Journal of Membrane Science 280 (2006) 815–823

Blended chitosan and polyvinyl alcohol membranes for the

pervaporation dehydration of isopropanol
A. Svang-Ariyaskul ∗ , R.Y.M. Huang ∗∗ , P.L. Douglas, R. Pal, X. Feng, P. Chen, L. Liu
Department of Chemical Engineering, University of Waterloo, Waterloo, Ont., Canada N2L 3G1
Received 22 April 2005; received in revised form 24 February 2006; accepted 1 March 2006
Available online 27 June 2006

Abstract
Homogeneous membranes were prepared by casting the solution of blended chitosan and polyvinyl alcohol (PVA) on a glass plate. The percent
weight of chitosan in the membrane was varied from 0 to 100%. The membrane thickness was in the range of 15–30 ␮m. The membranes were
heat treated at 150 ◦ C for an hour. After that the membranes were crosslinked by glutaraldehyde and sulfuric acid in acetone aqueous solution.
The membranes were tested at 30–60 ◦ C for dehydration performance of 50–95% isopropanol aqueous solutions. At around 90% of isopropanol
in the feed mixture, permeate flux increased whereas the percent of water in permeate tended to decrease when the feed temperature increased
for all membranes, except that the water content in permeate from the membrane containing 75 wt.% chitosan remained constant. The swelling
degree in water and the total flux increased with increasing chitosan content in membranes. The effect of temperature on permeate flux followed the
Arrhenius relationship. The permeate flux decreased when isopropanol in the feed increased for all membranes. However, water content in permeate
and isopropanol concentration in the feed formed complex relationship for different chitosan content membranes. Sorption did not appear to have
significant effects on separation. The membrane containing chitosan 75% performed the best. For a feed solution containing 90% isopropanol at
60 ◦ C, the permeate flux was 644 g/m2 h with water content of nearly 100% in the permeate. At 55% isopropanol in the feed at 60 ◦ C, the permeate
flux was 3812 g/m2 h. In the range of 55–95% of isopropanol in the feed, the water content in permeate was more than 99.5%. This membrane
showed very excellent performance with good mechanical strength. It is promising to develop this membrane for industrial uses.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pervaporation; Dehydration of isopropanol; Chitosan; Polyvinyl alcohol; Blended membrane

1. Introduction conductor industries [6]. Isopropanol is also more effective than

Pervaporation is a very high potential industrial process to
separate liquid mixtures especially dehydration of organic sol-
vents [1–3]. The best developed application is for the dehy-
dration of water–alcohol mixtures [1,2,4,5]. Dehydration of
isopropanol has received great attentions from industries due
to the price of isopropanol and its uses in various industries.
Isopropanol is generally used as solvent for oils, gums, waxes
and variety of cosmetics and as a cleaning agent in the semi-
∗ Corresponding author. Present address: School of Chemical & Biomolecular
Engineering, Georgia Institute of Technology, Atlanta GA 30332 USA;
Tel: 1 404 894 8477; Fax: 1 404 894 2866.
∗∗ Corresponding author. Tel.: +1 519 888 4567x3399;
fax: +1 519 746 4979.
E-mail addresses: apichit.s@chbe.gatech.edu (A. Svang-Ariyaskul),
ryhuang@engmail.uwaterloo.ca (R.Y.M. Huang).
ethanol for the medical applications.
As a hydrophilic material for pervaporation membranes, chi-
tosan has drawn a great attention in past decade [7–20]. In
addition to its high hydrophilicity, the good film forming prop-
erty, high mechanical strength, and chemical resistance make
chitosan very promising material. Besides, chitosan is a low cost
material that can be produced from chitin. Chitin can be found
from crustacean shells, which are waste from seafood industries.
Chitosan is a cyclo-aliphatic polymer; it contains active amino
groups and hydroxyl groups that can form hydrogen bonds with
water. Because of these two active function groups, chitosan can
be chemically modified. Chitosan can be crosslinked by several
chemicals such as glutaraldehyde [9,15,21,22], formaldehyde
[14,17,18,23], sulfuric acid [17,18,24], and multicomponent car-
boxylic acid [8].
Polyvinyl alcohol (PVA) is used as the first material for
pervaporation membranes for separation of water–ethanol mix-

0376-7388/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.03.001
816 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823
Fig. 1. Structures of chitosan and PVA.
tures [1–3]. The composite membrane was produced by GFT
(Gesellschaft für Trenntechnik). The PVA membranes also have
been widely used in various pervaporation dehydration appli-
cations in industries such as dehydrations of alcohols, esters,
acids, and volatile organic compounds [5]. PVA is an aliphatic
polymer containing hydroxyl groups. PVA can be crosslinked by
glutaraldehyde [25] and multicomponent carboxylic acids [8].
Structures of chitosan and PVA are illustrated in Fig. 1.
Blended polymer membranes are widely studied for perva-
poration dehydration. Blends of two oppositely charged poly-
mers form high density membrane structure and can result in
higher selectivity of membranes [10]. The examples of blended
polyelectrolyte membranes for pervaporation dehydration of
alcohols are blended chitosan and polyacrylic acid membranes
[10,12] and blended chitosan and sodium alginate membranes
[19]. However, it is well known that blending polyelectrolyte
materials causes a precipitate or coacervate in an aqueous
medium resulting from electrostatic interaction between two
charges [10]. The formation of heterogeneous solution prohibits
the possibility of uniform membrane synthesis.
Membranes from blended polymers, which are not oppositely
charged, are also widely studied [8,17,18,26,27]. The blend
properties of polymer possess the intrinsic chemical, physical,
mechanic, and morphological properties of each polymer. The
advantages from each polymer can be combined by blending
two polymers.
Membranes based on either chitosan or PVA for dehydration
of organic solvents have been studied. Chanachai, Jiraratananon,
and associates [17,18] reported a good pervaporation perfor-
mance for dehydration of alcohol by using blended membranes
of chitosan and hydroxyethylcellulose crosslinked by formalde-
hyde and sulfuric acid. The total permeation flux was not very
high but the selectivity was excellent. The Vauclair group [26]
investigated the use of blended PVA and poly(acrylic acid-co-
maleic acid) membranes for pervaporation dehydration of light
oils (mixtures of alcohols containing carbon from two to five
atoms in a molecule). Water content in permeate from their work
was higher than 90 wt.% for the range of 13.4–68.7 wt.% feed
water. However, the total flux was also quite low. Rhim and asso-
ciates [27] conducted the research on pervaporation dehydration
of ethanol by using metal-ion-exchanged blended PVA and sul-
fosuccinic acid membranes. Good pervaporation performance
was reported. The Wu group [8] successfully studied the perfor-
mance of composite membranes of blended chitosan and PVA
cast on top of polysulfone ultrafiltration membranes crosslinked
by multifunctional carboxylic acid for dehydration of ethanol.
The selectivity was quite high but the total flux was not high
enough. They found that the mechanical strength, stability, and
resistance to water of the blended membranes were better than
those of pure PVA membranes.
The polymer membrane density can be increased by anneal-
ing under heat for a certain period of time [30]. Annealing helps
increase the thermal stability of the membrane. Nawawi and
Huang [11] annealed chitosan membranes at 150 ◦ C for 1 h to
increase the membranes stability. Membranes of this study were
heat treated at the same conditions as Nawawi and Huang [11].
Glutaraldehyde is an effective crosslinker for chitosan
membranes. There are a number of research groups
[9,13,15,17,21,22,29] using glutaraldehyde to crosslink chitosan
membranes for pervaporation dehydration and their membranes
performed very well. Lee et al. [13] reported that chitosan
composite membranes crosslinked by glutaraldehyde showed
higher selectivity and flux than those crosslinked by glyoxal and
terephthaldehyde thanks to higher flexibility of glutaraldehyde.
Glutaraldehyde (HCO–C3 H6 –CHO) consists of two aldehyde
groups (CHO), which can be attached to amino groups (NH2 )
in chitosan and hydroxyl groups (OH) in chitosan and PVA.
Crosslinked PVA membranes for pervaporation dehydration by
gluaraldehyde performed well [25,28]. Thus, glutaraldehyde
was used as the crosslinker in this study. Sulfuric acid per-
formed as catalyst [13,15,25] and an ionic crosslinking agent
for chitosan [13,14,16].
Due to the excellent properties of chitosan and PVA for per-
vaporation dehydration applications [8], blends of chitosan and
PVA were modified and further investigated to produce a promis-
ing membrane for industrial applications.
2. Experimental
2.1. Materials
Chitosan flakes (Flonac-N) with MW of 100,000 (99% N-
deacetylation degree) were obtained from Kyowa Technos,
Chiba, Japan. Polyvinyl alcohol (99% hydrolized) with MW
of 133,000 was purchased from Fischer Science, Canada. All
other chemicals – isopropanol, acetic acid (glacial), acetone,
glutaraldehyde, and sulfuric acid – were obtained from BDH,
Toronto, Canada. Deionized water was produced by the Univer-
sity of Waterloo, Waterloo, Canada.
2.2. Membrane preparation
Chitosan was dissolved in deionized water with 2 wt.% acetic
acid to form 1 wt.% chitosan solution. Chitosan solution was fil-
tered to remove undissolved particles and impurities. Ten weight
percent PVA aqueous solution was prepared by dissolving PVA
into water at 100 ◦ C. Chitosan and PVA solutions were mixed
in different proportions under stirring for at least 24 h to make
sure that the new solution was completely homogeneous. The
membrane abbreviations were listed in Table 1.
Solutions were then degassed in a vacuum chamber. The
solutions were poured into a block and dried in the ambient
 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823
Table 1
Abbreviations of blended chitosan and PVA membranes
Abbreviation Wt.% in the membrane
Chitosan PVA
CS 100 0 tion in the solution-diffusion models. The dry membrane weight
CSPVA7525 75 25
CSPVA5050 50 50
CSPVA2575 25 75
PVA 0 100
conditions. The membranes were annealed at 150 ◦ C for an
hour. Then, the membranes were immersed into the crosslinking
solution consisting of 1.5 wt.% glutaraldehyde (GA), 0.5 wt.%
sulfuric acid, 48 wt.% of acetone and deionized water for 25 min.
Membranes were dried under ambient conditions. The thick-
ness of the dried membranes was 18–25 ␮m. By heat treatment,
PVA can be thermally crosslinked. The chemical and thermal
crosslinking reactions are described in the Fig. 2.
2.3. Pervaporation
The isopropanol concentration in the feed for pervaporation
dehydration ranged from 50 to 95 wt.%. The feed temperature
was kept at 60 ◦ C for the studies of feed concentration effects.
For the studies of feed temperature influences, the feed tem-
perature was varied from 30 to 60 ◦ C at the feed isopropanol
content of 90 wt.%. The experiment was repeated at least twice
in order to reduce the experimental inaccuracies for each mem-
brane in pervaporation. Two pieces of each membrane (i.e.
CSPVA7525) were tested to confirm the reproducibility of the
membrane. Experimental results were averaged to be evaluated.
Average absolute difference of permeate flux for each condition
was less than 5% and of permeate water concentration was less
than 2%.
Fig. 2. Chemical and thermal crosslinking reactions for blended chitosan and
PVA membranes.
817
2.4. Sorption
Sorption experiment was conducted to determine the solubil-
ity of water and isopropanol in the membranes at equilibrium
state. Sorption is one of the control steps in pervaporation separa-
was measured. The blended membranes of chitosan and PVA
were soaked into various concentrations of isopropanol solu-
tions for at least 3 h to reach equilibrium at room temperature.
The membranes were carefully blotted off the liquid at the sur-
face with tissue paper as quickly as possible to remove the excess
liquid and wet membranes were weighed. The liquid adsorbed in
the membranes was collected and analysed for the liquid com-
position by gas chromatography. The swelling degree of the
membrane was calculated by the following.
swelling degree = [weight of liquid adsorbed]
× 100/[weight of dry membrane].
For sorption, experiment was repeated at least four times due to
scatter of weight of liquid adsorbed in the membrane. At least
four measurements were used to calculate the average. However,
the water concentration in the adsorbed liquid was very close to
one another. Experimental results were averaged to be evalu-
ated. Average absolute difference of weight of liquid adsorbed
for each condition was less than 10% and of adsorbed water
concentration was less than 3%.
3. Results and discussions
3.1. Effects of feed concentration
As can be seen from Fig. 3a, the rise of isopropanol
feed composition resulted in the reduction of total perme-
ate flux. This is very typical in the dehydration by perva-
poration. This is because the increase of water feed con-
tent elevates the membrane swelling degree and consequently
leads to the rise of mass transport. For the isopropanol
feed composition from 50 to 95 wt.%, generally the total
permeation rate ranged from the maximum to the mini-
mum is CS > CSPVA7525 > CSPVA5050 > CSPVA2575 > PVA
membranes. However, at high concentrations of feed iso-
propanol, the higher the PVA ratio in the membrane, the lower
the water concentration in permeates. That some points in Fig. 3b
did not meet these explanations should be due to experimental
errors. This could be due to the structure of PVA and chitosan.
PVA is aliphatic hydrophilic polymer but chitosan is cyclo-
aliphatic hydrophilic polymer. Therefore, PVA structure is more
compact than that of chitosan.
At lower isopropanol feed concentrations (<80 wt.%), the
CSPVA5050 membranes showed the highest total flux. The rea-
sons are not quite obvious. However, one of the explanations
could be from the fact that the combination of chitosan and
PVA in the CSPVA5050 membrane formed a loose polymer
network. If a membrane consists of only one component such
as chitosan or PVA, the polymer matrix formed should be more
condensed. The CSPVA5050 membrane structure could form
818 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823
Fig. 3. Effects of concentration on (a) total flux, (b) water content in the permeate
at 60 ◦ C.
the least condensed polymer network because the equal weights
of two polymers were combined. The intrinsic structure proper-
ties of PVA and chitosan do not show dominant effects on total
permeate flux at high isopropanol feed content (>80 wt.%) but
they do at low isopropanol content (<80 wt.%). The details can
be found in topic 3.2.
Based on Fig. 3b, water content in permeate from
CSPVA7525 remained constant over the whole range and was
over 99.7 wt.%. It suggests that the swelling degree of the
membrane did not affect the selectivity of CSPVA7525. The
water concentration in permeate from the CSPVA5050 mem-
brane gradually increased with an increase in isopropanol feed
content from 70 to 95 wt.%. This could result from the fact
that the swelling degree of the membrane is reduced by the
increase in feed isopropanol content. Eventually, the coupling
mass transport decreases and it brings about the increase of water
permeation. It is in the opposite direction for the water content
in permeate from other membranes: CS, PVA, and CSPVA2575.
Water concentration in permeate decreased gradually when the
isopropanol composition in the feed mixture increased from 50
to 95 wt.%. This could attribute to the fact that the increase
in isopropanol feed concentration enhances the driving force
for isopropanol transport across the membrane. However, this
behaviour does not show the important effects because the water
content in permeate does not change significantly.
Fig. 3a and b showed a complicated relationship between the
total and partial permeation and water content in permeate with
isopropanol feed concentration from membranes with different
ratio of chitosan and PVA. The detail explanation will be dis-
cussed in topic 3.2.
3.2. Effects of chitosan ratio in the membranes on the
pervaporation performance with various isopropanol feed
concentration
Fig. 3a and b show the effects of the membrane composi-
tion on the pervaporation performance – flux and water con-
tent in permeate – at 60 ◦ C for the separation of isopropanol
(90–95 wt.%). At 90 and 95 wt.% isopropanol in the feed, total
flux increased gradually with the chitosan content in the mem-
brane. It confirmed the explanation previously about the effects
of chitosan composition that the higher chitosan in the mem-
brane, the higher the total permeation flux. At 80 wt.% feed
isopropanol, the total flux tended to increase with the chitosan
content but the maximum total flux was at 50 wt.% chitosan. As
described before, it is believed the least compact structure of
polymer blends from the CSPVA5050 membrane enhances the
mass transport across the membrane.
Wu et al. [8] studied the pervaporation dehydration of ethanol
by using blended chitosan and PVA membranes on polysulfone
ultrafiltration support. The membranes was crosslinked by mul-
tifunctional carboxylic acid and heated at 80 ◦ C. They observed
almost the same tendency of total flux versus chitosan com-
position at 96 wt.% isopropanol feed content and 50 ◦ C. From
their studies, the total flux increased gradually but the selectivity
decreased sharply when the chitosan content in the membrane
increased.
The change of water permeate content upon isopropanol
feed concentration from this study was different from Wu and
associates’ work and it was complicated. From this work, the
maximum water permeate content was from the CSPVA7525
followed by CS, CSPVA5050, PVA and CSPVA2575 mem-
branes respectively. From this point, it is believed that the
structure of polymer did not influence the selectivity directly
because the highest water concentration in permeate was not
from the PVA membrane which is more compact than the CS
membrane. It points out that a more compact membrane is not
necessary to yield a higher selectivity. The other two points are
the hydrophilicity and alignment of polymer chains in the poly-
mer matrix.
The hydrophilicity of chitosan relies on its hydroxyl groups
(OH) and amino groups (NH2 ) while that of PVA depends upon
only hydroxyl groups (OH). According to Fig. 1, there was a 2/7
hydroxyl group and a 1/7 amino group per carbon in chitosan and
a 1/2 hydroxyl group per one carbon in PVA. Oxygen has higher
electro negativity than nitrogen. Therefore, a hydroxyl group can
form stronger hydrogen bonds with water (H2 O) than an amino
group. However, OH can also form stronger hydrogen bonds
with isopropanol (C2 H5 OH). This could be one reason why
membranes with a higher content of chitosan (50–100 wt.%)
in the polymer produced higher water permeation fluxes. How-
ever, as can be seen in Fig. 2, a certain amount of hydroxyl
groups in PVA was changed to be an ether group (–O–) by ther-
mal crosslinking between PVA monomeric units. The increase
of thermal crosslinking degree leads to the rise of membrane
 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823 819

hydrophobicity. It could be another source that made the higher

PVA content (75–100 wt.%) in membranes less hydrophilic.
The alignment of polymer chains in the polymer network
also plays a crucial role in the separation performance. This is
essential because it is the consideration of the entire membrane
property not the structure of one component polymer. The mor-
phological structures of polymer network highly influence the
free volume in the matrix and eventually affect the solubility and
diffusivity of feed components through the membranes.
From Fig. 3a and b, total flux from the PVA membrane was
lower but the water content was higher than those from the
CSPVA2575 membrane. It suggests that the PVA membrane
is more condensed than the CSPVA2575 membrane. This could
be attributed to polymer network of PVA membrane since it
is more condensed. The insertion of small amount of chitosan
(25 wt.%) could make certain parts of PVA compact network dis-
torted and lead to higher free volume in the network. The further
increase of chitosan in a membrane allows higher mass transport
of water across membrane. As can be seen from Fig. 3b, water
content in permeate increased sharply when chitosan composi-
tion in a membrane increased from 25 to 75 wt.%. Even though
the polymer matrix of CSPVA2575 membranes is likely to be
more compact than that of CSPVA5050 membranes, both total
flux and water concentration in permeate from the CSPVA5050
Fig. 4. Effects of feed temperature on (a) total flux and (b) water content in
membrane were higher than those from the CSPVA2575 mem- permeate at isopropanol feed concentration of 90 wt.%.
brane. This could be due to the fact that chitosan is more water
permselective than PVA under the treatment conditions in this
study. This explanation is the same as that for the higher total However, due to the increase of water concentration gradient,
flux and permeate water concentration from the CSPVA7525 it enhances water transport across the membrane. That is why
membrane than that from the CSPVA5050 membrane. However, permeate water concentration of CSPVA7525 and CSPVA5050
permeate water content from the CS membrane was lower but membranes remained almost constant. This is a kind of trade-off
the total flux was higher than those from the CSPVA7525 mem- results and makes the water content in permeate not change upon
brane. This could be because of the fact that polymer matrix of feed concentration in the range of 90–95 wt.% isopropanol.
the CSPVA7525 membrane is more condensed than that of the
CS membrane. It is possible that the PVA chains fill in free vol- 3.3. Effects of temperature on pervaporation performance
ume amongst chitosan rings and this leads to higher density of
polymer network in the CSPVA7525 membrane. The right pro- As can be seen from Fig. 4a, the total permeation increased
portion of chitosan and PVA in a membrane will result in the best with feed temperature for all five membranes at 90 wt.% feed
selectivity. Thus, in this case, the CSPVA7525 membrane is the isopropanol. It could be due to the fact that the increase of feed
best. Also, the permeate flux from the CSPVA7525 membrane temperature elevates the polymer thermal mobility and conse-
was the second highest and not so much lower than that from quently leads to the rise of mass transport across the membrane.
the CS membrane, the highest flux. In short, the CSPVA7525 The other source of this behaviour is the change of penetrants’
membrane performs the best pervaporation separation amongst diffusivities. Increasing temperature brings about higher molec-
other membranes. ular diffusivity [31–34]. Higher diffusivity allows molecules to
Interestingly, Fig. 3b suggests that CSPVA7525 and penetrate through membrane faster and results in an increase of
CSPVA5050 membranes swelled significantly compared to the total flux. In addition, the increase of feed temperature could
other membranes. If the membranes do not swell, the permeate result in earlier phase transition of liquid inside the membrane
water increases with the increase of feed water. This is because because the required enthalpy for the transition reaches faster
of the rise of a driving force across membrane, in this case, water when there is more heat supplied. The diffusivity of vapour is
concentration gradient. As can be seen from Fig. 3b, water in higher than liquid; therefore, the mass transport is faster and the
permeate from CS, PVA, and CSPVA2575 membranes increased total flux increases. Moreover, from Fig. 4a, the higher percent
when the water in the feed mixtures increased. It implies that content of chitosan in membrane allowed higher permeation at
there is no important swelling effect from these membranes. high isopropanol feed composition in accordance with the ear-
In contrast, permeate water from CSPVA7525 and CSPVA5050 lier explanation. Fig. 4a shows that total flux increased when
membranes was almost constant with the change of feed concen- chitosan proportion in the membrane increased.
tration. If membranes swell importantly, permeate water concen- According to 4b, water content in permeate remained
tration decreases or while feed water concentration increases. constant upon the change of feed temperature from CS,
820 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823

CSPVA7525, and CSPVA5050 membranes while that from Table 2

CSPVA2575 and PVA membranes decreased with the increase of Activation energy of total and partial permeation of each membrane at feed
solution of 90 wt.% isopropanol
feed temperature. It infers that water content in permeate mem-
branes with high chitosan percentage (50–100 wt.%) tended to Membrane type Activation energy (kJ/mol)
be constant while that from membranes with high PVA com- ET EW EIPA EW − EIPA
position (75–100 wt.%) tended to decrease with the feed tem-
CS 18.69 18.66 2.96 15.70
perature. For CSPVA2575 and PVA membranes, the decrease of CSPVA7525 16.44 16.44 – –
water content in permeate upon feed temperature could be due to CSPVA5050 38.81 33.70 38.23 −4.53
the fact that the increase of thermal mobility of polymer chains CSPVA2575 40.43 39.59 56.23 −16.64
allows both water and isopropanol transfer across membrane PVA 41.13 40.05 75.01 −34.96
easier and eventually the selectivity is reduced.
Fig. 4a shows that the total flux following the Arrhenius rela-
tionship with feed temperature. The Arrhenius relationship is the difference of activation energy from water and isopropanol
expressed in Eq. (1). permeations decreased when PVA composition in the mem-

 brane increased. This confirms that the increase of PVA content
−Ep in the membrane reduces the permeability of both water and
J = Ap exp . (1)
RT isopropanol through the membrane. Higher activation energy
means that molecules require higher energy to penetrate through
Water and isopropanol permeation also performed Arrhenius the membrane; however, higher activation energy is only one
relationship with feed temperature according to Fig. 5a and b. factor. The explanation of another factor, the influences of pre-
The permeate from CSPVA7525 membrane contained more than exponential factor, will be described later in this section.
99.999% water. The amount of water flux was almost equal to In addition, activation energies of total and water permeations
the total flux. It means that the water permeation controlled over were very close as shown in Table 2. It suggests that water
the total permeation. flux has a control of total flux. Except for the CS membrane,
Table 2 shows activation energy for total and partial perme- activation energy for isopropanol permeation was higher than
ation and the difference of activation energy from water and that for water permeation. It implies that water consumes less
isopropanol permeations. The activation energies were calcu- amount of energy for permeation and has higher permeability
lated from Eq. (1). Generally, as can be seen from Table 2, than isopropanol. Eq. (2) shows the water content in permeate
activation energy for total and partial permeation was higher and as a function of feed temperature. This equation does not offer
the exact number that corresponds to the experimental results
due to the existence of experimental errors.
1
yW =  . (2)
AIPA EW −EIPA
1+ AW exp RT

Positive value of EW − EIPA means that water content in perme-

ate increases with temperature while the negative value means
that permeate water content decreases with temperature. The val-
ues from CSPVA5050, CSPVA2575, and PVA membranes were
negative and water content in permeate from these membranes
decreased with temperature according to Fig. 4b. However, from
Fig. 4b, water permeate content from the CS membrane did not
change with feed temperature but the value of EW − EIPA was
positive. This could be because of the experimental errors plus
the effects of pre-exponential factor in Eq. (1).

3.4. Sorption effects

Sorption is the other significant step other than diffusion in

Fig. 5. Arrhenius relationship between (a) water flux and feed temperature and
(b) isopropanol flux and feed temperature at isopropanol feed concentration of
90 wt.%.
solution-diffusion models. This section is to determine the influ-
ences of sorption in pervaporation performance. According to
Fig. 6a, the swelling degree of the membrane increased when
the isopropanol content in the solution decreased. This is due
to the fact that all membranes are highly hydrophilic and this
characteristic results in the increase of solution adsorbed in the
membrane when water concentration in solution increases. At
35, 75, and 100 wt.% isopropanol in the solution, the membrane
 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823
Fig. 6. Effects of chitosan composition in membranes on (a) swelling degree
and (b) amount of water adsorbed in membranes.
swelling degree remained the same over the change of chitosan
content in a membrane while at 100 wt.% water, the swelling
degree increased with the increase of chitosan composition in a
membrane. It suggests that the proportion of chitosan and PVA
in a membrane only affects the membrane swelling behaviour in
pure water. It implies that all membranes are highly hydrophilic
because the existence of isopropanol does not allow the mem-
branes with various chitosan composition to swell differently.
However, in pure water, membranes with higher proportion of
chitosan swelled in a higher degree. This could be because of
the intrinsic properties of chitosan that its structure is looser than
that of PVA.
Fig. 6b confirms that all membranes are highly hydrophilic
because in both 35 and 75 wt.% isopropanol aqueous solutions,
water adsorbed in the membranes was higher than 80%. The
change of adsorbed water concentration had an interesting rela-
tionship with chitosan content in membranes in both 35 ant
75 wt.% isopropanol solutions. The amount of water adsorbed
in 75 wt.% isopropanol solution was higher than in 35 wt.% iso-
propanol solution at lower chitosan contents (0 and 25 wt.%).
This could result from that at higher water concentrations, the
membrane swells to a higher degree and it consequently results
in the increase of free volume in polymer matrix. It implies that
coupling transport has a high influence on mass adsorption in
PVA and CSPVA2575 membranes. Therefore, solution adsorbed
had higher concentration of both water and isopropanol. At
higher chitosan content (50, 75, and 100 wt.%), adsorbed water
concentration increased and reached the peak at 75 wt.% chi-
tosan in 35 wt.% isopropanol solution while an amount of water
adsorbed in 75 wt.% isopropanol solution decreased and reached
the lowest point at 75 wt.% chitosan. Amount of water adsorbed
821
Table 3
Pre-exponential factor of total and partial permeation of each membrane at feed
solution of 90 wt.% isopropanol
Membrane type Pre-exponential factor (g/m2 h)
AT AW AIPA AIPA /AW
CS 13.38 13.35 2.96 0.22
CSPVA7525 12.29 12.29 – –
CSPVA5050 18.68 18.62 16.59 0.89
CSPVA2575 20.35 19.97 23.34 1.17
PVA 20.23 19.78 29.48 1.49
in 35 wt.% isopropanol solution was higher than that in 75 wt.%
solution.
This is due to the fact that 35 wt.% solution contains a higher
amount of water; hence, water has a higher driving force than iso-
propanol and this forces membranes to adsorb less isopropanol.
It seems that membrane with higher content of chitosan is
susceptible to driving force (concentration gradient) and the
CSPVA7525 membrane is the most.
However, according to Fig. 3b, permeate water concentration
was the lowest from the CSPVA2575 membrane but the highest
from the CSPVA7525 membrane. It suggests that mass cou-
pling transfer across the membrane has higher influences on the
CSPVA2575 membrane than the CSPVA7525 membrane. This
contradicts the results from sorption experiment. Therefore, it
indicates that sorption, a static process, does not have a great
impact on separation but diffusion, a dynamic process, controls
the separation.Table 3
3.5. Comparison of results with others’ studies
The results from this study are very impressive. Table 4 shows
a comparison of pervaporation performance from this work with
others’ studies for the pervaporation dehydration of isopropanol.
These membranes are homogeneous membranes unless pointed
out otherwise. According to Table 4, it can be seen that flux and
water content in permeate from the CSPVA7525 membrane are
higher than those from homogeneous membranes at the same
isopropanol feed concentration and feed temperature. For the
comparison of CSPVA7525 membrane with commercially avail-
able membranes, it can be seen that flux from CSPVA7525
membrane is lower about 2–3 times lower than fluxes from
crosslinked PVA and silica membranes [35]. However, it is not
a drastic difference. Basically, commercially available mem-
branes are composite membranes and have a very thin selective
layer. It is not surprising that fluxes from composite membranes
are higher than those from homogeneous ones. Besides, the
separation by using commercial membranes, crosslinked PVA
and silica membranes [35], was operated at 70 ◦ C which was
higher than the separation by using the CSPVA7525 membrane.
The increase of feed temperature results in higher flux. Flux
from composite chitosan membranes from Lee et al. [13] is
much higher than from the CSPVA7525 membranes but the
feed temperature was 80 ◦ C. Again, not surprising, the higher
feed temperature (20 ◦ C) from the work of Lee and associates
results in much higher flux than that from this work. Permeate
822 A. Svang-Ariyaskul et al. / Journal of Membrane Science 280 (2006) 815–823

Table 4
Comparison of pervaporation performance for the dehydration of isopropanol with others’ studies
Membrane %IPA in the feed T (◦ C) Flux (g/m2 h) %Water in permeate References

CSPVA7525 90 60 644 >99.999 This work

Crosslinked PVAa,b 91 70 1350 95.7 Gallego-Lizon et al [35]
Silicaa,b 92 70 1900 85.6 Gallego-Lizon et al. [35]
Crosslinked CSa on PSf 90 80 2733 82.0 Lee et al. [13]
CS/HEC 90 60 175 >99.9 Chanachai et al. (2002)
Asymmetric PVA 90 70 100 98.4 Yu et al. [25]
PANi doped with PAA 85 60 180 90.0 Lee et al. [13]
Crosslinked CS 90 30 400 97.5 Nawawi and Huang [11]
Two-ply CS and sodium alginate 90 60 554 99.6 Moon et al. [14]

CS: chitosan; PVA: polyvinyl alcohol; PSf: polysulfone; HEC: hydroxyethylcellulose; PANi: polyaniline; PAA: polyacrylic acid. Note that numbers appeared in
Table 4 are not the exact number from others’ studies. These numbers are the approximation from those studies’ graphs.
a Composite membranes.
b Commercial available membranes from Sulzer Chemtech, Germany.

water concentration from this work is higher than that from other
membranes. Therefore, it can be concluded that CSPVA7525
membrane is promising to be developed for industrial uses.
4. Conclusions
Blended chitosan and PVA membranes were fabricated to use
for pervaporation dehydration of isopropanol aqueous solution.
The following conclusions can be drawn from the experimental
results.
• Total flux increases with an increase of either feed water con-
centration or feed temperature for all membranes.
• It is found that blended membrane with chitosan to PVA ratio
of 3/1 performed the best pervaporation performance—high
flux and excellent selectivity. Water content in permeate from
this membrane remained constant upon the change of either
feed concentration or feed temperature and it was around 100
wt% water in permeate.
• In general, the total flux increased with the chitosan content
in a membrane while selectivity had a complex relationship
with membrane composition.
• Sorption did not play an important role in the separation for
this system. It is possible that diffusion controlled over the
selectivity of this process.
Acknowledgements
The authors are truly grateful for the financial support for
this research from the Natural Science and Engineering Research
Council of Canada. We also thank Kyowa Technos, Chiba, Japan
for the donation of chitosan samples.
Nomenclature
AIPA pre-exponential factor for isopropanol perme-
ation (M/L2 t)
Ap pre-exponential factor (M/L2 t)
Aw pre-exponential factor for water permeation
(M/L2 t)
EIPA apparent activation energy of isopropanol perme-
ation (ML2 /t2 )
Ep apparent activation energy of pervaporation per-
meation (ML2 /t2 )
Ew apparent activation energy of water permeation
(ML2 /t2 )
J total flux (M/L2 t)
JIPA isopropanol flux (M/L2 t)
Jw water flux (M/L2 t)
R gas constant (ML2 /t2 T mol)
T absolute temperature of feed solution (T)
yw mass fraction of water in the permeate
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