Journal of Membrane Science 401402 (2012) 175189

Contents lists available at SciVerse ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Mathematical modeling and cascade design of hollow ber membrane contactor

for CO2 absorption by monoethanolamine
Somnuk Boributh a , Wichitpan Rongwong a , Suttichai Assabumrungrat b , Navadol Laosiripojana c ,
Ratana Jiraratananon a,
a
Department of Chemical Engineering, King Mongkuts University of Technology Thonburi, Bangkok 10140, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
c
The Joint Graduate School of Energy and Environment, King Mongkuts University of Technology Thonburi, Bangkok 10140, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: The absorption of CO2 from the gas mixture (CO2 CH4 ) by polyvinylideneuoride (PVDF) hollow ber
Received 4 October 2011 membrane contactor using monoethanolamine (MEA) as the absorbent was performed. The mathemat-
Received in revised form 6 January 2012 ical model has been developed to predict the absorption performance. The model is validated with the
Accepted 31 January 2012
experimental results for estimating the wetting ratio (x*) as the function of liquid velocity and MEA con-
Available online 9 February 2012
centration. The suitable hollow ber membrane module with effective ber length of 50 cm is selected
for the design of multistage membrane contactors. The absorption ux of multistage membrane contac-
Keywords:
tor is simulated based on the value of x* obtained from the experiments. The three-stage cascade design
Carbon dioxide
Cascade design
is selected to compare the system performance with different gas and liquid ow patterns. The results
Membrane contactor of the simulation show that the individual gas ow (G-ID) gives higher performance compared to the
Membrane wetting gas ow in series (G-IS) for all operating conditions studied. The three different ow patterns of liquid
including (i) liquid ow in series (L-IS), (ii) liquid ow in series with splitting (L-ISS) and (iii) liquid ow in
series with recycle (L-ISR) are compared. At low MEA concentration (0.25 M), the L-ISR can improve the
system performance at low liquid velocities, while L-ISS shows the highest performance at high liquid
velocities. For the system with high MEA concentration (1.0 M), L-ISR can improve the performance at
low to moderate liquid velocities, whereas L-ISS does not improve the system performance at any liquid
velocity.
2012 Elsevier B.V. All rights reserved.

1. Introduction and compactness [1]. Therefore, the research on CO2 absorption

Natural gas is the clean energy that has been widely used for
several purposes such as transportation and electricity generation.
The main constituents of natural gas are CH4 and CO2 with traces of
other impurities. The removal of CO2 from natural gas prior to use is
necessary since it reduces the heating value, causes pipe line corro-
sion and takes up volume in the transportation. Generally, CO2 can
be captured by amine based absorption in various mass transfer
contactors such as packed, plate and spray columns. Neverthe-
less, these conventional contactors have limitations in operation,
i.e., ooding, foaming and channeling. In addition, high capital
and operation costs are also the major disadvantages of these
contactors for the real application. To overcome these problems,
the hybrid process called gasliquid membrane contacting process
has been developed. This process provides the additional advan-
tages in terms of its high contact area per unit volume, modularity
Corresponding author. Tel.: +66 2470 922; fax: +66 2428 3534.
E-mail address: ratana.jir@kmutt.ac.th (R. Jiraratananon).
using membrane contactors has been intensively studied by many
researchers [26].
For gasliquid membrane contactors, the microporous
hydrophobic hollow ber membranes are generally employed as
the phase barrier. The membrane provides the contact between
gas and liquid phases without dispersing one phase into another
phase. However, the membrane adds the additional resistance
to the overall mass transfer, especially in case of the partially
wetted mode where the membrane pores are partially pene-
trated by the liquid absorbent. In the operation, the non-wetted
mode is preferred to achieve highest absorption performance.
Although the highly hydrophobic membrane is used, the par-
tial wetting can occur owing to many factors. The degree of
membrane wetting depends on the structural characteristics
of membrane, operating pressure of gas and liquid phases
and the nature of liquid absorbent in contact with the mem-
brane surface. Additionally, the direct contact of the polymeric
membrane surface with the liquid absorbent over a prolonged
operation time can lead to morphological change and gradual
membrane wetting [7,8]. Many researchers have addressed the

0376-7388/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2012.01.048
176 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

negative effects of membrane wetting on the process performance

[911].
The mathematical models have been widely proposed to inves-
tigate the degree of membrane wetting and the effect of membrane
wetting on the absorption efciency of the membrane contactors.
Wang et al. [12] developed the two dimension model to predict
CO2 absorption and validated the model with the experimental
results. They reported that the reduction of the overall mass trans-
fer coefcient could reach 20% when the membrane pores were
5% wetted. Mavroudi et al. [9] proposed the rst-order expression
to describe the membrane resistance change with time of physical
absorption of pure CO2 . Khaisri et al. [10] developed the mathe-
matical model for investigating mass and heat transports based on
resistance-in-series model to describe the inuence of wetting on
the process performance. Lu et al. [11] presented the model taking
into account the effect of membrane pore size distribution and pres-
sure drop of liquid ow in hollow bers on the membrane wetting.
These models employed similar basic equations and correlations
for describing the mass transfer. However, they presented different
focuses and the experimental data used to validate the models were
also obtained from different experimental conditions, including gas Fig. 1. Mass transfer regions and resistance-in-series in partially wetted mode for
compositions and liquid absorbents. Although it may be possible to gasliquid membrane contacting process.
apply the results from some mathematical models for designing the
membrane gas absorption process, from our knowledge, there has
been no much report in the literature. Recently, we published the
suitable design of the membrane contacting process for physical gas-lled pores, and membrane for liquid-lled pores, respectively.
 are the outer,
H represents Henrys constant, and do , di , dln , and dln
absorption of CO2 [13]. The main objective of the present work is to
propose a simple mathematical model to validate the experimental inner, and logarithmic mean diameters of non-wetted and wetted
data in order to obtain the important parameter (wetting ratio, x*). membranes, respectively. E is enhancement factor accounting for
From a separation point of views, a membrane contactor is one of the effect of chemical reaction on absorption determined by the
the unit processes, which should be designed as a multistage cas- following:
cade module in the real application. The study of multistage cascade
membrane contacting process could bring about important practi-  
cal criteria of the process design for improving the overall efciency (Ha )2 (Ha )2 (Ha )2
E
E= 1)
+ + 1)
+1 (2)
of the process. 2(E 1)2
4(E (E
In this work, the absorption of CO2 from the gas mixture contain-
ing CH4 using PVDF hollow ber membrane contactor by MEA was
where Ha* and E are Hatta number and asymptotic innite
performed. The effects of operating conditions including gas/liquid
ow rates, MEA concentration and gas composition on absorption enhancement factor, respectively. These parameters can be esti-
ux were studied. The mathematical model has been developed to mated by the followings:
predict the system performance and the membrane wetting. The

wetting ratio (x*) is estimated by validating the model with the k2 DA,L CR,L

experimental results. The suitable module length is employed in Ha = (3)
kL
the multistage cascade design of membrane contactor based on the
parameter (x*) obtained from the experiments. The performance of
the systems with different gas and liquid ow patterns is compared. where k2 is the second-order reaction rate constant (between CO2
The effects of splitting () and recycle ratio () are investigated. The and MEA), Di,L is diffusivity of species i in liquid solution and CR,L is
results of process design at different operating conditions are also the concentration of absorbent.
presented.
   13
CR0,L DR,L Di,L
2. Theory E = 1+ (4)
vR Ci,L Di,L DR,L

2.1. Mass transfer in gasliquid membrane contactor

where R is a stoichiometric coefcient of reaction, DR,L is diffusivity
The operation of gasliquid membrane contactors can be clas- of absorbent in liquid phase, CR0,L and Ci,L is the concentration of
sied into 3 modes including non-wetted (dry) mode, partially absorbent at inlet and concentration of species i in liquid phase
wetted mode, and wetted mode. Generally, the operations of mem- which is in equilibrium with gas phase, respectively.
brane contactors are performed in a partially wetted mode in which In addition, Eq. (1) can be expressed in term of resistances as
there are four mass transfer regions as shown in Fig. 1 and the shown in Eq. (5);
resistance-in-series model for partially wetted hollow ber module
can be written following Eq. (1): 
Rtot = RL + RM + RM + RG (5)
1 1 1 1 1
= +   + + (1)
KL dln EkL di EkM dln HkM dln HkG d0 where Rtot , RL , RM , RM and RG are total resistance, liquid phase
where KL is the overall mass transfer coefcient and kL , kG , kM , and resistance, wetted membrane resistance, non-wetted membrane
 are the mass transfer coefcients of liquid, gas, membrane for
kM resistance, and gas phase resistance, respectively.
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189 177

2.2. Individual mass transfer coefcients 3. Mathematical model

2.2.1. Gas side mass transfer 3.1. Model development

For the gas ow in the shell side, Yang and Cussler [14] proposed
the correlation to predict the gas side mass transfer coefcient (kG ) Mathematical model has been developed to predict the chemi-
as the following; cal absorption of CO2 by gasliquid membrane contacting process
using MEA as the absorbent. The model is validated with the
kG dh d
 0.93
experimental results for estimating the value of wetting ratio (x*).
Sh = = 1.25 h Re Sc 0.33 (6)
Di,G L Additionally, the absorption performances of multistage mem-
brane contactor with different cascade designs are also predicted
where Sh is Sherwood number, Sc is Schmidt number, Re is Reynolds by the model simulation based on the wetting ratio as a function of
number, Di,G represents the diffusivity of component i in the gas operating conditions obtained from the experiments. The model is
mixture (see Appendix A for the calculation), L is the ber length derived based on the following assumptions;
and dh is the hydraulic diameter.
1. Steady state and isothermal conditions
2.2.2. Liquid side mass transfer 2. Constant total pressure in gas phase (no pressure drop) along the
For liquid ow in the lumen side, Yang and Cussler [14] also ber length
proposed the liquid side mass transfer coefcient (kL ). 3. Ideal gas behavior
4. No axial mixing in phases
kL di d
 0.33
5. Membrane with uniform properties including pore size, tor-
Sh = = 1.62 i Re Sc (7)
Di,L L tuosity, porosity, thickness, hydrophobicity and pore size
distribution
Eq. (7) is valid for Gz > 20. 6. No property change of membrane over a period of operation time
7. The wetting ratio (x*) depends only on liquid velocity and MEA
2.2.3. Membrane mass transfer concentration.
For the non-wetted zone of the membrane pores, the mem-
brane mass transfer coefcient can be estimated by the following The schematic diagram describing the mass transfer of CO2 from
equation [15]; gas phase to liquid phase through the hydrophobic microporous
membrane is depicted in Fig. 2. For a small element with ber length
DG,eff M z and contact area Ai , the mass balance of CO2 transfer from gas
kM = (8)
 M dry phase to liquid phase is written as the following;

where dry is the dry thickness of the membrane,  M is membrane FA,i = FA,i+1 JA,i Ai (13)
tortuosity and M is membrane porosity. The gas effective diffusiv-
ity (DG,eff ) is determined by the interactions between the molecules where FA and fA are the molar ow rate of CO2 in gas phase and
(molecular diffusion) as well as the interactions of the molecules liquid phase, respectively. JA,i is absorption ux of CO2 determined
with the pore wall (Knudsen diffusion). The gas effective diffusivity by the following;
is estimated using the following equation;
JA,i = KL,i (CA,i CAL,i ) (14)
1 1 1
= + (9) where KL,i is local overall mass transfer coefcient, CAL,i is the bulk
DG.eff DG,M DG,Kn concentration of CO2 in liquid phase and C* A,i is the CO2 concentra-
tion in liquid phase in equilibrium with the bulk concentration of
where DG,M and DG,Kn are the Fickians molecular diffusion coef-
CO2 in gas phase given by the following equation;
cient and the Knudsen diffusion coefcient of gas, respectively.
The molecular diffusion coefcient of gas (DG,M ) is calculated PAG,i
from the kinetic gas theory; CA,i = (15)
H

0.001858T 3/2 where PAG,i is the partial pressure of CO2 in gas phase estimated as
DG,M = (10) the following;
1/2 2
PMA AB D
PAG,i = yA,i Ptot (16)
where MA is the gas molecular weight, P and T are the gas pressure
and temperature, respectively.  AB is characteristic length, the col- where yA,i and Ptot are mole fraction of CO2 in gas phase and the
lision integral D is dimensionless function of temperature which total pressure of gas phase, respectively. The mole fraction of CO2
is calculated by empirical equations (see Appendix A). The Knud- can be estimated from the molar ow rate as;
sen diffusion coefcient (Dg,Kn ) can be calculated by the following
FA,i
equation; yA,i = (17)
FA,i + FI,i

T where FI,i is molar ow rate of inert gas not absorbed by the liquid
DG,Kn = 4850dpore (11)
MA absorbent. Therefore, FI is constant along the ber length and is
equal to the molar ow rate at inlet feed gas (FI0 ).
For the wetted part of the membrane pores, the membrane mass The contact area (Ai ) for each small element is determined
transfer coefcient can be expressed as [15]; from the following:

 Di,L M Ai =
(di + x M ) z (18)
kM = (12)
 M wetted
where x* is wetting ratio representing the degree of membrane
where wetted is the wetted thickness of the membrane. wetting.
178 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

Fig. 2. The schematic diagram showing mass balance of a small element in gasliquid membrane contacting process.

Table 1 from deionized water and monoethanolamine (MEA, 99.8 mol%)

Membrane and membrane module specications.
obtained from QrC, Malaysia.
Properties Descriptions

Experimental module Designed module

Membrane 4.2. Experimental procedures

Fiber i.d. 800 m 800 m
Fiber o.d. 1166 m 1166 m The experimental set up of gasliquid membrane contactor is
Average pore radius 0.08 m 0.08 m
illustrated in Fig. 3. In this work, all experiments were performed
Porosity 0.7 0.7
Tortuositya 3 3 at a room temperature (25 C) and atmospheric pressure. The ow
Module rates of feed gas consisting of CO2 and CH4 supplied from the com-
Number of ber 100 518 pressed gas cylinders were individually adjusted and controlled by
Shell diameter 1.6 cm 3.64 cm
the mass ow controllers, (Brooks Model 4800 series). The set point
Effective length 22 cm 50 cm
controller (Brooks Model 0254) was used to control and monitor
a
Reported by Khaisri [10]. the ow rate of each gas entering the module. In the experiments,
the gas mixture was fed through the shell side of the membrane
Substitute Eqs. (14), (15) and (18) into Eq. (13) gives Eq. (19): module, counter-currently to the absorbent ow into the tube side
  of the bers. A peristaltic pump (I/P digital Masterex model 7592-
yA,i Ptot 45) delivered the absorbent from the absorbent reservoir through
FA,i = FA,i+1
KL,i (di + x M ) CAL,i z (19)
H a rotameter to the membrane module. The inlet and outlet gas vol-
umetric ow rates were measured by a digital gas ow meter (Bios
The average absorption ux can be determined by Eq. (20) as fol-
International, DC-lite). The inlet and outlet concentrations of CO2
lowing:
and CH4 were analyzed by the Gas analyzer (Cubic, Gasboard-3200).
(FA,0 FA,N ) Before entering the gas analyzer, the moisture in the outlet gas was
JA,av = (20)
removed by the water trap. Since CH4 is the ammable gas, the
Ai
methane-rich gas was vented outside the laboratory building by
3.2. Numerical solutions the pipe line in which the ame arrestor was installed at the end.
In addition, CH4 detector (BW technologies, GasAlert MicroClip)
For the counter ow operation, the inlet conditions of gas and with response range of 05 vol.% was also installed to detect any
liquid phases are known, while the outlet conditions of gas and liq- leakages and ensure safety operation.
uid are unknown. To solve this problem, the shooting method is All of the data were collected after the experiments reached the
applied. The procedure begins by assuming the outlet concentra- steady state. The results of each run were averaged from four times
tion of CO2 in liquid phase. The simulation starts from the gas feed of sampling. The absorption uxes were calculated from the mea-
inlet to the outlet. Along the axial direction, the ber is divided into surements of CO2 concentration and the gas ow rate at the inlet
many small elements with identical length (z). In each element, and outlet. The Absorption ux can be determined by the following
the set of equations (Eqs. (1), (19) and (20)) including overall mass equation:
transfer coefcient (KL,i ) and CO2 absorption ux are employed. The
outlet liquid compositions are determined by applying the mass
 
QG,in CAG,in QG,out CAG,out
balance equation along the ber length. MATLAB was employed in JA = (21)
A
solving.

4. Experimental where QG,in and QG,out are the gas ow rates at inlet and outlet,
respectively. CAG,in and CAG,out are the concentrations of CO2 at inlet
4.1. Materials and outlet, respectively. A is mass transfer area. In addition, the
removal efciency dened as % removal was also reported. It is
The polyvinylideneuoride (PVDF) hollow ber membranes estimated by the following equation:
were purchased from Altrateck (China). The specications of the
membrane and membrane module are shown in Table 1. Carbon  
QG,in CAG,in QG,out CAG,out
dioxide (CO2 , 99.8 vol.%), methane (CH4 , 99.9 vol.%) were obtained % removal = 100% (22)
QG,in CAG,in
from Thai Industrial Gases PLC. The absorbent used was prepared
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189 179

Fig. 3. Experimental set up of gasliquid membrane contacting unit.

5. Results and discussions
5.1. Experimental results
Fig. 4(i) shows of the effect of liquid velocity and MEA concen-
tration on the absorption ux. It was found that the absorption
ux increased moderately with liquid velocity, but the increase
was more signicant with increasing MEA concentration. From liq-
uid velocity 0.10.4 m s1 , the absorption ux increased roughly 21
and 25%, for MEA concentrations of 0.5 M and 1.0 M, respectively.
The increase in liquid velocity could increase the liquid phase mass
transfer coefcient (Eq. (7)) resulting in the increase of overall mass
transfer coefcient (KL ). In addition, the driving force of the system
which is the concentration difference of CO2 at gasliquid interface
and bulk liquid is enhanced with increasing liquid velocity, while
increasing MEA concentration resulted in enhanced chemical reac-
tion rate between CO2 and MEA. The similar results were reported
in the literature [3,5,13].
The effects of gas velocity and gas composition on absorption
ux are depicted in Fig. 4(ii). It was found that increasing in gas
velocity did not affect the absorption ux as observed from the con-
stant absorption ux. Atchariyawut at el. [16] reported the same
trend of results for absorption of CO2 from CO2 CH4 gas mixture
using PVDF hollow ber, the CO2 ux remained constant when the
gas velocities were varied from 1.0 to 8.0 m s1 . Khaisri et al. [5]
also found that for physical absorption of CO2 using PTFE mem-
brane, the CO2 ux remained constant while the gas velocity was
increased. Meanwhile, the absorption ux increased approximately

(i) 2.5
(ii)
1.2
1.0 M
CO2 flux (x10 mol/m .s)

CO2 flux (x10 mol/m .s)

2 1
2

0.5 M
2

0.25 M 0.8
1.5
-3

-3

0.125 M
0.6
1
0.4
40 %vol. CO2
0.5
0.2 50 %vol. CO2

0 0
0.05 0.15 0.25 0.35 0.45 0.55 0.06 0.07 0.08 0.09 0.1 0.11
Liquid velocity, vl (m/s) Gas velocity, v g (m/s)

Fig. 4. (i) Effect of liquid velocity on absorption ux of CO2 at various MEA concentrations (yCO2 = 0.4, QG = 0.5 l/min) (ii) effect of gas velocity on absorption ux of CO2 at
different CO2 concentrations in gas phase (CMEA = 0.125 M, vl = 0.3 m s1 ).
180 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

14.3% when CO2 concentration in gas phase was increased from 5.3. Resistance analysis
40 to 50 vol.% as a result of the enhanced driving force for mass
transfer. In this work, the experiments were performed at the liquid
velocities in the range of 0.10.4 m s1 . For the process design, it
is assumed that the wetting ratio (x*) correlation given by Eq. (23)
can be used to predict the wetting ratio with the liquid velocities
5.2. Membrane wetting estimation
up to 1.0 m s1 , which is still in the laminar ow region. By using
Eq. (23), at MEA concentration of 1.0 M, the values of x* for liquid
The data obtained from the experiments were validated with the
velocities of 0.6, 0.8 and 1.0 m s1 are 0.1025, 0.1045 and 0.1062,
proposed model for estimating the membrane wetting. The degree
respectively, or the increase is not signicant. The total resistance of
of membrane wetting is expressed in term of wetting ratio (x*),
the partially wetted membrane can be determined by Eq. (1) or (5).
dened as the ratio of the length of the liquid lled pores to the
The gas phase mass transfer coefcient (kG ) is calculated from Eq.
membrane thickness (x* = wetted /M ). The values of x* were deter-
(6), the liquid phase mass transfer coefcient (kL ) is determined
mined by adjusting the value (x*) in the model until the absorption  ) membrane
from Eq. (7), the non-wetted (kM ) and wetted (kM
ux obtained from the simulation was very close to or equal to
mass transfer coefcients are determined from Eqs. (8) and (12),
the experimental data. The difference allowed between these two
respectively. The enhancement factor (E) accounting the chemical
values did not exceed 0.1%. In Fig. 5(i), the dots represent the wet-  is estimated by Eq. (2).
reaction expressed in the terms of kL and kM
ting ratio obtained from validation of the experiments with the
The resistance contributions of gas, non-wetted membrane, wet-
model, while the trend lines are used to obtain the wetting ratio
ted membrane and liquid phases are dened as RG /Rtot , RM /Rtot ,
correlation as a function of the operating conditions. It can be seen  /R
RM tot and RL /Rtot , respectively and are shown in Fig. 6. For MEA
that x* increases with liquid velocity and MEA concentration. The
concentration of 0.25 M (see Fig. 6(i)), the gas phase resistance is
increase in MEA concentration leads to signicant reduced surface
around 3% and the non-wetted membrane resistance is less than 1%
tension and contact angle between the membrane surface and solu-
for all liquid velocities. At low liquid velocities (0.10.2 m s1 ), the
tion. These could increase the membrane wetting. Lu et al. [11]
liquid phase resistance dominates the overall resistance (8060%),
reported that the membrane wetting observed from ux decline
while the estimated resistances for wetted membrane are in a
for absorption with 1.0 M MEA was higher than that of 0.5 M MEA.
range of 1636%. For moderate liquid velocities (0.30.4 m s1 ), the
They discussed that the increase in aqueous organic solution con-
wetted membrane resistances become comparable to the liquid
centration would affect the pore wetness on account of alternation
phase resistances and the wetted membrane resistance contribu-
of solution properties. It is also observed that at low MEA concen-
tions are around 4657%. At high liquid velocities (0.61.0 m s1 ),
tration (0.125 and 0.25 M), the increase of x* with liquid velocity
the overall resistance is controlled by the wetted membrane resis-
is more signicant compared to that of high concentrations. Due
tance (6169%). It can be observed that the contribution of liquid
to the distribution of membrane pore sizes, the large pores may
phase resistance greatly decreases with liquid velocity. In contrast,
be penetrated by liquid absorbent [11,17]. With high MEA concen-
the wetted membrane resistance signicantly increases with liquid
trations, the liquid absorbent can easier penetrate the large pores
velocity due to the increase in x*. Fig. 6(ii) shows the contribution
compared to the low MEA concentration. However, there are lim-
of individual resistance at MEA concentration 1.0 M. The gas phase
ited numbers of large pores which can be wetted. Therefore, the
and non-wetted membrane phase resistances are about 6.5 and
wetting ratio is limited to the typical value. It can be observed from
1.0%, respectively, for all liquid velocities. For low to moderate liq-
Fig. 5(i) that the values of x* for all MEA concentrations become
uid velocities, the resistances of wetted membrane are comparable
close at high liquid velocity. Boributh et al. [17] studied the effect
to liquid phase resistances. At high velocities, the wetted mem-
of pore size distribution on membrane wetting. It was found that at
brane resistance dominates mass transfer of system. By comparing
any liquidgas pressure difference, the membrane wetting would
the liquid phase resistance of the system with MEA concentrations
occur in the pores with size equal to and larger than the criti-
of 0.25 and 1.0 M, it is found that the resistance contribution of
cal radius. Fig. 5(ii) reveals that gas velocity and gas composition
liquid phase of 0.25 M is clearly higher than that of 1.0 M. It is
do not affect the membrane wetting in range of the experiments
because higher MEA concentration could signicantly improve the
(gasliquid ow rate ratios (QG /QL ) in range of 0.452.0). The sim-
rate of reaction which is expressed in term of enhancement factor
ilar result was reported by El-Naas et al. [18]. They found that at
(E) leading to reduced liquid phase resistances [19].
low QG /QL range (approximately 1.02.0), the membrane wetting
was quite constant. While, at high QG /QL range (2.33.5), the wet-
5.4. Suitable module length
ting decreased with increasing QG /QL . This is especially true when
the membrane has signicant large pores. Therefore, the effects of
Previous experiments on CO2 absorption by membrane contact-
gas phase velocity and composition on wetting ratio were ruled out
ing process have been carried out using the hollow ber modules
and the correlation expressing x* as a function of liquid velocity and
with effective lengths of 1030 cm [5,11,20,21]. These laboratory
MEA concentration was developed:
modules provide enough mass transfer area for observing the effect
of operating conditions on the absorption performance. However,
0.1787
x = (0.0725CMEA
2
0.1456CMEA + 0.0803)ln vL + 0.1062CMEA these modules are not suitable for the pilot or industrial scales since
they provide too low contact areas to achieve high removal ef-
(23)
ciency. Therefore, in the design of membrane contacting process for
the real application, the suitable membrane module specications
In the simulation, if the value of x* estimated from above equation is (especially module length) should be carefully considered.
negative (at very low liquid velocity and low MEA concentration), The hollow ber modules have received wide attention due to
x* is adjusted to be zero. The above correlation is assumed to be providing very high mass transfer area. Although, most hollow ber
able to predict the value of x* for higher liquid velocity, but is in the modules are designed for pressure-driven membrane processes
range of laminar ow. The system performance of the multistage (rather than concentration-driven processes) such as MF and UF
cascade membrane contacting process (presented later in Section processes, they can also be employed as membrane contactors.
5.5) is simulated based on the membrane wetting obtained from One of the most well-known transverse ow hollow ber modules
this correlation. is the Liqui-Cel Exra-Flow modules commercialized by CELGARD
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189
(i) 0.12
0.1
Wetting ratio ( x* )
0.08
0.06
1.00 M
0.04 0.50 M
0.25 M
0.02 0.125 M
0 0.04
0.05 0.15 0.25 0.35 0.45
Liquid velocity, v l (m/s)
Fig. 5. Simulation results of (i) effect of liquid velocity and MEA concentration on wetting ratio (yCO2 = 0.4, QG = 0.5 l/min), (ii) effect of gas velocity and CO2 concentration in
gas phase on wetting ratio (CMEA = 0.125 M, vl = 0.3 m s1 ).
Fig. 6. Contribution of individual resistance to overall resistance (i) MEA concentration = 0.25 M, (ii) MEA concentration = 1.0 M, (QG = 0.5 l/min, yCO2 = 0.40).
LLC (Charlotte, USA). These module are 20.3118.6 cm length. Pall
Corporation provides the modules of hydrophobic hollow ber
membranes (PVDF, PP and PTFE) called Microza module. The avail-
able commercial module lengths are in range of 13222.7 cm.
Gabelman and Hwang [1] recommended the commercially avail-
able parallel ow hollow ber modules provided by various sources
which would be suitable for membrane contactors and the module
lengths are 17.8304.9 cm.
From the above information, the module with an effective ber
length of 50 cm is selected for the design of multistage membrane
contacting process. The selected length is also in the same range
as the membrane module used by Yeon et al. [22] for absorption
of CO2 from ue gas using pilot-scale membrane contactor (PVDF
membrane) with module length of 52 cm. To maintain the dynamic
behavior of gas ow in the shell side, the packing density of ber
in the design module is xed to be the same as the experimen-
tal module. The specications of designed module are summarized
in Table 1. It is assumed that the wetting behavior occurring in
this module can be predicted by Eq. (23) because the membrane
specications are the same as those of in the experimental module.
5.5. Design of multistage cascade membrane contacting process
The design approach is schematically shown in Fig. 7. From
the experimental and modeling results, the correlation for
181
(ii) 0.09
0.08
Wetting ratio ( x* )
0.07
0.06
40 %vol CO2
0.05 50 %vol. CO2
0.06 0.07 0.08 0.09 0.1 0.11
Gas velocity, v g (m/s)
determining the wetting ratio is obtained (Eq. (23)). The suitable of
module length and membrane characteristics used in the designed
are as shown in Table 1. The important parameters affecting the
performance of the multistage cascade membrane contactor are
investigated, i.e., number of module, MEA consumption, gas ow
pattern and liquid ow pattern. The simulation was performed for
the Reynolds number 89890 and 414.23, for the liquid side and
gas side, respectively. The system performance is evaluated based
on the total feed gas which is the indicator that the system is able
to handle high feed gas capacity.
5.5.1. Number of modules
The module arrangement of the multistage cascade membrane
contacting process is shown in Fig. 8. The liquid absorbent is fed in
the lumen of the hollow bers, counter currently to the gas ow
in the shell side. Fig. 9 presents the total feed gas for achieving
90% CO2 removal for the system using different number of mod-
ules. It is found that the total feed gas increases with number of
module because the contact area is increased leading to improved
absorption capacity.
For the proposed model, the effect of pressure drop on mem-
brane wetting as well as system performance is not included. From
the previous results, the membrane wetting is only a function of liq-
uid velocity and MEA concentration. Therefore, to lower the effect
of pressure drop which is proportional to the module length on the
182 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

Experiments
Wetting ratio (x*) Suitable membrane module
Modeling

Multistage cascade design

Number of module

Gas flow pattern

Liquid flow pattern

Suitable process design

Fig. 7. The design approach for multistage cascade gasliquid membrane contacting process.

Fig. 8. The multistage cascade gasliquid membrane contacting process.

membrane wetting, the appropriate number of modules should be
considered. The pressure drop ( P) of liquid ow in the lumen of
the ber is determined using the HagenPoiseuille equation;
32vL L
P =
di2
where  is liquid viscosity, L is ber length and di is inner diame-
ter of the ber. For the gas phase, the pressure drop is much lower
compared to that of liquid phase [11], thus, the pressure of the gas
is depicted in Fig. 10. It is found that pressure difference linearly
increases with number of module for all liquid velocities. Theo-
retically, the liquid can penetrate the membrane pores when the
pressure difference between liquid and gas sides is higher than
(24) the wetting pressure. In contrast, the gas bubble formation would
occur if the pressure difference between gas and liquid phases
( PGL = PG PL ) is greater than bubbling pressure [23]. The wet-
ting pressure or/and bubbling pressure ( PC ) can be determined
by Laplace equation;
side is assumed constant over the ber length. In gasliquid mem- 2 cos 
PC = (25)
brane contacting process, the pressure difference between liquid rP
and gas phases signicantly affects the operation mode. The cal-
where  is surface tension of the liquid absorbent (see Ref. [24]),
culated maximum liquidgas pressure difference ( PLG = PL PG )
 is contact angle and rP is average pore radius. The membrane

16 160 vl = 0.2 m/s

14 140 vl = 0.6 m/s
Maximum liquid-gas pressure

vl = 1.0 m/s
difference, PL-G (kPa)

12 120
Total feed gas (l/min)

(Pc = 104.93 kPa)

10 100

8 80

6 60
1.0 M
4 0.5 M 40

2 0.25 M 20

0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6
Number of module Number of module

Fig. 9. The simulation results of the effect of number of module on total feed gas to Fig. 10. The calculated maximum liquidgas pressure difference, PLG at different
achieve 90%CO2 removal at different MEA concentrations (vl = 0.5 m s1 , yCO2 = 0.4). number of modules and liquid velocities.
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189 183

(i) 25 (ii) 20
Non-wetted mode 18 Non-wetted mode
20 16 Partially wetted mode
Partially wetted mode
% MEA consumption

% MEA consumption
14
Wetted mode Wetted mode
15 12
10
10 8
6
5 4
2
0 0
0.1 0.3 0.5 0.7 0.9 1.1 0.1 0.3 0.5 0.7 0.9 1.1
Concentration of MEA in feed liquid (mol/l) Liquid velocity, v L (m/s)

(iii) 20 (iv) 35
Non-wetted mode
18
30
16 Partially wetted mode

% MEA consumption
% MEA consumption

Non-wetted mode 25
14 Wetted mode
12 Partially wetted mode 20
10
Wetted mode 15
8
6 10
4
5
2
0 0
0.15 0.25 0.35 0.45 0.55 0.65 0 20 40 60 80 100
Gas velocity, v G (m/s) Concentration of CO 2 in feed gas (%Vol)

Fig. 11. The simulation results of total %MEA consumption of threemodule cascade for three different operation modes including non-wetted, partially wetted (wetting
ratio estimated using Eq. (23)) and completely wetted modes: (i) At different MEA concentrations (vl = 0.2 m s1 , vg = 0.5 m s1 and yCO2 = 0.4); (ii) at different liquid veloc-
ities (vg = 0.5 m s1 , yCO2 = 0.4 and CMEA = 0.25 M); (iii) at different gas velocities (vl = 0.2 m s1 , yCO2 = 0.4 and CMEA = 0.25 M); (iv) at different gas compositions (vl = 0.2 m s1 ,
vg = 0.5 m s1 and CMEA = 0.25 M).

wetting results in performance deterioration, while the bubble for-
mation causes gas loss during the operation [13,23]. Therefore, the
pressures of gas and liquid phases must be carefully controlled.
Generally, the pressure of liquid side is adjusted to be slightly
higher than that of gas side. The value of PLG must be kept pos-
itive or equal to zero over the ber length. If PLG is xed to
be zero at liquid outlet, the pressure of liquid at the inlet must
be adjusted to be greater than or equal to the value of pressure
drop of liquid ow over the ber length. For the hollow ber
5.5.2. MEA consumptions
Fig. 11 presents the simulation results of the total %MEA
consumption for three-module cascade at different operating
conditions of the three cases: non-wetted mode (x* = 0), par-
tial wetted mode (x* estimated using Eq. (23)) and wetted
mode (x* = 1.0). The consumption of MEA is dened as the
ratio of moles of MEA consumed to the moles of MEA in feed
((CMEA,feed CMEA,out )/CMEA,feed 100%). It can be obviously seen
that the system operated in non-wetted mode shows highest value
membranes used in this work (rP = 0.08 m,  = 93.4 ), MEA con-
centration of 0.25 M, the wetting pressure calculated from Eq. (25)
is 104.93 kPa. Therefore, the membrane wetting should not be
observed from our experiments although the operation was car-
ried out at the conditions of highest wetting ratio (0.4 m s1 and
CMEA 1.0 M). However, due to the distribution of membrane pore
size, the large pores may be wetted even the pressure difference
( PLG ) is lower than the wetting pressure estimated based on the
average pore size. Hence, the pressure drop over the length must
not exceed the wetting pressure. From Fig. 10 it can be seen that
at highest liquid velocity (1.0 m s1 ), the systems with the num-
ber of module up to four modules show the maximum liquidgas
pressure difference lower than critical wetting pressure. For four-
module cascade, the pressure difference is about 92 kPa which is
quite close to the critical wetting pressure. To ensure that the
pressure drop would not signicantly affect the membrane wet-
ting, the pressure difference should be moderately lower than
the critical wetting pressure. Therefore, the three-module cascade
which shows the pressure drop around 66.9 kPa is selected for our
design.
of %MEA consumption followed by partially wetted mode and
completely wetted mode, respectively. These reveal that the non-
wetted mode offers highest absorption performance resulted in
highest MEA consumption. For completely wetted mode, variation
of MEA concentration, gas velocity, liquid velocity as well as gas
composition slightly affects MEA consumption since the overall
resistance is dominated by the membrane phase.
Fig. 11(i) shows that at lower MEA concentrations, the percent-
ages of MEA consumption are higher compared to those of higher
concentrations since the amount of MEA consumed in the system
with higher MEA concentration is higher than that of lower MEA
concentration due to higher rate of reaction. However, because of
the very high amount of MEA in the system with high MEA concen-
tration, the MEA consumption of high MEA concentration is still
lower than that of lower MEA concentration. The effect of liquid
velocity on MEA consumption is depicted in Fig. 11(ii). At lower
liquid velocities, the percentages of MEA used for the reaction with
CO2 are higher compared to those of higher liquid velocities due
to longer contact time. Fig. 11(iii) reveals the %MEA consumption
for the system with different gas velocity. It is found that the %MEA
184 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

Module 1 Module 2 Module 3

1

0.8

CCO2,i/CCO2,feed in gas phase

0.6

0.4

Fig. 12. Schematic diagram of three-module cascade membrane contactors with

different gas ow patterns (i) individual gas ow (G-ID), (ii) gas ow in series (G-IS).
consumption slightly changes with increasing gas velocity. As men-
tioned previously in Section 5.1, the gas phase velocity did not affect
the absorption ux, thus, the increase in gas velocity does not affect
%MEA consumption. Fig. 11(iv) presents the effect of CO2 concen-
tration in gas phase on %MEA consumption. It can be seen that the
consumption of MEA increases with CO2 concentration due to the
enhanced driving force.
5.5.3. Gas ow patterns
Fig. 12 shows two different gas ow patterns; (i) individual gas
ow (G-ID), the gas is fed separately into each module to achieve
the desired %CO2 removal at the outlet of each module, (ii) gas ow
in series (G-IS), which is similar to that in Fig. 8. The result from
Section 5.3 shows that the resistance in gas phase is only 3 and
6.5% for MEA concentration of 0.25 and 1.0 M, respectively. There-
fore, the effect of gas velocity on absorption ux can be neglected.
0.2 G-ID
G-IS
0
0 1 2 3
z/L1
Fig. 13. Simulation results of the concentration prole of CO2 in gas phase of two
different gas ow patterns for achieving 90%CO2 removal.
However, the concentration of CO2 in gas phase considerably inu-
ences the absorption ux since the gas composition directly affects
the driving force of the system. Fig. 13 presents the concentration
prole of CO2 in gas phase along the length of three module cascade
for achieving CO2 removal of 90%. The values of CCO2,i /CCO2,feed at
the inlet and outlet are 1.0 and 0.1, respectively. For G-IS, the gas
is fed to the rst module at z/L = 3 and leaves from the last mod-
ule at z/L = 0 (the gas ow direction is from the right to the left
hand side). It is known that the 3 module arrangement is equiv-
alent to one module with the length 3 times of a single module.

(i) 20 (ii) 9

18 8
Total feed gas (l/min)

16 7
Total feed gas (l/min)

14 6
12
5
10
4
8
3
6
4 G-ID 2 G-ID
2 G-IS 1 G-IS
0 0
0 0.2 0.4 0.6 0.8 1 1.2 0 0.2 0.4 0.6 0.8 1
Concentration of MEA in feed liquid (mol/l) Liquid velocity, v l (m/s)

(iii) 35
25
(iv)
G-ID G-ID
30
G-IS 20 G-IS
Total feed gas (l/min)

Total feed gas (l/min)

25
15
20

10
15

10 5

5 0
10 30 50 70 90 110 10 30 50 70 90 110
%Removal of CO 2 Concentration of CO 2 in feed gas (%Vol.)

Fig. 14. Comparison of total feed gas of two different gas ow patterns: (i) at different MEA concentrations (vl = 0.5 m s1 , yCO2 = 0.4 and CO2 removal = 90%) (ii) at various
liquid velocities (CMEA = 0.25 M, yCO2 = 0.4 and CO2 removal = 90%); (iii) at different %CO2 removal (vl = 0.5 m s1 , CMEA = 0.25 M and yCO2 = 0.4); (iv) at different gas compositions
(vl = 0.5 m s1 , CMEA = 0.25 M and CO2 removal = 90%).
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189 185

6 same, 1.0 and 0.1, respectively. Therefore, the similar concentration

prole is observed.
G-ID Fig. 14(i) compares the total feed gas of two different gas ow
Required MEA solution (l/min)

5
G-IS patterns at various MEA concentrations. The simulation result
reveals that G-ID gives higher performance compared to G-IS for
4 all MEA concentrations. The total feed gas of G-ID is higher than
that of G-IS roughly 17 and 33% for MEA concentrations of 0.125
3 and 1.0 M, respectively. This trend can be explained that at low
MEA concentrations, the percentage of MEA consumption in the
Module 1 is higher than that of high concentration. The absorption
2 rate signicantly decreases in the next module. This results in the
slight reduction of CO2 concentration in gas phase for Module 3,
1 but the decrease is more signicant for Module 1. Therefore, the
driving force of two gas ow patterns at lower MEA concentration
is closer compared to at high concentration.
0
Fig. 14(ii) illustrates that G-ID has higher system performance
0 1 2 3 4 5 6 7
than G-IS for all liquid velocities. For G-IS, the total feed gas
Total feed gas (l/min) increases with liquid velocity. In case of G-ID, the total feed gas
sharply increases at low liquid velocities (0.10.2 m s1 ), then,
Fig. 15. Comparison of required MEA solution of two different gas ow patterns for
achieving 90% CO2 removal at various total feed gases. there is a slight increase at moderate velocities (0.30.5 m s1 ),
and a gradual decrease at high velocities (0.61 m s1 ). These can
be explained by referring to the resistance analysis (Section 5.3).
Therefore, the CO2 concentration decreases continuously along the At low liquid velocities, the mass transfer resistance is dominated
length from z/L = 3 to z/L = 0 which is the same as that observed for by liquid phase, thus, the system performance is considerably
one module with module length of 3L (150 cm). When the gas mix- enhanced with increasing velocity. For the moderate liquid veloc-
ture at high CO2 concentration is fed into Module 3, CO2 is partially ities, the wetted membrane resistance becomes comparable to
absorbed and the CO2 concentration is greatly reduced in this mod- the liquid phase resistance leading to a slight improve in absorp-
ule. The reductions in CO2 concentration for Modules 2 and 1 are tion ux, whereas at high velocities, the system is controlled by
less signicant because the driving force for G-IS can be ranked as the wetted membrane resistance. Increasing in liquid velocity
Module 3 > Module 2 > Module 1. In case of G-ID, the gas ow direc- could increase membrane wetting rather than improving the liquid
tion is the same as G-IS. The gas is individually fed to one module phase mass transfer, resulting in gradual absorption performance
to achieve 90% removal at the outlet of each module. The values deterioration. The performance comparison of two different gas
of CCO2,i /CCO2,feed at the inlet and outlet for each module are the ow patterns at various % CO2 removals and gas compositions is

Fig. 16. Schematic diagrams of three-module cascade membrane contactor with different liquid ow patterns (i) liquid ow in series (L-IS), (ii) liquid ow in series with
splitting (L-ISS), (iii) liquid ow in series with recycle (L-ISR).
186 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

(i) (ii) 9
9
8.5 8.5

8 8

Total feed gas (l/min)

Total feed gas (l/min)

7.5 7.5

7 7

6.5 6.5

6 6

5.5 5.5

5 5

4.5 4.5
4 4
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1

Liquid velocity, v l (m/s) Liquid velocity, v l (m/s)

Fig. 17. Simulation results of (i) effect of liquid velocity on total feed gas at different splitting ratios, (ii) effect of liquid velocity on total feed gas at different recycle ratios
(CO2 removal = 90%, CMEA = 0.25 M, vl = 0.5 m s1 and yCO2 = 0.4).

(i) (ii) 21
9
8.5 19

Total feed gas (l/min)

8 17
Total feed gas (l/min)

7.5
15
7
6.5 13

6 11
5.5
9
5
7
4.5
4 5
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Liquid velocity, v l (m/s) Liquid velocity, v l (m/s)

Fig. 18. Comparison of total feed gas for three different liquid ow cascades (i) MEA concentration = 0.25 M, (ii) MEA concentration = 1.0 M, (CO2 removal = 90% and yCO2 = 0.4).

represented in Fig. 14(iii) and (iv), respectively. G-ID shows higher with ow rate of QL,R is recycled and is combined with the original
system performance for all values of % CO2 removals and gas feed before entering Module 1.
compositions. The total feed gas into the system decreases with Fig. 17(i) depicts the effect of splitting ratio () on system
increasing % CO2 removal and CO2 concentration in feed gas for performance of L-ISS at different liquid velocities (with MEA con-
both gas ow patterns. centration of 0.25 M). It is found that L-ISS shows higher system
Fig. 15 depicts the comparison of MEA solution required for performance compared to L-IS ( = 0) at high liquid velocities,
achieving 90% CO2 removal at various total gas ow rates. It is whereas the splitting ratio of 0.3 gives the highest system perfor-
clearly seen that required MEA solution for G-IS is much higher mance. The total feed gas of L-ISS with splitting ratio of 0.3 is higher
compared to that of G-ID. At total gas feed of 5.92 l/min, the required than that of L-IS ( = 0) around 16.7% at liquid velocity 0.9 m s1 . The
MEA solution for G-IS is approximately 5.1 l/min, while that of G-ID effect of recycle ratio () on system performance for L-ISR at vari-
is only 1.5 l/min. These reveal that MEA solution is more effectively ous liquid velocities (MEA concentration 0.25 M) is represented in
used in case of G-ID. Therefore, the gas ow pattern of G-ID is Fig. 17(ii). It is found that L-ISR can moderately improve system
selected to study the effect of liquid ow pattern in the multistage performance at low liquid velocities. The Highest system perfor-
cascade contactors. mance is observed at recycle ratio of 1.0. The total feed gas of L-ISR
with recycle ratio of 1.0 is greater than that of L-IS ( = 0) roughly
5.5.4. Liquid ow patterns 7.7% at liquid velocity 0.1 m s1 .
The schematic diagrams of three-module cascade with differ- Fig. 18(i) and (ii) compares the system performance of three
ent liquid ow patterns are shown in Fig. 16. The rst liquid ow different liquid ow patterns. For MEA concentration of 0.25 M, L-
pattern is (i) Liquid ow in series (L-IS), which is similar to that in ISR can moderately improve the system performance at low liquid
Fig. 12(i). The second liquid ow pattern is (ii) Liquid ow in series velocities, whereas L-ISS considerably enhances the performance
with splitting (L-ISS), from which the total liquid feed is partially at high liquid velocities. For MEA concentration of 1.0 M, the sys-
fed into Module 1 and the split liquid is partly combined with the tem performance can be signicantly increased by L-ISR at low to
stream leaving Module 1 before entering Module 2. It is noted that moderate liquid velocities (0.10.5 m s1 ). The total feed gases are
before entering module 3, the remained liquid is combined with the enhanced approximately 44.6 and 7.3% for liquid velocities of 0.1
liquid leaving Module 2. The third liquid ow pattern is (iii) Liquid and 0.4 m s1 , respectively. The L-ISS does not improve the system
ow in series with recycle (L-ISR), from which the liquid feed ow performance at any liquid velocity. The reason for these differ-
rate to each module is the same. After leaving Module 3, the liquid ent results for typical MEA concentrations is due to the different
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189 187

membrane wetting behaviors. At low MEA concentration, the val-
ues of x* greatly increase with liquid velocity (Section 5.2). At
high liquid velocities, the wetted membrane resistance controls the
overall resistance, and L-ISS can reduce membrane wetting ratio by
reducing the liquid ow rate in each module resulting in improv-
ing the performance. On the other hand, at low liquid velocities,
the overall resistance is dominated by liquid phase resistance, and
L-ISR can enhance the mass transfer coefcient of liquid phase by
increasing the liquid velocity in each module leading to enhanc-
ing absorption ux. In case of high MEA concentration, the wetting
ratio slightly increases with liquid velocity, and the liquid phase
resistance is comparable to wetted membrane. The reduction of
liquid ow in the module by splitting (L-ISS) does not consider-
ably reduce the membrane wetting; thus, the system performance
is not enhanced for all liquid velocities. L-ISR can improve system
performance at low to moderate liquid velocities, because in this
range the liquid phase resistance still inuences the system. The
increase of liquid velocity can improve the mass transfer in liquid
phase rather than increasing the membrane wetting. The results of
multistage design based on wetting ratio obtained from the exper-
imental results reveal that different wetting behaviors at various
operating conditions (liquid velocity and MEA concentration) sig-
nicantly affects the design of membrane contactors.
application. The operation of multistage cascade membrane con-
tactor offers several advantages including the improved system
performance and the use of MEA effectively. However, the design
may be different depending on the conditions of each system.
Therefore, the experimental study is still necessary in order to
obtain the specic results for being used in the process design.
Acknowledgments
The authors gratefully acknowledge the nancial support from
the Royal Golden Jubilee program and Senior Research Scholar
Grant from Thailand Research Fund (TRF) and from King Mongkuts
University of Technology Thonburi (KMUTT).
Appendix A.
The diffusivity of CO2 in gas mixture (CO2 CH4 ), DCO2,G can be
calculated by the following [25]:
1/2
0.001858T 3/2 (1/MCO2 + 1/MCH4 )
DCO2 ,G = 2
(A.1)
PAB D

where MCO2 and MCH4 are the molecular weights of CO2 and CH4 ,
6. Conclusions
respectively. P is pressure in atm,  AB is characteristic length (m),
D is Collision integral. These parameters can be estimated by the
The experiments of CO2 absorption by MEA using PVDF hol-
followings;
low ber membrane contactor were carried out. The mathematical
model has been developed to predict the system performance. A + B
The experimental results were validated with the proposed model AB = (A.2)
2
for estimating the wetting ratio (x*) as function of liquid velocity
and MEA concentration. At low MEA concentration, the value of where  A and  B are characteristic lengths of CO2 and CH4 , respec-
x* greatly increases with liquid velocity, while that of high con- tively, and it can be determined as;
centration slightly increases with velocity. The resistance analysis
demonstrates that for MEA concentration of 0.25 M, the liquid  
1.585Vb,A
phase resistance dominates the overall resistance at low liquid A = (A.3)
1 + 1.3 2
velocities. The wetted membrane resistance becomes comparable
to that of liquid phase at moderate velocities, and controls the
system at high liquid velocities. For MEA concentration of 1.0 M, where Vb is liquid molar volume at normal boiling point (cm3 /mol).
the wetted membrane resistance is comparable to the liquid phase The value of can be estimated by the following;
resistance for low to moderate liquid velocities, and dominates the
overall resistance at high velocities. 1.94 103 p2
The suitable hollow ber membrane module with effective ber = (A.4)
Vb Tb
length of 50 cm is selected for the design of multistage membrane
contactors. The three-module cascade is selected based on the pres- where p is dipole moment (Debye). Tb is boiling temperature (K).
sure drop. The system performance is evaluated as the total feed The Collision integral (D ) is in function of temperature deter-
gas and MEA consumption. By comparing three different modes of mined as;
operation, the non-wetted mode presents highest MEA consump-
tion followed by partially wetted mode and completely wetted a c e g
D = + + + (A.5)
mode, respectively. Different gas and liquid ow patterns are com- (T )b exp(dT ) exp(fT ) exp(hT )
pared. For gas ow pattern, G-ID shows higher system performance
compared to G-IS for all operating conditions studied. In case of liq- where a, b, c, d, e, f, g and h are constants. T* can be calculated as the
uid ow pattern, L-ISS achieves the highest performance at splitting following equation;
ratio () of 0.3, while that of L-ISR is obtained at recycle ratio () of
1.0. For low MEA concentration (0.25 M), the L-ISR can moderately T
improve the system performance at low liquid velocities, while T = (A.6)
AB
L-ISS considerably enhances the performance at high liquid veloc-
ities. For the system with high MEA concentration (1.0 M), L-ISR
where is Boltzmanns constant and AB is characteristic energy
can improve the performance at low to moderate liquid velocities,
determined by;
whereas the L-ISS does not improve the system performance at any
liquid velocity. 1/2
In conclusion, this work presents the design of multistage cas- AB =( A B) (A.7)
cade membrane contacting process for chemical absorption of
CO2 that has never been reported in the literature. The process where A and B are characteristic energy of CO2 and CH4 , respec-
design gives the insight and guideline for the scale up for real tively.
188 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189

Nomenclature
Greek letters
A contact area (m2 ) D collision integral for molecular diffusion (dimen-
CA concentration of CO2 in bulk liquid (mol m3 ) sionless)
CAG,in inlet concentration of CO2 in gas phase (mol m3 ) Boltzmanns constant (J K1 )
CAGout , outlet concentration of CO2 in gas phase (mol m3 )  AB characteristic length (m)
CA,eq concentration of CO2 at gasliquid interface (mol  density (kg m3 )
m3 ) dry dry membrane thickness (m)
CR,L concentration of absorbent (mol m3 ) wetted wetted membrane thickness (m)
dh hydraulic diameter (m), dh = ds2 n d02 /ds + n d0 split ratio (dimensionless)
di inner diameter of membrane (m) recycle ratio (dimensionless)
dint interfacial diameter (m2 ) M membrane porosity (dimensionless)
dln logarithmic mean diameter of non-wetted mem-  kinematic viscosity (cm2 s1 )
brane (m), dln = d0 dint /ln(d0 /dint ) R stoichiometric coefcient of reaction
dln logarithmic mean diameter of wetted membrane M membrane tortuosity (dimensionless)
 =d
(m), dln int di /ln(dint /di ) i characteristic energy of species i (J K1 )
d0 outer diameter of membrane (m)
dpore average pore size diameter of membrane (m)
ds module diameter (m)
DG,eff gas effective diffusivity (m2 s1 ) References
DG,Kn Knudsen diffusion coefcient (m2 s1 )
DG,M Fickians molecular diffusion coefcient (m2 s1 ) [1] A. Gabelman, S.-T. Hwang, Hollow ber membrane contactors, Journal of Mem-
Di,G diffusivity of component i in gas mixture (m2 s1 ) brane Science 159 (1999) 61106.
[2] P. Keshavarz, J. Fathikalajahi, S. Ayatollahi, Analysis of CO2 separation and
Di,L diffusivity of component i in liquid solution (m2 s1 ) simulation of a partially wetted hollow ber membrane contactor, Journal of
E enhancement factor (dimensionless) Hazardous Materials 152 (2008) 12371247.
E asymptotic innite enhancement factor [3] S. Atchariyawut, R. Jiraratananon, R. Wang, Separation of CO2 from CH4 by using
gasliquid membrane contacting process, Journal of Membrane Science 304
fA molar ow rate of CO2 in liquid phase (kgmol s1 ) (2007) 163172.
FA molar ow rate of CO2 in gas phase (kgmol s1 ) [4] A. Bottino, G. Capannelli, A. Comite, R. Di Felice, R. Firpo, CO2 removal from a
FI0 molar ow rate of inert component in gas phase gas stream by membrane contactor, Separation and Purication Technology 59
(2008) 8590.
(kgmol s1 ) [5] S. Khaisri, D. deMontigny, P. Tontiwachwuthikul, R. Jiraratananon, Comparing
Gz Graetz number (dimensionless) membrane resistance and absorption performance of three different mem-
Ha* Hatta number (dimensionless) branes in a gas absorption membrane contactor, Separation and Purication
Technology 65 (2009) 290297.
H Henrys constant (kPa m3 kgmol1 ) [6] M. Mavroudi, S.P. Kaldis, G.P. Sakellaropoulos, Reduction of CO2 emissions by
JA,i absorption ux of CO2 (mol m2 s1 ) a membrane contacting process[small star, lled], Fuel 82 (2003) 21532159.
KL overall mass transfer coefcient (m s1 ) [7] R. Wang, D.F. Li, C. Zhou, M. Liu, D.T. Liang, Impact of DEA solutions with and
without CO2 loading on porous polypropylene membranes intended for use as
kG gas mass transfer coefcient (kgmol m2 kPa1 s1 )
contactors, Journal of Membrane Science 229 (2004) 147157.
kL liquid mass transfer coefcient (m s1 ) [8] Y. Lv, X. Yu, S.-T. Tu, J. Yan, E. Dahlquist, Wetting of polypropylene hollow ber
kM gas-lled pores membrane mass transfer coefcient membrane contactors, Journal of Membrane Science 362 (2010) 444452.
(m s1 ) [9] M. Mavroudi, S.P. Kaldis, G.P. Sakellaropoulos, A study of mass transfer resis-
tance in membrane gasliquid contacting processes, Journal of Membrane
kM liquid-lled pores membrane mass transfer coef- Science 272 (2006) 103115.
cient (m s1 ) [10] S. Khaisri, D. deMontigny, P. Tontiwachwuthikul, R. Jiraratananon, A mathe-
k2 second-order reaction rate constant (L mol1 s1 ) matical model for gas absorption membrane contactors that studies the effect
of partially wetted membranes, Journal of Membrane Science 347 (2010)
L length of hollow ber membrane (m) 228239.
Mi molecular weight of component i (kg kgmol1 ) [11] J.-G. Lu, Y.-F. Zheng, M.-D. Cheng, Wetting mechanism in mass transfer process
n number of bers of hydrophobic membrane gas absorption, Journal of Membrane Science 308
(2008) 180190.
N number of stages [12] R. Wang, H.Y. Zhang, P.H.M. Feron, D.T. Liang, Inuence of membrane wetting
P total system pressure (kPa) on CO2 capture in microporous hollow ber membrane contactors, Separation
PA partial pressure of CO2 (kPa) and Purication Technology 46 (2005) 3340.
[13] S. Boributh, S. Assabumrungrat, N. Laosiripojana, R. Jiraratananon, Effect of
QG total volumetric ow rate of gas phase (m3 s1 ) membrane module arrangement of gasliquid membrane contacting process
QL total volumetric ow rate of liquid phase (m3 s1 ) on CO2 absorption performance: a modeling study, Journal of Membrane Sci-
Re Reynolds number (dimensionless) ence 372 (2011) 5786.
[14] M.C. Yang, E.L. Cussler, Designing hollow-ber contactors, AIChE Journal 32
RG gas phase resistance (s m1 )
(1986) 19101916.
RL liquid phase resistance (s m1 ) [15] H. Kreulen, C.A. Smolders, G.F. Versteeg, W.P.M. Van Swaaij, Determination
RM gas-lled pores membrane resistance (s m1 ) of mass transfer rates in wetted and non-wetted microporous membranes,
RM liquid-lled pores membrane resistance (s m1 ) Chemical Engineering Science 48 (1993) 20932102.
[16] S. Atchariyawut, R. Jiraratananon, R. Wang, Mass transfer study and modeling
Rtot total resistance (s m1 ) of gasliquid membrane contacting process by multistage cascade model for
Sc Schmidt number (dimensionless) CO2 absorption, Separation and Purication Technology 63 (2008) 1522.
Sh Sherwood number (dimensionless) [17] S. Boributh, S. Assabumrungrat, N. Laosiripojana, R. Jiraratananon, A modeling
study on the effects of membrane characteristics and operating parameters
T temperature (K) on physical absorption of CO2 by hollow ber membrane contactor, Journal of
x* wetting ratio (dimensionless) Membrane Science 380 (2011) 2133.
yCO2 molar fraction of CO2 in gas mixture (dimensionless) [18] M.H. El-Naas, M. Al-Marzouqi, S.A. Marzouk, N. Abdullatif, Evaluation of the
removal of CO2 using membrane contactors: membrane wettability, Journal of
Membrane Science 350 (2011) 410416.
[19] P.S. Kumar, J.A. Hogendoorn, P.H.M. Feron, G.F. Versteeg, Approximate solution
to predict the enhancement factor for the reactive absorption of a gas in a liquid
owing through a microporous membrane hollow ber, Journal of Membrane
Science 213 (2003) 231245.
 S. Boributh et al. / Journal of Membrane Science 401402 (2012) 175189
[20] S.-H. Lin, K.-L. Tung, W.-J. Chen, H.-W. Chang, Absorption of carbon dioxide by
mixed piperazine-alkanolamine absorbent in a plasma-modied polypropy-
lene hollow ber contactor, Journal of Membrane Science 333 (2009) 3037.
[21] Y.-S. Kim, S.-M. Yang, Absorption of carbon dioxide through hollow ber
membranes using various aqueous absorbents, Separation and Purication
Technology 21 (2000) 101109.
[22] S.-H. Yeon, K.-S. Lee, B. Sea, Y.-I. Park, K.-H. Lee, Application of pilot-scale mem-
brane contactor hybrid system for removal of carbon dioxide from ue gas,
Journal of Membrane Science 257 (2005) 156160.
189
[23] V.Y. Dindore, D.W.F. Brilman, P.H.M. Feron, G.F. Versteeg, CO2 absorption at ele-
vated pressures using a hollow ber membrane contactor, Journal of Membrane
Science 235 (2004) 99109.
[24] G. Vazquez, E. Alvarez, J.M. Navaza, R. Rendo, E. Romero, Surface tension of
binary mixtures of water + monoethanolamine and water + 2-amino-2-methyl-
1-propanol and tertiary mixtures of these amines with water from 25 C to
50 C, Journal of Chemical & Engineering Data 42 (1997) 5759.
[25] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids, 4th
ed., McGraw-Hill, Inc, New York, 1987.