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Front. Chem. Eng.

China 2007, 1(4): 385389


DOI 10.1007/s11705-007-0070-0

RESEARCH ARTICLE

Experimental studies on the influence of porosity on


membrane absorption process
GAO Jian, REN Zhongqi, ZHANG Zeting, ZHANG Weidong ( )
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Higher Education Press and Springer-Verlag 2007

Abstract Eight kinds of flat membranes with different


micro-structures were chosen to carry out the membrane
absorption experiments with CO2 and de-ionized water or
0.1 mol L1 NaOH solution as the experimental system.
According to experimental results, the membrane pores shape
(stretched pore and cylinder pore) and membrane thickness
do not affect the membrane absorption process, and the
membrane porosity has only little influence on membrane
absorption process for slow mass transfer system. However,
the influence of porosity on the membrane absorption process
became visible for fast mass transfer system. Moreover, the
mass transfer behavior near the membrane surface on liquid
side was studied. The results show that the influence of
membrane porosity on mass transfer relates to flow condition,
absorption system and distance between micro-pores, etc.
Keywords membrane absorption, mass transfer coefficient,
porosity, mass transfer resistance

Introduction

Membrane absorption, which combines the advantages of


membrane separation process and traditional absorption
process, is a novel separation technique. In this process, the
gas phase and liquid phase flow along the different sides of
membrane and contact with each other through the membrane
porous. The membrane absorption technique has the advantage of operational flexibility without the limitation of flooding and entrainment. In 1985, Zhang and Cussler [1,2] used
hollow fiber membrane to remove acid gas such as SO2 and
CO2. Many studies on mass transfer mechanism and its
application were reported [35] since then.
Unfortunately, studies about the influence of micro-pore
membrane on the mass transfer behavior in the membrane
Translated from Journal of Chemical Engineering of Chinese
Universities, 2007, 21(1): 1419 [: ]
E-mail: zhangwd@mail.buct.edu.cn

absorption process were quiet lack. Kreulen et al. [6] studied


the CO2 absorption process with de-ionized water in hollow
fiber contactor with various porosities. They believed that the
whole membrane area should be used to calculate the mass
transfer coefficient, and the porosity had no influence on
the mass transfer performance. However, Kim et al. [7] and
Baudot et al. [8] pointed out that the porosity had a significant
influence on the mass transfer performance, and the mass
transfer area should be the micro-pore area of membrane.
These two viewpoints are conflicting. Moreover, in the study
on air-CO2 absorption with de-ionized water in hollow fiber
contactor with 30% of porosity, Huseni el al. [9] calculated
that the ratio of apparent mass transfer area with the whole
membrane area was 0.58. They explained that this difference
was the results of the non-ideal flow on the shell side of the
hollow fiber membrane contactor. From the discussion above,
the view about the influence of porosity on the membrane
absorption process is still in confusion.
In this work, various absorbents were used in membrane
absorption for the absorption of CO2. The influences of
membrane micro-pore shapes, membrane thickness and
porosity on mass transfer behavior were investigated experimentally. Moreover, the mass transfer behavior of CO2 on the
micro-pore on the membrane surface of the liquid phase side
was studied.

Experimental

In order to avoid the influence of non-ideal flow of the shell


side in the hollow fiber membrane absorption process, the flat
membrane module was used as shown in Fig. 1. Two vessels
with 300 mm in length, 150 mm in width and 25 mm in height
were connected together, between which the flat membrane
was placed in. When polytetrafluoroethylene (PTFE) flat
membrane was used, nylon wire meshes were used as
support. The parameters of membranes were listed in Table 1.
In our study, pure CO2 (gas phase) was used to eliminate
resistances in gas phase and membrane. Either de-ionized
water or 0.1 mol L1 NaOH solution was used as absorbent.

386
can be reached after 30 min. The aqueous samples were taken
from the outlet of the liquid phase at preset time intervals. The
double indicator titration method [10] was used to determine
the concentration of solute (CO2) or bivalent ion (CO32) in
the outlet of the liquid phase. Therefore, the overall mass
transfer coefficient can be written as follows
KL =
DC = PxH Fig. 1 Schematic diagram of experimental setup
1: CO2 cylinder; 2: depressed valve; 3: adjustive valve; 4: four
way valve; 5: liquid seal tank; 6: U-pressure metre; 7: pump;
8: membrane module; 9: tank of absorbent; 10: stock liquid tank;
11: clip
Table 1 Parameters of membranes
No
1#
2#
3#
4#
5#
6#
7#
8#

Material
PTFE
PTFE
PTFE
PTFE
PP
PP
PP
PP

Thickness of membrane /m
6

4.15x10
2.10x106
1.15x106
1.04x106
5.20x104
5.20x104
5.20x104
1.52x103

LxCout
ADC

Cout
(De-ionized water as absorbent)
2

(1a)
(1b)

DC = PxH (0.1 mol L1 NaOH solution as absorbent) (1c)


where A is the membrane area, P is the pressure on the
gas side, H is the Henry coefficient of CO2 in water, L is the
velocity on the liquid side, Cout is the outlet concentration of
the solute (CO2) or bivalent ion (CO32).

Porosity /%
45.0
73.0
93.0
51.0
1.5
11.5
39.8
13.8

Note: PTFE membrane was provided by the Soldier Center of the Quartermaster Research Institute of the General Logistics Department of PLA,
PP membrane was prepared by authors (being boring by laser).

The mass transfer resistance in gas phase can be ignored


for the absorption of pure CO2. Before the experiment, pure
CO2 was flowed into the vessel for 30 min to replace the air,
and then the outlet of the gas phase was closed. The velocity
of absorbent ranged 00.003 m s1. The volume of absorbed
CO2 was measured by a soap film flow meter in the unsteadystate experiments for a preset time interval. In steady-state
experiments, the fresh absorbent was used. The steady state

Results and discussion

The PTFE flat membranes used have a network formation as


shown in Fig. 2(a). The polypropylene (PP) flat membranes
have regulated cylinder pores as shown in Fig. 2(b). In the
prior studies, it was indicated that the role of the membrane is
only to separate the gas phase and liquid phase and provide a
steady interface between gas and liquid phases. As the micropores were fully filled with gas phase, the pore size was much
greater than the molecular mean free path of CO2 under
experimental conditions, the flow of gas through micro-pore
was viscose flow. Although the micro-pore size is large, PP
membrane could also divide the two phase and provide steady
mass transfer interface due to the large membrane thickness.
The regular cylinder pores of PP are benefit for the mechanism study on the membrane absorption process. In this
work, the influences of the membrane thickness and porosity
on the mass transfer in the membrane absorption process

Fig. 2 Photograph for PTFE membrane and PP membrane

387
under various membrane micro shapes conditions were
investigated.

3.2 Influence of the porosity on mass transfer when the


liquid phase kept stagnant

3.1

When the absorbent was kept stagnant in the experiment, the


membrane absorption process is an unsteady state process.
De-ionized water and 0.1 mol L1 NaOH solution were used
as absorbents, respectively. The overall mass transfer coefficients of 1#3# and 5#7# are shown in Fig. 5. Compared
with the steady state process, the mass transfer coefficient
is small, because only molecular diffusion occurred in the
unsteady state process. In addition, when de-ionized water is
used as absorbent, the mass transfer coefficients of 1#3# and
5#7# do not vary with porosity. However, when 0.1 mol L1
NaOH solution is as absorbent, the mass transfer coefficients
of 1#3# and 5#7# increase with increasing porosity. The
reason will be further discussed below.

Influence of the membrane thickness

For the PP membrane with cylinder pores, the porosity of 6#


and 8# membrane is similar; the membrane thickness of 8# is
bigger than that of 6#. For the expanded PTFE membrane, the
porosity of 1# and 4# is similar, the thickness of 1# is bigger
than that of 4#. As shown in Figs. 3 and 4, for either PP or
PTFE membrane, the membrane thickness almost has no
influence on mass transfer when either de-ionized water or
0.1 mol L1 NaOH solution is used as absorbent. Since pure
CO2 was used, the mass transfer resistance of gas phase can
be ignored, and the membrane resistance was just the resistance to gas diffusion through the gas itself in the micro-pores
of the membrane. In the case of low absorbability, the mass
transfer resistance of membrane phase is usually small as a
fraction of the total resistances.
Therefore, the mass transfer coefficients are similar for
various thickness of membrane under different flow rates in
membrane absorption experiments. However, the mass transfer performance of PP and PTFE are seriously different, which
will be discussed in the followings.

(a) de-ionized water as absorbent

3.3 Influence of porosity on mass transfer with de-ionized


water as absorbent
With de-ionized water as absorbent and the velosity of liquid
phase at 0.002 m s1, the influence of porosity on mass transfer is shown in Fig. 6. It is indicated that the porosity almost
has no influence on the mass transfer coefficient for either

(b) 0.1 mol L1 NaOH solution as absorbent

Fig. 3 Influence of membrane thickness on mass transfer for PP membrane

(a) de-ionized water as absorbent

(b) 0.1 mol L1 NaOH solution as absorbent

Fig. 4 Influence of membrane thickness on mass transfer for PTFE membrane

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Fig. 5 Influence of porosity on mass transfer when velocity of


absorbent is 0 m s1

Fig. 6 Influence of porosity on mass transfer when de-ionized


water is used as absorbent and uL = 0.002 m s1, uL = 0.003 m s1

PTFE or PP membranes. It is also obtained from the below


discussion that the influence of porosity on mass transfer
coefficent is mainly caused by concentration profile near the
liquid phase membrane surface. As shown in Fig. 2(a), there
are many nodes on the surface of PTFE membrane, in which
the gas and liquid phases cannot directly contact, and form the
dead spot of mass transfer. The diffusion behavior of the
solute from the gas/liquid interface to the dead spot is similar
to that of the solute from the gas/liquid interface of cylider
pores to the non mass trasnfer zone. Then the influences of
porosity on mass transfer of these two cases are similar too.
In our previous studies [11,12], the mechanism for the
influence of porosity on mass transfer in the membrane
absorption process has been discussed. The pores of the membrane were considered as a circular pore. The interval between

the pores was set as d. The thicnness of mass transfer boundary layer near the membrane surface was set as l, which
reflected the diffusion distance of the solute in absorbent. The
diffusion of solute in mass transfer boundry layer was mainly
molecular diffusion. In the case of l>d, the concentration
profile of the solute could cover the whole membrane surface
as shown in Fig. 7(a), here the effect of the membrane surface
porosity on mass transfer is small. In the case of l<d, the
concentration profile of the solute could not cover the whole
membrane surface as shown in Fig. 7(b), here the porosity has
a large influence on the membrane absorption process.
When the velocity of liquid phase is increased, the flowing
boundry layer became thin, which resultes in the mass transfer boundry layer, l, small. When the case of l>d changes to
the case of l<d, the influence of porosity on the mass transfer
become more obvious. Thus, in oder to study the influence
of porosity on mass transfer, the liquid phase flow rate was
increased. As shown in Fig. 8, it is indicated that the mass
transfer coefficient increases with increasing porosity when
the liquid phase flow rate at 0.003 m s1. It is because that the
mass transfer boundary layer became smaller with increased
liquid phase flow rate. From the discussion memtioned above,
here the mass transfer area was not the full membrane surface
area, and it is related with porosity of membrane. The higher
porosity leads to higher mass transfer coefficient. The comparison of calculated thickness of boundary layer based on
Prandt boundary layer theory and half pore interval of the PP
membrane is shown in Table 2. With the absorbent flow rate
at 0.002 m s1, it is the case of l>d; with the absorbent flow
rate at 0.003 m s1, it is the case of l<d. Thus the porosity
will influence the the mass transfer.
3.4 Influence of porosity on mass transfer with
0.1 mol L1 NaOH solution as absorbent
When 0.1 mol L1 NaOH solution is used as absorbent, CO2
is converted rapidly and almost had no diffusion on the liquid
phase due to the enhancement effect of chemical reaction,
thereby l tends to be 0. According to the description above,
the porosity should have a large influence on the membrane
absorption process. The results of membrane absorption
experiments with 0.1 mol L1 NaOH solution as absorbent
are shown in Fig. 8. Combining Fig. 6 and the discussion
above, the porosity almost has no influence on the mass transfer coefficient for PP and PTFE membranes, when de-ionized
water is used as absorbent and the liquid phase flow rate
was at 0.002 m s1. However, when 0.1 mol L1 NaOH is

Fig. 7 Schematic of the solute diffusing on the membrane surface of liquid side

389

Fig. 8 Influence of porosity on mass transfer with 0.1 mol L1 NaOH solution as absorbent
Table 2 Comparison between the thickness of boundary layer of concentration and the pore interval of PP membrane, when de-ionized water
is absorbing
Velocity
/ (m s1)
0.002
0.003

Boundary layer
of concentration
/ (l m1)
4.1x104
1.2x104

Half pore interval of PP membrane, d/m


5#

6#

7#

3.4x104

2.7x104

1.5x104

used as absorbent, the mass transfer coefficient increases


with increasing porosity as shown in Fig. 8. Moreover, the
amplitude of mass transfer coefficient variation increases
with increasing liquid phase flow rate, i.e. the degree of
influence of porosity on mass transfer became bigger. This is
consistent with the reported literatures [11].

Conclusions

In the membrane absorption process, the membrane thickness


almost has no influence on mass transfer behavior for
stretched-pore and cylinder-pore membranes. When deionized water is used as absorbent, the influence of membrane
porosity on the mass transfer coefficient is small in the low
velocity of liquid phase; while the mass transfer coefficient
increases with increasing porosity in increased velocity. When
0.1 mol L1 NaOH solution is used as absorbent, the porosity
had a large influence on the mass transfer coefficient, even
though the velocity of liquid phase is low. When the velocity
of absorbent increases, the influence of porosity on mass
transfer becomes larger. According to the previous studies
on mass transfer behavior near the membrane surface of the
liquid side, it is indicated that the influence of porosity on the
mass transfer performance is by the means of mass transfer
area.
Nomenclature
A
membrane area, m2
Cout outlet concentration of CO2 or CO32, mol m3
H
Henry coefficient of CO2 in water, mol m3 Pa1

KL
L
P
uL

mass transfer coefficient of liquid phase, m s1


flow rate of the absorbent, m3 s1
pressure on the gas side, Pa
velocity of absorbent, m s1

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