Separation and Purication Technology 74 (2010) 242252

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Separation and Purication Technology

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

Study of pervaporation for dehydration of caprolactam through blend

NaAlgpoly(vinyl pyrrolidone) membranes on PAN supports
Tianrong Zhu, Yunbai Luo, Yanwen Lin, Qin Li, Ping Yu , Ming Zeng
College of Chemistry and Molecular Sciences, Wuhan University, Luojia Street, Wuhan 430072, PR China

a r t i c l e

i n f o

Article history:
Received 1 April 2010
Received in revised form 12 June 2010
Accepted 14 June 2010
Keywords:
Pervaporation
Caprolactamwater solutions
Composite membranes
Poly(vinyl pyrrolidone)
Permeance

a b s t r a c t
To improve or develop a new caprolactam dehydration process, pervaporation (PV) separation of
caprolactamwater solutions was investigated using a composite membrane consisting of a selective
sodium alginate (NaAlg)poly(vinyl pyrrolidone) (PVP) blend membrane as top layer and a polyacrylonitrile (PAN) ultraltration (UF) membrane as substrate. The selective layer was physically blended and
crosslinked with glutaraldehyde. The membranes were characterized by SEM, FTIR, XRD, and contact
angle measurements. The effect of PVP content in the blend membranes on the pervaporation performance was investigated. The ux was increased by the addition of PVP and the separation factor was also
increased when the PVP content was in the range of 020 wt.%. The blend membrane containing 20 wt.%
PVP exhibited excellent PV properties with a ux of 1634.4 g/(m2 h) and separation factor of 1610.6 at
323 K, for 50 wt.% caprolactam. Besides, operating temperature and feed composition on pervaporation
performances were investigated. The results showed that the membranes permeation ux increased
with increasing feed temperature and the water concentration, while separation factor decreased. The
normalized permeation uxes in terms of water permeance, caprolactam permeance and selectivity
were also introduced to evaluate the membranes performance. The evaluated results revealed that the
separation performances of NaAlgPVP composite membranes were strongly related to their intrinsic
hydrophilic/hydrophobic nature as well as the operating parameters.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Pervaporation (PV) is one such type of cost effective and
eco-friendly clean membrane separation technology, which is
considered as a prospective industrial separation process. As its
separation efciency relies on the differences in sorption and diffusion properties of the permeating molecules, PV has been widely
studied for separation aqueousorganic azeotropes, closely boiling
mixtures, isomers, as well as being safe to handle the heat-sensitive
compounds [1,2]. The solutiondiffusion model has been widely
used to describe the PV separation process [35]. Fig. 1 shows the
overall mass transfer resistance composed of the resistance of the
top layer and the resistance of the support layer. It is held that
PV mass transport process consists of ve fundamental processes:
(a) diffusion through the feed boundary layer; (b) selectively sorption into the membrane top layer; (c) diffusion of the dissolved
species across the membrane matrix; (d) desorption out of the top
layer; and (e) diffusion through the porous support to the permeate side of the membrane using a vacuum on the permeate side.

Corresponding author. Tel.: +86 27 68772263; fax: +86 27 68776726.

E-mail address: yuping@whu.edu.cn (P. Yu).
1383-5866/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.06.012

The mass transfer resistance on the feed and vapor side is usually
considered to be negligible. Thus, in a composite membrane, only
the active layer plays a role in selecting components and controlling permeation. Compare with all other membrane processes the
phase change occurred during material transport [6].
Caprolactam (C6 H11 NO) is one of the most important intermediates in the polymer industry, which is synthesized via the
cyclohexanone oximation and Beckmann rearrangement route
using highly concentrated sulfuric acid by neutralizing the reaction
mixture with aqueous ammonia [7]. The crude caprolactam phase
consists of 6570 wt.% caprolactam, 11.5 wt.% ammonium sulfate
and water. The industrial processes utilized for ber production
are sensitive to quality uctuations; so high purity of commercial caprolactam (>99.8%) is most often required by articial ber
industry. Water is the most important impurity in the nal caprolactam purication because the existence of water can hinder the
growth of molecular weight [8]. However, since caprolactam is
very heat-sensitive substance, to prevent decomposition, crystallization under a reduced pressure distillation through triple-effect
evaporation sets has been thoroughly investigated and used for
the purication in recent years, but which suffers from high operating costs, high energy consumption, and the pollutants being
transferred to a second phase. It is hence difcult to purify the

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243

Nomenclature
Ji
permeation ux of component i (g/(m2 h))
J
pervaporation permeation ux (g/(m2 h))
Di
diffusion coefcient of component i (m2 /s)
adsorption coefcient of component i (mol/(m3 Pa))
ki
pi,feed
vapor pressure of component i in feed (kPa)
pi,permeate vapor pressure of component i in permeate (kPa)
pi,active vapor pressure of component i in active layer (kPa)
Qi
membrane permeance component i (g/(m2 h kPa))
pi,permeate vapor pressure of component i in support layer
(kPa)
mole fraction of component i in the feed
xi
yi
mole fraction of component i in the permeate
saturation vapor pressure of pure i in the feed liquid
p0i,feed
temperature (kPa)
ppermeate permeate pressure (kPa)
J0
pre-exponential factor of the permeation ux from
the Arrhenius equation (g/(m2 h))
EJ
apparent activation energy of the ux (kJ/mol)
EQ
apparent activation energy of the permeance
(kJ/mol)
R
gas constant (J/(mol K))
T
absolute temperature (K)
A
effective membrane area (m2 )
W
weight of penetrant (g)
t
permeation measuring time (h)
Greek letters
membrane membrane selectivity

pervaporation selectivity
i
activity coefcient of component i in the feed

membrane thickness (m)

Subscripts
i
component i, either water or caprolactam
active
active layer
support support layer
1
water
2
caprolactam

caprolactam just by thin-lm distillation, crystallization, melt crystallization by suspension [9]. So its purication by PV has been
studied by Zhang et al. [10], who tried to remove the water from
caprolactamwater mixtures through a poly(vinyl alcohol) membrane crosslinked with glutaraldehyde. A good separation factor
was obtained though the permeation ux was not very good, which
exhibited an obvious trade-off behavior in pervaporation performance.
To improve its separation efciency, membrane modications
are often required with both higher ux and selectivity. Among the
various modication methods [1113], polymer blending proves
to be an effective way to fabricate membranes with a favorable
synergistic effect of the two polymers [14,15]. Natural polymers
are often preferred to synthetic polymers due to the abundant
availability, biocompatibility, and commercial viability. Sodium
alginate (NaAlg) is a natural polysaccharide extracted from seaweed, which shows excellent water sorption properties [16,17].
But very often membranes made from a single polymer suffering
from the inherent drawback of trade-off between ux and selectivity [18]. Poly(vinyl pyrrolidone) (PVP) is an idea hydrophilic
membrane material, which can easily blend with other organic
or inorganic compounds. PVP is chosen as the additive to blend

Fig. 1. Partial pressure, concentration proles and mass transport in the composite
pervaporation membrane.

with NaAlg, with the aim of increasing the permeation ux without appreciably reducing the selectivity. Recently, many successful
examples using blend membranes based on the PVP have been
reported in the eld of pervaporation for dehydration of organic
solvents and separation of azeotropic mixtures, such as CSPVP
[19,20], PVAPVP [21] and CAPVP blend membranes [22]. To
reduce excessive swelling, polymer blending is accompanied by
crosslinking and annealing which can all strongly inuence permeability or selectivity [23].
PV composite membranes consist of thinner skin layer coated
on a porous support layer, which are often widely used in industry
by achieving a higher permeation rate and sufcient mechanical
strength. Nowadays, no studies are available by both improving the ux and separation factor for caprolactam dehydration
using NaAlgPVP/PAN composite membrane. Therefore, in this
paper, a new composite membrane for caprolactam dehydration
is provided and characterized. Experimental data showed that
the NaAlgPVP/PAN composite membranes had both higher ux
and selectivity for dehydration of caprolactamwater mixture. It
indicates that our work shown in this manuscript makes some
progress in separation of caprolactamwater mixture. Particularly,
the normalized permeation uxes in terms of water permeance,
caprolactam permeance and selectivity were calculated to evaluate
the membranes performance.

2. Experimental
2.1. Materials
Sodium alginate (NaAlg, Mw 204,000) and poly(vinyl pyrrolidone) (PVP, K-30, Mw 30,600) were both purchased from
Sinopharm Chemical Reagent Co., Ltd. Glutaraldehyde (GA, 25 wt.%
in water) was supplied by Aldrich Chemicals (USA). Caprolactam (chemical pure) was obtained from Baling Petrochemical Co.
Ltd (SINOPEC, China). Porous ultraltration membrane of polyacrylonitrile (PAN) (cut-off Mw 5 104 ) with pure water ux of
500 l/m2 h bar was obtained from the Development Center of Water
Treatment Technology (China). All the chemicals were used without further purication. Deionized water was used in preparing the
aqueous feed solutions for the pervaporation experiments.

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T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

2.2. Preparation of crosslinked NaAlgPVP composite membranes

The technique of NaAlgPVP composite membrane preparation
follows a procedure reported in Ref. [24]. The casting procedure is
as follows: rstly, formulation of casting solution, NaAlg (2 g) was
dissolved in 100 ml of water with constant stirring. PVP particles
were dispersed in water, sonicated for 30 min, added to the previously prepared NaAlg solution. To this solution, HCl as a catalyst
and a certain amount of crosslinking agent (glutaraldehyde) was
added and the reaction was started. Blend solutions were prepared
by mixing these solutions in different ratios (w/w), stirred for 24 h
at room temperature. After being ltered and keep overnight to
remove the non-dissolved solids and bubbles, the polymer solution
was cast on a clean Plexiglas using a casting knife.
Secondly, the preparation of composite membranes was done.
Phase inversion is the usual procedure for fabrication of asymmetric
PAN at-sheet membranes. PAN porous ultraltration membranes
as supported membranes, which had been treated with about
4 wt.% 1 N sodium hydroxide solution for 24 h, were washed and
rinsed by about 4 wt.% 1 N hydrogen chloride solution and deionized water till neutrality and air-dried. Then, the prepared solutions
were casted onto PAN porous ultraltration membranes held on a
glass plate with the aid of a casting knife made in our laboratory.
The membranes in the gelatination state were allowed to evaporate
slowly till dried at room temperature. Finally, the membranes were
annealed in vacuum at temperature 80100 C for 1 h for thermal
crosslinking.

2.3.3. X-ray diffraction (XRD)

The XRD patterns of the membrane samples were characterized
by a Germany Bruker D8 Advance X-ray diffractometer using Cu K
radiation. The angle of diffraction was varied from 8 to 50 using a
step size of 0.02 .
2.3.4. Contact angle measurements
The relative hydrophilicity of a surface can be qualitatively
determined by measuring the contact angle of a water drop (5 l)
deposited onto the membrane surface. Contact angle was measured
by DSA100 instrument using static sessile drop method with gonio
meter (Germany, Kruss Company). To reduce evaporation effect,
measurements were made as quickly as possible (less than 10 s).
Furthermore, membranes were dried under vacuum desiccators
before being tested.
2.4. Swelling experiments
The dry NaAlgPVP blend membranes with different mass
ratios were weighed before being immersed in feed mixtures of
caprolactamwater at 40 C in a thermostatic bath for 48 h. The
swollen membrane sample was taken out from the solution, wiped
with lter paper to remove the surface liquid, and then quickly
weighed. All experiments were repeated at least three times. The
results were averaged.
The degree of swelling (DS, %) was calculated by:
DS (%) =

2.3. Characterization of membranes

2.3.1. Scanning electron microscopy (SEM)
SEM was used to study the morphology of the various composite
membranes. All specimens were coated with a conductive layer
of sputtered gold. The morphologies of the crosslinked NaAlgPVP
composite membranes were observed with SEM (FEI Quanta 200,
Holland).
2.3.2. Fourier transform infrared (FTIR) spectroscopy
The interaction between NaAlg and PVP, the crosslinking reaction of blend membrane with GA were both conrmed using the
Nicolet AVATAR 360 FTIR Spectrophotometer. FTIR spectra were
recorded within the range of 4000500 cm1 .

Ws Wd
100
Wd

(1)

where Wd and Ws were the weights of the dried and swollen membranes, respectively.
2.5. Pervaporation experiments
Fig. 2 represents the schematic diagram of the experimental
pervaporation set-up. The membrane was installed in a stainlesssteel membrane cell with the effective surface area of 72.35 cm2 in
contact with feed mixture. The feed solution was continuously circulated from a feed tank at a relatively high ow rate 200 l/h to the
upstream side of the membrane in the cell at the desired temperature by a pump. The feed temperature in the range of 4060 C was
monitored by a digital vacuometer and the feed solution contained
3070 wt.% caprolactam. Pervaporation experiments were carried

Fig. 2. Schematic diagram of pervaporation apparatus. (1) Feed tank; (2) liquid level meter; (3) heater; (4) circulation pump; (5) rotor ow meter; (6) membrane cell; (7)
collecting bottle; (8) liquid nitrogen cold trap; (9) buffer vessel; (10) vacuum pump; V15: valves; T: temperature control; P: vacuum pressure gauge.

T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

245

Fig. 3. Morphology of NaAlgPVP composite membranes: (a) top surface, (b)(d) cross-section of membranes.

out by maintaining atmospheric pressure on the feed side while on

the permeate side about 10 mbar within 1 mbar with a vacuum
pump. Upon reaching steady-state conditions which was obtained
after about 1 h throughout the experiments, permeate vapor was
collected in liquid nitrogen traps with certain intervals (1 h), and
weighted to calculate the permeate ux. The composition of permeate was determined by GC to calculate the separation factor. Here
the composition of the condensed liquid was analyzed by a SP3400
gas chromatography with a FID detector (made in China) under the
following conditions: PEG-20M capillary column, 2 m 6 mm i.d.;
temperature, 170 C; carrier gas, nitrogen; ow rate, 30 ml min1
[10]. The compositions of the liquid feed mixtures were analyzed by
measuring the refractive index within an accuracy of 0.0001 units
using high-precision Abbe Refractometer (Atago NAR-3T, Japan),
which can be calculated by using previously established standard
graph of refractive index versus known mixture composition. The
refractometer prism was maintained at 25 0.1 C.
The permeation ux (J, g/m2 h) was dened as follows:
J (g/m2 h) =

W (g)
A (m2 ) t (h)

xwater /xcaprolactam

Ji =

Di ki
(pi,feed pi,permeate ) = Qi (pi,feed pi,permeate )

= Qi,active (pi,active pi,permeate )

= Qi,support (pi,permeate pi,permeate )
(4)

(2)

where W is the weight of penetrant, A is the effective membrane

area and t is the measuring time.
The separation factor was calculated by:
ywater /ycaprolactam

were proposed and evaluated to clarify the contribution by the

nature of the membrane to separation performance. Following the
solutiondiffusion mechanism, the overall mass transfer resistance
was composed of the resistance of the whole membrane or the
resistance of the active layer and the resistance of the support
layer. The driving force in pervaporation is a gradient in chemical potential across the membrane, which can be expressed in
experimentally measurable quantities such as partial pressures.
The permeate side is considered to be negligible if the downstream
pressures applied are close to vacuum. The basic transport equation
for pervaporation can be written as [25]:

On the basis of Raoults law (feed side) and Daltons law (permeate side) it is equal:
Ji = Qi (xi i p0i,feed yi ppermeate )

(5)

(3)

where xwater , xcaprolactam and ywater , ycaprolactam are the mole fraction
of water and caprolactam in the feed and permeate, respectively.
In order to distinguish between intrinsic membrane properties
and the inuence of the experimental operation conditions, normalized permeation ux (permeance) and membrane selectivity

where Ji is the permeation ux, Qi is the permeance of the membrane for i (which equals the permeability coefcient divided by
the membrane thickness), xi , yi are the mole fraction of i in the feed
and the permeate, respectively,  i is the activity coefcient of i in
the feed liquid and p0i,feed is the saturation vapor pressure of pure i
in the feed liquid temperature, ppermeate is the permeate pressure.

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T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

Fig. 4. Interaction between the blended polymers and the crosslinking mechanism of NaAlg with GA.

The activity coefcient of water ( 1 ) and caprolactam ( 2 ) can

be calculated by using Van Laar equation:

1.0429x1
ln(1 ) = 1.5810
1.0429x1 1.5810x2

ln(2 ) = 1.0429

1.5810x2
1.0429x1 1.5810x2

3.1. Membrane characterization

2
(6)

2
(7)

The p01,feed (water) and p02,feed (caprolactam) are determined from

the Antoine equation:
log(p01,feed ) = 8.07131

1730.63
T + 233.426

(8)

log(p02,feed ) = 6.78000

2344.00
T + 273.150

(9)

where T in degree Celsius ( C).

The membrane selectivity (membrane ) is an intrinsic property of
the membrane material, which is dened as the ratio of the water
permeance over the caprolactam permeance.
membrane =

Qwater
Qcaprolactam

3. Results and discussions

(10)

3.1.1. SEM analysis

SEM images of the crosslinked NaAlgPVP composite membranes are presented in Fig. 3. Fig. 3(a) shows the top surface of
the crosslinked NaAlgPVP membrane. There are no aws in the
surface and the cross-section of the NaAlgPVP blend membrane
with the PVP content of 10 wt.%, which indicates that the compatibility between NaAlg and PVP is quite good. From Fig. 3(b)
the multilayer structure of composite membrane is observed very
clearly: an active layer, a supported porous layer and a substrate.
The total thickness of dry composite membrane NaAlgPVP/PAN
for pervaporation is found to be about 80100 m. It is observed
that a uniform NaAlgPVP thin dense layer with thickness of about
35 m is properly cast on the top of the PAN substrate in Fig. 3(c)
and (d).

3.1.2. FTIR analysis

The homopolymer solutions of NaAlg, PVP and their blend solutions were optically clear. No phase separation or precipitation
was observed even after keeping the mixture for a longer time at

T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

Fig. 5. FTIR of NaAlg membrane, PVP powder and NaAlgPVP blend membranes.

ambient temperature. Fig. 4 represents the interaction between the

blended polymers and the crosslinking mechanism of NaAlg with
GA.
Based on the above related reaction, the results of crosslinked
NaAlgPVP blend membranes can be analyzed by FTIR spectra.
Fig. 5 shows the spectra of pure PVP, pure NaAlg, uncrosslinked
NaAlgPVP and GA crosslinked NaAlgPVP blend membranes containing different PVP contents. The spectrum of NaAlg showed the
peaks around 3389, 2934, 1605,1415, and 1036 cm1 , indicating the
stretching of OH, aliphatic CH, OC O (asymmetric), OC O
(symmetric), and COC, respectively. The spectrum of the PVP
showed peaks around 3446, 2967, 1650 and 1385 cm1 indicating the stretching of OH, aliphatic CH, NC O (asymmetric),
and CN, respectively. By comparing uncrosslinked with that of
crosslinked blend membrane, it is clearly displayed that COC
stretching vibrations around 1036 cm1 boost up connected with
the weakening of the relative intensity of the OH bands, indicating
the interaction of GA with the blend membrane. It can be observed
in the spectra of the crosslinked NaAlgPVP membranes that with
the increase of PVP content, the band at 3383 cm1 becomes more
pronounced with a slight shift to higher wave numbers and the carbonyl group at 1650 cm1 is shifted to higher wave numbers and
simultaneously the peak intensity increased. These phenomena
suggest that NaAlg and PVP could form intermolecular hydrogen
bonding between the OH groups of NaAlg and the C O groups of
PVP. The presence of such OH O C interactions implied a good
compatibility of NaAlg and PVP in the blend membranes.

3.1.3. XRD results

Fig. 6 shows the effect of PVP content on the crystallinity of the
membranes. The XRD spectrum of the NaAlg membrane shows a
broad peak at a diffraction angle (2) of 13.5 and two sharp diffraction peaks at 2 of 22.4 and 29 . The PVP powder exhibits two
dispersive diffraction peaks at 2 of 12.4 and 21 . It is found that
the NaAlg membrane has the highest crystallinity. With the addition of PVP, the blend membranes exhibit less crystalline domains
than the pure NaAlg. This indicates that the amorphous regions and
the polymer chains exibility increase, thereby making it easier for
small molecules to transport through and possibly resulting in an
increase in permeation ux of the NaAlgPVP blend membranes
over the NaAlg membrane.

247

Fig. 6. XRD of pure NaAlg membrane, PVP powder and NaAlgPVP blend membranes.

3.1.4. Contact angle results

The pervaporation performance of a composite membrane is
related to the hydrophilicity of the separation layer. As shown
in Fig. 7, the contact angles decrease with PVP content in the
NaAlgPVP blend, which means that the membrane of higher PVP
content has a higher relative hydrophilicity, mainly because of
more polar groups of the unreacted carbonyl in blend membrane,
as it is shown in FTIR. These free carbonyl groups form hydrogen
bonding with H2 O.
3.2. Swelling results
Membrane swelling controls PV performance. Hence, the degree
of membrane swelling (DS) is important. The results of different
blend membranes in different feed mixtures (5070 wt.% water)
are given in Fig. 8. It can be seen that the higher content of PVP
in the blend membrane leads to the higher degree of membrane
swelling. This suggests that the hydrophilicity of the NaAlgPVP
blend increased with increasing PVP content. The free carbonyl
group of PVP forms hydrogen bonding with H2 O when the membrane is exposed to caprolactamwater mixtures, so the membrane
is easy to swell. Furthermore, the XRD results indicate a more ex-

Fig. 7. Effect of PVP content on the contact angle of NaAlgPVP blend membranes.

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T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

Fig. 8. Effect of PVP content on the degree of swelling of NaAlgPVP blend membranes for 50, 60, 70 wt.% caprolactam aqueous solution.
Table 1
Effect of PVP concentration in the NaAlgPVP coating solution on pervaporation
performance of the NaAlgPVP/PAN composite membrane (for 50 wt.% caprolactam
at 323 K).
NaAlgPVP membranes

Pervaporation results

NaAlg/PVP mass ratio

GA content (wt.%)

J (g/(m2 h))

100/0
90/10
80/20
70/30

0.5
0.5
0.5
0.5

534.7
1473.6
1610.6
930.5

1123.7
1509.3
1634.4
2012.4

ible membrane structure. As the water concentration in the feed

increases, the amorphous regions of the membrane become more
swollen.
3.3. Pervaporation performances
3.3.1. Effect of PVP content in blend membranes on pervaporation
performances
Table 1 shows the effect of PVP content in blend membranes
on permeate ux and separation factor for 50 wt.% caprolactam at
323 K. The incorporation of PVP into NaAlg matrix had a signicant
effect on both permeation ux and separation factor. When the PVP
content increased from 0 to 30 wt.%, the permeation ux increased
which was consistent with the swelling behavior of the membranes
in the feed mixture. Another important factor affecting the ux was
the changing trend of crystallinity. The free volume and the polymer chains exibility of the membranes increased with the addition
of PVP. Whereas the PVP content increased from 0 to 20 wt.%, the
separation factor increased from 534.7 to 1610.6 and then dropped
to 930.5 when the PVP content reached 30 wt.%. The separation factor rstly increased because the membrane of higher PVP content
had a more compact network. Furthermore, introduction of PVP
could signicantly enhance the hydrophilicity of the membranes

as it has strong polarity and hydrophilic groups. The formation of

hydrogen bonding between the membranes and water was hence
promoted. Therefore the afnity between water and membranes
increased accordingly, which was conrmed by the contact angle
measurement. The dropped separation factor may be caused by
the exceeding swell membranes and increase of free volume. A
promising result achieved for the NaAlgPVP blend membranes
was that both the permeation ux and selectivity went up simultaneously with the increase of PVP content in the range of 020 wt.%,
which seemed not to be in accordance with the trade-off rule that
commonly existed between the selectivity and the ux [23]. When
the blend membrane contains 20 wt.% PVP and 80 wt.% NaAlg, the
membrane shows the highest separation factor of 1610.6 and a permeate ux of 1634.4 g/(m2 h). The reason should be that the effect
of hydrogen bonding and swelling on separation factor could reach
a balance state within this range.
The total ux and selectivity from the present study (for
50 wt.% caprolactam at 50, 55 C) were compared with other
composite membranes reported in literatures and presented in
Table 2. Although the membranes are made from different materials and preparation techniques, the dehydration performance of
the crosslinked NaAlgPVP composite membrane prepared in this
study shows a comparable, good ux and selectivity.
3.3.2. Effect of feed composition
The effect of caprolactamwater composition on pervaporation
performances tested at 323 K by using the NaAlgPVP blend membrane of 20 wt.% PVP is shown in Fig. 9. These gures indicate that
not only the ux but also the separation factor are strongly dependent on the feed composition. The feed concentration range from
30 to 70 wt.% of water was chosen by considering the concentration changes from the triple-effect evaporation sets. In addition,
aqueous solution becomes stiff and saturated when the caprolactam content in feed solution is above 70 wt.% at room temperature
[10]. It can be seen from Fig. 9(a) that with the water concentration rising from 30 to 70 wt.% the total ux increased from 843 to
2552 g/(m2 h) while the selectivity decreased from 2895 to 721.
The higher uxes can be explained by the stronger swelling in
the blend matrix due to the strong afnity of PVP toward water,
which has been observed in the swelling experiments. Although
the blend membranes are crosslinked, as the water concentration
in the feed increases, the amorphous regions of the membrane
are more swollen and the polymer chains become more exible,
resulting in both water and caprolactam molecules more easily
diffusion through membranes. So the water and caprolactam ux
were both increased (as shown in Fig. 9(b)) but the separation factor
decreased. This trade-off was generally observed in pervaporation
processes [28,29].
3.3.3. Effect of feed temperature
Temperature is an important operating parameter in pervaporation because it affects both the sorption and diffusion rates.
Hence it can signicantly affect the performance of membranes.
The effect of feed temperature on the pervaporation performances
is revealed in Fig. 10 for the different PVP content and the feed
water concentration of 50 wt.%. When temperature increased from

Table 2
Comparison of composite membrane separation performance with literatures.
Membranes
PVA crosslinked with 0.5 wt.% Gal
PVA/PAN composite membranes
PVA/PES composite membranes
GA crosslinked NaAlgPVP composite membrane

Thickness
(m)
2535
80100
110 5
80100

Caprolactam in
feed (wt.%)

Temperature ( C)

Total ux
g/(m2 h)

Separation
factor

Reference

50
50
50
50
50

50
55
55
50
55

900
1802
790
1634.4
2220.5

575
890
200
1610.6
1354.7

[26]
[10]
[27]
Present work

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249

Fig. 9. Effect of the feed concentration on the pervaporation performances through crosslinked NaAlgPVP composite membranes with 20 wt.% PVP at 323 K.

313 to 338 K, the uxes increased continuously (Fig. 10(a)) but the
separation factors and water concentration in permeate side both
decreased (Fig. 10(b) and (c)). According to free volume theory, an
increase in temperature increases thermal mobility of the poly-

mer chains, which generates extra free volume within the polymer
matrix, resulting in more water and caprolactam molecules permeating to the membrane. In addition, the vapor pressure of water and
caprolactam in the feed mixture increased with increasing of the

Fig. 10. Effect of the feed temperature on the pervaporation performances through crosslinked NaAlgPVP composite membranes with different PVP contents at 50 wt.%
caprolactam.

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Fig. 11. Temperature dependence of (a) permeance at 40 wt.% caprolactam aqueous solution, (b) permeance for 30 wt.% PVP.

feed temperature, and the vapor pressure at the permeate side was
not affected. As a result, the driving force increased with the feed
temperature rising. The diffusion rate of water and caprolactam
molecules was enhanced, leading to high permeation ux. All of
these lead to an increase in ux and a decrease in separation factor
with feed temperature increasing. It is worth pointing out that the
separation factors decrease sharply but the water concentrations
in permeate side decrease slightly [30].
The temperature dependence of the pervaporation ux and permeance can be expressed by Arrhenius equations [31,32]:

Ji = J0 exp

EJ
RT

(11)

 E 
Q

Qi = Q0 exp

(12)

RT

where J0 , Q0 , EJ and EQ are the pre-exponential factor, apparent

activation energy of the permeation ux and the membrane permeance, respectively. R indicates the gas constant (J/(mol K)) and T
is absolute temperature (K).
The difference between EJ and EQ is the molar heat of vaporization HV , expressed as follows.
HV = EJ EQ

(13)

Fig. 11 shows Arrhenius plots (ln Q versus 1/T) through

NaAlgPVP composite membranes according to Eq. (12). It can be
found that the temperature dependence of the pervaporation permeance agrees well with the Arrhenius relationship. The evaluated
values EJ according to Eq. (11), EQ and HV according to Eq. (13)
are presented in Table 3.
As can be seen in Table 3, EQ of water is observed to decrease
whereas EQ of caprolactam increases a litter, comparing the blend

membrane of 10 wt.% PVP with 30 wt.%. These results suggest that

the energy barrier for water has decreased while caprolactam
increased. And then water can more readily transport though the
material and the permeance of water has become less temperature
dependence, and vice versa. Duo to the EQ decreases for water, the
penetrant permeance should increase after increasing content of
PVP.
Also in Table 3, the total activation energies calculated from total
uxes of water and caprolactam for 60 and 70 wt.% caprolactam in
the feed are 32.90 and 38.75 kJ/mol, respectively. The former is distinctly lower than the latter, this is due to the membrane swelling,
and thus results in a lowered permeation activation energy for the
penetrants to transport through the membrane material.
As can be seen in Table 3, the activation energies of water calculated from either the ux (EJ ) or the permeance (EQ ) are much
lower than those of caprolactam for the different blend membranes.
Therefore, more energy is required for caprolactam molecules to
transport across the membrane at the same conditions [33]. The
lower activation energies of water than caprolactam are reected
by the intrinsic properties of hydrophilic membrane materials.
By comparing EJ with EQ , it can be found that the former are
remarkably higher than the latter, which in turn indicates that
the ux and the separation factor are more strongly dependent on
the feed temperature than the permeance and selectivity. These
behaviors can be explained that permeance and selectivity only
depend on membrane intrinsic properties for evaporation but ux
and separation factor are also dependent on experimental operating conditions for both evaporation and solution/diffusion. As
shown in Table 3, the molar heat of vaporization HV for water or
caprolactam are almost the same between the two different blend
membranes or caprolactam concentrations investigated, which is
consistent with the previous reports in the dehydration of aqueous

Table 3
Activation energy data for blend membranes at 40 wt.% caprolactam and for feed solutions at 30 wt.% PVP.
HV (kJ/mol)

Activation energy (kJ/mol)

EQ
Water
NaAlgPVP mass ratio
90/10
32.45
70/30
18.91
Caprolactam in feed (wt.%)
60
16.24
70
17.43

EJ

Water

Caprolactam

Caprolactam

Total

Water

Caprolactam

44.66
47.90

55.12
41.62

55.10
41.55

91.78
91.90

22.65
22.64

47.12
44.00

53.86
32.71

32.90
38.75

32.83
38.72

96.06
77.62

16.59
21.29

42.20
44.91

T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

251

Fig. 12. Effect of the feed concentration and temperature on the pervaporation performances in terms of (a) water permeance, (b) caprolactam permeance, (c) and (d)
selectivity and separation factor through crosslinked NaAlgPVP composite membranes with 20 wt.% PVP.

alcohol systems through lled-hydrophilic polymeric membranes

[34].
3.3.4. Permeance and selectivity
The performance of pervaporation membranes is typically
described in terms of permeation ux and separation factor. These
quantities depend heavily on the operating conditions, which
obscures the role of the driving force in the pervaporation process [25]. So the permeance and membrane selectivity are used to
describe the intrinsic membranes performance. Partial permeate
uxes are required to calculate the permeance of the components
(see Eq. (4)). When the blend membrane contains 20 wt.% PVP, the
water and caprolactam permeances as a function of water concentration in the feed at the different operating temperatures are
illustrated in Fig. 12. It can be seen from Fig. 12(a) and (b) that
the permeances of both water and caprolactam increase continuously with increasing water feed concentration. This implies the
highly hydrophilic NaAlg and PVP membrane material, resulting
in the higher degree of swelling. The sorption of the NaAlgPVP
blend membrane increases and the EQ decreases for water (from
Table 3), corresponding to increase in the permeances of water.
It is interesting that caprolactam permeance also increases. This
increase of caprolactam permeance with water feed concentration
reveals a coupling effect between caprolactam and water permeation through the membrane [33]. That is to say, membrane

swelling or plasticization effect changes the membrane properties and results in the facilitation of transport of the caprolactam
component through the membrane. But no obvious temperature
dependence is observed, which is in accord with the conclusion
from the EJ higher than EQ . Because the temperature effect on permeance is complicated. The reason may arise from the fact that
permeant ux and permeant driving force are both increased with
increasing temperature. The driving force combines two temperature dependent factors:  i and pi,feed . When temperatures rise, the
activity coefcients ( i ) of penetrates are quite close at different
temperatures but the saturation vapor pressure (pi,feed ) of penetrates also increases. Since the downstream pressure is very low
compared with the upstream pressure, it can be neglected. Thus,
the saturation vapor pressure of the feed composition contributes
more to the driving force. Consequently, the increase in permeances is due to the combination of uxes and the driving force
effects mentioned above. A similar behavior was observed by Sanz
and Gmehling [35] for the membrane PERVAP 2201 for binary
water/isopropanol mixtures.
The difference of separation factor and selectivity is compared
in Fig. 12(c) and (d). With the water concentration and feed temperature raising both the separation factor and selectivity reveal
decreasing trend. The effect of water concentration on decreases
of both separation factor and selectivity is easily explained by the
excessive swollen of this highly hydrophilic membrane, resulting in

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T. Zhu et al. / Separation and Purication Technology 74 (2010) 242252

enlarging interstitial space of polymer chains and declining separation performance. The effect of temperature may be caused by the
interactions between permeating molecules and membrane. The
swollen membrane matrix at higher temperature also facilitates
the transport of caprolactam along with water molecules, thereby
the separation factor decreases. Compared with separation factor
versus selectivity from Fig. 12(c) and (d), in spite of the similarity
between the separation factor and selectivity plots, some differences still can be found after intensive comparison. This divergence
may be resulted from the fact that separation factor combines both
intrinsic membrane properties and inuence of the experimental
operating conditions. While selectivity is mainly dominated by the
membrane transport properties and excludes the effect of experimental operating conditions [36]. Consequently, selectivity can
reect intrinsic membrane performance.
4. Conclusion
The membranes were prepared by blending NaAlg with
poly(vinyl pyrrolidone), and then crosslinked with glutaraldehyde. The interaction between NaAlg and PVP polymer and the
crosslinking reaction were revealed by FTIR. With increasing PVP
concentration, XRD conrmed that crystallinity of the crosslinked
NaAlgPVP active layer decreased, while contact angle implied
hydrophilicity of the membranes improved. Pervaporation separation of the NaAlgPVP/PAN composite membranes was tested for
caprolactamwater mixtures. The blend membranes showed good
performance in pervaporation dehydration of caprolactam aqueous
solutions. It was demonstrated that introducing PVP could enhance
the hydrophilicity of the membranes and is in favor of increasing
permeation ux. Especially, as the PVP content in blend membranes
increases from 0 to 20 wt.%, the separation factor also increased.
Of all the blend membranes prepared the membrane of 20 wt.%
PVP was the best one since it exhibited both high permeation ux
and separation factor. In addition, the permeances and selectivity
excluding the effect of operating conditions on performance evaluation made many pervaporation papers more useful and clarify the
contribution of intrinsic membrane properties to separation performance more easily rationalized. The experimental results also
indicated that the NaAlgPVP composite membrane had superior
dehydration performances for caprolactamwater mixtures.
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