Conventional Equilibrium Reactor

Modeling of Steam Methane

Reforming and Water Gas Shift for
Hydrogen Production Using Aspen
HYSYS
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Contents
Abstract..................................................................................................... ii
1 Background .......................................................................................... 1
2 Process description ................................................................................ 1
3 Model Description .................................................................................. 2
4 Simulation Results ................................................................................. 4
5 Conclusion ............................................................................................ 5

Abstract
This Aspen HYSYS example models steam methane reforming (SMR) from natural
gas and water gas shift (WGS) reaction for hydrogen production at the rate of
3.781e4 Nm3/h.

The methane reforming and water gas shift reactions are simulated with HYSYS
equilibrium reactors. CO2 capture is simulated with the absorber using rate-based
distillation model, hydrogen product is purified with splitter, and process CO2
emissions are estimated as well.

It can be used as a starting point for more complicated model development.

ii
1 Background
Hydrogen is the most abundant element in the universe making up to 75% of the
normal matter by mass and over 90% by number of atoms. It is recognized as a
capable energy carrier in the future. Hydrogen energy has the potential to become
energy resource and can reduce the dependency on fossil fuel in the future.

Nowadays, hydrogen is produced on a large scale via natural gas reforming. The
state-of-the-art technology is steam methane reforming (SMR), where methane
reacts with steam to produce a hydrogen-rich syngas. SMR is widely used and is a
mature technology in hydrogen production industries.

A commonly SMR system consists of three sequential units, namely reformer, shift
reactor and separation units. Shift reactor involves a WGS reaction in which carbon
monoxide reacts with steam to produce carbon dioxide and hydrogen gas. The
purpose of water gas shift (WGS) on the other hand, is to reduce the carbon
monoxide production and optimize the production of hydrogen.

In this example, the objective is to simulate SMR and WGS reactions using equilibrium
reactor block.

2 Process description
This example is based on the flowsheet in the paper of “Report on optimal plants for
production of low-carbon H2 with state-of-the-art technologies”[2] and
“Thermodynamic Analysis of Hydrogen Production via Chemical Looping Steam
Methane Reforming Coupled with Situ CO2 Capture”[3]. The process is divided into
five main steps: steam methane reforming, syngas high temperature water gas shift,
syngas low temperature water gas shift, CO2 capture and hydrogen purification.

Equilibrium reactions using HYSYS equilibrium reactor are considered to simulate the
steam methane reforming and syngas water shift process. The whole flowsheet is
shown in Figure 1.

Figure 1: SMR hydrogen production with carbon capture from shifted syngas

To obtain blue hydrogen, the CO2 produced during the synthesis process needs to be
captured and successively stored.

1
In this model, the absorber column has packing inside it and is divided into 20 stages
in the simulation. The synthesis gas enters the column at the bottom and the
lean DEPG solvent enter the column on stage 1. CO2 is absorbed by the solvent in the
column. Clean gas comes out from top of the absorber and the rich solvent leaves
absorber from the bottom and is sent to a valve.

After the valve, rich DEPG pressure is reduced from 2645 KPa to 275.8 KPa. The
pressure is selected to avoid release of CO2 while allowing some recovery of work
of pressurization. The retrieved gases (e.g. H2, CO2, CH4) are compressed and sent
back to the absorber. The rich solvent then goes through a valve and 3 flash tanks
to release CO2 from the DEPG solvent by reducing pressure to 27.52 KPa. The
regenerated lean DEPG solvent is pumped back to the absorber.

The CO2 capture model flowsheet is illustrated in Figure 2.

Figure 2: DEPG process flowsheet of Aspen HYSYS simulation

3 Model Description
This Aspen HYSYS example models steam methane reforming at the rate of 3.781e4
Nm3/h H2 from natural gas[3]. The model includes the following key features:

 HYSYS equilibrium reactor for steam methane reforming and water gas shift

 Equilibrium reactions for CH4, H2O, CO, CO2, and H2

 Rate-based model for distillation column simulation for CO2 capture

 Hydrogen purification through component splitter

 Process CO2 emissions

The main reactions occurring during the process are:

2
The correlation between equilibrium constant and reaction temperature is available
in HYSYS library for both reactions. Meanwhile, the data is available in the book:
“Hydrogen Energy and Hydrogen Producing Technologies” [4]. Both data set predicts
similar results. Therefore, this example directly applies HYSYS reaction library data
for both equilibrium reactions. The equilibrium data is listed in table 1 and table 2 for
steam methane reforming and water gas shift, respectively.

Table 1: Equilibrium data for steam methane reforming

T, C Keq T, C Keq
93.33333 7.81E-19 704.4444 14.26
148.8889 6.84E-15 760 63.43
204.4444 7.79E-12 815.5556 242.6
260 2.17E-09 871.1111 816.6
315.5556 2.19E-07 926.6667 2464
371.1111 1.02E-05 982.2222 6755
426.6667 2.66E-04 1037.778 17010
482.2222 4.34E-03 1093.333 39670
537.7778 4.90E-02 1148.889 86640
593.3333 0.4098 1204.444 178400
648.8889 2.679

Table 2: Equilibrium data for water gas shift reaction

T, C Keq T, C Keq
93.33333 4523 621.1111 2.27
148.8889 783.6 648.8889 1.966
204.4444 206.8 676.6667 1.72
232.2222 119 704.4444 1.512
260 72.75 732.2222 1.34
287.7778 46.7 760 1.202
315.5556 31.44 787.7778 1.08
343.3333 22 815.5556 0.9813
371.1111 15.89 843.3333 0.894
398.8889 11.8 871.1111 0.8192
426.6667 9.03 898.8889 0.754
454.4444 7.05 926.6667 0.697
482.2222 5.61 954.4444 0.647
510 4.55 982.2222 0.6037
537.7778 3.749 1037.778 0.5305
565.5556 3.13 1093.333 0.4712
593.3333 2.653 1148.889 0.4233
1204.444 0.3843

3
4 Simulation Results
The key simulation results of the reformer and water gas shift are listed in Table 3.

Table 3: Simulation results of SMR and water gas shift

CO2
mol % SMR inlet SMR outlet WGS HT outlet WGS LT outlet Capture
outlet
H2 - 43.82 56.17 57.61 1.02
CO - 14.61 2.26 0.82 0.09
CO2 - 0 12.34 13.78 96.26
H2O - 38.48 26.14 24.7 1.11
CH4 100 3.09 3.09 3.09 1.51
T, C 371.1 857.2 400 300 37.9

Mass flow, kg/h 8333 36407 36407 36407 17078

P, kPa 2465 2465 2465 2465 27.52

The operating conditions for SMR and WGS reactors are shown in Table 4.

Table 4: Operating conditions for SMR and WGS

SMR WGS HT WGS LT

Reactor Inlet Temperature [C] 857.2 400 300
Reactor Inlet Pressure [kPa] 2465 2465 2465

The influence of reaction temperature and steam to carbon ratio (mole base) in the
reformer are analyzed and illustrated in Figure 3 and Figure 4, respectively.

0.5
0.45
Hydrogen mol fraction in the sygas

0.4
0.35
0.3
0.25
0.2
0.15
0.1
600 650 700 750 800 850 900 950 1000

Temperature, C

4
 Figure 3: Temperature influence on hydrogen yield from feedstock of natural gas

0.55
0.525
Hydrogen mol fraction in the sygas
0.5
0.475
0.45
0.425
0.4
0.375
0.35
1 1.5 2 2.5 3 3.5 4

Steam to Carbon ratio, mole base

Figure 4: Steam to Carbon ratio influence on hydrogen yield from feedstock of natural gas

The process CO2 emissions including both material streams and utilities are reported
in Home | Flowsheet Summary and shown in Table 5.

Table 5: Results of CO2 emissions

Net CO2
Source Feed Product Utility
emission
Stream Natural Gas Gas CO2*

CO2 emission, kg/h 1.75E+05 2.94E+04 1.90E+04 1.05E+04 -1.35E+05

Carbon fee, Cost/h 8925 1498 968 534 -6892

* CO2 represents that 1.891e4 kg/h CO2 is captured in the process, so the net CO2
emission is negative.

5 Conclusion
This example shows how to model steam methane reforming and syngas water gas
shift using Aspen HYSYS. The reformer and two water gas shift reactors are simulated
with HYSYS conventional equilibrium reactors. DEPG is used to capture CO2 from
syngas which goes into component splitter to get purified hydrogen. In addition, the
process CO2 emissions are estimated. This example can be used as a starting point
for more sophisticated model development.

5
References

[1] K. Eyalarasan, Melake Daniel Tesfamariam, et al., “Design of Process Plant for
Producing Hydrogen from Steam Reforming of Natural Gas”: International Journal of
Engineering Research & Technology (IJERT), ISSN: 2278-0181, Vol. 2 Issue 12,
December – 2013;

[2] Cristina Antonini, Mijndert van der Spek, Daniel Sutter,et al.,” Report on optimal
plants for production of low-carbon H2 with state-of-the-art technologies”: ACT
ELEGANCY, Project No 271498;

[3] Andy Antzara, Eleni Heracleous, et al., “Thermodynamic Analysis of Hydrogen

Production via Chemical Looping Steam Methane Reforming Coupled with Situ CO2
Capture”: Energy Procedia 63 (2014) 6576-6589;

[4]Sufang WU, Book “Hydrogen Energy and Hydrogen Producing Technologies”:

Zhejiang University Press.