2012

101 11 25~27

Paper number: X00-002

Capturing carbon dioxide from synthesis gas by pressure swing adsorption at

mid-high and room temperature
Yu-Hau Shih 1, Fei-hong Chen 1, Yu-Jie Huang 1, Hong-sung Yang 2, Cheng-tung Chou 1*
1

Department of Chemical and Materials Engineering, National Central University

Center for General Education, Hwa-Hsia Institute of Technology
*Email: t310030@ncu.edu.tw

NSC Project No. NSC-101-3113-E-008-004

s

Abstract

f
K LDF
Kf

This study utilized two PSA process to separate high

purity hydrogen and to capture CO2 from syngas, which
is the effluent stream of water-gas-shift reactor:
dual-bed 6-step process at mid-high temperature by
K2CO3-promoted hydrotalcite and two-stage dual-bed
8-step process at room temperature by AC5-KS and
13X-Ca. Dual-bed 6-step process at mid-high
temperature could achieve 90.15% purity and 98.98%
recovery of CO2, and 94% recovery of H2. Furthermore,
two stage dual-bed 8-step process at room temperature
also could achieve above 90% of recovery and purity of
CO2.
Keywords: water-gas-shift reaction, pressure swing
adsorption , CO2 capture , H2 purification
NOMENCLATURE
A
cross-sectional area of packing bed (cm2)
Cp
heat capacity of gas mixture (J/Kmol)
~
heat capacity of component i (J/Kmol)
C pi

heat capacity of adsorbent (J/Kg)

C ps
Ci
D
Dax,i
Deff
Dm,i
Dp, dp
h
Hi

k
ni

ni

q
qm,i
R
Rp
yi
z
,b
p

Dc/rc2
Dc0/rc2
Ea

f
t
T

particle density (g/cm3)

fluid density (g/cm3)
linear driving force coefficient (s-1)
external film mass transfer coefficient
(cm/s)
micropore diffusivity (s-1)
limiting diffusivity at infinite temperature
(s-1)
activation energy of micropore diffusion
(J/mole)
particle tortuosity
fluid viscosity (g/cms)
time (s)
temperature (K)

1. Introduction
In recent years, increasing concentration of CO2 in
the atmosphere is requiring mankind to consider ways
of controlling emissions of this greenhouse gas to the
atmosphere. As required by the U.S. Department of
energy, it is important to be able to concentrate the
captured CO2 into >90% concentration that is suitable
for underground storage. At present, electric power
generated by coal accounts for about 36% of the energy
supply in the world. Using coal more efficiently and
turning it into a clean energy source is an important
issue for the whole world. An integrated gasification
combined cycle (IGCC) is a potential electric power
technology that turns coal into synthesis gas, which can
be burned to generate power. The CO composition in
syngas reacts with steam to generate CO2 and H2 via the
water-gas-shift reaction, CO + H2OCO2 + H2. In this
study pressure swing adsorption(PSA) is utilized to
separate CO2 and H2 from syngas at mid-high and room
temperature by two different adsorbent. PSA is a cyclic
process that separates gas mixtures based on the
difference of adsorption capacity of each component on
an adsorbent. This technology consists of gas adsorption
at high pressure and desorption at low pressure to
produce high-purity products. The purified H2 can be
sent to gas turbine for generating electrical power or can
be used for other energy source.
Yang et al. [1] studied several operating conditions
for a dual-column PSA process with zeolite 5A to
concentrate the H2/CO mixture (70/30 volume %)
system. Their results show that hydrogen could be

concentration of component i
bed diameter (cm)
axial dispersion coefficient (cm2/s)
effective diffusivity (cm2/s)
molecular diffusion coefficient for multiple
systems (cm2/s)
particle diameter (cm)
heat transfer coefficient (J/Kcm2s)
adsorption heat of component i (J/mole)
average thermal conductivity (J/Kcms)
adsorptive quantity on the solid phase of
component i (mole/cm3)
equilibrium adsorptive quantity on the solid
phase of component i (mole/cm3)
mole flow rate (mole/s)
saturated adsorptive quantity on the solid
phase of component i (mole/g)
gas constant (82.06 atmcm3/gmolK)
particle radius (cm)
molar fraction of component i in the gas
phase (dimensionless)
axial coordinate (cm)
bed porosity (dimensionless)
particle porosity (dimensionless)

2012
101 11 25~27

concentrated from 70% to 99.99%. In our study PSA

process are investigated in two different procedures:
using AC5-KS and 13X-Ca by the two-stage dual-bed
8-step process at room temperature and using
K2CO3-promoted hydrotalcite by the dual-bed 6-step
process at mid-high temperature. According to literature
[2-3], K2CO3-promoted hydrotalcite is a chemisorbent
that adsorb CO2 at mid-high temperature and it does not
adsorb other gases, such as CO, H2 and H2O.
The feed gas entering the PSA process consists of CO,
CO2 and H2 according to National Energy Technology
Laboratory (NETL) report at 2009 [4]. In our study it is
assumed that the gas mixture from which water has been
removed enters the PSA processes. Fig.1 shows a
conventional process scheme to produce hydrogen by
coal gasification[5].

Paper number: X00-002

s qm ,i bi yi n P n
i

ni

1 j 1 b j y j j P
n

nj

(4)

where
qm,i ai ,1ai ,2 T ni ni ,1 ni , 2 / T
bi bi ,0 exp bi ,1 / T

Linear driving force model:

Ni
KL
t

D F

N*
N
i

(5)

Linear driving force coefficient [6]:

R p n*i s
R p2 n*i s
r2
1
=
+
+ c
K LDF 3k f Ci 15 p Deff Ci 15Dc

Fig.1 Conventional process flow sheet for the

production of hydrogen from coal gasification

(6)

Micropore diffusivity:
Dc

2. Methodology

2
c

Mathematical Modelling
In the non-isothermal dynamic model, the following
assumptions are made:
(1) the linear driving force model is used because mass
transfer resistance between the gas phase and solid
phase exists.
(2) the equilibrium adsorptive quantity is estimated by
using the extended Langmuir isotherm equation.
(3) the ideal gas law is applicable.
(4) non-isothermal operation is considered.
(5) only axial concentration and temperature gradient
are considered.
(6) the pressure drop along the bed can be neglected
due to large particle size.
These assumptions are used in the following equations:

Dc0
rc2

Ea

exp

RT

(7)

2.1

Overall mass balance:

q A P T

(1 ) A
i 1

ni
t

Effective diffusivity [7]:

Dp k f
Dm, j

RT

z z

n
(1 ) A i

R t T
t
i 1,2, , n 1

f
2.0 1.1
D
f m, j

D p u b f

0.6

(9)

2.2

PSA Process
Two PSA processes, a dual-bed 6-step at mid-high
temperature process and a two-stage dual-bed 8-step at
room temperature process, are studied to separate CO2
from the effluent stream in the water-gas-shift reactor.
The effluent stream, as cited in the report of NETL [4],
has a composition of 28% CO2, 40 % H2, 5% CO and
27% H2O. We assume that water is removed before
entering the PSA. Therefore the inlet composition is
38.36% CO2, 6.85% CO, and 54.79% H2.

(1)

Mass balance for component i:

ADax,i P yi yi q A yi P

(neglecting the Knusden diffusion and

D m ,i
surface diffusion)
(8)
External film mass transfer coefficient [8]:

Deff

(2)
2.3

Energy balance:

Ak zT z C qT Dh T T

Dual-bed 6-step PSA Process at mid-high

temperature using K2CO3-promoted hydrotalcite

C p P 1 A t ni C piT Hi 1 sC ps A Tt
R t
i 1
n

The procedure of dual-bed 6-step process is shown

in Fig. 2.
(3)

Step 1:feed pressurizrion (step time :10s)

Extended Langmuir-Freundlich isotherm equation:

Step2:high pressure adsorption (step time: 20s)

2012
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Paper number: X00-002

Step3:continue adsorption (step time:10s)

(VII)
(VIII)

Step4: cocurrent depressurization (step time:10s)

Step5: vacuum desorption (step time:20s)

The step time for two stage is shown in table 2.

Step6:purge (step time:10s)

Less-adsorbed product

Feed

Feed

Step 1

CO2 product

Step 2

Less-adsorbed product

Feed
Step 4

Less-adsorbed product

Step
time(s)
H2-PSA
CO2-PSA

Less-adsorbed product

Feed

countercurrent purge
product pressurization

Table 2 Step time for two stage

20
150

10
10

10
10

25
50

10
10

10
10

20
150

25
50

CO2 product

Step 3

Less-adsorbed product Less-adsorbed product

CO2 product
Step 5

Feed

CO2 product Feed

Step 6

Fig.3 Procedure of the dual-bed 8-step PSA process

Fig.2 Procedure of 2-bed 6-step PSA process
The physical parameters of adsorption bed and
sorbent are shown in Tables 3 and 4.

The physical parameters of adsorption bed is shown

in Table 1.

Table 3 Physical parameters of bed

Bed length(cm)
730
Bed diameter(cm)
240
Operating temperature
303K
Feed pressure
7atm
Vacuum pressure
0.1atm

Table 1 Physical parameters of bed and adsorbent

Bed length(cm)
100
Bed diameter(cm)
100
*
Adsorbent(hydrotalcite)
1.563(g/cm3)
density
*
Adsorbent(hydrotalcite)
0.85 J/g.K
heat capacity
Bed void
0.37
Operating temperature
673.14K
Feed pressure
25atm
Vacuum pressure
0.1atm
#
LDF k value
3 min-1
*Alpay and Ding[9] #Sircar et al.[10]
2.4

Table 4 Physical parameters of adsorbent

Dual-bed 8-step PSA Process at room temperature

using AC5KS and 13X-Ca

AC5-KS

13X-Ca

Adsorbent
density(g/cm3)

0.85

1.24

Adsorbent heat
capacity(J/K-g)

0.87

0.92

Adsorbent
diameter(cm)
Adsorbent
porosity

0.29

0.3

0.627

0.38

The procedure of dual-bed 8-step process is shown

in Fig. 3.
3. Results and Discussion
(I)
(II)
(III)
(IV)
(V)
(VI)

feed pressurization
high pressure adsorption
continuous adsorption
continuous adsorption
Countercurrent depressurization
continuous depressurization

3.1

Adsorption isotherms of 13X-Ca and AC5-KS

The adsorption isotherms of CO, CO2 and H2 on

13X-Ca and AC5-KS were measured by Rodrigues et al.
[11,12]. The adsorption data were fitted by employing

2012
101 11 25~27

the extended Langmuir-Freundlich isotherm equation.

The fitting parameters are detailed in Table 5. Figures 4
and 5 also show a good fitting for all the components
over all of the pressure and temperature ranges studied.
Table

Paper number: X00-002

(a)

Langmuir-Freundlich isotherm fitting

parameters of CO, CO2 and H2 on
13X-Ca and AC5-KS

13X-Ca
ai,1(mole/Kg)
ai,2(mole/K
Kg )
bi,0(1/bar)
bi,1(K)
ni,1(-)
ni,2(K)
AC5-KS
ai,1(mole/Kg)
ai,2(mole/K
Kg )
bi,0(1/bar)
bi,1(K)
ni,1(-)
ni,2(K)

CO
-1.36
2.32 x10-2

CO2
1.64
1.33 x10-2

H2
-0.649
1.96 x10-2

9.36 x10-4
1.583x103
2.63 x10-1
79.505

6.566x10-5
3.204x103
-1.218
576.276

6.797 x10-6
2.042 x103
1.43
-158.364

16.4
4.47 x10-5

25.1
-4.18 x10-2

6.57
3.70 x10-2

9.397 x10-5
2.292 x103
1.599
-277.975

9.719 x10-5
1.856 x103
1.675
-275.04

4.338 x10-6
1.913 x103
2.652
-527.941

(b)

(c)

(a)

Fig.5 Adsorption isotherms of (a) CO (b) CO2 (c) H2 on

adsorbent AC5-KS. (experimental data from
Rodrigues et al. [12])
3.2

(b)

Dual-bed 8-step PSA process simulation

Influence of feed pressure of CO2-PSA stage: All the

operating variables such as vacuum pressure, bed length,
feed rate and step time are fixed, except for feed
pressure. Because the amount of gas adsorbed on
13X-Ca increases as feed pressure increases, the flow of
the strong adsorptive component to the bottom of the
bed during desorption increases. Fig.6 shows that as
feed pressure increases, the CO2 purity and recovery in
top product decreases because CO2 adsorption quantity
become larger. Furthermore, the H2 recovery in top
product decreases since the amount of H2 adsorbed
increases and the H2 purity in top product increases
since the amount of CO and CO2 decreases in top
product. As feed pressure increases, the CO2 purity in
bottom product decreases since the amount of H2 flows
to bottom increases.

(c)

Fig.4 Adsorption isotherms of (a) CO (b) CO2 (c) H2 on

adsorbent 13X-Ca. (experimental data from
Rodrigues et al. [11])

2012
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Paper number: X00-002

(a)
1.2
18
16

40

1.0
14
12
10

0.8

y(t)/y0

20

Recovery(%)

Purity(%)

30

6
4

10

0.4

2
0

0.6

0
4

0.2

Feed Pressure(atm)
CO2 purity
CO2 recovery

0.0

(b)
95

0.0

84

0.5

1.0

1.5

2.0

2.5

t/t*

90
82

simulation(this study)
experimental data(Sircar et al.)
simulation(Sircar et al.)

Purity(%)

80

80

75
78

70

Recovery(%)

85

Fig.7 Breakthrough curve of K2CO3-promoted hydrotalcite

with inlet CO2 mole fraction y0=0.4 at 673.14K

65
76
60
55

74
4

1.2

Feed Pressure(atm)
H2 purity
H2 recovery

1.0

Fraction of CO2 desorption

(c)
100
98

92.8

96

92.6

Purity(%)

92
92.2
90
92.0

Recovery(%)

94
92.4

88
91.8

86

91.6

84

91.4

82
4

0.8

0.6

0.4

0.2

0.0

Feed Pressure(atm)
CO2 purity
CO2 recovery

(d)

Cumulative N2(mole/kg of promoted hydrotalcite)

6.0

24

simulation(This study)
experiment data(Sircar et al.)
simulation(Sircar et al)

22

20
5.0
18

Recovery(%)

Purity(%)

5.5

Fig.8 Desorption curve of K2CO3-promoted hydrotalcite

4.5
16

4.0

3.4

Best operating conditions

The best operating conditions for two PSA process
are obtained. The results of best operating condition for
dual-bed 8-step process at room temperature are 87.82%
purity and 78.55% recovery of H2 as top product, and
91.97% purity and 97.8% recovery of CO2 as bottom
product as shown in Fig.9. For dual-bed 6-step process
at mid-high temperature the best operating condition
gives 88.16% purity and 94% recovery of H2 as top
product, and 90.15% purity and 98.98% recovery of
CO2 as bottom product as shown in Fig.10.

14
4

Feed Pressure(%)
H2 purity
H2 recovery

Fig.6 Effect of feed pressure on (a) CO2 in top product

(b) H2 in top product (c) CO2 in bottom product (d) H2
in bottom product

3.3 Program verification for the case of

K2CO3-promoted hydrotalcite
To confirm the accuracy of our model, the
simulation program is verified by comparison with the
results of breakthrough curve from Sircar et al. [2] as
shown in Fig.7, and desorption curve from Sircar et
al.[8] as shown in Fig.8. Figures 7 and 8 show that the
agreement between our simulation results and
experimental data from literature [2,13] is very close.

2012
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establishment of the experimental system.

top product flow rate:

351508(STP)/min
H 2 purity:99.98%
H 2 recovery:78.55%

41.4% CO 2
1.3% CO
57.3% H 2
feed product
flow rate:
792444L(STP
)/min

Paper number: X00-002

5. Acknowledgements
The authors gratefully acknowledge the financial
support received from the National Science Council of
the Republic of China, Taiwan under Contract No. NSC
101-3113-E-008 -004.

H2PSA
303.14K
Adsorbent:AC5 - KS

6. References
1.

bottom product flow

rate:338390 L(STP)/min
CO 2 purity:75.87%
CO 2 recovery:100.%

2.

top product flow rate:

82002L(STP)/min
H2 purity:87.82%
H2 recovery:78.55%

3.
75.87% CO2
2.27% CO
21.86% H2
feed product
flow rate:
431315L(STP
)/min

CO2 PSA
303.14K
Adsorbent:13X-Ca

4.
bottom product flow
rate:338390 L(STP)/min
CO2 purity:91.97%
CO2 recovery:97.80%

5.

Fig.9 Results of the two stage of the 2-bed 8-step PSA

process at room temperature

6.

top product flow rate:

12747L(STP)/min
H2 purity: 88.16%
H2 recovery:94.07%
38.36% CO2
6.85% CO
54.79% H2
feed product
flow rate:
22025L(STP)
/min

7.

CO2 PSA
673.14K
Adsorbent:
K2CO3-promoted hydrotalcite

8.

bottom product flow

rate: 9275L(STP)/min
CO2 purity: 90.15%
CO2 recovery:98.98%

9.

Fig.10 Results of the 2-bed 6-step PSA process at

mid-high temperature

10.

4. Conclusions and Future work

11.

Pressure swing adsorption (PSA) is utilized to capture

CO2 from the exit stream of water-gas-shift reactor at
mid-high temperature and room temperature. The PSA
process at mid-high temperature can save on energy
consumption by reducing the temperature of the exit
stream from the water-gas-shift reactor in order to
capture CO2 at room temperature, and the energy which
is required to raise the temperature of the purified
hydrogen for combustion use. The calculated results for
both 2-bed 6-step at mid-high temperature and 2-bed
8-step at room temperature PSA processes are shown in
Figures 9 and 10. In the future, our project will proceed
with syngas which contains water vapor and

12.

13.

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of Hydrogen Mixtures by a Two-Bed Pressure Swing
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potential applications " ,AIChE J., 54, 8048-8062,
2008.
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"Chemisorption of carbon dioxide on potassium
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Interface Science, 308, 30-39, 2007
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on Activated Carbon and Silica Gel AIChE
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A. Gorbach, M. Stegmaier and G. Eigenberger,
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coefficients on particle-to-fluid mass transfer
coefficients in packed beds. Correlation of Sherwood
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Y. Ding and E. Alpay, "Equilibria and kinetics of CO2
adsorption on hydrotalcite adsorbent",Chemical
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