Separation and Purication Technology 99 (2012) 91103

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Separation and Purication Technology

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

Effect of polymer extrusion temperature on poly(vinylidene uoride) hollow ber

membranes: Properties and performance used as gasliquid membrane contactor
for CO2 absorption
Nayef Ghasem , Mohamed Al-Marzouqi, Nihmiya Abdul Rahim
Department of Chemical & Petroleum Engineering, UAE University, Alain City, United Arab Emirates

a r t i c l e

i n f o

Article history:
Received 10 May 2012
Received in revised form 23 July 2012
Accepted 31 July 2012
Available online 31 August 2012
Keywords:
Poly(vinylidene uoride)
PVDF
Hollow ber membranes
Extrusion temperature
Membrane absorption
CO2 absorption
TIPS method

a b s t r a c t
In this study, poly(vinylidene uoride) (PVDF) hollow ber membranes were fabricated via thermally
induced phase separation (TIPS) method using 28% PVDF polymer and 72% triacetin solvent. The dope
solutions were prepared at four different extrusion temperatures (140 C, 150 C, 160 C and 170 C).
The fabricated membranes were characterized using scanning electron microscopy (SEM), mercury
porosimeter to measure membrane average pore diameter, gas permeation test was employed to measure membrane effective surface porosity. The separation of carbon dioxide (CO2) from methane (CH4)
by using a gasliquid membrane contactor was studied in order to conrm the potential of the process
using the fabricated hollow ber membranes. The experiments were performed in a membrane contactor
constructed with the fabricated microporous PVDF hollow bers. Aqueous sodium hydroxide (NaOH)
solution was utilized as the liquid absorbent. The effect of the gas ow rate on the CO2 ux was investigated. It was found that the PVDF membranes exhibited increased pore size, water contact angle, membrane strength, membrane porosity, effective surface porosity with preparation temperature. Countercurrent ow mode was employed; the CO2 ux increased with membrane extrusion temperatures.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Carbon dioxide is believed to be the main gaseous contaminant
in the atmosphere. The emission of greenhouse gases such as CO2
to environment causes climatic changes. The greenhouse gas is believed to increase the temperature of the earth, accompanying this
temperature increase is extreme weather and a projected sea level
rise which will in turn be problematic for coastal cities. Therefore,
emission of this gas to atmosphere should be low, necessitating its
removal. The process for removing carbon dioxide from industrial
gases can be achieved by absorption into aqueous solutions of alkanolamines and caustic solutions. Conventional gas processes, such
as gasliquid absorption column, for the removal of CO2 suffers
from weak points such as ooding, foaming, entraining, channeling, and high capital and operating costs. Gasliquid membrane
contactors for absorption of pollutant gas deemed promising
replacement technology. A comprehensive and excellent review
of the recent developments in membrane-based technologies for
CO2 capture can be found elsewhere [1]. In a membrane contactor
utilized for CO2 gas absorption, a gas mixture ows on one face of a
hydrophobic microporous membrane while a liquid absorbent
Corresponding author. Tel.: +971 3 713 3546; fax: +971 3 762 4262.
E-mail address: nayef@uaeu.ac.ae (N. Ghasem).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.07.021

ows on the other side, gas disseminated from the gas side across
the membrane and approaches the gasliquid interface, once the
pollutant enters the liquid phase, it can simply dissolve, or it can
react with other chemicals present in the liquid. In hollow ber
membrane contactor, phase separation after absorption operation
is not necessary because one phase is not dissolved into other
phase in the module. By contrast, membrane can introduce an
additional resistance to mass transfer, membrane pores should
be small to stop the penetration of absorbents into the pores, the
smaller the pore radius, the larger the liquid entry pressure. Membrane contactor has a few advantages over conventional gas
absorption process, such as high surface area per unit volume,
operational exibility, low cost, being easy to scale up. Scaling up
of membrane technology from laboratory to industrial scale was
studied by Luis et al. [2]. In order to prevent aqueous absorbents
from passing through membrane pores into the gas side, membrane used in membrane absorption is usually hydrophobic. Polymeric hollow ber membranes were fabricated, characterized and
tested for CO2 removal using various polymers; polyethersulfone
[3], poly(vinylidene uoride) [412], polypropylene [13], LDPE
[14] and polyetherimide [15]. In gasliquid membrane contactor,
the membrane pores should not be lled with liquid (wetting)
but with gas (nonwetting mode). Liquid phase diffusivity is lower
than gas phase diffusivity; mass transfer resistance through liquid

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Nomenclature
AT
Cg,in
Cg,out
Ci
Ci,m
Ci,s
Ci,t
CL,in
CL,out
Di
dp
di
do
H
Kol
L
Lp
m
M
m
p
P

total area of membrane, m2

inlet gas concentration, mol m3
outlet gas concentration, mol m3
concentration of component i; 1: CO2, 2: CH4, 3: NaOH
concentration of component i in the membrane section,
mol m3
concentration of component i in the shell section,
mol m3
concentration of component i in the tube section,
mol m3
inlet liquid concentration, mol m3
outlet liquid concentration, mol m3
diffusion coefcient of component i; 1: CO2, 2: CH4, 3:
NaOH
pore diameter, m
inner diameter of hollow ber diameter, m
outer diameter of hollow ber diameter, m
Henrys constant
overall mass transfer coefcient, m s1
length of hollow ber membrane, m
effective pore length, m
physical solubility
molecular weight of gas, g mol1
distribution factor
pressure, Pa
total gas permeance, mol m1 Pa1 s1

lled pores is much higher than that through gas lled pores
[1623]. Actually, membrane absorption is thought to be a
promising technology to decrease the emission of greenhouse
gas. Many efforts have been made to resolve the wetting problem
by the development of new membrane materials or hydrophobic
modication of available membranes [2427]. Membrane structure and performance depend upon different factors; methods of
fabrication, polymer choice, composition and quenching temperature. Membrane structure can be affected quite drastically by
changing one or more of these variables; furthermore, spinning
factors such as dope extrusion temperature and extrusion rate,
take-up speed, air gap, bore uid type and ow rate must be optimized at the best condition in order to produce the high performance membrane [28,29]. In this study, microporous PVDF
hollow ber membrane was prepared by thermally induced
phased separation method, and investigated for the effect of dope
solution extrusion temperature on the membrane structure and
performance. Membrane contactor modules were constructed
using the in house fabricated membranes and was used in the
absorption of CO2 from CO2/CH4 gas mixture in aqueous NaOH
solution. The observed membrane performance was based on
membrane structure. Furthermore, simulation of the CO2 absorption via gasliquid membrane contactor was performed and the
simulation results were compared with the experimental data at
various extrusion temperatures.
2. Experimental
2.1. Materials
Poly(vinylidene uoride) (PVDF) (Solef 6020/1001) was purchased from Solvay company, France. Glycerol triacetate (triacetin)
and ethanol was purchased from Sigma Aldrich; purity is more
than 99%. All materials were used as received without further
purication.


p
Pd
PK
PP
Pu
Qg
QL
R
rp,m
r1
r2
R
T

l
Vz
V
z

mean pressure, Pa
down stream pressure, Pa
gas permeance by Knudsen ow regime, mol m2
Pa1 s1
gas permeance by Poiseuille ow regime, mol
m2 Pa1 s1
upstream pressure, Pa
inlet gas ow rate, m3 s1
inlet liquid ow rate, m3 s1
universal gas constant, 8.314 J mol1 K1
mean pore radius, m
inner tube radius, m
outer tube radius, m
inner shell radius, m
absolute temperature, K
viscosity of gas, Pa s
velocity of uid inside the module in z-direction, m s1
average velocity, m s1
axial distance, m

Greek letters
q
polymer density, g cm3
w
membrane surface porosity
e
membrane porosity
n
dimensions module length, z/L
f
dimensionless module radius, r/R

2.2. Preparation of hollow ber membrane

Hollow ber membranes were fabricated using prepared
1000 g of dope solutions consist of 28% PVDF polymer and 72%
triacetin liquid solvent. Thermally induced phase separation
(TIPS) method was used for this purpose (Fig. 1). The dope solution was prepared and extruded at four different temperatures
(140, 150, 160, 170 C). The pore uid used was triacetin and
water as quenching tank uid. The mixture was kept at each
extrusion temperature for 3 h; 1 h under gentle mixing and 2 h
without mixing for degassing function. The uniform solution is
then extruded by gear pump under the pressure of nitrogen
(11.2 bars) through the spinneret to the quenching water tank
at room temperature and then winded by a take up winder rotated in a water trough. The spinneret outer and inner diameters
were 1.5 and 1.1 mm, respectively. The hollow ber membrane
spinning conditions is shown in Table 1. The solvent left over
in the hollow ber membrane was extracted by ethanol which
was removed by transferring the bers from ethanol tank into
distilled water container.
2.3. SEM observation
Samples of the bers where picked from the water bath where
membranes were stored, cut into pieces and then freeze-dried via a
freeze dryer (EYELA, FD-1000, Japan) to reach a dry hollow ber
membranes while keeping the membrane structure without deformation or shrinkage. Freeze-drying works by freezing the membranes and then reducing the surrounding pressure to allow the
frozen water in the material to sublimate directly from the solid
phase to the gas phase. The dried membranes were then fractured
in liquid nitrogen to obtain clear cross section and then sputtered
with gold coater (NeoCoater, MP-19020NCTR, Japan). The SEM
micrographs of the gold sputtered membranes were obtained via
scanning electron microscopy (JEOL, NeoScope JCM 5000, Japan).

N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

93

Fig. 1. Schematic diagram of the thermally induced phase separation (TIPS) process, (1) dope vessel, (2) bore liquid vessel, (3) gear pump, (4) bore liquid ow meter, (5)
spinneret, (6) quench tank, (7) water trough, (8) control panel, (9) N2 cylinder, (10) mixer, (11) pressure gauge.

Table 1
Hollow ber membranes spinning conditions.
Spinning parameters

Values

Dope composition
Extrusion temperature
Bore uid and solvent
Dope solution ow rate
Bore uid ow rate
Take up winder
Spinneret dimensions, OD/ID
Quenching bath temperature
Air gap

28%PVDF/72% triacetin
140, 150, 160, 170 C
Triacetin
5 g/min
7 g/min
10 rpm
1.5/1.1 mm
26 C
7 cm

The SEM micrographs for inner surface, outer surface and crosssection of the bers were taken at various magnications with
an accelerating voltage of 15 kV.
2.4. Strength of hollow ber membranes
The tensile stress of the hollow ber membranes were measured via autograph testing machine (Shimadzu Co. AGS-20NJ Series, Japan). A hollow ber membrane, length 100 mm, was xed
vertically between two pairs of tweezers separated by a gap of
80 mm. The ber was extended at a constant elongation velocity
of 20 mm/min until it was broken. The measurement for each type
of bers was repeated ve times, the averages of ve readings were
considered.
2.5. Contact angle measurement
Contact angle measurement is a method used to gain information about the hydrophilicity/hydrophobicity of the membrane
surface, if the solid surface is hydrophobic, the water contact angle
will be larger than 90. Highly hydrophobic surfaces made of low
surface energy (e.g. uorinated polymers such as PVDF, PTFE)
materials may have water contact angles as high as 120. Some

materials with highly rough surfaces may have a water contact angle even greater than 150, due to the presence of air pockets under
the liquid drop [30]. The inner and outer surface contact angle of
the hollow ber membranes was measured. The inner surface contact angle was measured because in the CO2 absorption process the
liquid solvent is owing in the lumen side of the hollow bers. The
inner surface contact angle was measured by gentle longitude cutting of the hollow ber using sharp blade. The inner surface of the
ber is exposed to sensible drop master (Kyowa Interface Science
Ltd., Japan) where the contact angle is measured. At least 5 points
were used for the contact angle measurement and the average value was calculated.
2.6. Measurement of critical liquid entry pressure of water (LEPw)
The LEPw is the lowest pressure necessary to force water
throughout the membrane pores and is used to evaluate the wettability resistance of the membrane. Water was sent to the lumen
region of the membrane by a diaphragm pump. The pressure, at
which the rst droplet of water appeared on the outer surface of
membrane, is the LEPw of the tested ber. The pressure of water
was increased gradually with a step size of 0.1 bars. LEPw depends
on the maximum pore size of membrane. The hollow ber membrane used in gasliquid membrane contactor application should
have enough resistance to penetration of liquid into membrane
pores (low wettability) to guarantee long term stability. The liquid
entry pressure was measured for this purpose using the unit similar to that used in the gas permeation test; except that the unit is
opened from both sides and water is owing instead of gas, a valve
at the exit of the membrane module is manipulated to maintain
desired pressure in the module.
2.7. Porosity measurements
Membrane porosity is measured for the gap in the structure of
membrane calculated by the relations presented by Chabot et al.
[31], and the membrane skin porosity (effective surface porosity)

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Fig. 2. Schematic diagram of gas permeation test unit.

employing the gas permeation test method (Fig. 2); the higher
membrane porosity, the higher membrane mass transfer coefcient. The membrane porosity is measured by immersing a number
of the prepared hollow ber membranes in water for quite a few
days to take away the remaining solvent and pack the pore with
water totally. Then, the water in the lumen side of the membranes
was detached by blowing air for a short period of time, and then
the length and the weight of the wet membrane were measured.
The membranes were dried at 4045 C overnight in an oven and
the length and weight of dried membranes were measured. Eq.
(1) was used for calculation of membrane porosity (e).
1

qm

 q1

qm

where qp is polymer density (1.78 g/cm3 for Solef PVDF 6020/

1001) and qm is membrane density which is calculated by:

qm

qp

G
1G
q 1  E

where qw is density of water (1 g/cm3), G is mass fraction of

polymer in the membrane and E is overall shrinkage of membrane
during drying, G and E are calculated by Eqs. (3) and (4),
respectively.

weight of dry membrane

weight of wet membrane

E 1  1  Sl3

3
4

where Sl the longitudinal shrinkage of the hollow ber is, was

obtained by:

Sl

length of wet membrane  length of dry membrane

length of wet membrane

The effective surface porosity for skin layer is measured using

gas permeation test method (Fig. 2). The hollow ber membranes
were cut into pieces, 30 cm in length, and packed into module.
One end of the hollow ber membranes bundle were blocked with
epoxy resin, and the end was bonded with shell walls and kept
open. The feed gas (He) at variable pressure 0.10.2 MPa was
blown through the shell side of the module and the volumetric
ow rate of the permeated gas through the walls to the inner tube
side is measured using soap ow meter and digital gas ow meter
as a double check. The feed gas pressure was controlled by a digital

pressure regulator. The equations used for calculating of the mean

pore size and the effective surface porosity are described by Li [32].
It was assumed that membrane pores are straight and cylindrical
in shape and permeation of gas is under the Poiseuille and Knudsen
ow regimes in parallel connection. The gas permeance under the
Poiseuille ow regime is given by:

Pp

1 r2p:m w

p
8l RT Lp

The gas permeance under Knudsen ow regime is:

Pk


0:5
2 8RT
r p;m w
3 pM
RT Lp

Hence, the total permeance of permeated gas is:

P Pk Pp


0:5
2 8RT
r p;m w
1 r2p;m w


p
3 pM
RT Lp 8l RT Lp

:
Linearization of Eq. (8) as a function of mean gas pressure p


P A Bp

where


0:5
2 8RT
r p;m w
3 pM
RT Lp

10

1 r 2p;m w
8l RT Lp

11

In the above equations, P is total gas permeance (mol m2 Pa1 s1), R is universal gas constant (8.314 J mol1 K1), T is absolute
temperature (K), M is molecular weight of gas (g/mol), rp,m is the
mean pore radius (m), l is viscosity of gas (Pa s), w is the surface
porosity (Ap/AT), where AP is area of pores and AT is total area of
 is mean presmembrane, and LP is effective pore length (m) and p
sure (Pa):


p



Pu Pd
2

12

where Pu is upstream pressure and Pd is downstream pressure.

Experimentally obtained gas permeance is plotted versus mean
pressure, which should result in a straight line. The intercept (A)
of the straight line with the ordinate and slope (B) are used in the

N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

following equations to calculate the mean pore size and the effective surface porosity.

r p;m


0:5
16 B 8RT

l
3 A pM

Lp

!
8lRT
B
r 2p;m

13

14

 plot, the mean

Using the intercept (A) and the slope (B) of P versus p
pore radius (rp,m) and effective surface porosity (w/Lp) is calculated.
The experimental is performed at room temperature.
It should be noted that the above approach is valid for the membrane skin layer. Consequently, the mean pore size and the effective surface porosity obtained by Eqs. (6)(14) are those for skin
layer [15].
2.8. Pore size measurements
Pore size and Pore size distribution were measured with mercury
porosimeter (AutoPore IV 9500 Automatic Mercury Porosimeter,
Micromeritics, USA). To perform an analysis, the sample was dried
in a shallow pan at 150 C for one hour then it was loaded into a penetrometer consists of a sample cup connected to a metal-clad, precision-bore, and glass capillary stem. The penetrometer was
sealed using grease and placed in a low pressure port, where the
sample is evacuated to remove air and moisture. The penetrometer
cup and capillary stem are then automatically backlled with
mercury. Excess mercury is automatically drained back into the
internal reservoir; only a small amount remains in the penetrometer. As pressure on the lled penetrometer increases, mercury intrudes into the samples pores, beginning with those pores of
largest diameter. Data are automatically produced using the low
and high pressure data points, along with values entered, such as
the weight of the sample, weight of the assembled penetrometer
with sample before low pressure analysis and the weight of the penetrometer loaded with mercury after low pressure analysis. The
AutoPore IV operating software generates tabular and graphical reports of percentage pore volume vs. diameter.

95

2.9. Gas absorption assessment

The membrane performance was tested by means of three
membrane modules prepared from self made hollow ber
membranes fabricated at three different extrusion temperatures
(150, 160 and 170 C). Each membrane module was constructed
by potting 6 hollow ber membranes in a shell (Perspex, 10 mm
in inner diameter, and 30 cm in length). The effective hollow ber
membrane length is about 26 cm. The experimental diagram apparatus is shown in Fig. 3. The membrane modules were operated at
xed operating conditions (Table 1). CO2 is present over a broad
range of concentration in the gas stream mixed with CH4. CO2 content is 530% by volume for crude natural gas, any CO2 gas concentration can be used as feed gas to the membrane contactor. The
increase in CO2 concentration resulted in an increase of CO2 ux,
as the increase in CO2 concentration led to the enhancement of
the driving force of the system [9]. In the present work the gas mixture consists of 9 vol.% CO2 and 91% CH4 was used as a feed gas and
was fed to the shell side at variable ow rate 10160 ml/min, 298 K
and atmospheric pressure. An aqueous sodium hydroxide solution
(0.5 NaOH) was used as absorbent and supplied to the lumen side
of the module at the ow rate of about 10 ml/min. Gas ow rate at
the inlet and outlet of the module was measured by mass ow controller (Alicat Scientic, range 0500 ml/min, Sable Systems International, Inc., USA) and the gas exit concentration was measured
using gas chromatography (Shimadzu, Japan). The liquid ow rate
is adjusted to 10 ml/min via single channel peristaltic pump (MiniPlus 3, Gilson, Inc., USA). The temperature was kept at 298 K, the
gas phase pressure was atmospheric, and the liquid phase pressure
was controlled about 0.05 atm higher than the gas phase pressure
by a liquid level controller placed about 50 cm above the upper end
of the membrane module. Steady state was reached about 30 min
after the start of the experiment.

3. Mathematical model
A steady state mathematical model that described the material
balance has been carried out on a shell-and-tube membrane contactor system [3336]. The membrane contactor consists of three

Fig. 3. Schematic diagram of the experimental apparatus used in CO2 absorption.

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Fig. 4. Schematic diagram of the hollow ber section used in the model equations.

segments: tube, membrane, and shell section. The gas mixture

(CO2 and CH4) ows through the shell side, whereas the solvent
ows through the tube side in a counter-current run as shown in
Fig. 4. The gas mixture is fed to the shell side (at z = L), while
the solvent go through the tube lumen side (at z = 0). Carbon dioxide is removed from the gas mixture by diffusing through the
membrane pores. The solubility of CH4 is negligible compared to
that of CO2 in aqueous NaOH, consequently, CO2 dissolved in
absorbent liquid and react with NaOH. The gas mixture leaves
the other side of membrane as pure methane. The percent removal
is affected by membrane morphology, CO2 solubility in the absorbent liquid, absorbent concentration, liquid and gas ow rates and
operating conditions.
The model is developed for a segment of a hollow ber, as
shown in Fig. 4, through which the solvent ows with a fully developed laminar parabolic velocity prole. The ber is surrounded by
a laminar gas ow in an opposite direction to that of the liquid.
Based on Happels free surface model [37], only portion of the uid
surrounding the ber is considered which may be approximated as
circular cross section. Thus, symmetry may be considered at the
outer portion of the uid surrounding the ber (at r = r3).

f r=R; n z=L
di;t Di;t =R2 ; di;m Di;m =R2 ; di;s Di;s =R2

ci;t Di;t =L2 ; ci;m Di;m =L2 ; ci;s Di;s =L2

ki;t V z =L; ki;s V z =L:
The velocity distribution in the tube side is assumed to follow
Newtonian laminar ow [38]:

"

V z-tube

 2 #
f
2V 1 
f1

18

The tube side boundary conditions are given as:

Solvent inlet side : n 0 C CO2 C CH4 0; C NaOH

500 mol=m3
Solvent exit side : n 1

@C i;t
0 convective flux
@n

@C i;t
0 axial symmetry
@f

3.1. Tube side (0 6 r 6 r1)

Tube center : f 0

Inside the hollow ber membrane, the basic steady state equations are as follows (1: CO2, 2: CH4, 3: NaOH):

Inner radius : f 1 C i;t mi C i;m i CO2 ; CH4 solubility

0 d1t

0 d2t

"
@ 2 C 1;t
@f2
"
@ 2 C 2;t
@f2

#
1 @C 1;t
@ 2 C 1;t
@C 1;t
c1t

 k1t
RCO2
2
f @f
@n
@n

15

#
1 @C 2;t
@ 2 C 2;t
@C 2t
c2t

 k2t
f @f
@n
@n2

16

0 d3t
where

@f

1 @C 3;t
@ 2 C 3;t
@C 3;t
c3t
 k3t
RNaOH
f @f
@n
@n2

21
22

The steady state material balance for the transport of CO2, CH4
inside the membrane, no reaction is taking place in this zone
(nonwetting mode).

"

"

17
0 d2m

@ 2 C 1;m
@f2

20

3.2. Membrane section (r1 6 r 6 r2)

0 d1m
"
@ 2 C 3;t

19

@ 2 C 2;m
@f2

#
1 @C 1;m
@ 2 C 1;m
c1m
f @f
@n2

23

#
1 @C 2;m
@ 2 C 2;m
c2m

f @f
@n2

24

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Table 2
Parameters used in the simulation of PVDF membrane contactor modules.
Parameter

Values

Reference
3

Inner tube diameter (m)

Outer tube diameter (m)
Inner module diameter (m)
Module length (m)
Total number of tubes
DCO2 ;tube (m2/s)
DCO2 ;shell (m2/s)
DCO2 ;mem (m2/s)
Dsolv ;tube (m2/s)
kNaOH (m3/mol s)
m 1=H ()
Porosity, e
Tortuosity, s

0.4  10
1.0  103
8  103
26  102
6
2.35  106 exp (2199/T))
1.855  106
DCO2 shell e=s
0:5  DCO2 tube
10(11.9162382/T)/1000
H = 2.82  106 exp (2044/T)/(RT)
Based on %PVDF used
(2  e)2/e

Measured by SEM
Measured by SEM
Measured
Measured
Measured
Versteeg and Van Swaaij [41]
Cussler [42]
Estimated
Estimated
Zanr et al. [43]
Versteeg and Van Swaaij [41]
Measured
Iversen et al. [44]

3.3. Shell side (r2 6 r 6 r3)

Table 3
Internal and external ber diameters.
Extrusion temperature, T (C)

ID (mm)

OD (mm)

150
160
170

0.42
0.39
0.38

1.0
1.1
1.1

The steady state material balance for the transport of CO2 and
CH4 in the shell side:

0 d1s

Boundary conditions are given as:

Membranetube interface : f f1

C CO2 ;m C CO2 ;t =mCO2

@f2
"
@ 2 C 2;s

#
1 @C 1;s
@ 2 C 1;s
@C 1;s
c1s
 k1s
f @f
@n
@n2

27

#
1 @C 2;s
@ 2 C 2;s
@C 2;s

 k2s
c2s
f @f
@n
@n2

28

25

0 d2s

26

Gas inlet side : n 1 C CO2 ;s C CO2 ;initial C CH4 ;s C CH4 ;initial

@f2

The boundary conditions:

Membraneshell interface : f f2
C i;m C i;s ; i; CO2 ; CH4

"
@ 2 C 1;s

29

Fig. 5. SEM micrographs of cross section, inner and outer surface of PVDF hollow ber membranes prepared at different dope temperatures 150, 160 and 170 C.

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Fig. 6. SEM micrographs cross section of PVDF hollow bers prepared from different dope temperature 150, 160 and 170 C.

Gas exit side : n 0

Free surface : f 1

@C i;t
0 convective flux
@n
@C i;t
0 symmetry
@n

Shellmembrane interface : f f2

30

31

C i;s C i;m

i CO2 ; CH4

extrusion temperature should be 30 C higher than the polymer

crystallization temperature [45], for such dope composition, the
current experiment revealed that extrusion temperature should
be at least 50 C higher than dope crystallization temperature to
successfully prepare high quality PVDF hollow ber membranes.
4.2. Physical characteristics

32

4. Results and discussion

Table 3 shows the internal and external diameters of PVDF

hollow ber membrane prepared from three different dope temperatures. The effect of extrusion temperature on ber inner and
outer diameter is insignicant since the same spinneret was used
at xed operating conditions. The only parameter varies is the
polymer extrusion temperatures.

4.1. Preparation of hollow ber membranes

4.3. Membrane morphology

Three of the four studied dope solutions were successfully produced hollow ber membranes, the solutions were prepared and
extruded at three temperatures (150 C, 160 C and 170 C), by
contrast, it was not possible to fabricate hollow ber membranes
at 140 C. The fail to prepare bers at 140 C is attributed to the
high dope viscosity at this operating temperature, the dope solution could not pass through the spinneret even under high nitrogen
pressure, accordingly, the experiment under this operating temperature was not doing well and be unsuccessful to fabricate hollow bers. The crystallization temperature of 28%PVDF/72%
triacetin is around 100 C, contrary to previously stated that the

Shown in Fig. 5 are SEM micrographs for the membrane cross

section, inner and outer surface of typical hollow ber membranes
prepared at three different extrusion temperatures (150, 160 and
170 C). The membranes had a microporous structure. The membrane porosity of the prepared membrane increased with extrusion
temperature as seen from the spherulites structure, where their
size increased with temperature, the increase in the particle size
increased the void volume between the particles and hence increased membrane porosity [46]. The dope polymer solution is
inuenced by the preparation temperature, as the dope temperature increased the viscosity of PVDF solution decreased, resulting

The parameters used in the simulation are shown in Table 2.

The simultaneous partial differential equations were solved using
software COMSOL [39,40].

Fig. 7. Membrane fabrication temperature versus membrane external and internal water contact angle.

N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

99

Fig. 8. Effect of extrusion temperature on break strain and stress.

in smooth polymer ow and forming smooth structures with uniform pore size. Fabrication of hollow ber membranes at temperatures lower than 150 C was not possible due to high polymer
viscosity at low dope temperatures. The spherulites size distribution varies from inner to external surface. Close to membrane outer
surface the membrane is denser and the size of the spherulites particles decreases with increases extrusion temperature (Fig. 6).
4.4. Membrane water contact angle
Measures of the hydrophobicity of the membrane surfaces were
done by using the water contact angle method. Water contact angles were measured by using sessile drop methods. The angle was
obtained from a sequence of images of the growing drop. The captured images were then analyzed. The result of all measurements
was taken from the mean of at least ten single measurements. In
the case of water, the membranes are said to be hydrophobic if
the contact angle exceeds 90.The hydrophobic property of PVDF

membranes were inuenced by membrane surface roughness

and porous surfaces of the membranes. The values of membrane
water contact angles of internal and external surfaces as a function
of extrusion temperature are shown in Fig. 7. Hydrophobicity of
the membranes plays an important role in reducing or eliminating
wetting problems from occurring during the CO2 absorption process. When the membrane was fully or partially wetted, the membrane resistance increased and the overall mass transfer coefcient
of the process is reduced. In order to eliminate the wetting problems, the membranes must have high hydrophobicity with contact
angles higher than 90. The gure revealed that high extrusion
temperatures lead to increase in membrane water contact angle.
4.5. Mechanical strength measurements
Fig. 8 shows the effect of dope extrusion temperature on the
break stress and break strain of PVDF hollow ber membranes. It
can be seen that the membrane strength increased by increasing

Fig. 9. Effect of extrusion temperature on membrane skin pore radius and effective surface porosity estimated using gas permeation test.

100

N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

dope extrusion temperature, this is attributed to the fact that,

increasing dope temperature forms dense skin layer on the membranes outer surface with smaller pore size.

is based on the assumption that the skin layer governs the gas transport. The mean pore size and the effective surface porosity obtained
by the gas permeation test approach are those for skin layer. The results revealed that as the dope temperature increased surface pore
radius decreased and effective surface porosity increased. This performance is accredited to fact that, close to membrane outer surface,
the size of the spherical clusters are lower than that in the bulk cross
section far from the outer membrane edges and a skin dense layer
exists close to outer surface due to solvent evaporation along the
7 cm air gap, the smaller the spherulites the lower the space between the cluster and hence decreased pore radius.

4.6. Pore size and effective surface porosity, membrane skin layer

4.7. Membrane porosity

The results for the effect surface porosity and pore size is shown
in Fig. 9. The results were obtained using gas permeation test which

As extrusion temperature increased membrane porosity increased. Spherulites diameter increased by increasing polymer

Table 4
Effect on extrusion temperature on percent membrane porosity measure with
mercury porosimeter.
Extrusion temperature (C)

Average pore diameter (nm)

Percent porosity

150
160
170

202
602
831

31.7
38.5
56.6

Fig. 10. Effect of extrusion temperature on LEPw.

Fig. 11. CO2 ux as a function of inlet gas ow rate for three model membranes using 0.5 M NaOH as liquid solvent, module membrane consists of six bers, module active
length: 260 mm, average membrane diameter: 0.4 mm, module inner diameter: 8 mm, pressure: 1 atm, temperature: 27 C (Table 2). Absorbent ow rate: 10 ml/min. Lines
are the model perditions.

N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

101

showed that as the extrusion temperature increased the lowest entrance pressure of water increased; that is attributed to the dense
layer formed at outer surface of the membrane which resulted in
decreased surface pore radius with increased extrusion temperature as a result of solvent evaporation through the long air gap.
Accordingly, high temperature and long air gap was useful increasing the critical penetration of water and therefore avoiding membrane wetting. In general, membrane overall porosity increased
with extrusion temperature, and the dense skin layer with low
pore radius protects the membrane from being wetted with the
absorbent liquid.

4.9. Performance tests for absorption of CO2 and model verication

Fig. 12. Surface plot of % removal of CO2, arrows represent velocity eld, gas ow
rate: 100 ml/min, liquid ow rate: 10 ml/min.

extrusion temperature due to the increase in the polymer concentration brought about by the evaporation of the solvent at the outer
surface. Thus porosity and permeability increased because the pores
form between the spherulites. SEM observations for cross section,
inner and outer surface of the membranes prepared in PVDF/triacetin system were shown in Fig. 5. Spherulites diameter increased and
large pores formed between spherulites by increasing temperature.
However, close to outer surface, skin layer is formed with small particle size, the effect of high temperature and long air gap (7 cm) resulted in much higher polymer concentration layer at the outer
surface. Thus, membrane lowest penetration pressure (LEPw) increased. The formation of the dense layer at the outer surface can
be attributed to the multitude spherulites that occur at high concentration of the polymer forming dense skin layer on membrane edges
[47,48]. Overall, the percent porosity and pore size increased with
polymer extrusion temperature (Table 4).
4.8. Lowest entrance pressure of water (LEPw)
Fig. 10 shows the relation between LEPw of membranes fabricated with various dope extrusion temperatures. The results

The CO2 ux at specic inlet gas ow rate increased with polymer extrusion temperature (Fig. 11). The mathematical model
equations were solved by COMSOL software package. The model
and experimental results were in good agreement. As the dope
preparation temperature increased spherulites cluster size increased (except at the membrane outer skin layer, spherulites
diameter decreased, membrane pore size decreased and effective
surface porosity increased), consequently the rate of CO2 absorption increased. The effect of membrane dense skin layer with temperature on mass transfer could be the negligible; the dense layer
was useful in increasing the lowest liquid penetration pressure,
which protects the membrane from being wetted with liquid solvent. Accordingly, the difference in CO2 absorption performance
mainly came from the inner structure of the membranes [7].
The mathematical model surface plot for the percent removal of
CO2 at inlet gas ow rate 100 ml/min and liquid absorbent ow of
10 ml/min is shown in Fig. 12. The gure shows complete removal
of CO2 at this gas ow rate was not possible. The increase in the
ux with inlet gas ow rate is due to increased molar amount of
CO2 being absorbed by the absorbent liquid per area per time.
Fig. 13 shows the Wilson plot of mass transfer resistance versus
V0.93, the results shows good t with V0.93. Similar trend was
found by Feng et al. [7]. The mass transfer resistance decreased
for membranes prepared at high polymer extrusion temperature.
The performance of PVDF membrane in contactor application
was compared with reference values as shown in Table 5. The
CO2 absorption ux of the current system can be considered
acceptable compared to other systems. For additional information

Fig. 13. Mass transfer resistance of three model membranes vs. V0.93.

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N. Ghasem et al. / Separation and Purication Technology 99 (2012) 91103

Table 5
Comparison of process performance of PVDF hollow ber membranes.
Membrane

Pore size (nm)

Liquid absorbent

Gas mixture

Process performance
2

1

Ref.
4

PVDF

200

Water

20:80
CO2:CH4

CO2 ux (mol m s ) = (416)  10

Kol (m s1) = (15)  105

PVDF

200600

AMP MEA

20:80
CO2:N2

CO2 ux (mol m2 s1) = (14)  104

Kol (m s1) = (18)  107

[49]

PVDF

5.66

Water

20:80
CO2:CH4

CO2 ux (mol m2 s1) = (15.4)  104

Kol (m s1) = (0.82)  105

[6]

PVDF

831

NaOH

9:91
CO2:CH4

CO2 ux (mol m2 s1) = (13.2)  103

Kol (m s1) = (13)  104

Current work

on the recent results using different kinds of membrane materials

and different solvents that are under research were reported by
Luis et al. [1].

5. Conclusion
Thermally induced phase separation method was successfully
employed to fabricate hollow ber membranes at three different
extrusion temperatures. It was found that extrusion temperature
should at least 50 C higher the polymer crystallization temperature in order to attain membrane with rational absorption performance. The fabricated membranes were characterized and tested
for the absorption of CO2 from natural gas. The results revealed
that fabrication at high extrusion temperatures resulted in better
quality membranes with high porosity, high strength and high removal efciency. High air gap resulted in dense skin layer at the
outer surface of the fabricated membrane. The intense skin cover
was useful in increasing the critical liquid penetration pressure
of water and avoiding wetting troubles. The experimental outcomes disclosed that increased extrusion temperatures improved
the membrane quality and hence increased the percent removal
of CO2.
Acknowledgements
The authors would like to acknowledge the nancial support
provided by the Japan Cooperation Center, Petroleum (JCCP), and
the technical support of the Nippon Oil Research Institute Co.,
Ltd. (JX-NRI).
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