Article

pubs.acs.org/IECR

Theoretical Study on CO2 Absorption from Biogas by Membrane

Contactors: Eect of Operating Parameters
Zhien Zhang, Yunfei Yan,*, Li Zhang, Yuanxin Chen, Jingyu Ran, Ge Pu, and Changlei Qin

Key Laboratory of Low-grade Energy Utilization Technologies and Systems (Chongqing University), Ministry of Education of PRC,
Chongqing 400044, China

William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, Ohio 43210,
United States
S Supporting Information
*

ABSTRACT: Biogas upgrading and utilization is a novel technology to obtain resource-ecient vehicle fuel. In this study, a
mass transfer model for CO2 absorption from biogas into potassium argininate (PA) solutions was developed. The computational
uid dynamics (CFD) methods were employed to solve the dierential equations in three domains of the membrane contactor.
The simulations were focused on the characteristics of both gas and absorbent phases to demonstrate the concentration
distributions in axial and radial directions in the module. The simulated results were in excellent agreement with experimental
data when considering the eect of initial CO2 concentration and gas velocity. Furthermore, the eect of operating pressure, ow
pattern, ow condition, and modules in series on the membrane performance was investigated. The results showed the purity of
CH4 reached 95% with the operating pressure of 0.9 MPa. It was found that a uid in the turbulent condition or counter-current
conguration had a signicant eect on improving the contactor performance. The simulation results also indicated that the use
of two modules could increase CO2 removal and obtain high CH4 purity. Finally, the results conrmed that the developed 2D
model was able to predict the behavior of CO2 separation in the membrane contactors.

1. INTRODUCTION
With the growing crisis in energy, biogas is regarded as a kind
of green and renewable energy that could replace the traditional
fossil fuels. However, the initial biogas contains a large amount
of CO2. In order to reuse biogas, the purity of CH4 used in
vehicle fuel should be above 95%. Thus, it is crucial to improve
the utilization eciency of biogas and make it to be a substitute
of natural gas. Currently, there are a variety of methods for CO2
capture from biogas including physical and chemical
absorption, pressure and temperature swing adsorption,
cryogenic refrigeration, and membrane technology.13
Recently, the membrane absorption method, which
combines the advantages of chemical absorption and
membrane technique has drawn researchers attention. This
novel technology provides no channeling, ooding, or foaming
issues; it is small in size, lightweight, and is easy to operate in
comparison with conventional separation methods.4 Thus, a
large number of scholars have investigated acid gas removal
from a gas mixture using a membrane module experimentally
and theoretically.
Some studies have been investigated the eects of uid and
membrane module properties on the contactor performance.59 Ghadiri et al.10 proposed a 2D mathematical model
for CO2 stripping in nano porous membrane contactors. It
revealed that the system with a higher liquid velocity or slower
gas velocity provided better CO2 stripping performance. The
similar phenomenon was also reported by Hassanlouei et al.11
They examined the eects of absorbent concentration and
porosity-to-tortuosity ratio on CO2 removal in the nonwetting
mode. Increasing the liquid concentration leaded to increasing
the percentage of CO2 capture. Meanwhile, the membrane with
2014 American Chemical Society

a higher porosity-to-tortuosity ratio improved the absorption

process due to the decrease of membrane mass transfer
resistance. Wang et al.12 investigated the inuences of
membrane length, membrane diameter, and wetting ratio on
CO2 absorption performance. They recommended that a
shorter membrane module was preferred for thinner membranes to avoid the ineective part of the membrane contactor.
Meanwhile, it was suggested that the operation without wetting
was good for the CO2 stripping process. So far, there is some
work focusing on the experiments of CO2 membrane
absorption from biogas considering the eect of operating
conditions. However, the biogas upgrading in a hollow ber
membrane contactor (HFMC) using CFD approaches was
rarely reported.
Previous modeling investigations are mainly concentrated on
acid gas separation from ue gas or natural gas.13,14 AlMarzouqi et al.15 developed a comprehensive 2D mathematical
mass transfer model for CO2 physical absorption from CO2/
CH4 gas mixture using a HFMC. Also, they modied the above
mass transfer model for chemical absorption of CO2 using
monoethanolamine (MEA) and NaOH liquid solutions.16
Shirazian et al.17 carried out the numerical simulation CO2
removal from CO2/N2 gas mixture in membrane contactors.
Faiz et al.18 used a mathematical model for CO2 capture from
natural gas at high pressure up to 5 MPa. These works revealed
that the proposed models could predict well for CO2 separation
Received:
Revised:
Accepted:
Published:
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July 15, 2014

August 14, 2014
August 21, 2014
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by hollow ber membrane modules. Some researchers also

concentrated on the mathematical modeling of H2S or SO2
absorption using gasliquid hollow ber membrane contactors.1921 There is no study regarding CO2 separation
from biogas using various absorbent solutions in membrane
contactors.
In addition, absorbent is a very signicant factor for the gas
liquid membrane system. A variety of physical and chemical
solutions, as well as mixed aqueous solvents, have been
performed in membrane gas absorption elds. In the case of
physical absorption, water and methanol are the common
absorbents that are widely used in research,22,23 but using the
physical method could not get high CO2 removal eciency.
Although the chemical solvents provide high CO2 absorption
eciency, mature technology, and easy operation, the
regeneration performance of the absorbent is required to be
improved. In order to make use of an absorptiondesorption
cycle to capture CO2, Abanades et al.24 compared the absorbent
cost and performance in a range of systems. In our previous
publication, the absorption and regeneration performance of
various absorbent solutions were systematically concluded.4
Regarding single absorbent, the order of CO2 absorption
performance was MEA > diethanolamine (DEA) > 2-amino-2methyl-1-propanol (AMP) > triethanolamine (TEA) > Nmethyldiethanolamine (MDEA), whereas the generation
performance order was TEA > MDEA > DEA > AMP >
MEA. Recently, hot potassium carbonated (K2CO3) solution
has been proved to be a promising alternative of conventional
amine solutions for CO2 separation.25,26 It was reported that
the performance of dierent absorbent solutions for CO2
absorption was blend of DEA and MDEA < MDEA < DEA
< AMP < K2CO3. Currently, there is a few studies reporting the
amino salts used as the liquid solutions in the gasliquid
membrane absorbers.27
In the present study, a comprehensive mass transfer model is
proposed for CO2 capture from biogas. PA solutions are used as
the absorbent for the nonwetted conditions because arginine
with an amino group in carbonate solution shows excellent
characteristics like low volatility, ionic property, and resistance
to oxidative and thermal degradation. The eects of gas velocity
and composition, operating pressure, ow pattern, ow
condition, and module connection form are systematically
observed. The aim of this work is to theoretically capture CO2
from biogas containing 40% CO2 and 60% CH4 and to obtain
high purity of CH4 production. The model predictions are then
validated with the experimental data obtained from the
literature using TEA, DEA, and MEA as the absorbent
solutions.

Figure 1. Schematic diagram of the membrane module for nonwetting.

nonwetting mode. The set of governing equations are then

numerically solved in these simulations.
2.1. Mass Transfer Equations with Chemical Reaction
in the Tube. The material balance for any species in the tube
domain considering the chemical reaction can be written as
C
2Ci ,tube
1 Ci ,tube
i ,tube
+ Ri
+
+
Di ,tube
r
r r
z 2
Ci ,tube
= Uz,tube(r )
z

(1)

The reaction mechanisms and kinetic parameters between

CO2 and chemical solutions are shown in Tables 1 and S1
(Supporting Information). The velocity prole of the uid in
the bers is assumed to follow Newtonian laminar ow33

r 2
Uz,tube(r ) = 2Uav,tube1

r1

(2)

2.2. Mass Transfer Equations through the Membrane.

In the case of the nonwetted mode, the steady-state continuity
equation for gas diusion in the membrane is
C
2CCO2,mem
1 CCO2,mem
CO2 ,mem
=0
+
DCO2,mem
+

r
r
r
z 2

2. MASS TRANSFER THEORY

A material balance was implemented on the gasliquid
membrane contactor for developing and solving the governing
equations. The model was divided into three domains, that is,
the tube side, the membrane, and the shell side. Figure 1
demonstrates the model domains of the membrane module in
this study. Regarding the transport process of CO2 in the
HFMC, biogas containing of CO2 and CH4 ows into the shell
side of the module and passes through the membrane section in
the nonwetted mode. Then, CO2 reacts with absorbents in the
lumen side, and ows out at the outlet of tube. The model is
developed considering the following assumptions: (1) steady
state and isothermal condition; (2) Henrys law for the gas
liquid interface; (3) ideal gas behavior; and (4) operated in the

(3)

2.3. Mass Transfer Equations in the Shell. The steadystate continuity equation for gas transport in the shell side can
be expressed as
C
2CCO2,shell
1 CCO2,shell
CO2 ,shell

+
+
DCO2,shell

r
r
r
z 2
CCO2,shell
= Uz shell(r )
z

(4)

Assuming Happels free surface model, the laminar parabolic

velocity distribution in the shell side may be written as34
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Table 1. Kinetic Parameters for the Reaction between CO2 and Absorbent
system

k2 (m3 mol1 s1)

CO2-TEA
CO2-DEA
CO2-MEA
CO2PA

4.52 10 exp(2688/TL)
2.375
10(10.992152/TL)/1000
(2.58 1016exp(8654/TL)CArg + 4.32 1013exp(6666/TL))CCO2

k2kH2O/k1 (m6 mol2 s1)

k2kamine/k1 (m6 mol2 s1)

2.2 106

4.37 104

reference

28, 29
31
32
30

Table 2. Diusion, Solubility Coecients and Other Constants Used in Calculations

CO2H2O

parameter

CO2-TEA

CO2-DEA

CO2PA

CO2-MEA

35

1.8 105(/)

35

8.314

19

1.008

1.118

1.09

1.077

1.345

viscosity of absorbent (mPa s1)

1.86 106exp(16400/RTL)

2.194

1.625

1.8

1.276

Henrys law constant (mol mol1)

0.83

0.602

0.8

0.86

0.66

diusion coecient of CO2 in the

tube (m2 s1)
diusion coecient of absorbent in
the tube (m2 s1)

2.35 106exp(2199/TG)

1.95 109

1.05 109

1.4 109

1.18 106exp(2199/TL)

7.11 1010

4.97 1010

7.7 1010

Uz,shell

H2O
DCO
(H O /PA )0.82
2
2

r 2

= 2Uav,shell 1 2

r3

(r /r3)2 (r2/r3)2 + 2ln(r2/r )

4
2
3 + (r2/r3) 4(r2/r3) + 4ln(r2/r3)

reference

1.8 105

diusivity of CO2 in the shell

(m2 s1)
diusivity of CO2 in the membrane
(m2 s1)
gas constant of CO2 with absorbent
(m3 atm1 mol1 K1)
density of absorbent (kg m3)

H2O
0.5DCO
(H O /PA )0.82
2
2

36, 37, 37,

38, 30
30, 39, 40,
41, 42
43, 44, 45,
46, 42
30, 47, 48,
49, 30
49, 47, 48,
49, 49

Table 3. Parameters of the Membrane Contactor and

Operating Conditions Used in this Simulation50

(5)

3. NUMERICAL SOLUTION PROCEDURE

The governing equations for CO2 absorption in a HFMC
related to the tube, membrane, and shell region with the
appropriate boundary conditions (listed in Table S2 in the
Supporting Information) were solved numerically using the
software of COMSOL Multiphysics. This software ran nite
element analysis which was combined with error control and
adaptive meshing using the numerical solver of PARDISO. The
solver is thread-safe, high-eciency, robust, memory ecient
and easy to use for solving the dierential equations. A
computer (Intel Core i54200U CPU @ 1.60 GHz and 4.00
GB RAM) was employed to solve the set of equations. The
computational time for solving the mathematical model was
about 3 min. It should be noted that the software generated
triangular meshes in the domain. A large amount of elements
(52938 elements) were then created with scaling. Table 2 lists
the transport properties of the gasliquid system used in this
work.

parameter

symbol

value

ber inner radius (m)

membrane thickness (m)
Happels free surface model radius (m)
module inner diameter (m)
membrane length (m)
membrane area (m2)
number of bers
membrane porosity
membrane tortuosity
packing density
gas temperature (K)
liquid temperature (K)
operating pressure (MPa)
gas ow rate (L h1)
liquid ow rate (L h1)

r1

r2
D
L
S
n

TG
TL
p
QG
QL

180
45
402a
0.018
0.32
0.176
500
0.45
(2 )/
0.3125
298
303
0.1
12
200

Estimated from Mehdipour et al.25

from 30 to 50%. The error variations for CO2 absorption

eciency, ux, and CH4 recovery are from 0.12 to 6.14%, from
0.63 to 9.68%, and from 1.63 to 9.84%, respectively. Because
the maximum error is blow 10% in these simulations, the
proposed model is reliable for the simulation of biogas
upgrading in a HFMC. It is also noted that increasing the
CO2 content adversely aects the module performance. This is
due to the fact that the mass transfer resistance at the boundary
layer of gas phase decreases with an increase in CO2 content.
As described, it is noted that the three indexes have slight
change because the driving force for the mass transfer process is
mainly provided by liquid phase. Thus, CO2 content has an
insignicant eect on the biogas upgrading technique in actual
operations. The impacts of this factor in actual production
could be negligible. The previous work51 conrms the current
study.

4. RESULTS AND DISCUSSION

4.1. Model Validation. The developed mass transfer model
was validated with the experimental data reported in the
literature.50 The membrane module specications and operating conditions used in this study are illustrated in Table 3.
Three aqueous liquid solutions of 20 wt % TEA, DEA, and
MEA were used as the absorbents for the validation. As listed in
Table S3 (Supporting Information), the membrane performances of dierent values of CO2 content in the biogas are
presented. The CO2 content in the gas mixture was investigated
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Figure 2. Eect of gas velocity on the module performance: (a) CO2 removal eciency, (b) CO2 ux, and (c) CH4 recovery (line represents
simulation results and symbol denotes experimental data: initial CO2 concentration, 40%; absorbent concentration, 10 wt %; UL, 0.06 m s1).

Figure 4. Presentation of the contours of PA solution inside the tube

(initial CO2 concentration, 40%; absorbent concentration, 10 wt %;
UG, 0.32 m s1; UL, 0.06 m s1).

concluded that lower velocity of the gas provides a high-purity

CH4 production, which is good to be a substitute of
conventional fossil fuels. According to this gure, the mass
transfer model could well predict the biogas upgrading process
in the membrane module. It is also found that the model results
are higher than the corresponding values in the experiments.
This is caused by the long-term operation and membrane
wettability issues in the experimental tests which deteriorate the
membrane performance.
4.2. Concentration Distribution in the HFMC. Figure 3
illustrates the concentration gradient of gas phase outside bers.
The dimensionless concentration of CO2 along the membrane
length has a downward trend from 1.0 to 0.14. The ux vectors
also show the ow process of biogas in the shell side of the
membrane contactor. As observed, the binary gas mixture
enters into the module from the inlet of the shell (z = L) and
then diuses into the bers via the pores. The gas mixture after

Figure 3. Presentation of dimensionless concentration distribution of

CO2 inside the shell (initial CO2 concentration, 40%; absorbent
concentration, 10 wt %; UG, 0.32 m s1; UL, 0.06 m s1).

In addition, the model validation for CO2 removal eciency,

CO2 ux, and CH4 recovery as a function of gas phase velocity
is plotted in Figure 2. The liquid concentration was 10 wt %. It
should be pointed out that with an increase of gas velocity the
CO2 removal eciency and CH4 recovery noticeably decrease.
The decreasing rates of MEA and DEA are higher than that of
TEA due to higher reaction rate with CO2. However, the CO2
ux dramatically increases when the gas velocity increases. This
is due to the fact that the increment of gas velocity enhances
the mass transfer process in the membrane contactor. It can be
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Figure 7. Eect of operating pressure on the HFMC performance for

various absorbents (initial CO2 concentration, 40%; PA concentration,
5 wt %; UG, 0.32 m s1; UL, 0.06 m s1).

Figure 5. Dimensionless concentration of (a) absorbent and (b) CO2

along the length of membrane contactor (initial CO2 concentration,
40%; absorbent concentration, 10 wt %; UG, 0.32 m s1; UL, 0.06 m
s1).

Figure 6. Concentration prole of CO2 in the radial direction at z/L =

0.5 (initial CO2 concentration, 40%; absorbent concentration, 10 wt
%; UG, 0.32 m s1; UL, 0.06 m s1).

the removal process emits at the outlet of the shell for the
following regeneration procedure. As shown in Figure 4, the
contours of liquid concentration using 10 wt % PA solution as
the absorbent in the tube side are plotted. The absorbent is fed
into the tube from inlet of the membrane module (z = 0). It is
noted that the PA concentration decreases along the module
length in the tube side due to the increment in the amount of
absorbed CO2. Additionally, the concentration of absorbent in
the center of the module is the highest, and then it gradually
decreases to the tube-membrane interface.
4.3. Concentration Prole in the Axial Direction.
Figure 5a depicts the dimensionless concentration proles of
the absorbents in axial direction at the gasliquid contact
interface. It can be seen from the gure that PA has the best

Figure 8. Eect of ow condition on the HFMC performance for

various absorbents (initial CO2 concentration, 40%; absorbent
concentration, 10 wt %; UG, 0.32 m s1; UL, 0.06 m s1).

absorption performance of CO2 among them, and the outlet

concentration ratio reaches nearly zero due to more solutions
reacting in the reaction. Instead, the outlet dimensionless TEA
concentration is around 0.8 which shows poor absorption
performance. Figure 5b shows the axial dimensionless
concentration of gas at the membrane-shell interface using
the four liquid solutions. All of these four curves show a similar
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Figure 9. Eect of ow conguration on the HFMC performance for various absorbents (initial CO2 concentration, 40%; absorbent concentration,
10 wt %; UG, 0.32 m s1).

When considering the operation at high pressures, the equation

for CO2 diusivity in the shell side may be written as52
DCO2,shell = 107

1/2
T1.75
g (1/ MCO2 + 1/ MCH4)

p[(VCO2)1/3 + (VCH4)1/3 ]

(6)

where the diusion volumes of CO2 and CH4 are 26.9 and 24,
respectively.53 It can be clearly seen from Figure 7 that a high
pressure provides better separation performance due to the
enhancement in the gas mass transfer process.18 The ux of
CO2 considerably increases to 20.4 from 12.3 mol m3 h1. At
the same time, the CO2 removal eciency and CH4 recovery
increase from 69.1% to 100% and from 84.6% to 100%,
respectively. When the pressure is 0.9 MPa, the percentage of
CH4 recovery reaches higher than 95%. It indicates that the
biogas upgrading process operated at 0.9 MPa could meet the
requirements of the CH4 production as using 5 wt % aqueous
solvent. Generally, other parameters like absorbent concentration and liquid velocity could be changed to improve the
contactor performance under atmospheric conditions.
4.6. Eect of Fluid Condition. In terms of turbulent
condition, the steady state material balance for CO2 absorption
in the tube side is given by54

Figure 10. Dimensionless concentration distribution of CO2 along the

module length in the shell side of HFMCs (initial CO2 concentration,
40%; absorbent concentration, 5 wt %; UG, 0.32 m s1; UL, 0.06 m
s1).

downward trend along the membrane module length. The

outlet CO2 dimensionless concentrations with TEA, DEA,
MEA, and PA are 0.86, 0.39, 0.21, and 0.14, respectively.
4.4. Concentration Prole of CO2 in the Radial
Direction. As illustrated in Figure 6, the CO2 concentration
proles for various solvents at z/L = 0.5 in r direction of the
membrane contactor are plotted. With respect to this gure, the
concentration value drops from the shell to the tube due to the
concentration dierence of CO2. The reason is due to the fact
that the diusivity of CO2 in the shell is much larger than that
in the tube or membrane section. In particular, the CO2
concentration has a signicant drop cross the membrane side
and then reaches the minimum at the center of the tube due to
the chemical reaction.
4.5. Eect of Operating Pressure. In this section, the
operating pressures in the range of 0.1 and 3 MPa were
investigated. A 5 wt % PA solution was used as the absorbent.

C
2Ci ,tube
1 Ci ,tube
i ,tube
+ Ri
(Di ,tube + DiT,tube)
+
+
r
r r
z 2
Ci ,tube
= Uz,tube(r )
(7)
z
T
DCO
2 ,tube

1/2
0.08Uz,tube 0.3164Re1/4
r1

T
r3
8
ScCO

(8)

The comparisons of separation performance between the

laminar and turbulent ows are depicted in Figure 8. As
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4.8. Eect of Serial Modules. Very few studies focusing

on the serial modules have been conducted in previous
literature.55,56 As depicted in Figure 10, CO2 dimensionless
concentration along the module length for single and two
modules is plotted. The outlet CO2 dimensionless concentration for the rst module is 0.38, whereas this value decreases
to 0.14 at the outlet of the second module. This can be
explained by the fact that the gasliquid contact area increases,
which further increases the amount of absorbed CO2 in the
liquid phase.55 Figure 11 shows the modeling results from
dierent absorbent solutions using one module or two modules
in series. It should be noted that the percentages of CO2
removal and CH4 recovery moderately increase when using two
modules. Particularly, the solution which has a high reaction
rate with CO2 gives superior module performance. Regarding
MEA and PA solutions, the CO2 removal eciency and CH4
recovery increase about 25 and 10% compared to the use of
one module, respectively.

5. CONCLUSIONS
In the present study, the simulations of biogas purication in a
HFMC were studied. A wide-ranging 2D mass transfer model
for CO2 removal and CH4 recovery was proposed in the
nonwetted conditions. PA aqueous solutions with dierent
concentrations were used as the absorbents in the gasliquid
system. The model predictions showed good consistency with
the experimental data obtained from previous literature. The
eects of operating pressure, ow pattern, ow condition, and
serial module on the removal of CO2 were investigated. The
simulated results showed that operation under high pressure
could benet the biogas upgrading process. In the case of 5 wt
% PA solution, the percentage of CH4 recovery was higher than
95% when the operating pressure reached 0.9 MPa. The
turbulent ow gave higher CO2 removal eciency and CH4
production purity than the laminar ow. Theoretical results also
indicated that the membrane performance in the countercurrent condition was better than that in the cocurrent
condition. Additionally, when two modules in series were
employed, the absorption performance was obviously improved. Thus, in this work the established mathematical model
was able to simulate the gas removal process using the
membrane technology. It was also shown to be an eective
method instead of traditional separation techniques applied in
the biogas purication eld.

Figure 11. Eect of serial module on the HFMC performance for

various absorbents (initial CO2 concentration, 40%; absorbent
concentration, 5 wt %; UG, 0.32 m s1; UL, 0.06 m s1).

illustrated from the series of bar charts, it is found that the

membrane performance of a turbulent ow is better than that
of a laminar ow due to the increment in the diusion process
of liquid in the tube. For physical absorption, the CO2
absorption eciency, CO2 ux and CH4 recovery in a turbulent
ow dramatically increase by 14.6%, 6.6%, and 3.0 mol m3 h1
in comparison with a laminar ow, respectively. In terms of
chemical absorption, DEA, MEA, and PA reach the complete
removal when considering turbulent uid conditions. Thus,
higher absorption eciency could be obtained when operating
under turbulent ow conditions.
4.7. Eect of Flow Conguration. Figure 9 shows the
inuence of uid direction on the membrane performance at
various absorbent velocities. It is clearly seen that the countercurrent ow gives better contactor performance with the same
liquid velocity than the cocurrent ow conguration. The
cocurrent ow pattern indicates that with an increase in
absorbent velocity, the CO2 removal eciency increases from
65.3% to 85.1%, and the percentage of CH4 recovery increases
from 86.1% to 94.0%. For the counter-current model, the CO2
removal eciency increases to 95% from 77.4%, whereas the
recovery of CH4 increases to 98.0% from 91.0%. This is due to
the reason that the counter-current ow condition provides
greater driving force for the CO2 transport in the HFMC.55

ASSOCIATED CONTENT

* Supporting Information
S

Reaction mechanisms and rates between CO2 and dierent

absorbents (Table S1), boundary conditions for the model
domains (Table S2); comparisons between model predictions
and experimental data for various CO2 contents (Table S3).
This material is available free of charge via the Internet at
http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: yunfeiyan@cqu.edu.cn. Tel.: +86 236 510 3114. Fax:

+86 236 511 1832.
Author Contributions

The manuscript was written through contributions of all

authors. All authors have given approval to the nal version of
the manuscript.
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Notes

gasliquid contacting process using microporous PVDF hollow fibers.

J. Membr. Sci. 2006, 285, 272.
(6) Rajabzadeh, S.; Yoshimoto, S.; Teramoto, M.; Al-Marzouqi, M.;
Matsuyama, H. CO2 absorption by using PVDF hollow fiber
membrane contactors with various membrane structures. Sep. Purif.
Technol. 2009, 69, 210.
(7) Rajabzadeh, S.; Teramoto, M.; Al-Marzouqi, M. H.; Kamio, E.;
Ohmukai, Y.; Maruyama, T.; Matsuyama, H. Experimental and
theoretical study on propylene absorption by using PVDF hollow
fiber membrane contactors with various membrane structures. J.
Membr. Sci. 2010, 346, 86.
(8) Rajabzadeh, S.; Yoshimoto, S.; Teramoto, M.; Al-Marzouqi, M.;
Ohmukai, Y.; Maruyama, T.; Matsuyama, H. Effect of membrane
structure on gas absorption performance and long-term stability of
membrane contactors. Sep. Purif. Technol. 2013, 108, 65.
(9) Zhang, Z. E.; Yan, Y. F.; Zhang, L.; Ju, S. X. CFD investigation of
CO2 capture by methyldiethanolamine and 2-(1-piperazinyl)-ethylamine in membranes: Part B. Effect of membrane properties. J. Natural
Gas Sci. Eng. 2014, 19, 311.
(10) Ghadiri, M.; Marjani, A.; Shirazian, S. Mathematical modeling
and simulation of CO2 stripping from monoethanolamine solution
using nano porous membrane contactors. Int. J. Greenhouse Gas
Control 2013, 13, 1.
(11) Hassanlouei, R. N.; Pelalak, R.; Daraei, A. Wettability study in
CO2 capture from flue gas using nano porous membrane contactors.
Int. J. Greenhouse Gas Control 2013, 16, 233.
(12) Wang, Z.; Fang, M.; Yu, H.; Ma, Q.; Luo, Z. Modeling of CO2
Stripping in a Hollow Fiber Membrane Contactor for CO2 Capture.
Energy Fuels 2013, 27, 6887.
(13) Al-saffar, H. B.; Ozturk, B.; Hughes, R. A comparison of porous
and non-porous gas-liquid membrane contactors for gas separation.
Inst. Chem. Eng. 1997, 75, 685.
(14) Franz, J.; Schiebahn, S.; Zhao, L.; Riensche, E.; Scherer, V.;
Stolten, D. Investigating the influence of sweep gas on CO2/N2
membranes for post-combustion capture. Int. J. Greenhouse Gas Control
2013, 13, 180.
(15) Al-Marzouqi, M. H.; El-Naas, M. H.; Marzouk, S. A. M.; AlZarooni, M. A.; Abdullatif, N.; Faiz, R. Modeling of CO2 absorption in
membrane contactors. Sep. Purif. Technol. 2008, 59, 286.
(16) Al-Marzouqi, M.; El-Naas, M.; Marzouk, S.; Abdullatif, N.
Modeling of chemical absorption of CO2 in membrane contactors. Sep.
Purif. Technol. 2008, 62, 499.
(17) Shirazian, S.; Pishnamazi, M.; Rezakazemi, M.; Nouri, A.; Jafari,
M.; Noroozi, S.; Marjani, A. Implementation of the finite element
method for simulation of mass transfer in membrane contactors. Chem.
Eng. Technol. 2012, 35, 1077.
(18) Faiz, R.; Al-Marzouqi, M. CO2 removal from natural gas at high
pressure using membrane contactors: Model validation and membrane
parametric studies. J. Membr. Sci. 2010, 365, 232.
(19) Faiz, R.; Al-Marzouqi, M. H2S absorption via carbonate solution
in membrane contactors: Effect of species concentrations. J. Membr.
Sci. 2010, 350, 200.
(20) Fasihi, M.; Shirazian, S.; Marjani, A.; Rezakazemi, M.
Computational fluid dynamics simulation of transport phenomena in
ceramic membranes for SO2 separation. Math. Comput. Model. 2012,
56, 278.
(21) Luis, P.; Garea, A.; Irabien, A. Modelling of a hollow fibre
ceramic contactor for SO2 absorption. Sep. Purif. Technol. 2010, 72,
174.
(22) Mavroudi, M.; Kaldis, S. P.; Sakellaropoulos, G. P. Reduction of
CO2 emissions by a membrane contacting process. Fuel 2003, 82,
2153.
(23) Zhang, H. Y.; Wang, R.; Liang, D. T.; Tay, J. H. Modeling and
experimental study of CO2 absorption in a hollow fiber membrane
contactor. J. Membr. Sci. 2006, 279, 301.
(24) Abanades, J. C. R.; Edward, S.; Anthony, E. J. Sorbent Cost and
Performance in CO2 Capture Systems. Ind. Eng. Chem. Res. 2004, 43,
3462.

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors would like to thank for nancial support from
Fundamental Research Funds for the Central Universities (No.
CDJZR14145501), National Natural Science Foundation of
China (No. 50906103), Chongqing Science and Technology
Talent Training Plan (No. cstc2013kjrc-qnrc90002), and China
National Tobacco Corp Chongqing Branch (No.
NY20130501010010).

NOMENCLATURE
C = concentration (mol m3)
D = diusivity (m2 s1)
J = ux (mol m2 h1)
k = reaction rate constant (m3 mol1 s1)
L = module length (m)
m = Henrys constant (mol mol1)
M = molecular weight (g mol1)
n = number of bers
p = operating pressure (MPa)
Q = volumetric ow rate (L h1)
r = radial coordinate (m)
R = gas constant (m3 atm mol1 K1)
Ri = overall reaction rate of any species (mol m3 s1)
Re = Reynolds number
Sc = Schmidt number
T = temperature (K)
U = velocity (m s1)
V = diusion volume

Greek Letters

= membrane porosity
= membrane tortuosity
= packing density
= membrane thickness (m)
= removal eciency or recovery (%)
Subscripts

av = average
G = gas
in = inlet
L = liquid
mem = membrane
T = turbulence
out = outlet

REFERENCES

(1) Tippayawong, N.; Thanompongchart, P. Biogas quality upgrade

by simultaneous removal of CO2 and H2S in a packed column reactor.
Energy 2010, 35, 4531.
(2) Alonso-Vicario, A.; Ochoa-Gomez, J. R.; Gil-Ro, S.; GomezJimenez-Aberasturi, O.; Ramrez-Lopez, C. A.; Torrecilla-Soria, J.;
Domnguez, A. Purification and upgrading of biogas by pressure swing
adsorption on synthetic and natural zeolites. Microporous Mesoporous
Mat 2010, 134, 100.
(3) Zhang, Y.; Sunarso, J.; Liu, S.; Wang, R. Current status and
development of membranes for CO2/CH4 separation: A review. Int. J.
Greenhouse Gas Control 2013, 12, 84.
(4) Zhang, Z. E.; Yan, Y. F.; Zhang, L.; Ju, S. X. Hollow Fiber
membrane contactor absorption of co2 from the flue gas: Review and
perspective. Global NEST J. 2014, 16, 355.
(5) Atchariyawut, S.; Feng, C.; Wang, R.; Jiraratananon, R.; Liang, D.
T. Effect of membrane structure on mass-transfer in the membrane
14082

dx.doi.org/10.1021/ie502830k | Ind. Eng. Chem. Res. 2014, 53, 1407514083

Industrial & Engineering Chemistry Research

Article

contactor: modeling and simulation. Ind. Eng. Chem. Res. 2007, 46,
2576.
(46) Masoumi, S.; Keshavarz, P.; Ayatollahi, S.; Mehdipour, M.;
Rastgoo, Z. Enhanced carbon dioxide separation by amine-promoted
potassium carbonate solution in a hollow fiber membrane contactor.
Energy Fuels 2013, 27, 5423.
(47) Park, S. W.; Choi, B. S.; Lee, J. W. Chemical absorption of
carbon dioxide with triethanolamine in non-aqueous solutions. Korean
J. Chem. Eng. 2006, 23, 138.
(48) Zhang, H. Y.; Wang, R.; Liang, D. T.; Tay, J. H. Theoretical and
experimental studies of membrane wetting in the membrane gas
liquid contacting process for CO2 absorption. J. Membr. Sci. 2008, 308,
162.
(49) Constantinou, A.; Barrass, S.; Gavriilidis, A. CO2 absorption in
polytetrafluoroethylene membrane microstructured contactor using
aqueous solutions of amines. Ind. Eng. Chem. Res. 2014, 53, 9236.
(50) Yan, S. P.; Chen, J. A.; Ai, P.; Wang, Y. Y.; Zhang, Y. L. CO2
removal from biogas by using membrane absorption technology.
Trans. Chin. Soc. Agric. Eng. 2012, 11, 196.
(51) Yan, Y. F.; Zhang, Z. E.; Zhang, L.; Wang, J. L.; Li, J. S.; Ju, S. X.
Modeling of CO2 separation from flue gas by methyldiethanolamine
and 2-(1-piperazinyl)-ethylamine in membrane contactors: effect of
gas and liquid parameters. J. Energy Eng. 2014, DOI: 10.1061/(ASCE)
EY.1943-7897.0000215.
(52) Fuller, E. N.; Schettler, P. D.; Giddings, J. C. A new method for
prediction of binary gas-phase diffusion coefficients. Ind. Eng. Chem.
1966, 58, 18.
(53) Cussler, E. L. Diusion: mass transfer in uid systems, 3rd ed.;
Cambridge University Press: New York, 2009.
(54) Bakhshali, N.; Tahery, R.; Banazadeh, H. Modeling and
simulation of mass transfer in tubular gas-liquid membrane contactors
for turbulent flow conditions and comparison of results with laminar
flow. Middle East J. Sci. Res. 2013, 13, 1419.
(55) deMontigny, D.; Tontiwachwuthikul, P.; Chakma, A. Using
polypropylene and polytetrafluoroethylene membranes in a membrane
contactor for CO2 absorption. J. Membr. Sci. 2006, 277, 99.
(56) Dindore, V.; Brilman, D.; Versteeg, G. Modelling of cross-flow
membrane contactors: Mass transfer with chemical reactions. J.
Membr. Sci. 2005, 255, 275.

(25) Mehdipour, M.; Karami, M. R.; Keshavarz, P.; Ayatollahi, S.

Analysis of CO2 separation with aqueous potassium carbonate solution
in a hollow fiber membrane contactor. Energy Fuels 2013, 27, 2185.
(26) Saidi, M.; Heidarinejad, S.; Rahimpour, H. R.; Talaghat, M. R.;
Rahimpour, M. R. Mathematical modeling of carbon dioxide removal
using amine-promoted hot potassium carbonate in a hollow fiber
membrane contactor. J. Natural Gas Sci. Eng. 2014, 18, 274.
(27) Lu, J. G.; Zhang, H.; Ji, Y.; Fan, F.; Liu, C. Amino acid-salt-based
complex absorbents for CO2 capture in a membrane contactor. Energy
Fuels 2010, 24, 4617.
(28) Hikita, H.; Asai, S.; Ishikawa, H.; Honda, M. The kinetics of
reactions of carbon dioxide with monoethanolamine, diethanolamine
and triethanolamine by a rapid mixing method. Chem. Eng. J. 1977, 13,
7.
(29) Park, S. W.; Choi, B. S.; Kim, S. S. Absorption rate of carbon
dioxide into aqueous polyethylene oxide solution containing
triethanolamine. J. Ind. Eng. Chem. 2006, 12, 199.
(30) Shen, S.; Feng, X.; Zhao, R.; Ghosh, U. K.; Chen, A. Kinetic
study of carbon dioxide absorption with aqueous potassium carbonate
promoted by arginine. Chem. Eng. J. 2013, 222, 478.
(31) Xu, S.; Wang, Y. W.; Otto, F. D.; Mather, A. E. Kinetics of the
reaction of carbon dioxide with 2-amino-2-methyl-1-propanol
solutions. Chem. Eng. Sci. 1996, 51, 841.
(32) Barth, D.; Tondre, C.; Delpuech, J. J. Stopped-flow
investigations of the reaction kinetics of carbon dioxide with some
primary and secondary alkanolamines in aqueous solutions. Int. J.
Chem. Kinet. 1986, 18, 445.
(33) Bird, R. B.; Stewai, W. E.; Lightfoot, E. N. Transport Phenomena,
2nd ed.; John Wiley & Sons: New York, 2002.
(34) Happel, J. Viscous flow relative to arrays of cylinders. AIChE J.
1959, 5, 174.
(35) Faiz, R.; El-Naas, M. H.; Al-Marzouqi, M. Significance of gas
velocity change during the transport of CO2 through hollow fiber
membrane contactors. Chem. Eng. J. 2011, 168, 593.
(36) Garcia, J. E. Density of Aqueous Solutions of CO2. Lawrence
Berkeley National Laboratory 2001, No. http://escholarship.org/uc/
item/6dn022hb#page-1.
(37) A lvarez, E.; Gomez-Daz, D.; La Rubia, M. D.; Navaza, J. M.
Densities and viscosities of aqueous ternary mixtures of 2(methylamino)ethanol and 2-(ethylamino)ethanol with diethanolamine, triethanolamine, N-methyldiethanolamine, or 2-amino-1methyl-1-propanol from 298.15 to 323.15 K. J. Chem. Eng. Data
2006, 51, 955.
(38) Reitmeier, R. E.; Sivertz, V.; Tartar, H. V. Some properties of
monoethanolamine and its aqueous solutions. J. Am. Chem. Soc. 1940,
62, 1943.
(39) Maham, Y.; Liew, C. N.; Mather, A. E. viscosities and excess
properties of aqueous solutions of ethanolamines from 25 to 80C. J.
Solution Chem. 2002, 31, 743.
(40) Rinker, E. B.; Oelschlager, D. W.; Colussi, A. T.; Henry, K. R.;
Sandall, O. C. Viscosity, density, and surface tension of binary mixtures
of water and N-methyldiethanolamine and water and diethanolamine
and tertiary mixtures of these amines with water over the temperature
range 20100 C. J. Chem. Eng. Data 1994, 39, 392.
(41) Amundsen, T. G.; i, L. E.; Eimer, D. A. Density and viscosity
of monoethanolamine + water + carbon dioxide from (25 to 80) C. J.
Chem. Eng. Data 2009, 54, 3096.
(42) van Holst, J.; Kersten, S. R. A.; Hogendoorn, K. J. A.
Physiochemical properties of several aqueous potassium amino acid
salts. J. Chem. Eng. Data 2008, 53, 1286.
(43) Shirazian, S.; Ashrafizadeh, S. N. Mass transfer simulation of
carbon dioxide absorption in a hollow-fiber membrane contactor. Sep.
Sci. Technol. 2010, 45, 515.
(44) Cheng, M. D.; Caparanga, A. R.; Soriano, A. N.; Li, M. H.
Solubility of CO2 in the solvent system (water+monoethanolamine
+triethanolamine). J. Chem. Thermodyn. 2010, 42, 342.
(45) Paul, S.; Ghoshal, A. K.; Mandal, B. Removal of CO2 by single
and blended aqueous alkanolamine solvents in hollow-fiber membrane
14083

dx.doi.org/10.1021/ie502830k | Ind. Eng. Chem. Res. 2014, 53, 1407514083