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Energy Procedia 37 (2013) 2307 – 2315

GHGT-11

Mechanism Modeling of Elevated Temperature Pressure Swing

Adsorption Process for Pre-combustion CO2 Capture
Yan Zheng, Yixiang Shi*, Shuang Li, Ningsheng Cai
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering,
Tsinghua University, Beijing 100084, China.

Abstract

The elevated temperature pressure swing adsorption (PSA) is a promising technology for pre-combustion CO2
capture in Integrated Gasification Combined Cycle (IGCC) power plant by taking the advantages of high partial
pressure (1.0-2.0 MPa) of CO2 in the syngas after water-gas shift reaction. An elementary reaction kinetic model was
developed to predict the CO2 adsorption capacity and adsorption kinetic behavior for potassium promoted
hydrotalcite-like compound (K-promoted HTlcs). Thermo gravimetric analysis (TGA) and a high pressure adsorption
apparatus were respectively used below atmospheric pressure and above atmospheric pressure. The results indicate
that the modeling results agreed well the experimental results. The elevated temperature PSA system modeling
framework is developed by considering comprehensive coupling effects from mass, heat, and momentum transport
mechanisms. The modeling framework is implemented in the gPROMS commercial simulation platform by
integrating adsorption bed with dynamic boundary condition and realistic operating procedures. The presented
modeling framework can be further applied for the system optimization and controller design for multi-column
elevated temperature PSA processes.

©
© 2013 TheAuthors.
2013 The Authors.Published
PublishedbybyElsevier
Elsevier Ltd.
Ltd.
Selection and/orpeer-review
Selection and/or peer-reviewunder
underresponsibility
responsibility
of of GHGT
GHGT

Keywords: CO2 capture, elevated temperature PSA ;elementary reaction; adsorption kinetics, K-promoted HTlcs

1. Introduction

The elevated temperature pressure swing adsorption (PSA) based on K-promoted HTlcs solid sorbent
is a promising technology for pre-combustion CO2 capture in Integrated Gasification Combined Cycle
(IGCC) power plant by taking the advantages of high partial pressure (1.0-2.0 MPa) of CO2 in the syngas
after water-gas shift reaction [1-3]. And the sensible heat can be saved without cooling the gas down to
ambient temperature which is critical for traditional pressure swing adsorption units. As a important

* Corresponding author. Tel.: +86-10-62789955

E-mail address: shyx@tsinghua.edu.cn.

1876-6102 © 2013 The Authors. Published by Elsevier Ltd.

Selection and/or peer-review under responsibility of GHGT
doi:10.1016/j.egypro.2013.06.112
2308 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315

technology route for pre-combustion CO2 capture, the optimal design of PSA bed and system is also
significantly crucial for improving the gas separation efficiency and for lowering system costs based on
high CO2 adsorption capacity sorbent. Since experimental studies on PSA unit are expensive, time-
consuming and labor-intensive, quantitative mechanism models for the reactions and transport within the
PSA beds and dynamic system simulation are essential for elevated temperature PSA technology
development. A validated mechanism modeling framework offers not only a means to better understand
the complex physical-chemical phenomena governing PSA bed performance that are not readily
accessible experimentally; it also can be useful system design tools by accounting for the effects of
system configuration and operating conditions.
In recent years, several PSA bed models using hydrotalcite based solid sorbent differing widely in
terms of the complexity have been developed. Ding and Alpay developed Langmurian model for describing
the equilibrium adsorption properties [4, 5]. In most of the models in the published literature, mass transfer is
usually represented by the linear driving force (LDF) approximation, and commonly with the detailed reaction
and transport mechanisms within the sorbent particles neglected. Ritter et al. [6-7] developed nonequilibrium
model and provided the detailed reaction mechanism for the equilibrium and kinetic behavior of CO2 in K-
promoted HTlcs, and extended the temperature range of the model to 300-500 [8]. However, few of the
existing models relate with the mechanism model of K-promoted HTlcs considering reversible adsorption,
diffusion, and reaction phenomena to the PSA bed reaction and transport characteristics. Furthermore, few
studies existed in the high pressure adsorption model of K-promoted HTlcs which is significantly
important for the accurate application for elevated temperature PSA technology in pre-combustion CO2
capture. In addition, for a given mathematic modeling framework, although most of the model parameters
are determined from experiments or from literature, some of the parameters are still needed to be adjusted
to ensure good agreement between the model results and the experimental data. The uncertainty in the
estimated parameter will surely influence the model reliability and accuracy. The more the parameters are
determined independently through experiments or characterization techniques, the more robust the model
is.
In this study, a dynamic modeling frame work for the separation of CO2 and H2 at elevated
temperature using multi-bed pressure swing adsorption based on hydrotalcite sorbent is developed. An
elementary reaction kinetic model was developed to predict the CO 2 adsorption capacity and adsorption
kinetic behavior for K-promoted HTlcs and validated by TGA and high pressure fixed bed testing data.
The elevated temperature PSA system modeling framework is then developed in gPROMS commercial
simulation platform by considering comprehensive coupling effects from mass, heat, and momentum
transport mechanisms.

2. Experimental

2.1. Adsorbents and gases

Adsorbents used to adsorb CO2 are 25wt% potassium carbonate impregnated hydrotalcites (MG70,
Sasol Germany GmbH), 25wt% K-HTLCS in the following passage. High-purity H2, Ar, and He
(99.99%), and purity CO2 (99.99%) are used in experiments.

2.2. Gravimetric adsorption and desorption

A thermo gravimetric analyzer was used to measure the dynamic adsorption and desorption behavior
of CO2 on the hydrotalcite sorbent. The sample was activated at 400 for a specified length of time 6h in
muffle furnace. Then in TGA, the sample was further activated in helium flowing at about 100 mL min-1
 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315 2309

and 1 atm for 30min at 400 before adsorption experiment at setting temperature. The gas was then
switched to CO2 at 40 mL min-1 flow rate and He at 60 mL min-1 flow rate at 1 atm in the adsorption tests,
and the gas was switched back to helium gas after 30min for beginning of desorption process. All of the
CO2 adsorption amounts on the sorbent were based on the weight of the sample at the end of the
activation period in TGA.

2.3. Dynamic adsorption capacity tests in a packed-bed reactor

Dynamic adsorption experiments are conducted in a packed-bed reactor, which is capable of keeping a
pressure up to 7.0 MPa and a maximum temperature of 700 , with a diameter of 5.5mm and a height of
10mm. High pressure gas is depressurized by the pressure regulator to the experimental pressure demand.
Certain mass flow rate is controlled by a mass flow controller (MFC), whose value is controlled and
displayed on the PC terminal. A spiral duct heat exchanger and a gas-liquid separator are set downstream
to cool down gas flow. Pressure is detected both before the adsorption column and before back pressure
regulator. A QIC-20 gas analysis system (Hiden, England) is installed for detecting the emission gas on-
line. The mass spectrometer will detect all gas components concentration for every 0.2 second. In
adsorption experiment, purified H2 is fed into the adsorbent packed-bed at the very beginning, and the
emission gas is detected by the on-line mass spectrometer.

3. Mechanism modeling framework of elevated temperature PSA bed

3.1. Adsorption and desorption kinetics

Ritter et al. [6-8] developed a nonequilibrium kinetic model with three reversible reactions of low,
intermediate and fast kinetics, which was fitted successfully to the long cycle time experiment. Meis et al.
[9]
further proposed that K-promoted HTlcs have a higher adsorption capacity because defects are
increased, since doping K+ substitutes a Mg2+, and additional oxygen vacancies at the surface are created.
Therefore this paper proposed a mechanism model for describing the adsorption and desorption process
as shown in Fig.1.

1 CO2 g +O(s) A CO2 g +O(s) CO2 ad

Mg Al -O-K +CO2 Mg Al OK -CO2

2 E+A B or Mg -O-K +CO2 MgOK -CO2

Mg (O)-OH+CO2 Mg (O)OH-CO2
3 D+A C
or Mg -O+CO2 MgO-CO2

Figure 1. Adsorption and desorption process of K-promoted HTlcs

The model involves three reversible reactions. It assumes that the adsorbent have three activation sites
(O(s), D, E) for adsorbing CO2. Where, A indicates the adsorbed CO2 intermediate on the adsorption sites
on the sorbent surface. D indicates all types of the normal sites for CO2 chemical adsorption [10, 11]. E
indicates all types of the potassium modified sites for CO2 chemical adsorption [11]. B (E-CO2) and C (D-
CO2) indicate the transformation phase of E and D, respectively. CO2 in the bulk gas was weakly but also
very fast adsorbed by site O(s) to form phase A (CO2 (ad)). Then Phase A can be bound by either site D
2310 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315

or site E. However, since K related site E is a more basic site, site E reacts with phase A more rapidly.
The mathematic equations for this kinetic model are as follows:
dq A
=k f qO s PCO SA kb q A k1 f qE q A +k1b qB k 2 f q D q A +k 2 b qC (1)
2
dt
dqB
=k1 f qE q A k1b qB (2)
dt
dqC
=k 2 f qD q A k 2 b qC (3)
dt
qO(s), qA, qB, qC, qD and qE represent the corresponding site concentrations based on the K-promoted
HTlcs removed the weight of CO2. The total site concentrations qtotal of B, C, D, E and the ratio of K
related site to not related site can be obtained if the adsorbent is chosen. According to collision theory[12],
1
kf = , =Af EXP E f / RT (4)
q A ,s 2 RT
SA represents the surface area. q A ,s =q A +qO s , which is related to the activation time and temperature.
The adsorption capacity of per kilogram adsorbent (based on the on the weight of the sample at the end
of the activation period) can be calculated:
q CO2
q q q q
A A,0
q q M / 1+ q +q +q
B B ,0
M . (5) C C ,0 CO2 A,0 B ,0 C ,0 CO2

The reaction rate calculation is following the mass action kinetic expressions with Arrhenius form
expressions.

3.2. Governing equations

To simply the calculation, the flow pattern of gas is assumed to be axially dispersed plug flow model.
Gas components are treated as ideal gas. The temperature variation is modeled by the energy balance
equations, while here the temperature is assumed to be constant by neglecting the heat transfer processes.
The proposed elevated temperature PSA column model considered the simultaneous mass and momentum
balances in adsorption bed and sorbent particle level. The pore diffusion model is also incorporated to
consider the effects of the pore diffusion process on adsorption performance.
The mass balance equation and momentum balance equations are summarized in Table 1.

Table 1. Governing equations

Balance Equations
2
C C vC 1 q qi 3k f ,i
Bulk gas phase mass balance i
D z
i i

b
b i
= Ci
p
Ci |r =R i 1, 2, N
2
t z z t t Rp p

b
,
p p
Ci 1 Ci 1 qi
Particle mass balance
2
R p De ,i
p
z =[0, L] i 1, 2, N
2 p
t Rp r r t
p
,
qi Cip
Boundary conditions: k f ,i Ci Ci |r =R
p
=De ,i |r =R , |r =0 =0 , z =[0, L] i 1, 2, N
p

r p

r
P 150 v 1 b
M 1 b
Momentum balance 2 3
1.75 3
v v
x dp b
dp b
 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315 2311

3.3. Typical PSA process steps and boundary conditions

Typical PSA process steps usually include feed, pressurization, pressure equalization pressurization,
pressure equalization depressurization, purge and blow down, etc. A complete PSA system can be set up
by connecting key operating steps, together with multi-bed connected by valve equations. The boundary
conditions for each key step are listed in the following table for common possible elevated temperature
PSA operating steps.

Table 2.Boundary conditions of PSA process steps

Steps z=0 z= L
Ci C v
Adsorption Dz vin Ci 0 Ci ,in ,v vin
i
=0 =0
z z , z
C Ci v
Pressure Equalization Depressurization
i
=0 v 0 =0 =0
z , z , z

Ci v Ci
Blow Down =0 =0 =0 v 0
z , z z ,
Ci v Ci
Purge =0 =0 Dz vin Ci 0 Ci ,in v vin
z , z z ,
Ci Ci
Pressure Equalization Pressurization =0 v 0 Dz vin Ci 0 Ci ,in v vin
z , z ,

4. Results and Discussion

4.1. Model calibrations and validations

4.1.1. TGA adsorption/desorption curves

During model calibration process of the proposed adsorption kinetics model, a few parameters have
been allowed to vary and be turned. A comprehensive computation approach for model parameter
estimation was carried out for get an appropriate parameter set to best fit the experimental data under
different sets of operating conditions, such as operating temperature and gas compositions.

45
45
o 20% CO2 TGA
40
250 C TGA 40 40% CO2 TGA
o
300 C TGA 80% CO2 TGA
35 o 35
350 C TGA 20% CO2 Simulation
o

30
250 C Simulation 30 40% CO2 Simulation
o
300 C Simulation 80% CO2 Simulation
25
qCO2(mg/g)

o
25
qCO2(mg/g)

350 C Simulation

20 20

15 15

10 10

5 5

0 0
0 600 1200 1800 2400 3000 3600 0 600 1200 1800 2400 3000 3600
Time (s)
(a) Time (s) (b)

Figure 2. Experimental and simulation results of the CO2 adsorption and desorption in K-promoted HTlcs at different temperature (a)
and different CO2 content (b)
2312 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315

Fig.2(a) and Fig.2(b) show the model calibration results by comparison with the TGA experimental
curves for K-promoted HTlcs in the temperature range 250-350 , and with different CO2 content in
CO2/He mixture gas compositions (20% CO2, 40% CO2 and 80% CO2 content). The set of kinetic model
parameters is given in Table 3. It can be seen from Fig. 2 that the calculated adsorption and desorption
TGA curves agree well with the experimental data. However, it should be noted that the simulated
desorption process is a little bit slower than the experimental results, which indicated that it is still crucial
for model parameter turning in the future works. And, the experimental results indicate that in the temperature
extent of 250-350 , both of the adsorption rate and amount of the K-promoted HTlcs sorbent increase significantly
with the temperature.

Table 3. Parameters for adsorption and desorption kinetic model of K-promoted HTlcs

Parameters(Unit) Values Parameters(Unit) Values Parameters(Unit) Values

-1 -1
Af 4.98E-7 E1,f ( J mol ) 5.00E4 A2,b (s ) 49.0
Ef ( J mol-1) 4.00E4 A1,b (s-1) 5.45E3 E2,b (J mol-1) 7.00E4
-1 -1 2 -1
Ab (s ) 0.767 E1,b ( J mol ) 6.50E4 SA(m kg ) 2.1E4
Eb ( J mol-1) 2.00E4 A2,f (kg mol-1 s-1) 3.10E2 qtotal ( mol kg-1) 4.704
-1 -1 -1
A1,f ( kg mol s ) 55.7 E2,f ( J mol ) 6.00E4 (qB+qE)/(qC+qD) 1.091

4.1.2. Predictions of breakthrough curves of fixed bed

For further testing the applicability of the mechanism model, the simulation results of fixed bed model
integration with detailed adsorption/desorption kinetics model are compared with the breakthrough curves
of lab-scale fixed reaction at 300 with overall pressure at 0.1 MPa and 1.0 MPa. Fig.3 (a) and Fig.3 (b)
show that the calculated breakthrough curves agree well with the experimental data both at the
atmosphere pressure and 1.0 MPa. This further demonstrates the model applicability for PSA process
modeling, especially the capability for being used at higher pressures.

0.4 0.4

0.3 0.3
2
XCO

o
2

Temperature 300 C
XCO

o
0.2 Temperature 300 C
Pressure 0.1 MPa 0.2
Pressure 1 MPa
40% CO2 and 60% H2
40% CO2 and 60% H2
0.1 Experimental
0.1 Experimental
Simulation
Simulation
Blank run(Ar)
Blank run(Ar)
0.0
0 500 1000 1500 2000 2500 3000 0.0
0 2000 4000 6000 8000 10000
Time(s)
(a) (b) Time(s)

Figure 3. Experimental and simulation results of the CO2 adsorption and desorption in K-promoted HTlcs in the fixed bed reactor at
atmosphere pressure (a) and pressure 1.0 MPa (b)

Table 4. Parameters for fixed bed modeling

Parameters(unit) Values Parameters(unit) Values

Operating temperature ( ) 300 Bed void fraction, b 0.7
Flow rate(mL min-1) 100 Bed inner diameter(m) 0.011
 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315 2313

Particle density(kg m-3) 2600 Bed length(m) 0.068

From the experimental results and modeling results, it can be seen that the increasing operating
pressure lead to longer breakthrough time, and also the adsorption capacity will be higher.

4.2. Mechanism model applications in elevated temperature PSA process simulation

As an application case, the column dimensions are chosen as the pilot-scale test setup in our lab, which
is 0.089m bed inner diameter and bed length 1.8m. Fig. 4(a) and Fig.4 (b) show the breakthrough curves
at different flow rate at 1.0 MPa and 2.0 MPa, respectively. It can be seen that longer breakthrough time
will be attained with low flow rate at both pressures. The breakthrough time significantly increases when
Flow rate decreases from 1 Nm3 h-1 to 0.5 Nm3 h-1. Compared the breakthrough curves at different
pressures with the same flow rate, high pressure is favorable. This is the advantage of high pressure
separation.
0.45 0.45
3 3
0.5 Nm 0.5 Nm
0.40 3 0.40
1 Nm 1 Nm
3

3
0.35 1.2 Nm 0.35 1.2 Nm
3

0.30 0.30

0.25 0.25

XCO2
XCO2

0.20 0.20

0.15 0.15

0.10 0.10

0.05 0.05

0.00 0.00
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Time (s) Time (s)
(a) (b)

Figure 4. Simulation of breakthrough curves at different flow rate (0.5, 1, 1.2 Nm3 h-1) at 1.0 MPa (a) and 2.0 MPa (b)

Fig. 5 shows the variation of CO2 content distribution along the axis of the column with adsorption
time at 2.0 MPa pressure with 1 Nm3 h-1 flow rate. It can be seen that CO2 front moves forward with
CO2 content distribution for choosing an appropriate
adsorption time. Long adsorption time causes the leak of CO 2, and reducing the purity of product H2 and
the recovery rate of CO2. Short adsorption time reduces bed efficiency.
0.45 0.45
o
60 s 250 C
0.40 600 s 0.40 o
300 C
1200 s o
350 C
0.35 0.35
1800 s
0.30 0.30

0.25 0.25
XCO2

XCO2

0.20 0.20

0.15 0.15

0.10 0.10

0.05 0.05

0.00 0.00
0.0 0.3 0.6 0.9 1.2 1.5 1.8 0 2000 4000 6000 8000 10000
Axial (m) Tims (s)

Figure 5. Simulation of CO2 content distribution along the axis Figure 6. Simulation of CO2 breakthrough curves at
with adsorption time at 2.0 MPa, flow rate 1 Nm3 h-1 different temperature at 2.0 MPa

Fig.6 shows the breakthrough curves at 250 , 300 and 350 at 2.0 MPa with 1Nm3 h-1 flow rate.
It can be seen as the temperature increases, the breakthrough time decreases, which agree with the TGA
experiments. Since in the temperature extent of 250-350 , both of the adsorption rate of the K-promoted
HTlcs sorbent increase significantly with the temperature, the higher the temperature, the longer
2314 Yan Zheng et al. / Energy Procedia 37 (2013) 2307 – 2315

breakthrough curve time. While, at 250 temperature, there is a very steep rising of the breakthrough
curve at the beginning of the column. It is because that the adsorption rate at such a temperature is
relatively slow, therefore the breakthrough time is very short. When the CO2 front reaches at the end of
the bed, the CO2 content is kept at around 10% which will lead to the jump of the CO2 content at the end
of the column.

5. Conclusion

The elevated temperature PSA system modeling framework is developed in the gPROMS commercial
simulation platform by considering comprehensive coupling effects from mass and momentum transport
processes in both bed bulk gas and sorbent particles. An elementary reaction kinetic model was developed
to predict the CO2 adsorption capacity and adsorption kinetic behavior for K-promoted HTlcs. The model
involves three reversible reactions. It assumes that the adsorbent have three activation sites (O(s), D, E)
for adsorbing CO2. The modeling and experimental results in TGA adsorption and desorption
performance curves of K-promoted HTlcs agreed well in the temperature range 250-350 and in the CO2
content at 20% CO2, 40% CO2 and 80% CO2 content. And the experimental results indicate that in the
temperature extent of 250-350 , both of the adsorption rate and amount of the K-promoted HTlcs
sorbent increase significantly with the temperature.
The applicability of the fixed bed model for being utilized at higher pressures by integration with
detailed adsorption/desorption kinetics are further validated by comparing the modeling results with the
breakthrough curves of lab-scale fixed reactor. As an application case, the effects of operating pressure,
adsorption time and flow rate on the adsorption performance and CO2 content distribution along the
column with the pilot-scale test setup in our lab (0.089m bed inner diameter, bed length 1.8m) has been
studied. The presented modeling framework can be further applied for the system optimization and
controller design for multi-column elevated temperature PSA processes.

Acknowledgements

This work is supported by National High Technology Research and Development Program of China
(2011AA050651), and International S&T Cooperation Program of China (2010DFA72730).

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