Chemical Engineering Science 64 (2009) 1 -- 8

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Chemical Engineering Science

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Carbon dioxide stripping in ceramic hollow fibre membrane contactors

Sirichai Koonaphapdeelert, Zhentao Wu, K. Li
Department of Chemical Engineering & Chemical Technology, Imperial College, London, South Kensington, London SW7 2AZ

A R T I C L E I N F O A B S T R A C T

Article history: Ceramic hollow fibre membrane contactors have been applied to carbon dioxide stripping from mo-
Received 8 July 2008 noethanolamine (MEA) solution at high temperature where most polymeric membranes would fail to
Received in revised form 13 September 2008 operate. The experimental results show that the membrane contactors are immune from hydrodynamic
Accepted 15 September 2008
problems, such as flooding and loading, since the gas and liquid phases can totally be separated by the
Available online 1 October 2008
hollow fibre membranes. The height of transfer unit (HTU) of the contactor was determined to be as
Keywords: low as 15 cm and is dependent on the fluid velocities. The mass transfer coefficients were theoretically
Desorption predicted and found to be within a reasonable deviation. The mass transfer resistance in the liquid phase
Membranes was found to be the majority of the total resistance.
Separation 2008 Elsevier Ltd. All rights reserved.
Carbon dioxide
Membrane contactor
Amine solution

1. Introduction
CO2 stripping from amine solution is a major part of the
absorptiondesorption process to remove acid gas impurities such
as CO2 and H2 S from gas streams. The removal of acid gas impu-
rities is usually carried out in two separated contacting towers;
one for gas absorption and the other for gas stripping (Kohl and
Nielsen, 1997). The importance of the removal process has been
extensively highlighted as it is considered to be the most used and
proven technology to capture CO2 , i.e. the most important green-
house gas, from post-combustion flue gases in order to battle global
warming (Simmonds and Hurst, 2004). In fact, almost all the current
CO2 capture plants are based on amine absorption process such
as Sleipner project in Norway, Petronas Fertilizer Co. in Malaysia,
etc. (International Environmental Agency, 2005; Yaki et al., 2004).
Therefore, a great deal of interest has been paid to the R&D in
CO2 -amine absorption system in the last few decades.
One of the major achievements in the area of CO2 capture is the
application of membrane contactors for gas absorption which has
been studied by a number of research groups (Dindore et al., 2004;
Falk-Pedersen and Dannstrom, 1997; Feron and Jansen, 1995; Feron
and Jansen, 2002; Karoor and Sirkar, 1993; Kim and Yang, 2000;
Mavroudi et al., 2003; Rangwala, 1996). The membrane contactors
can provide superior process efficiency compared to conventional
equipment, and can potentially reduce capital and operational costs,
owing to their high interfacial area per volume and membrane func-
tions (Li and Chen, 2005). There are several pilot-scale plants that
Corresponding author. Tel.: +44 207 5945676; fax: +44 207 5945629.
E-mail address: Kang.Li@imperial.ac.uk (K. Li).
have employed membrane contactors for CO2 capture. For example,
a large scale pilot plant for CO2 removal from flue gas was built and
has been studied by the TNO in the Netherlands for years (Feron and
Jansen, 1997). Another pilot-scale plant that employs a membrane
contactor for CO2 capture is at the Nanko Power plant in Osaka,
Japan (Simmonds and Hurst, 2003; Simmonds et al., 2002).
Compared to the extensive studies on CO2 absorption, there are
relatively scarce literature information on the development of CO2
stripping (desorption) despite the fact that the stripping unit is highly
energy-consuming and is responsible for the main operational cost
of the process (Tobiesen et al., 2005). A few studies on CO2 stripping
from aqueous amine solution were based on conventional plate or
packed columns only (Burkett, 1977; Disli, 1996; Kershenbaum et al.,
1991; Weiland et al., 1982; Xu et al., 1995). Unlike for CO2 absorption,
there has never been any report on the application of membrane
contactors at higher temperature for stripping purpose so far.
Lack of such studies is believed to be linked to the limited thermal
and chemical stabilities of commercial membranes available. There
have been several reports on the morphological changes of polymeric
membranes after having been in contact with amine solution for a
short period. The enlargement of the pore entrances of the surface
of polypropylene (PP) membranes when contacted with water for
only 72 h was reported (Barbe et al., 2000). The surface morphology
and surface roughness changes in PP microporous hollow fibres that
led to the wetting of the membranes were observed by Wang et al.
(2004). Also, it was found that the performance of polymeric mem-
brane contactors significantly dropped after two weeks of operation
due to the problem of membrane wetting (Dindore et al., 2004). CO2
stripping from amine solution is usually conducted at temperature
of 100 C, at which most polymeric membranes commercially avail-
able are unable to withstand.

0009-2509/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2008.09.010
2 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8

Recently, a novel type of membrane contactors, which employ

porous ceramic hollow fibre membranes instead of polymeric mem-
branes, has been developed. The ceramic membranes offer better PAi L
chemical and thermal stabilities and can be used at high tempera- V
PAM
ture and/or in chemically harsh conditions. The previous work of the
authors has already demonstrated that the ceramic membrane con- CAi CA
tactors could be used for benzenetoluene distillation at high tem- PA
perature (Koonaphapdeelert et al., 2008). As ceramic hollow fibre
membranes could be modified to be hydrophobic (Koonaphapdeelert
and Li, 2007), the membrane contactors can potentially be used for
aqueous applications such as CO2 stripping from amine solution. In
this study, hydrophobic ceramic hollow fibre membrane contactors
were, for the first time, used for CO2 stripping from amine solution.
The module capacity, performance, effects of operating parameters, Vapour Bulk Vapour Film Membrane Liquid Film Liquid Bulk
and mass transfer model are studied in order to gain more insight
Fig. 2. Mass transfer of solute A from the liquid phase to the vapour phase through
of the ceramic membrane process. membrane pores.

2. Theory
Table 1
The mass transfer process in hollow fibre membrane contactors The parameters used for CO2 -MEA VLE correlation.
can be described by the concept of overall mass balance and com- Parameter Value
ponent mass balance (Seader and Henley, 2006). Fig. 1 presents the
A3 47.91+112.8
schematic diagram of the stripper. At steady state, overall mass bal- B3 0.76151.668
ance of the column gives the operating line, C3 0.0029+0.007

Lout x Lout xout

y=
Vin (1 x) + Lout x Lout xout
where V and L are the molar vapour and liquid flow rate, mol/s; y
and x are the mole fraction of the solute A, which is CO2 , in the
vapour and the liquid phases, respectively.
The mass transfer of the solute A is proportional to its concentra-
tion gradient, as illustrated in Fig. 2. Apart from vapour and liquid
film layers normally described by the two-film theory, there is also
a membrane phase in the middle between the two films. Since the
membranes are hydrophobic, the membrane pores are assumed to
be filled with vapour as long as the pressure difference between gas
Lin
xin
Vout
yout
V L
y x
(1)
and liquid phases does not exceed the membrane wetting (break-
through) pressure. The differential mass balance equation of the so-
lute A on the liquid phase may be written as:
dx
L = KL ndi (CA CA ) (2)
dz
or
dx
L = KL ndi (x x ) (3)
dz
where z is the distance measured from the bottom of the column; KL
and KL are the overall liquid phase mass transfer coefficient based on
the liquid concentration, m/s, and on the liquid mole fraction driving
force, mol/m2 s, respectively. KL = KL cT , in which cT is the total con-
centration of liquid, mol/m3 ; n is the number of hollow fibres; di is
the inner diameter of the hollow fibre, m; CA is the concentration of
solute A in the liquid bulk, mol/m3 ; CA is the equilibrium concentra-
tion of solute A; and x* is the equilibrium mole fraction of solute A.
The vapourliquid equilibrium (VLE) data of CO2 in 2.5 M
MEAwater system are reported in the literatures (Burkett, 1977;
Disli, 1996; Weiland et al., 1982), usually in a form of correlation
between equilibrium CO2 partial pressure (PCO ) and carbonation
2
ratio (), which is the ratio between mole of CO2 and mole of MEA
in the solution. The correlation proposed by Burkett (1977) was
selected as it covers the temperature and carbonation ratio ranges
found in this study.

PCO = exp[A3 + B3T + C3T 2 ]/760 (4)
2
l
Vin
where PCO is the partial pressure (bar) and T is liquid temperature
2
( C). The constants A3, B3, and C3 are defined in Table 1. The equilib-
yin
rium liquid mole fraction x* can be determined by Eq. (4). Then the
mole fraction driving force in the liquid film (xx*) can be calculated.
Integrating Eq. (3) from bottom to the top of the hollow fibre
Lout column gives
xout  l  xin
L 1
dz = l = dx (5)
Fig. 1. Schematic diagram of the amine stripping in a hollow fibre contactor. o KL .ndi xout (x x )
 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8 3

where l is the length of the hollow fibre, m; xout and xin are the liquid Table 2
The properties of hollow fibre membrane modules.
mole fractions at the outlet and the inlet of the column, respectively.
Eq. (5) may be usually rewritten as: Module parameters Module 1 Module 2 Module 3 Unit

Module diameter 1.27 1.27 1.27 cm

l = HTU NTU (6) Fibre outer diameter 0.11 0.20 0.11 cm
Fibre inner diameter 0.08 0.16 0.08 cm
in which; Number of fibre 20 10 35
Effective length 18 18 18 cm
Column area 1.27 1.27 1.27 cm2
L 
HTU = = L (7) Liquid flow area 0.10 0.20 0.18 cm2
KL ndi KL a Gas flow area 1.08 0.95 0.95 cm2
Void faction 0.86 0.75 0.75
Surface area/volume 431 472 806 m2 /m3
and
Packing factor 689 1109 1935
 xin
1
NTU = dx (8)
xout (x x )

where height of transfer unit (HTU) and NTU are the height and
number of transfer units, respectively. HTU represents the efficiency
of the equipment, i.e. the smaller the HTU, the better the efficient
separation. NTU is a measure of the difficulty in separation: a large
NTU means hard separation. In Eq. (7), L is the liquid velocity, m/s;
a is the interfacial area per volume, m1 .
KL can be theoretically predicted by a resistance-in-series model
as (Kreulen et al., 1993)
1 1 di 1 di 1 by a needle valve installed at the bottom of the column. Pure ni-
= + + (9)
KL HkG do HkM dm EkL
where kG , kM and kL are the individual mass transfer coefficients in
gas film, membrane and liquid film, respectively. E is the enhance-
ment factor due to the chemical reaction of CO2 in the liquid phase,
H is the Henry's law constant of CO2 in water. do , di and dm are
hollow fibre outer, inner and log mean diameters, respectively. The
details of parameter estimation are given in Appendix A.
3. Experimental
As the main objective of this study was to investigate the perfor-
mance of ceramic hollow fibre membrane contactors for CO2 strip-
ping, the experimental equipment was setup as shown in Fig. 3. The
setup was analogous to a packed column. However, the differences
were (1) packings replaced by ceramic hollow fibre membranes; (2)
absence of a reboiler normally located at the bottom of the column
to generate water steam as a stripping agent. Since the lab scale sys-
tem was relatively small, it would be difficult to constantly generate
a sufficient amount of steam. Therefore, pure nitrogen was employed
as a stripping gas instead.
The membrane module was immersed into a water bath and was
operated isothermally, controlled by a thermostat (Grant GD120,
UK). The liquid was circulated through the fibre lumens by a gear
pump (Cole-Parmer, IL). The liquid flow rate was manually controlled
trogen (BOC, UK) was used as a stripping gas and its flow rate was
precisely controlled by a mass flow controller (Brooks Instrument,
Model: 0152 & 5850TR). The concentration of CO2 in the gas phase
was monitored by using a gas analyser (Servomex, Model: 1440)
while the carbonation ratio of the liquid was monitored by a digital
pH meter (Hanna HI991011). The pressures on the shell and tube
sides were measured by pressure gauges (Omega, UK) while the tem-
peratures of fluids were determined by thermocouples and a data
logger (Omega, HH309).
3.1. Feed solution
The 2.5 Molar liquid feed solution was prepared from mo-
noethanolamine (MEA) (99%, AnalaR, UK) and deionised water; then
was loaded with CO2 by bubbling pure CO2 (BOC, UK) in a mag-
netically stirred vessel until reaching the carbonation ratio of 0.45,
a typical value for the liquid entering a stripper (Kohl and Nielsen,
1997). The carbonation ratio is a function of pH, temperature, and
MEA concentration, as follow (Disli, 1996):

 = 0.28315pH 0.005663T
0.021375( 12.1046) + 3.33843 (10)

where  is the carbonation ratio, T is liquid temperature ( C) and 

is the MEA concentration (%w/w). Thus carbonation ratio can be de-
termined by a calibrated pH meter which is an online measurement
for this purpose.

3.2. Membranes and modules

Surface modified alumina ceramic hollow fibre membranes pre-

Fig. 3. The experimental setup for CO2 stripping in a hollow fibre module.
pared at heat treatment temperature of 1400 C were selected for
this study because they have fairly high mechanical strength and
high hydrophobicity. Two sizes of hollow fibre membranes, ca. 1.2
and 2 mm in outer diameter, with different membrane pore sizes
and wall thickness were packed into three stainless steel modules
of which parameters are defined in Table 2. The details of mem-
brane preparation and module fabrication can be found elsewhere
(Koonaphapdeelert and Li, 2007; Koonaphapdeelert et al., 2008).
4 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8
4. Results and discussion
4.1. Membrane module capacity
In conventional contacting devices such as tray and packed
columns, excessively high gas per liquid flow ratio normally leads
to column flooding which is regarded as the capacity of the column.
The flooding limit is often illustrated by the generalised pressure
drop correlation (GPDC) which describes the balance between the
up-flowing gas momentum force and the gravitational forces acting
on the liquid droplets (Kister, 1992). The same correlation can be
applied to membrane contactors in order to compare their capac-
ity to those of conventional equipment. The flow parameters and
the capacity factors of the membrane contactors are calculated as
follows (King, 1980):
   
L G 0.5
Flow parameter =
G L
G2 FP 0.2
L
2
Capacity factor =
G L g
where L and G are the liquid and vapour mass fluxes, kg/h m2 , re-
spectively; FP is the packing factor; L is the liquid viscosity, mPa s;
G and L are the densities of vapour and liquid, kg/m3 , respec-
tively;  is the ratio between the density of water and the density of
liquid; and g is the constant gravity = 1.27108 m/h2 .
The capacity factor and the flow parameters are both entirely
dependent on the fluid flow rates and properties. In order to test
the hollow fibre modules against flooding, they were operated at
abnormally high fluid flow rates, ranging from 150 to 750 ml/min and
15003000 ml/min for liquid and stripping gas, respectively. Fig. 4
shows a plot of the capacity factors versus the flow parameters of
all the three membrane modules in the GPDC chart. As can be seen,
some data points lie outside the area of conventional GPDC, such
as those with the flow parameters greater than 10. Excessively high
flow parameters depict the high proportion of liquid flow rates to
gas flow rates, so the flooding limit decreases exponentially. Thus in
such condition there is a high risk of column flooding in conventional
equipment. Nevertheless, the membrane contactors could operate in
this region without any problem in the experiment.
Fig. 4 also shows that some data points are above the flooding
lines of random and structural packings (Peters and Timmerhaus,
1968). The maximum value of the capacity factors, obtained when
1 Flooding line with
stacked packing
Capacity Factor
0.1
Flooding line with
random packing
0.01
1E-3
0.01 0.1 1 10
Flow Parameter
Fig. 4. The GPDC of the hollow fibre modules (symbols:  = Module 1,  = Module
2 and  = Module 3).
0.40
Column Top Operation Line
0.35 Equilibrium
0.30
0.25
0.20
y
0.15
0.10 Driving force
0.05 Column Bottom
0.00
0.01 0.015 0.02 0.025 0.03
x
Fig. 5. The typical operating and equilibrium lines of the module.
the maximum stripping gas flow rate was used, is approximately
(11)
10 times higher than the limit of random packings and two times
higher than the limit of structural packings. At the same flow pa-
rameters, the capacity factors of Module 3 were higher than those
(12)
of Module 1 and 2 because it has a higher packing factor. There was
no sign of flooding observed in the experiment. The experimental
results also showed that membrane contactors were able to operate
even at exceedingly high liquid or gas flow rates without any hydro-
dynamic problems. Owing to the hydrophobicity of the membranes,
the total separation of gas phase from liquid phase is achieved. As
the result, the membrane contactors can operate with no flow con-
straints. Some researchers claimed that the turndown ratio, the ratio
between the maximum gas flow rate to the minimum gas flow rate,
of a membrane contactor is approaching infinity (Zhang and Cussler,
2003). The results of this study are supporting the claim.
The freedom of gas/liquid flow control can potentially benefit the
CO2 stripping unit. The gas flow rate can be as high as desirable
to increase the concentration driving force and enhance the perfor-
mance without fear of column flooding while the liquid flow rate can
be altered freely. However, it must be concerned that the pressure
difference between the gas and liquid sides needs to be carefully
controlled in order to prevent the penetration of one phase into the
other and the problem of membrane wetting (Li and Chen, 2005).
4.2. Module performance
The module performance can be measured in forms of HTU and
NTU. They can be determined via a graphical method which illus-
trates the relationship between the equilibrium and the operating
conditions from the bottom to the top of the stripping column, ac-
cording to Eqs. (7) and (8). Fig. 5 presents typical equilibrium and
operating lines at a given condition of the membrane contactor. The
equilibrium line is fixed and depends solely on operating tempera-
ture whereas the operating line depends on the fluid flows and the
solute concentration. The horizontal line represents the concentra-
tion driving force of CO2 in the liquid phase. At the bottom of the
column where the vapour mole fraction (y) of CO2 is zero, thus the
equilibrium liquid mole fraction (x*) is zero whereas the actual liq-
uid mole fraction (x) is much larger resulting in the largest driving
force. As the stripping gas flows up the column and gains more CO2
concentration, the driving force becomes smaller until it reaches the
point where x and x* are equal and no mass transfer occurs.
Fig. 6 presents the HTU of three modules used in the experiment.
The HTU can be explained by Eq. (7) which shows that HTU is the
product of liquid velocity (L ) and the reciprocals of KL and a. Due
to the small value of a in Module 1, its mass transfer efficiency of
the Module 1 was low as reflected by its high HTU. The similar
explanation also applies on the low HTU of Module 3 which is the
result of high interfacial area. The a of Module 3 was approximately
 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8 5

0.80 0.025
0.70
0.020
0.60 Module 2
0.50 Module 1
0.015
HTU (m)

Module 3

0.40
0.010
0.30
0.20 L = 5 cm/s
0.005 L = 7.5 cm/s
0.10 L = 10 cm/s
0.00 0.000
0.00 0.03 0.05 0.08 0.10 0.13 0.15 0.0 2.0 4.0 6.0 8.0 10.0
Liquid Flow (mol/s) Gas Velocity (cm/s)

Fig. 6. The HTU of three hollow fibre modules operated at 90 C Fig. 8. The effect of stripping gas velocity on  at different liquid flows, operated
in Module 2 at 90 C.

0.06
80 C
tained from the module when the liquid flow rate was the lowest
0.05 90 C and the operating temperature was 100 C. In a typical amine strip-
100 C per, the  is brought down from 0.45 in rich amine to 0.20 in lean
0.04 amine, so the target  is about 0.20 (Kohl and Nielsen, 1997). Thus,
approximately 20% of the CO2 loading was stripped off in such a

0.03
0.02
0.01
0.00
0.0 2.5 5.0 7.5 10.0 12.5
Liquid Velocity (cm/s)
Fig. 7. The effect of liquid flow rate on  at different temperature, operated in
Module 2.
806 m2 /m3 , almost double that of Module 1, so its HTU was much
smaller.
To compare the efficiency of the modules with conventional col-
umn packings, the height of equivalent theoretical plate (HETP) can
be calculated based on Eq. (13) (Sinnott, 1993)
ln(m(G/L))
HETP = HTU
(m(G/L) 1)
where m is the slope of the equilibrium line. The HETP of the modules
were approximately 1.22.0 times of HTU, depending on the operat-
ing condition. The HETPs of Module 3 were in a range of 1540 cm,
much lower than those of conventional packings which were re-
ported to be between 60 and 90 cm (Kohl and Nielsen, 1997).
4.3. Effects of operating parameters
In this study, the effects of operating parameters, comprising of
operating temperature, liquid flow rate and stripping gas flow rate,
on the performance of the column were examined. The operating
temperature was precisely controlled by a water bath at 80 C, 90 C,
and 100 C which are gradient temperatures normally found from
the top to the bottom of conventional stripping columns. , defined
as the difference between  of amine solution at the inlet and the
outlet at each operating condition, is used in the analysis. This 
represents the amount of CO2 stripped out after the liquid passed
through the column.
Fig. 7 presents the effect of liquid flow rate on  after the liq-
uid passed through the column at different temperature. As can be
seen, the maximum reduction of 0.04 in carbonation ratio was ob-
short column length of 18 cm in this condition. When the liquid flow
rate increased,  decreased but at a non-linear rate. The result can
be explained by the combined effects between the decrease in con-
tact time and the increase in mass transfer coefficient (Chung et al.,
2005). However, the latter is relatively little compared to the for-
mer. Therefore, the overall effect was the decrease in the amount of
15.0 CO2 stripped when the liquid flow was higher. The operating tem-
perature of the column also played an important role in the mem-
brane performance. As shown in Fig. 7, the higher  was obtained
at higher temperature at any given liquid flow rate. The reason is ob-
vious. When the temperature was higher, the equilibrium dissolved
CO2 concentration was shifted to a lower position resulted in the
increased driving force for CO2 mass transfer. Therefore, the higher
reduction of carbonation ratio was achieved.
Fig. 8 shows the effect of stripping gas flow rate on  at differ-
ent liquid flow rates while the operating temperature was hold at
90 C. The reduction of carbonation ratio ( ) increased when the
stripping gas flow rate increased. This is true, as the stripping gas
flow increases, the concentration of CO2 in the gas phase decreased
(13) resulting in a higher driving force. The operations at different liquid
flow rates showed the similar trend.
4.4. Mass transfer coefficients
The mass transfer coefficient is a measure of the number of
moles transferred per time-area-and-driving force (Seader and
Henley, 2006). It can be calculated directly from the experiment
result by using Eq. (7) and are shown in Fig. 9. As the liquid veloc-
ity increased, KL increased because the liquid flow regime became
more turbulent and, therefore, enhanced the mass transfer. KL also
depended on the operating temperature because the molecular
diffusion and chemical kinetic increase at higher temperature.
KL could be theoretically predicted based on the model in Eq. (9).
The predicted values are shown in solid lines in Fig. 9. They were
generally in the same order of magnitude of the experimental KL . The
predicted KL also exhibited the similar trend found in the experiment
that KL increased when liquid velocity increased. Nevertheless, it
was found that the mass transfer model seemed to over-estimate KL ,
compared to the experimental values.
Fig. 10 shows the contribution of liquid phase and combined gas
and membrane resistance to the total mass transfer resistance in
Module 3 at the operating temperature of 90 C. The mass transfer
6 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8

The module performance was measured in the forms of HTU and

9.0x10-4
. The HTU of hollow fibre modules depend on a few parameters,
8.0x10-4 comprising of fluid velocity, mass transfer coefficients, and surface
area per unit volume. The HTU of Module 3, which has the largest a
7.0x10-4 among three modules, is the lowest, indicating its high mass transfer
efficiency. The HTU of Module 3 was also found to be considerably
KL (m/s)

6.0x10-4 lower than those of conventional packings, showing its superior ef-
5.0x10-4 ficiency.
The mass transfer in the contactor was analysed and modelled
4.0x10-4 using a well-known resistance-in-series model. It was found that the
model can predict the values of KL reasonably well, but always with
3.0x10-4 over-estimation. The employment of a better mass transfer model
might help reducing such deviation. It was also found that the mass
2.0x10-4
transfer resistance mainly came from the resistance in the liquid,
0.0 2.5 5.0 7.5 10.0 12.5 15.0 rather than from the resistance in the membrane and gas phases.
Liquid Velocity (m/s) The results of this study show that the ceramic contactors can
be applied to a gasliquid stripping process at high temperature.
Fig. 9. The experimental and predicted overall mass transfer coefficients of CO2 in The contactors have the combined advantages of hollow fibre mem-
Module 2 (symbols  = 80 C,  = 90 C,  = 100 C, and = predicted values). branes and ceramic materials, which offer high interfacial area per
volume, total phase separation, and good chemical and thermal sta-
bilities. Further development focusing on the improvement of con-
Liquid Phase tacting modules and mass transfer model would help paving the way
Gas Phase for the ceramic hollow fibres to be used in practical amine strip-
ping. Another interesting prospect is the feasible of using ceramic
membrane contactors and ionic liquids for CO2 absorption at high
100% temperature, which would result in the elimination of unnecessary
% of Total Mass Transfer Resistance

flue-gas cooling down procedure (Schilderman et al., 2007; Tang

et al., 2005).
80%

Notation
60%

a interfacial area per volume for gasliquid mass transfer,

m1
40%
cT total solute concentration in liquid, mol/m3
C concentration of carbon dioxide, mol/m3
20% de hydraulic diameter of the hollow fibres, m
do , di , dm outside, inside and log mean diameters of the hollow
fibres, m
0% D diffusion coefficient of carbon dioxide, m2 /s
2.50 5.00 7.50 10.00 12.50 E enhancement factor
FP packing factor of the module
Liquid Velocity (cm/s)
g local gravity, 1.27108 m/h2
Fig. 10. Contribution of the liquid resistance and the combined gas and membrane G vapour mass flux based on the empty column area,
resistance to the total mass transfer resistance in Module 3 at 90 C  liquid kg/h m2
resistance, combined gas, and membrane resistance. H Henry's constant
H psuedo Henry's constant
HTU height of the transfer units, m
resistance in the liquid side was accounted for almost 90% of the total kL , k M , kG individual mass transfer coefficients in the liquid, mem-
resistance while that combined gas phase and membrane resistance brane, and vapour phases, m/s
was accounted for merely 10%. In this respect, the mass transfer re- K overall mass transfer coefficient based on concentration
sistance in the liquid phase was the major resistance that dominates driving force, m/s or the thermodynamic equilibrium
the entire mass transfer process. constant
K overall mass transfer coefficient based on mole fraction
5. Conclusions driving force, mol/m2 s
l length of the hollow fibre, m
In this study, ceramic hollow fibre membrane contactors have L molar liquid flow rate, mol/s
been introduced for CO2 stripping from amine solution. The module L liquid mass flux based on the empty column area,
capacity was evaluated by plotting the capacity factors obtained from kg/h m2
the experiment on the GPDC chart. The results showed that because Lp effective membrane pore length, m
the gas and liquid phases were totally separated by the membranes, m slope of vapourliquid equilibrium curve
the contactors could be operated very well even in the region of or- mi mass fraction of components i in solution
dinary column showing flooding or loading. The maximum capacity n number of the packed hollow fibres
factor tested in the experiment was at least 210 times higher than N mass transfer flux, mol/m2 s
the flooding line without any sign of flooding. NTU number of the transfer units
 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8 7

P CO2 partial pressure in the gas phase, Bar or operating CO2 reacts with some reactive components in the liquid, the
pressure, atm direct measurement of CO2 diffusivities in MEA solution cannot
pH pH value of carbonated MEA solution be made. Instead, the nitrous oxide (N2 O) analogy is employed
rj the ratio between the diffusivities of component Bj and to realise the estimation (Joosten and Danckwerts, 1972). The
A N2 O diffusivities data were from literatures (Sada et al., 1978;
Re Reynolds number, Re = de G G / G Tamimi et al., 1994). The CO2 diffusivities in MEA solution at high
Sc Schmidt number, Sc = G / G DG temperature can be estimated by using StokesEinstein equation.
Sh Sherwood number, Sh = kL .di /DL The viscosity of MEA solution at different temperature and CO2
T operating temperature, C or K loading can be predicted (Weiland et al., 1998).
V molar gas flow rate, mol/s (2) Gas-side mass transfer coefficient: The gas-side mass transfer co-
x mole fraction of carbon dioxide in the liquid phase efficient can be estimated by the following equation (Qi and
y mole fraction of carbon dioxide in the gas phase Cussler, 1985) which is valid fluid flows at low Reynolds num-
z distance from the bottom of the column, m ber. Since gas flows through the small gap between fibres in the
column, the Reynolds number is generally low.
Greek letters

 carbonation ratio  
kG de Re de 0.93 0.33

effective porosity of the membrane = 1.25 Sc , 0.5 < Re < 500 (A.2)
 viscosity of liquid or vapour phase, Pa s DG l
i stoichiometric coefficients in which Re is Reynolds number, Re = de G / ; Sc is Schmidt
 the ratio between the density of water and the density number, Sc = / DG ; de is the hydraulic diameter (4A/U);  and
of liquid  are the vapour density and viscosity, respectively. A is the cross
 density of liquid or vapour, kg/m3 section area of the column while U is the column wetted perime-
 superficial velocity, m/s ter which is the sum of internal column perimeter and the total
 defined as  = (E 1)(CAi CAo ) perimeter of all hollow fibres. The experimental diffusion coef-
 mass percentage of MEA in the solution, %w/w ficient of CO2 in pure nitrogen is 0.167 cm2 /s at 298 K and 1 atm
Superscript (Seader and Henley, 2006). The values at different temperature
and pressure can be predicted by using the empirical equation
* equilibrium of Fuller et al. (1966). Pure gas viscosity at high temperature is
computed using Sutherland's formula (Crane Company, 1988).
Subscript
The gaseous mixture viscosity can be approximated by Bromley
A carbon dioxide and Wilke method (Liley et al., 1998).
B MEA (3) Membrane mass transfer coefficient: The mass transfer coefficient
G gas phase in a porous membrane can be written as (Li et al., 2000);
in inlet
L liquid phase
DG,p
p
M membrane phase kM = (A.3)
out outlet Lp
p membrane pore
where DG ,p is the CO2 diffusivity (continuum and Knudsen) in the
P carbamate
membrane pores, m2 /s;
p , and Lp , are the porosity, and the ef-
w pure water
fective pore length of the hollow fibre membranes, respectively.
(4) Henry's Law Constants: it is important to ensure that Henry's law
Acknowledgements constants used in the model is defined as;

The authors gratefully acknowledge the research funding pro- c

vided by EPSRC in the United Kingdom (Grant no. EP/F027427/1). H = G (A.4)
cL

Appendix A. Mass transfer model
In order to predict the overall mass transfer coefficient (KL )
in Eq. (9), the gas, membrane, and liquid mass transfer coeffi-
cients, and Henry's law constants as well as enhancement factors
must be known. The derivation of each parameter is provided as
follows;
(1) Liquid side mass transfer coefficient: Since liquid is fed into the
fibre lumen, the liquid mass transfer coefficient for physical des-
orption, kL can be estimated from a well-known Lvque equa-
tion, which is valid in the cases of laminar flows (Lvque, 1928).
 2 1/3
k d d L
Sh = L i = 1.615 i (A.1)
DL lDL
where L is the liquid flow velocity, m/s; and DL is the diffusion
coefficient of CO2 in the liquid phase, m2 /s. Nevertheless, since
where H is the dimensionless Henry's law constant. cG is CO2
concentration in the gas phase. cL is the concentration of CO2 in
liquid phase and is in equilibrium with that in the gas phase. The
experimental values of Hi for CO2 in water and MEA at STP are
3090.7 kPaL/mol and 3903.8 kPa L/mol, respectively, (Browning
and Weiland, 1994), which can be converted into a dimensionless
form by multiplying with 4.03104 mol/kPa (Sander, 1999). The
Henry's law constant at high temperature can be predicted by
Van't Hoff equation (Atkins and De Paula, 2006):
(5) Enhancement Factor: The reversible reactions that occur when
CO2 is absorbed into MEA solution is presented in Eq. (A.5)
(Astarita, 1967; Astarita et al., 1983; Danckwerts and McNeil,
1967; Hikita et al., 1977)
CO2 + 2RNH2  +
 RNH3 + RNHCOO
(A.5)
Weiland et al. (1982) applied the mathematical analysis of As-
tarita to model a stripping column of CO2 -MEA system and
gave the following equation for calculating the enhancement
8 S. Koonaphapdeelert et al. / Chemical Engineering Science 64 (2009) 1 -- 8
factor (E):
  
DP D Kim, Y.-S., Yang, S.-M., 2000. Absorption of carbon dioxide through hollow fiber
E=1+ KCB 1 + 2 P KCAi
DA DB
Technology 21 (12), 101109.
( CA + CAi ) (A.6)
where D is the diffusion coefficients of the species. The subscripts
A, B, and P stand from free CO2 , MEA, and carbamate, respectively.
The diffusion coefficient of MEA molecules in water at different
concentration and temperature can be estimated (Snider et al.,
1993). The thermodynamic equilibrium constants (K) by using
the following equation (Weiland et al., 1982):
 2
1 
K= (A.7)
|CO2 |e 1 2
in which |CO2 |e is the equilibrium concentration of dissolved free
CO2 in the liquid phase which can be converted from PCO and
2 chemical data. In: Perry, R.H., Green, D.W., Maloney, J.O. (Eds.), Perry's Chemical
the Henry's law constants. The equations can finally be solved
with the aid of any powerful mathematical software, such as
Matlab or Mathematica .
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