFROR Excel sheet.27 The results of the industrial partner, while cooling water and process water unit
TPI and operating costs are then utilized in this DCFROR costs were obtained from El-Halwagi.38 The unit cost of steam
sheet where the MSP of 1,4-BDO is calculated as a function and chilled water were obtained from Kiss.37 Volumetric
of the operating and capital cost. The MSP is obtained by water treatment costs were obtained from an Industrial
adjusting the selling price of 1,4-BDO so that the net present Waterworld survey.39 Prices of sodium hydroxide, lime,
value is zero at an internal rate of return (IRR) of 10%. ammonia, and hydrochloric acid were taken from various
Table 4 describes the other assumptions required to arrive sources.33–36
at the MSP, which are derived mainly from Ou et al.28 and As bioconversion is a very water-intensive process,
Humbird et al.27 significant operating cost and capital is expended in removing

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016 1265
CC Satam, M Daub, MJ Realff Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol

Table 4. Main assumptions for economic from m/f through evaporation is directly a function of
calculations.27,28 the bioconversion 1,4-BDO titer. Thus, bioconversion
Plant life (years) 30 titer, bioconversion yield, and bioconversion rate, are very
Operating hours per year 7920 important parameters that impact MSP.
Equity 40%
Targeted improvement of the E. coli production
Loan interest rate 8.00% for 10 year loan
microorganism can result in higher 1,4-BDO titers; the
economic significance was assessed and will be discussed.
General plant depreciation IRS modified accelerated cost
recovery system Water is also used to recover 1,4-BDO from the retentate of
Steam plant depreciation Included in utility cost
the filtration systems. The cost benefit of recovering 1,4-BDO
versus the capital and operating expenses associated with the
Depreciation period (years)
processing of the additional wash water is also explored. The
General plant 7
sensitivity of MSP to the costs of glucose, energy, and capital
Steam/electricity system Included in utility cost
cost reductions is also explored as a part of the sensitivity
Construction period (years) 3
analysis.
% Spent in year −3 8.00%
% Spent in year −2 60.00%
% Spent in year −1 32.00%
Results
Start-up time (years) 0.5
Table 6 shows the TIC for a 100 KTA 1,4-BDO direct route
Revenues (% of normal) 50%
process. We see that the bioconversion section is about 61%
Variable costs (% of normal) 75%
of the plant TIC while the evaporator section contributes to
Fixed cost (% of normal) 100% about 13% of the TIC. The bioconversion reactor costs are
IRR 10.00% driven by the water content of the broth (because the broth
Income tax rate 39.00% is mostly water), which is a function of the rate and final titer
of 1,4-­BDO. Higher rates and BDO titers require less water
Table 5. Raw material and utility prices used in for the same annual 1,4-BDO production. Evaporator section
TEA simulations. costs are driven by the water load on the evaporator. The
Raw materials Price Source filtration systems contribute to about 16% of the cost and are
Dextrose $ 260 MT−1 Industry partner also driven by the water load.
Sodium hydroxide $ 0.42 kg−1 Fountain (USGS)33 Table 7 summarizes the consumption trends for major raw
Lime $ 0.12 kg−1 Miller (USGS)34 materials and utilities. The process requires almost 2 tons of
Ammonia $ 0.53 kg −1
USGS35
dextrose (dry weight) per ton 1,4-BDO, almost all of which
is consumed at the end of the bioconversion. Theoretically
Hydrochloric acid $ 0.05 kg−1 Bowen (ICIS)36
the maximum stoichiometric 1,4-BDO production,
LP steam $ 7.78 GJ −1
Kiss37
assuming no byproducts and no cell production and 100%
MP steam $ 8.22 GJ−1 Kiss37
conversion of carbon, is 0.75 tons 1,4-BDO/ton dextrose.
HP steam $ 9.88 GJ −1
Kiss37
This means the direct route has approximately 68% of the
Process water $ 1.5 m −3
El-Halwagi38
theoretical conversion of dextrose to 1,4-BDO. Unlike in
Chilled water $ 4.43 GJ−1 Kiss37
many cellulosic ethanol plants where corn stover is used,
Cooling water $ 0.1 m −3
El-Halwagi38 there is no dry biomass available for integrated power or
Wastewater volume $ 0.54 m−3 Industrial steam generation and the plant is a net electricity consumer.
treatment Waterworld39
In practice such an integration is feasible but not analyzed
BOD treatment $ 0.33 kg−1 Industry partner
here. The plant consumes about 7.0 MW of electricity, which
Natural gas $ 4.17 MMBTU−1 US EIA40 is about thrice the electricity consumption for a similar sized
*Electricity $ 0.0672 kWh−1 US EIA41 stand-alone corn grain ethanol plant,28 mainly due to the
MVR system. The plant is, however, able to offset some of
the same. Water volume determines the sizes of most process the thermal energy requirements as it produces fuel in the
equipment and thus dictates capital cost. Water load not only form of methane from an anaerobic digester for inactivated
increases evaporator and first distillation (water) column cells, which can offset about 32% of the energy required.
capital cost but also increases the operating cost of the same. The combustion of impure GBL, which comes off the top of
The hydraulic load on the downstream unit operations the BDO column, however, does not significantly offset the

1266 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

Table 6. TIC, equipment size and energy utilization for a 100 KTA 1,4-BDO direct route plant.
Area TIC (MM$) Equipment size Energy utilization Included units Cost estimation
source
Bioconversion 6.9 (12.3a) 6#b × 945 m3 each 19 kg h−1 LP steam for vessel Bioconversion reactors Industrial partner
fermenters heating, 4 354 760 kg h−1
chilled water (max.) for all
bioconversion reactors
Bioconversion 9.3 (3.1a) 6# × 94 m3 each 2 kg h−1 LP steam for vessel Bioconversion reactors, Industrial partner
fermenters heating, 435 476 kg h−1 seed
chilled water (max.) for all
fermenters
Bioconversion 5.5 (1.8a) 2474 BHP 2.3 MW Bioconversion reactor Douglas/Guthrie
air compressor correlations, Woods
Bioconversion 0.3 (0.2a) 2# × 8 m3 each —c Feed/product Douglas/Guthrie
sterilization vessels correlations, Woods
Bioconversion 1.6 (1.1a) 3# Scrubbers with 12 — Ethanol scrubber Douglas/Guthrie
stages each correlations, Woods
Microfiltration 2.1 350# Koch8338 MFd 0.5 MW Microfiltration system, Industrial partner
Diafiltration system
Ultrafiltration 2.7 171# DOW-SFP-2880d 0.7 MW Ultrafiltration system, Industrial partner
Diafiltration system
Nanofiltration 8.9 220# Koch8072d 1.1 MW Nanofiltration system, Industrial partner
Diafiltration system
Ion exchange 3.5 1# × 46 m3 (cation — Cation & Anion Douglas/Guthrie,
exchange) & 3# × 46 m3 Exchange vessel & Woods
each (anion exchange) resins
MVR evaporator 14.8 4# × 40 m3 each scrubbed 2.5 MW electricity & MVR Evaporator Body Douglas/Guthrie
system evaporator bodies with 8854 kg h−1 of LP steam & Scrubber Packing,
22 m3 packed volume MVR compressor,
each, 1# × 2709 BHP MVR feed-product
compressor, 9# × 427 m2 exchangers
each MVR feed product
exchangers, 1# × 153 m2
MVR steam heater
Water column 0.1 1# × 15 stage column, 12 710 kg h−1 chilled water Column vessel Douglas/Guthrie
1# × 11 m2 condenser, (condenser), 391 kg h−1 LP and trays, column
1# × 7 m2 reboiler steam (reboiler), condensers, reboilers
BDO column 2.8 1# × 122 stage column, 685 456 kg h−1 cooling water Column vessel Douglas/Guthrie
1# × 191 m2 condenser, (condenser), 21 826 kg h−1 and trays, column
1# × 377 m2 reboiler MP steam (reboiler), condensers, reboilers
Vacuum system 0.1 1# × 16 kg h−1/kPa-abs —e Douglas/Guthrie
unit
Other heat 4.4 7# × 434 m2 128 591 kg h−1 cooling water, Glucose sterilization, Douglas/Guthrie
exchangers 374 287 kg h−1 chilled water, broth sterilization, MVR
3328 kg h−1 LP steam waste cooling, water
column waste cooling,
BDO product cooling
Total 93.1
a
Purchase cost.
b
# Number of units.
c
Membrane specifications are for calculation of number of units only. They are not reflective of actual membranes used in the process.
d
Feed product sterilization is part of heat integration scheme. Energy utilization is embedded in other heat exchanger steam utilization.
e
Vacuum system is required mainly for startup. Normal operational power consumption is considered negligible compared to other energy
requirements.

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016 1267
CC Satam, M Daub, MJ Realff Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol

Table 7. Summary of 1,4-BDO direct route (tons Table 9. Summary of 1,4-BDO direct route with
are MT). and without MVR system.
Dextrose feed (dry ton ton−1 1,4-BDO) 2.0 Direct route Direct route
Process water consumed (m3 ton−1 1,4-BDO) 27.5 with MVR without MVR
Steam usage (GJ day−1) 1559 6825
Steam usage (GJ ton−1 1,4-BDO) 6.0
Steam cost (MM$ year−1) 4.8 27.0
Methane fuel value (GJ ton−1 1,4-BDO) 1.9
Cooling water (MT year ) −1
814 5831
Impure GBL combustion fuel value (GJ ton−1 1,4-BDO) 0.1
Cooling water cost (MM$ year−1) 0.6 4.6
Electricity usage (kWh ton 1,4-BDO)
−1
557.8
Electricity usage (MW) 7.0 4.6
MSP for 1,4-BDO ($ ton−1) 1816
Electricity cost (MM$ year ) −1
3.7 2.7
MVR evaporator drums TIC (MM$) 2.1 2.1
Table 8. Process water consumption in various MVR scrubber packing TIC (MM$) 0.3 0.3
units for the 1,4-BDO direct route. MVR compressor TIC (MM$) 6.0 —
Unit Process water Source/ MVR exchanger TIC (MM$) 6.6 —
consumption Destination
(cu. Meters water/ MVR LP steam makeup heater 0.4 —
MT 1,4-BDO) TIC (MM$)
Bioconversion 6.5 Feed Other heat exchangers TIC 4.4 20.8
Air scrubbers 4.4 Wastewater (MM$)
treatment MSP for 1,4-BDO ($/MT) 1816 2144
Microfiltration diafiltration 4.3 Feed
Ultrafiltration diafiltration 2.0 Feed
MVR system. The design without the MVR system utilizes
Nanofiltration diafiltration 3.9 Feed
low-pressure (LP) steam as the primary source of energy. The
Ion exchange bed rinse 5.1 Feed
evaporator streams in the non-MVR case are heat integrated
Ion exchange regeneration 1.2 Wastewater
for improved energy efficiency. The MSP of the process
chemical dilution treatment
with MVR was found to be about 15% lower. This reduction
MVR scrubber 0.12 Feed
is relative to a simple evaporator with heat integration of
Total 27.5
the feed and product streams. The MVR system reduced
the steam usage by 5266 GJ day−1 with an associated cost
thermal energy demand of the process and only offsets 2.4% decrease of 22 MM$ year−1. The TIC associated with the heat
of the energy demand. exchangers required for vaporization was also decreased by
Table 8 shows the process water consumption for various 9 MM$. Comparatively, 2.4 MW of additional electricity
units. The overall consumption is about 28 m3 ton−1 1,4-BDO was utilized with an associated electricity cost increase of
within the battery limits and this does not include water losses 1.0 MM$ year.
in cooling towers, utility blowdown systems, or transportation As mentioned before, the filtration systems utilize a
systems. Of this, 6.5 m3 ton−1 1,4-BDO is used for bioconversion countercurrent wash (diafiltration) system to recover 1,4-­
and the rest is used for 1,4-BDO recovery, primarily filtration BDO from the m/f, u/f, and n/f retentates. Figure 2(a), shows
associated with m/f, u/f, and n/f and ion exchange bed-wash the influence of m/f wash water (as a percentage of feed flow
systems. The bioconversion water consumption is comparable rate) on MSP. As the wash flow rate is increased, the m/f
to that of similar fermentation systems but the overall process area in the diafiltration section increases, and thus capital
water consumption is much higher than literature values for a cost increases. Downstream capital cost also increases with
corn or cellulosic ethanol production plant.42 wash water usage as this water ends up in the main stream,
The direct route utilizes an evaporator to vaporize water to increasing evaporator and first distillation column load, and
reduce the load on the first distillation column. Due to the thus associated capital and operating costs. Associated with
large amount of water that must be evaporated, the process an increased wash flowrate is a reduction in the number of
would be very energy intensive and thus very expensive. wash stages required to achieve a desired 1,4-BDO recovery.
The direct route circumvents this by using an MVR system Initially the increased wash rate leads to a decreased number
that compresses the evaporated vapor and condenses it to of stages and thus lower m/f capital cost, lowering the MSP.
provide heat of vaporization for the incoming evaporator As the wash flow is further increased, the filtration area
feed. Table 9 shows the direct route with and without the increases along with the evaporator and water column capital

1268 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

Figure 3. Influence of bioconversion broth 1,4-BDO titer


value on MSP.

Figure 3 shows the influence of 1,4-BDO titer on the MSP.


Every 10 g L−1 increase in titer values beyond 140 g L−1 is
expected to lower the cost of bio 1,4-BDO MSP by $0.07–
0.10 kg−1. The first Genomatica E. coli microorganisms in
2008 produced 1,4-BDO at titers of 5 g L−1, and this increased
to 140 g L−1 in 2016.43 In parallel, 1,4-BDO bioconversion
productivity increased to 2.1 g L−1 h−1. It seems likely that
further improvements have been and will be realized as
time passes. If the titer values are doubled to 240 g L−1, for
an optimized process, the 1,4-BDO cost would be 1 $ kg−1.
However, there will be a point where the titer cannot be
increased further due to the osmotic stress on the organism,
which suppresses growth and production formation.

Sensitivity analysis
Table 10 shows the sensitivity of MSP to various factors. The
MSP is sensitive to dextrose pricing, as expected, as it is the
Figure 2. Influence of diafiltration wash section water usage
primary raw material. Lowering dextrose pricing by 17%
on MSP.
reducing MSP by 6% to about 1.7 $ kg−1 1,4-BDO. We also
considered a combined energy scenario because natural gas
costs leading to increasing MSP with increasing wash water and energy prices are linked. A 40% and 28% decrease in
usage. electricity and natural gas pricing respectively only reduces
Figure 2(b) shows the influence of u/f wash water on MSP. the MSP by 4% indicating the process is insensitive to energy
The response of the MSP to u/f wash water flow is similar in pricing.
nature to m/f wash water flow. However, the initial decrease A capital cost reduction of 20%, however, produces a 9%
in MSP with increased wash water flow is less pronounced. reduction in MSP of 1,4-BDO, indicating that the process
This is because the u/f system is located downstream of the is highly capital intensive and thus sensitive to capital cost.
m/f system and the m/f wash water flow reduces the impact A capital cost change may occur due to the price of raw
of changes in u/f wash water flows. material for construction, or labor cost reductions, or process
Figure 2(c) shows the influence of n/f wash water as a equipment improvements that could lead to cheaper or
percentage of feed flow rate on MSP. The response of the MSP smaller equipment.
to n/f wash water flow is similar in nature to m/f wash water Income tax rate reductions of 18% and 33% (relative to the
flow. However, the initial decrease in MSP with increased base rate) from the base case lead to only a 1% and 2% change
wash water flow is also absent. in MSP respectively, indicating that within the range of

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016 1269
CC Satam, M Daub, MJ Realff Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol

Table 10. Influence of various factors on 1,4-BDO pricing.


Scenario Overall MSP ($ kg−1)
Low Normal High Low Normal High
Dextrose pricing (c/lb) 10 12 15 1.72 1.82 1.97
Combined energy pricing
Electricity ($ kWh) 0.04 0.0672 0.09 1.75 1.82 1.88
Natural gas ($/MMBTU) 3.0 4.17 6.0
Capital cost (%) 80 100 120 1.65 1.82 1.98
Income tax rate (%) 26 32a 39b 1.79 1.80a 1.82b
Plant lifetime (year) 20 25 30b 1.85 1.83 1.82b
Loan interest rate (%) 6 8 10 1.79 1.82 1.85
Operating hours per year 7000 7920 8500 1.92 1.82 1.78
a
Represents average scenario.
b
Represents scenario used for study.

income tax rates considered the MSP is insensitive to income but this might as well be a consequence of the higher purity
tax rate changes. specification imposed on the final BDO column to keep the
The MSP is insensitive to plant lifetimes with decrease in concentration of impurities like 2-P,HB-THF low. The final
plant lifetimes by 17% and 33% leading to MSP increases of bio-based 1,4-BDO product was used for the synthesis of
only 0.5% and 2% respectively. Similarly, the MSP was found poly(butylene terephthalate) (PBT). It was found that the
to be insensitive to loan interest rates (within the considered polymerization reaction proceeded in a similar manner
ranges) with increases and decreases of 25% (relative to the to petrochemical 1,4-BDO. The final bio-­BDO-­based
base interest rate) leading to only a 2% decrease and 2% PBT product, when tested, showed similar behavior to
increase in MSP respectively. The MSP is, however, sensitive PBT derived from petrochemical 1,4-BDO, with all tested
to the design plant operating hours per year. A 12% reduction properties being within specifications. DSM concluded that
in operating hours causes a 5% increase in MSP. A 7% there was no impact on functional behavior of PBT when
increase in operating hours causes a 2% increase in MSP. using bio-based 1,4-BDO.
The total capital investment (TCI) for a 100 KTA single
step bioconversion plant in this study was estimated to be
Critique of single step bioconversion
$337 million. Genomatica’s estimated TCI for a similar
process sized GENO BDO plant is $230 million.45 Estimates
Table 2 lists components, like 2-­(4′-­hydroxybutoxy) from TCI of a known GENO BDO plant17 using the
tetrahydrofuran (HB-THF), GBL and 2-pyrrolidone (2-P), methodology described by Weiss45 led to an estimated
which are unique to the biologically produced 1,4-BDO price of $256 million. These estimates are 32% lower
process.44 These are present in the distillate and thus are (Genomatica) and 24% lower (known plant) than the TCI
also found in the final product. These byproducts could of this study. As mentioned previously, we believe that this
potentially be detrimental to catalysts traditionally used for is due to a combination of our conservative assumptions
polymerization reactions involving petrochemically derived and undisclosed process improvements by Genomatica.
1,4-BDO. The final distillate from Genomatica’s patent22 As such, direct comparisons with the other process routes
should be greater than 99 wt% 1,4-BDO with less than to 1,4-BDO must be undertaken with care and with a
500 ppm of HB-THF, less than 5 ppm of 2-P, and less than similar framework and modeling assumptions. The process
300 ppm of BDO monoacetate ester. We did not model the observations, however, are not expected to change with such
BDO monoacetate ester in this study but we compensated assumptions and are expected to be representative of similar
for this by increasing the 1,4-BDO product purity to more single-step fermentation or bioconversion processes. One
than 99.5 wt%. DSM Engineering Plastics44 compared major observation is the high consumption of water, which
petrochemical 1,4-BDO with bio-based 1,4-BDO produced is expected for a bio-based process. This could potentially be
from Genomatica’s single-step bioconversion (GENO reduced by more efficient water reuse such as reutilization
BDO) process. They found that the GENO BDO process of evaporator overhead water for bioconversion, although
1,4-BDO has a higher purity than petrochemical 1,4-BDO information regarding potential treatment strategies for

1270 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

the same and adverse effects (if any) of water reuse on Bioproducts Institute at the Georgia Institute of Technology
bioconversion yields is unknown to us at this moment. for their support of this research effort.
Another concern is the high thermal energy requirements
for separation of water, which can be mitigated by moving
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1272 © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016
Modeling and Analysis: Direct bioconversion to make a polymer precursor, 1,4-butanediol CC Satam, M Daub, MJ Realff

Manuel Daub Matthew J. Realff


Manuel Daub works for 3M as a pro- Dr Matthew J. Realff is a professor of
cess engineer. He finished his master chemical and biomolecular engineer-
of science degree in chemical engi- ing at Georgia Tech and the associate
neering at TU Munich with a focus on director for the Renewable Bioproducts
chemical process technology. At the Institute. He completed his BEng at
time of the study he was a visiting re- Imperial College London, and a PhD
search scholar at the Georgia Institute at MIT. His research interests are in
of Technology. process systems engineering, with a focus on process
design and optimization.

© 2019 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 13:1261–1273 (2019); DOI: 10.1002/bbb.2016 1273

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