Separation and Purification Technology 48 (2006) 229–234

Removing benzene from aqueous solution using CMS-filled PDMS

pervaporation membranes
Fubing Peng, Zhongyi Jiang ∗ , Changlai Hu, Yanqiang Wang, Haiquan Xu, Jiaqi Liu
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China

Received 21 March 2005; received in revised form 9 July 2005; accepted 18 July 2005

Abstract

The preferential permeation of benzene over water was achieved with carbon molecular sieve (CMS)-filled polydimethylsiloxane (PDMS)
pervaporation membranes. The membranes were characterized by SEM and mechanical strength measurement. The effects of CMS content,
benzene concentration in feed solution, operating temperature and feed Reynolds number on the pervaporation properties of the CMS-filled
PDMS membranes have been studied. The results showed that the addition of CMS could enhance the mechanical stress of PDMS membranes.
With CMS content increasing, permeation flux decreased slightly but separation factor increased to some extent. With the increase of benzene
concentration in feed solution and Reynolds number of feed, permeation flux and separation factor both improved significantly. With operating
temperature increasing, permeation flux increased but separation factor decreased.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Pervaporation; Carbon molecular sieve; Polydimethylsiloxane; Membrane; Benzene

1. Introduction found that pervaporation separation properties improved and

Pervaporation has become one of the most promising
candidates for low-cost separation process, especially for
separation of azeotropic or close-boiling liquid mixtures.
Its application fields can be found in: (a) dehydration of
organic/water mixtures; (b) removal or recovery of organic
compounds from water; (c) separation of organic/organic
mixtures.
Benzene that widely used in the chemical and petrochem-
ical industry is a toxic volatile organic compound (VOCs)
and is classified as the first substances [1] that should be
removed from the VOCs aqueous solution as completely as
possible. It has been reported that pervaporation has obvi-
ous technical advantages among many common separation
methods when the mass fraction of benzene in the aqueous
solution is 0.1–10% [2].
Polydimethylsiloxane (PDMS), as a membrane material
for the preferential permeation of organic compounds, has
been widely researched and developed. te Hennepe et al. [3]
∗ Corresponding author. Tel.: +86 22 27892143; fax: +86 22 27892143.
E-mail address: zhyjiang@tju.edu.cn (Z. Jiang).
mechanical stress also increased when zeolite was filled into
the PDMS membranes. From then on, people continue to
research the preparation and separation properties of filled
PDMS membranes [4–7].
Active carbon is widely used in adsorption separation of
organic compounds because of its high adsorption selectivity
and capacity toward most hydrophobic organic compounds,
and active carbon-filled polymeric membranes have been
reported [4,5]. Unfortunately, with the increase of active
carbon content, permeation flux usually decreased while sep-
aration factor did not increase and even decreased. Duval et
al. [4] suggested that the negative results were due to the
inherent closed pores in the active carbon. Alternatively, car-
bon molecular sieve (CMS) with appropriate pore size, nar-
row pore size distribution, in particular interconnected pore,
can potentially constitute ideal filler for PDMS membranes
[8].
In this article, pervaporation properties of CMS-filled
PDMS membranes for benzene removal from aqueous solu-
tion were studied. The effects of CMS content and operation
conditions such as benzene concentration in feed solution,
operating temperature and feed Reynold numbers on the

1383-5866/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.07.029
230 F. Peng et al. / Separation and Purification Technology 48 (2006) 229–234
pervaporation properties of the filled membranes had been
investigated.
2. Experimental
2.1. Materials
Polyimide (PI) film was purchased from Tianjin Insulating
Materials Co., Tianjin, China. Phenolic aldehyde (PA) resin
solution was purchased from Tianjin Chemical Co., Tianjin,
China. Benzene was supplied by Tianjin Jiangtian Chemicals
Ltd., Tianjin, China. All the chemicals were of reagent grade
and were used without further purification. Double distilled
water was used throughout the study.
2.2. Preparation and characterization of CMS
The phenolic aldehyde resin film was prepared by dip-
coating method and allowed to dry at room temperature.
The CMS was fabricated by pyrolysis of polyimide [9,10]
film and phenolic aldehyde resin [11,12] film, respectively,
at 1073–1103 K with a heating rate of 1–3 K/min under nitro-
gen atmosphere with gas flow rate of 10−6 m3 /min. The CMS
was allowed to cool to room temperature under nitrogen
atmosphere. The microstructure of the prepared CMS was
adjusted by gas oxidization method [13] using N2 /O2 (19/1,
v/v) mixed gas at 573 K for 2 h with a heating rate of 5 K/min
and was cooled to room temperature under N2 /O2 mixed gas
atmosphere. The CMS prepared from polyimide and pheno-
lic aldehyde resin was designated as PI-CMS and PA-CMS,
respectively. Another kind of CMS (PSA-CMS) was supplied
by Southwest Chemical Engineering Institute. After having
been smashed and sifted out, CMS was put in the drying chest
for future use.
Specific surface areas of the PSA-CMS, PI-CMS and PA-
CMS were determined by gas adsorption–desorption method
through CHEMBET-3000 Chemical Adsorption Instrument
(QUANTACHROME Co., USA), which used nitrogen and
helium as medium at 293 K. The results are shown in Table 1.
2.3. Preparation and characterization of the filled
PDMS membranes
The above three types of CMS have been pretreated for
their even dispersion in the membrane casting solution. 107
RTV silicone rubber, solvent (heptane), catalyst (dibutyltin
dilaurate) and cross-linking agent (tetraethyl orthosilicate)
were homogeneously mixed with 1:1:0.02:0.1 of weight ratio
Table 1
The specific surface areas and particle size of different CMS
PSA-CMS PI-CMS
(300 mesh) (300 mesh)
Specific area (m2 /g) 373.4 ± 7.5 30.5 ± 1.0
Particle size (␮m) <50 <50
to prepare PDMS casting solution. CMS was evenly dispersed
in PDMS casting solution under stirring for 1 h. Then the
casting solution was degassed for a certain period. The CMS-
filled PDMS paste was cast with a casting knife on organic
glass plate; thus the formed membrane was dried and cured at
room temperature for 24 h. Finally, membranes were peeled
off from the organic glass plate. The membrane thickness was
about 200 ± 10 ␮m determined by micrometer.
The membrane samples were fractured in liquid nitrogen
and then coated with gold to observe the cross-section struc-
tures by Hitachi X-650 SEM. The tensile measurements were
performed on ZLL-30 Stress Testing System for characteriz-
ing the mechanical strength of CMS-filled PDMS membrane.
2.4. Pervaporation experiment
Pervaporation experiments were performed on the P-28
membrane module (CM-Celfa AG Company, Switzerland).
The effective surface area of the membrane in contact with
the feed mixture is 28.0 cm2 . The vacuum in the downstream
side of the membrane was maintained (1 kPa) using a vacuum
pump. After a steady state (about 2 h) was obtained, permeate
were collected in cold traps immersed in the liquid nitrogen.
The compositions of benzene and water were determined by
gas chromatography (Agilent 4890, USA). The separation
properties of membrane were mainly evaluated by two typical
parameters of permeation flux and separation factor.
3. Results and discussion
3.1. Membrane characterization
3.1.1. SEM analysis
In order to investigate the distribution of CMS in the filled
membrane, SEM characterization of the filled membrane has
been carried out. As shown in Fig. 1, PSA-CMS-filled PDMS
membranes are dense with no connected macroscopic voids
and PSA-CMS dispersed uniformly within the PDMS matrix.
The CMS particles were well adhesive with PDMS due to
the good compatibility between nonpolar CMS particles and
nonpolar PDMS. Therefore, no nonselective defects voids
could be found at the interface between the PDMS and CMS
particles.
3.1.2. Effect of CMS content on the mechanical strength
of the filled membranes
As shown in Fig. 2, tensile measurement results illustrated
that incorporating CMS into PDMS significantly enhanced
mechanical strength of PDMS membranes. The elongation
of PSA-CMS-filled PDMS membranes increased with CMS
content increasing from 0 to 7.2 wt%, and decreased when
PA-CMS CMS content was larger than 7.2 wt%. The maximum of the
(300 mesh)
elongation 193.5% could be obtained when CMS content
167.5 ± 3.4 was 7.2 wt%. The tensile stress of the filled membrane
<50
has the same changing tendency as the elongation, but the
 F. Peng et al. / Separation and Purification Technology 48 (2006) 229–234
Fig. 1. The SEM photographs of cross-section of the PSA-CMS-filled
PDMS membrane.
231
Fig. 2. Effect of PSA-CMS contents on the strength of PSA-CMS-filled
membranes.
maximum value 89969 kg/m2 was obtained when CMS
content was 10.0 wt%.
The enhancement of mechanical stress for the CMS-filled
PDMS membranes may be explained that CMS with large
specific surface area can pull polymer chains closer and CMS
played a role as physical cross-linker. When CMS content
is lower than 7.2 wt%, PDMS constitutes continuous phase.
With the increase of CMS content, tensile stress and elon-
gation of the membrane both increase. When CMS content
is higher than 7.2 wt%, CMS particles can interconnect and
the continuity of PDMS in the membrane is destroyed. When
the degree of filling is too high, the network of the mem-
brane was severely spoiled and mechanical strength appears
to decline. Hence, there is an optimum CMS content in
the PDMS membranes for the enhancement of mechanical
performance.
3.2. Effect of CMS content on pervaporation properties
Since CMS and PDMS are both hydrophobic materials,
CMS-filled PDMS membranes can thus be used for separat-
ing benzene–water mixture by pervaporation. The pervapora-
tion properties of the membranes with different CMS content
are shown in Fig. 3. These results indicated that separation
factor was improved significantly by filling the CMS in the
PDMS membrane because of the favorable absorption prop-
erties of CMS towards benzene molecule.
232 F. Peng et al. / Separation and Purification Technology 48 (2006) 229–234

As shown in Fig. 3, the permeation flux decreased slightly

with the CMS content increasing. The incorporation of CMS
into PDMS membrane could enhance the sorption of ben-
zene in the membrane, but the distribution of CMS in mem-
brane increased transport resistance of both benzene and
water molecules. Therefore, permeation flux for CMS-filled
PDMS membrane was less than that for unfilled PDMS
membrane. Comparing PSA-CMS-filled and PA-CMS-filled
PDMS membrane, permeation flux and separation factor
were almost similar. The results indicated that the effect
of precursor types for CMS preparation on pervaporation
properties of CMS-filled PDMS membrane was negligibly
little.

3.3. Effect of feed composition on pervaporation

properties

The effect of feed composition for CMS-filled PDMS

membranes on permeation flux and separation factor at 313 K
is shown in Fig. 4. CMS-filled PDMS membrane exhibited
very high permselectivity towards benzene in the feed com-
position ranging from 364 to 931 × 10−6 kg (benzene)/kg
(H2 O).
Separation factor increased with benzene concentra-
tion increasing. Both total permeation flux and perme-

Fig. 3. Effect of CMS contents on pervaporation properties of filled-

membranes. Benzene concentration in feed solution: 4.40 × 10−4 kg (ben-
Fig. 4. Effect of benzene concentrations in the feed on pervaporation prop-
zene)/kg (H2 O), operating temperature: 318 K, permeate pressure: 800 Pa,
erties of filled-membrane PI-CMS. Operating temperature: 313 K, permeate
feed flow rate: 1.61 × 10−5 m3 /s.
pressure: 600 Pa, feed flow rate: 1.61 × 10−5 m3 /s, CMS content: 2.83 wt%.
 F. Peng et al. / Separation and Purification Technology 48 (2006) 229–234 233

3.5. Effect of feed Reynolds number on pervaporation

properties

The feed flow passage in P-28 membrane module is

rectangular slot with the size of 3.4 × 10−3 m for a and
3.3 × 10−3 m for b. Therefore, the equivalent diameter de
of the feed flow passage can be obtained from:
2ab
de = (1)
a+b
The feed velocity u can be calculated according to feed vol-
ume flow:
Vs (a + b)2
u= (2)
πa2 b2
According to equivalent diameter and feed velocity, feed
Reynolds number can be calculated by:
de uρ 2ρVs (a + b)
Re = = (3)
µ πµab
where the density and viscosity of feed are replaced with that
of pure water due to benzene concentration in feed is very
low.
As shown in Fig. 6, total permeation flux and benzene
permeation flux both increased with the enhancement of feed

Fig. 5. Effect of feed temperatures on pervaporation properties of filled-

membrane PSA-CMS (300 mesh). Benzene concentration in feed solution:
3.40 × 10−4 kg (benzene)/kg (H2 O), permeate pressure: 700 Pa, feed flow
rate: 1.61 × 10−5 m3 /s, CMS content: 5.14 wt%.

ation flux of benzene increased with benzene concentration

increasing, but permeation flux of water remained nearly
unchanged.

3.4. Effect of operating temperature on pervaporation

properties

The effect of operating temperature on pervaporation

properties of CMS-filled PDMS membranes is shown in
Fig. 5. It could be observed that permeation flux increased
significantly and separation factor decreased considerably
with operating temperature increasing from 303 to 323 K.
It could be also seen that the relationship of perme-
ation flux and separation factor obeyed the Arrhenius-type
relationship.
When operating temperature increased, vapor pressure of
benzene in the upstream side of membrane increased. Vapor
pressure difference between the upstream side and down-
stream side of the membrane increased the transport driving
force and thus resulted in enhancement of permeation flux
of components. Water molecule, whose molecular volume is
smaller than that of benzene, becomes much easier to diffuse Fig. 6. Effect of feed Reynolds number on pervaporation properties of filled-
membrane PSA-CMS (300 mesh). Benzene concentration in feed solution:
through the PDMS membranes, resulting in the decrease of 3.8 × 10−4 kg (benzene)/kg (H2 O), operating temperature: 318 K, permeate
separation factor. pressure: 600 Pa, CMS content: 5.14 wt%.
234 F. Peng et al. / Separation and Purification Technology 48 (2006) 229–234
Reynolds number, whereas water permeation flux decreased a
bit. Meanwhile, separation factor increased with the enhance-
ment of feed Reynolds number.
With the increasing of Reynolds number, the turbulence of
feed solution increased and the thickness of boundary layer
decreased, i.e., the extent of concentration polarization on
the upstream surface of membranes decreased. Therefore,
mass transfer resistance of boundary layer on the upstream
of membrane decreased, which led to the increase of total
permeation flux correspondingly. Since permeation flux of
benzene increased while permeation flux of water decreased
a little with increasing of Reynolds number, separation factor
increased with Reynolds number increasing.
4. Conclusions
The pervaporation properties of CMS-filled PDMS mem-
branes for benzene removal from aqueous solution had been
investigated. Incorporation of CMS into PDMS membranes
could improve the pervaporation properties of the membrane
to some extent, and the total permeation flux could be as
high as 264.5 g/m2 h when CMS contents was 2.83 wt% and
benzene concentration in feed is 931 × 10−6 kg (benzene)/kg
(H2 O). The incorporation of CMS simultaneously increased
the mechanical strength of PDMS membranes, and the ten-
sile stress could reach 89969 kg/m2 when CMS content was
10.0 wt%. Permeation flux decreased slightly but separation
factor increased with CMS content increasing, and perme-
ation flux increased but separation factor decreased with
operating temperature increasing. Total permeation flux, per-
meation flux of benzene and separation factor all increased
with the increase of benzene concentration in feed solution
and feed Reynolds number.
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