386 Ind. Eng. Chem. Res.

2003, 42, 386-391

Pervaporation of Toluene/Alcohol Mixtures through a Coextruded

Linear Low-Density Polyethylene Membrane
J. P. G. Villaluenga,* M. Khayet, P. Godino, B. Seoane, and J. I. Mengual
Department of Applied Physics I, Faculty of Physics, Complutense University of Madrid, 28040 Madrid, Spain

The pervaporation characteristics of toluene/methanol, toluene/ethanol, and toluene/propanol

mixtures through a linear low-density polyethylene membrane were investigated at different
feed compositions. These characteristics were obtained from quantities such as the swelling
ratio, permeation rate, and selectivity. In all cases toluene permeates preferentially through
the membrane, with a separation factor up to 66 and fluxes varying between 0.1 and 1.4 kg/
m2‚h. Predictions based on the Flory-Huggins theory have shown that toluene is preferentially
sorbed by the membrane. The pervaporation flux increases and the selectivity decreases with
the toluene content in the feed. The experimental results show that pure-alcohol fluxes decrease
with the molecular size.

Introduction distillation of the alcohol/water mixture may be used

Pervaporation is a membrane technique used for the
separation of liquid mixtures by means of partial
vaporization across a permselective membrane. Because
pervaporation makes use of dense membranes, the
transmembrane mass transport can be described by the
solution-diffusion model widely accepted in gas separa-
tion operations.1,2 The transport process can be divided
into three steps: solution of the liquid mixture at the
upstream membrane surface, diffusion of the permeants
through the membrane, and desorption of the permeate,
in vapor form, at the downstream membrane side.
However, the study of the transport in pervaporation
is more complicated than that in gas separation because
the concentration in the membrane is generally higher,
which causes the swelling and plasticization of the
polymer matrix and strong coupling effects in the
sorption and diffusion processes.3,4 Coupling phenomena
are difficult to measure. It is also difficult to estimate
beforehand the extent of the phenomena in relation to
the separation properties, as several researchers have
pointed out.5,6 Nevertheless, a lot of progress has been
made in modeling the sorption step according to the
Flory-Huggins theory7-9 and UNIQUAC model.10 The
main approaches to describe mass transfer through the
membrane employ the Fick equations,11,12 the thermo-
dynamics of irreversible processes,1,4,13 or Stefan-
Maxwell equations.14,15
The applications of pervaporation processes for de-
hydration from alcoholic solutions and removal of
organics from aqueous solutions have been carried out
commercially for several years.16 However, there has
been no application of pervaporation for the separation
of organic mixtures in the chemical industry. Among
these separations, the removal of methanol from anhy-
drous organic liquid mixtures is required in many
situations such as methanol/methyl tert-butyl ether,
methanol/ethylene glycol, methanol/heptane, and metha-
nol/propanol.2,16 The literature on the separation of
toluene and alcohol by pervaporation is rather scarce.
Extraction of the alcohol with water and subsequent
* To whom correspondence should be addressed. Tel: (34)
91 394 4454. Fax: (34) 91 394 5191. E-mail: juanpgv@fis.ucm.es.
10.1021/ie020603e CCC: $25.00 © 2003 American Chemical Society
Published on Web 12/21/2002
to separate these mixtures. In comparison with distil-
lation, pervaporation is usually a more energy-saving
process because the selectivity is largely improved
because of the permselectivity of the membrane. The
performance of the membrane plays a key role in
determining the feasibility in the process. Several efforts
have been made to develop new materials in order to
obtain a suitable membrane for this particular organic/
organic mixture. For example, Park et al.17,18 investi-
gated the pervaporation of methanol/toluene and ethanol/
toluene mixtures through polymer blend membranes of
poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA).
It was observed that alcohols permeated preferentially
through all tested membranes. The flux decreased
gradually as the PVA content in the blend increased,
whereas the selectivity values increased. This offered a
convenient way of optimizing the separation perfor-
mance of the membranes by adjusting the blend com-
position of the polymer solution used for the preparation
of the membranes.
Separation of the toluene/ethanol mixtures by per-
vaporation, using adsorbent-filled membranes, was
investigated by Duval et al.19 Various activated carbons
and two different zeolites were used in this study. For
all of the carbons tested, the total flux through the
membrane decreased drastically with the addition of the
active carbon particles; however, the porous structure
of carbon seemed to have no effect on the selectivity.
The methanol removal of methanol/toluene mixtures by
pervaporation using polypyrrole (PPy) membranes was
also investigated by Zhou et al.20 Results showed that
the membranes displayed preferential permeation of
methanol and exhibited a good selectivity and an
acceptable permeation rate.
Huang et al.21 prepared composite chitin membranes,
supported by a porous poly(ether imide) substrate, for
the pervaporation separation of ethanol/toluene and
methanol/toluene mixtures. The chitin was obtained by
modifying chitosan to its original form chitin by the
N-acetylation reaction. It was reported that the total
flux, for both types of mixtures, decreased with the
incorporation of an acetyl functional group due to the
larger inter- or intramolecular bonding among the acetyl
groups. However, the N-acetylation made the chitosan
 Ind. Eng. Chem. Res., Vol. 42, No. 2, 2003 387

Table 1. Performance of Membranes in the Separation of

Toluene/Alcohol Mixtures by Pervaporation
feed concn Ta Jb
polymer alcohol (wt %) (°C) (kg/m2‚h) R ref
PAA-PVA MeOH 50 30 1.0 83c 17
EtOH 50 30 0.15 82c
PDMS EtOH 10 30 0.8 13 19
EPDA EtOH 10 30 0.06 62
PPy MeOH 10 57.5 0.29 420c 20
chitin EtOH 10 35 0.40 126c 21
MeOH 10 35 0.68 607c
CA MeOH 70 30 0.5 5c 22
PDMS MeOH 50 30 1.7 7 23
CTA MeOH 50 30 0.8 4c
LLDPE MeOH 50 30 0.46 22 this work
EtOH 60 30 1.0 27
a Feed temperature. b Overall flux. c Selectivity of alcohol over

toluene.
more efficient for the separation of alcohol/toluene
mixtures because the selectivity was increased signifi-
cantly depending on the alcohol content in the feed.
Bhat and Pangarkar22 have used polyimide and blends
of cellulosic membranes for the pervaporative separation
of methanol/toluene mixtures. All of the membranes
studied were methanol selective with acceptable per-
meation rates. Recently, Mandal and Pangarkar23 car-
ried out a systematic study on the pervaporation
separation of methanol/toluene mixtures by using dif-
ferent hydrophilic and hydrophobic membranes. They
showed that the hydrophilic membranes were methanol
selective, whereas the hydrophobic membranes prefer-
entially permeated toluene. Some pervaporation per-
formance data for the separation of toluene/alcohol
mixtures are given in Table 1.
The aim of the present study is to investigate the
pervaporation features of a coextruded linear low-
density polyethylene (LLDPE) membrane for the sepa-
ration of toluene/alcohol mixtures. The effect of the feed
composition on the membrane performance was studied
for toluene/methanol, toluene/ethanol, and toluene/
propanol mixtures over the entire range of mixture
composition. In addition, pervaporation experiments
with pure methanol, ethanol, propanol, butanol, and
octanol were performed to study the influence of the
nature of alcohol on the permeation through the LLDPE
membrane. The swelling process of the membrane was
investigated as a function of the concentration of toluene
in the liquid mixture.
Experimental Section
Membrane. The membrane is made of 1-octene-co-
ethylene copolymers with roughly 8% mole content of
the first comonomer. The membrane, which was ob-
tained by coextrusion, is composed of two layers of
Dowlex 2247 (F ) 0.917 g/cm3), with thicknesses of 3.5
and 16.0 µm, respectively, and a third layer of Dowlex
2291 (F ) 0.912 g/cm3) of 3.5 µm thickness. Both
materials are additive-free. The thicker Dowlex 2247
layer is sandwiched between the other two layers. The
extrusion rate is 88 rpm for the thinner layers and 29
rpm for the thicker one. The distance between the die
exit and the chill roll is 15 mm, with the temperature
at these points being 543 and 293 K, respectively.
Further details about the coextruded LLDPE membrane
have been reported elsewhere.24
Sorption Experiments. The equilibrium swelling
properties of the membrane in toluene/alcohol mixtures
Figure 1. Schematic representation of the pervaporation unit:
(a) constant-temperature bath, (b) pervaporation cell, (c) manom-
eter, (d) feed circulating pump, (e) pressure transducer, (f) cold
trap, (g) venting, (h) vacuum pump.
were measured by a gravimetric method. The dry
LLDPE membrane was weighted and, then, immersed
in a closed bottle containing either toluene, methanol,
ethanol, propanol, butanol, octanol, or a mixture of
toluene and alcohol. The bottle was placed in a ther-
mostated bath at 30 °C. After 24 h of immersion, the
swollen membrane was taken out of the liquid and
reweighed after the superfluous liquid was wiped out
with tissue paper. The increase in weight was equal to
the weight of the liquid sorbed by the membrane.
Pervaporation Experiments. The vacuum-pervap-
oration setup used is shown in Figure 1. The effective
membrane surface area was 28 cm2. The feed was
circulated over the membrane sample through meander-
type channels. The feed pressure was kept at 1.0 bar.
The permeate stream was evacuated by a vacuum
pump, and the permeate was collected alternatively in
two traps, cooled by liquid nitrogen. The downstream
pressure was monitored by a pressure transducer and
was maintained below 10-2 mmHg in all of the experi-
ments. The fluxes were determined by weighing the
sample collected in a determined time interval. The feed
and permeate compositions of all of the mixtures were
determined by measuring their refractive indexes with
a refractometer. The pervaporation selectivity of the
membrane was studied in terms of the separation factor,
R, which is defined as
y1/y2
R) (1)
x1/x2
where x and y are the weight fractions of the relevant
component in the feed and the permeate solutions,
respectively. Indexes 1 and 2 refer to the more perme-
able component (toluene) and less permeable one (al-
cohol), respectively.
In each run, it was observed that the concentration
in the feed solution after the completion of the experi-
ment was almost the same as that of the initial feed
solution. So, it could be considered constant throughout
the experiment. After the initial transient operation, at
least three samples were collected at each run to
determine the total flux, as well as the composition of
the permeate. The alternative use of two cold traps
allowed the permeate to be continuously sampled with-
out interrupting the experiment.
388 Ind. Eng. Chem. Res., Vol. 42, No. 2, 2003

Table 2. Properties of Different Compounds

boiling point molar volume
compound formula (°C) (cm3/mol)
toluene C7H8 111 106
methanol CH4O 64 40
ethanol C2H6O 78 58
propanol C3H8O 82 77
butanol C4H10O 117 92
octanol C8H18O 194 158

Table 3. Pure-Component Sorption and Pervaporation

Data
J S δ ∆δ
compound (10-6 kg/m2‚s) (g/100 g) χip (MPa1/2) (MPa1/2)
toluene 3.89 ( 0.01 6.5 2.1 18.2 2.2
methanol 0.308 ( 0.012 1.4 3.3 29.7 13.7
ethanol 0.273 ( 0.011 2.2 2.9 26.5 10.5
propanol 0.265 ( 0.013 0.7 3.8 24.4 8.4 Figure 2. Overall solubility of toluene/methanol, toluene/ethanol,
butanol 0.251 ( 0.011 <0.1 23.1 7.1 and toluene/propanol mixtures in a LLDPE membrane, as a
octanol 0.249 ( 0.012 <0.1 21.2 5.2 function of the liquid mixture composition.

The pervaporation experiments were conducted at a
feed temperature of 30 °C using, as the feed, either
toluene, methanol, ethanol, propanol, butanol, octanol,
or binary mixtures of toluene/methanol, toluene/ethanol,
and toluene/propanol. Toluene forms an azeotrope with
methanol with a 0.883 mole fraction of methanol at 63.5
°C. Azeotrope also exists in toluene/ethanol and toluene/
propanol with a 0.81 mole fraction of ethanol at 76.7
°C and with a 0.773 mole fraction of propanol at 80.6
°C, respectively. Physicochemical properties of the
compounds used in this work are given in Table 2.
Results and Discussion
The amounts of pure liquids sorbed in the coextruded
LLDPE membrane are given in Table 3. The degree of
swelling of the membrane is small, suggesting that
plasticizing effects of liquid molecules in the LLDPE
membrane may be considered as negligible. From Table
3, the amount of toluene sorbed was 6.5 g/100 g of dry
membrane. The degree of swelling of the membrane was
considerably reduced when the feed was methanol,
ethanol, or propanol, ranging from 0.7 to 2.2%. When
the feed consisted of pure butanol or octanol, it was not
possible to get precise experimental data of the sorption
of butanol and octanol in the membrane because they
were very low (less than 0.1/100 g of membrane). A
common approach, for describing polymer/liquid inter-
actions, is the solubility parameter model developed by
Hildebrand and Scott,4 which can be used to obtain a
rough estimation of the affinity between the LLDPE
polymer and the liquids used in this study. In the case
of liquids, the solubility parameter, δ, can be easily
calculated if thermodynamic data or characteristic
physicochemical properties are available.4 The method
of Hoftyzer-Van Krevelen25 can be applied to polymers
and allows the estimation in a very simple way. The
difference between the solubility parameters of a poly-
mer and a liquid, ∆δ, is a measurement of the affinity
between them. When ∆δ decreases, the affinity between
the polymer and liquid increases. The solubility param-
eter estimated for the LLDPE polymer is δ ) 16.0
MPa1/2, whereas the parameters calculated for alcohols
are given in Table 3. The solubility parameter difference
between the membrane and toluene is smaller than that
of membrane and alcohols. Thus, it can be hypothesized
that the compatibility between the LLDPE membrane
and toluene is better than that of LLDPE and alcohol.
The solubility parameter approach also predicts that the
affinity between large alcohols, such as butanol and
octanol, and the membrane is higher than that of small
alcohols, such as methanol or ethanol. The fact that the
membrane absorbs very little butanol and octanol, as
compared to methanol and ethanol, suggests that the
alcohol solubility in the membrane depends not only on
differences in the affinity liquid/membrane but also on
differences in the molar volume of the alcohols.
Other researchers23 have pointed out that the LLDPE
polymer is a nonpolar material due to the presence of
only C-C and C-H bonds in the backbone polymer
chains, whereas toluene is a nonpolar compound, and
alcohols can be considered as polar compounds to a
different extent. Thus, swelling results reveal that the
solubility rule of “like dissolves like” seems to be obeyed
because the coextruded LLDPE membrane sorbs much
more toluene than alcohol.
The extent of solubility or miscibility of a liquid with
the polymer membrane can also be explained by the
Flory-Rehner theory.26 Based on this approach, the
affinity between the polymer and a solvent can be
expressed in terms of one interaction parameter, χip,
which, in the case of equilibrium sorption of a pure
liquid in a polymer, can be calculated from the following
equation:
∆µi
) ln(1 - φp) + φp + χipφp2 ) 0 (2)
RT
where φp is the volume fraction of the polymer in the
polymer-liquid solution. As interaction between the
polymer and the solvent increases, the amount of liquid
inside the polymer membrane increases and χip de-
creases. Table 3 shows the interaction parameter values
obtained from the sorption data of pure liquids in the
LLDPE membrane. Affinity of toluene toward LLDPE
is higher than that of alcohols. Hence, sorption of
toluene in LLDPE is higher, as has been shown previ-
ously.
Liquid sorption experiments with mixtures of toluene
and methanol, ethanol, and propanol, respectively, were
also performed in order to study the preferential sorp-
tion of the toluene/alcohol system in the coextruded
LLDPE membrane at 30 °C. Figure 2 shows the overall
solubility for mixtures of toluene/methanol, toluene/
ethanol, and toluene/propanol as a function of the
composition of the external solution. A quasi-linear
 Ind. Eng. Chem. Res., Vol. 42, No. 2, 2003 389

increase in the total amount of liquid sorbed in the

membrane can be observed as the toluene concentration
increases, which indicates that toluene has a higher
solubility than do any of the alcohols.
The composition of the liquid sorbed in the membrane
can be estimated by a model derived from the Flory-
Huggins theory. At a given volume fraction of liquid in
the feed, vi, the volume fraction in the membrane, φi,
can be obtained by the following expressions:4

ln () ()
φ1
φ2
- ln
v1
v2
) (l - 1) ln ()
φ2
v2
- χ12[(v1 - v2) +

(φ2 - φ1)] - φ3(χ13 - lχ23) (3)

φ1 + φ2 + φ3 ) 1 (4)

In these equations indexes 1 and 2 refer to the liquid

components, l is the ratio of molar volumes of liquids 1
(toluene) and 2 (alcohol). The polymer volume fraction,
φ3, can be obtained from the overall sorption measure-
ments. The interaction parameters between the liquids
and the polymer, χ13 and χ23, were assumed to be
concentration-independent and were calculated from the
single liquid sorption data. The interaction parameter
between toluene and alcohol, χ12, was also assumed to
be concentration-independent and was calculated from
the Wilson equation using data taken from the litera-
ture.27 For practical reasons, the volume of liquid i, ui,
in the liquid mixture sorbed in the LLDPE membrane
is used instead of the volume fraction of component i,
φi, in the liquid-polymer phase. Values of ui can be easily
obtained as

ui ) φi/(φ1 + φ2) (5)

Parts a-c of Figure 3 show the predicted composition

of the sorbed liquid in the swollen LLDPE membrane,
as a function of the composition of the external liquid
mixtures studied. The results reveal that the toluene
content in the sorbed liquid was much higher than that
of any alcohol; on the other hand, the relative proportion
of toluene and alcohol in the membrane is nearly the
same irrespective of the type of alcohol. It is worth
noticing that the membrane sorbs more alcohol when
they are pure than when they are in mixtures with
toluene. In fact, the fraction of alcohol sorbed by the
membrane is significantly reduced even with a low
toluene content in the external mixture. Therefore, it
can be concluded that the alcohol penetration in the
LLDPE membrane is largely suppressed by the sorption Figure 3. Predicted composition of the sorbed liquid of (a) toluene/
of toluene. methanol, (b) toluene/ethanol, and (c) toluene/propanol mixtures
Pure-component pervaporation fluxes for toluene and in a coextruded LLDPE membrane, as a function of the liquid
mixture composition.
five different alcohols are given in Table 3. It can be
seen that the permeation rate of toluene is much higher
than that of alcohols. It is generally accepted that In the case of pure-alcohol pervaporation, the flux
pervaporation can be described by the solution-diffu- decreases as the alcohol molecular size, i.e., molar
sion mechanism that occurs in the following three volume, decreases. A small molecular size favors the
steps: sorption, diffusion, and desorption. According to diffusivity of the permeate in the membrane. By con-
this model and because of the low downstream pressure, sidering the molecular size of the alcohols as their
the permselective properties of pervaporation of coex- kinetic diameters, results suggest that the diffusivity
truded LLDPE membrane are determined by the rela- of alcohol in the membrane decreases in the following
tive solubility and diffusivity of the permeating compo- order: methanol > ethanol > propanol > butanol >
nents in the membrane. After comparison of the molar octanol. Based on sorption data, the solubility increases
volume of the liquids, it seems reasonable to think that in the following order: ethanol > methanol > propanol
the high permeation rate of toluene through the LLDPE > butanol ≈ octanol. Consequently, it seems that
membrane can be explained by its high solubility in the diffusivity and solubility increase in the same direction
membrane rather than its diffusivity. with respect to the alcohol molecular size.
390 Ind. Eng. Chem. Res., Vol. 42, No. 2, 2003

Figure 4. Total fluxes of toluene/alcohol mixtures through a

coextruded LLDPE membrane, as a function of the feed composi-
tion.

Figure 5. Toluene selectivity for methanol/toluene, ethanol/

toluene, and propanol/toluene, as a function of the feed composi-
tion.

To study the permeation performance of the mem-

brane, the separation of alcohol/toluene mixtures through
a LLDPE membrane was evaluated in the whole com-
position range. Figures 4 and 5 show the variation of
the total permeation rate and separation factor as a
function of the feed composition, respectively, for mix-
tures of methanol/toluene, ethanol/toluene, and pro-
panol/toluene. As can be observed, the flux increases and
the selectivity decreases with the toluene concentration
in the feed. In addition, the trend of the dependence of
flux and selectivity on the feed composition is almost
similar for all of the mixtures studied. As an example,
in the case of methanol/toluene mixtures, the flux
increases from 3.31 × 10-5 to 3.02 × 10-4 kg/m2‚s, and
the selectivity decreases from 66 to 7, as the toluene
volume fraction in the feed increases from 0.03 to 0.72.
The partial fluxes of alcohol and toluene were calcu-
lated by using the permeate composition data. The
results are given in Figure 6a-c, as a function of the
feed composition. As has been pointed out previously,
preferential sorption of toluene in the LLDPE mem-
brane seems to be responsible for the difference in
permeation rates between the aromatics and alcohols.
This behavior agrees with previous studies,23,28 in which
it was shown that preferential sorption determines the
overall selectivity to a large extent for rubbery mem-
branes, such as coextruded LLDPE. Furthermore, the
partial fluxes are drastically reduced in the presence of
Figure 6. Component fluxes of (a) methanol/toluene, (b) ethanol/
toluene, and (c) propanol/toluene mixtures through a coextruded
LLDPE membrane, as a function of the feed composition.
toluene, even for a low toluene content in the feed.
Similar results were found by Mandal and Pargarkar23
for the pervaporation separation of methanol/toluene
mixtures. They reported that the sorbed toluene tends
to create a hindrance to the transport of the alcohol,
through the void space in the membrane, which was the
reason for the lower extent of permeation of methanol.
In the present study, the coextruded LLDPE membrane
is preferably soluble to toluene rather to alcohols
because of the nonpolarity of the polymer chains,
leading to the toluene molecules to occupy the free
volume available in the polymer. This fact favors the
permeation of toluene and retards the permeation of
alcohol.

Conclusions
A coextruded LLDPE membrane was evaluated for
the separation of toluene/alcohol mixtures. The mem-
brane was found to be toluene-selective but with a poor
permeation rate.
The flux of toluene/methanol, toluene/ethanol, and
toluene/propanol mixtures through the LLDPE mem-
brane decreases and the selectivity increases with the
alcohol content in the feed solution. Furthermore, a
small influence of the nature of alcohol on the mem-
brane selectivity was observed.
Results also indicated that the preferential sorption
of the toluene in the coextruded LLDPE membrane
contributes to a great extent to the membrane selectiv-
ity. Finally, it was observed that the flux of pure alcohols
through the coextruded LLDPE membrane decreases as
the molecular size of the alcohol increases.
Literature Cited
(1) Wijmans, J. G.; Baker, R. W. The solution-diffusion model:
a review. J. Membr. Sci. 1995, 107, 1.
(2) Feng, X.; Huang, R. Y. M. Liquid separation by membrane
pervaporation: a review. Ind. Eng. Chem. Res. 1997, 36, 1048.
(3) Huang, R. Y. M.; Rhim, J. W. Separation characteristics of
pervaporation membrane separation processes. In Pervaporation
Membrane Separation Process; Huang, R. Y. M., Ed.; Elsevier
Publishers BV: Amsterdam, The Netherlands, 1991.
(4) Mulder, M. H. V. Thermodynamics principles of pervapo-
ration. In Pervaporation Membrane Separation Process; Huang,
R. Y. M., Ed.; Elsevier Publishers BV: Amsterdam, The Nether-
lands, 1991.
(5) Drioli, E.; Zhang, S.; Basile, A. On the coupling effect in
pervaporation. J. Membr. Sci. 1993, 81, 43.
(6) Kedem, O. The role of coupling in pervaporation. J. Membr.
Sci. 1989, 47, 277.
(7) Heintz, A.; Funke, H.; Lichtenthaler, R. N. Sorption and
diffusion in pervaporation membranes. In Pervaporation Mem-
brane Separation Process; Huang, R. Y. M., Ed.; Elsevier Publish-
ers BV: Amsterdam, The Netherlands, 1991; Chapter 10.
(8) Rhim, J.-W.; Huang, R. Y. M. Prediction of pervaporation
separation characteristics for the ethanol-water-nylon 4 mem-
brane system. J. Membr. Sci. 1992, 105, 105.
(9) Favre, E.; Nguyen, Q. T.; Schaetzel, P.; Clement, R.; Neel,
J. Sorption of organic solvents into dense silicone membraness
validity and limitations of Flory-Huggins and related theories.
J. Chem. Soc., Faraday Trans. 1993, 89, 4339.
(10) Heintz, A.; Stephan, W. A generalized solution-diffusion
model to the pervaporation process through composite membranes.
Part I. Prediction of mixture solubilities in dense active layer using
the UNIQUAC model. J. Membr. Sci. 1994, 89, 143.
(11) Dutta, B. K.; Ji, W.; Sikdar, S. K. Pervaporation: principles
and applications. Sep. Purif. Methods 1997, 25, 131.
(12) Jonquieres, A.; Clement, A. R.; Roizard, D.; Lochon, P.
Pervaporative transport modeling in a ternary system: ethyl
tertiary butyl ether/ethanol/polyurethaneimide. J. Membr. Sci.
1996, 109, 65.
Ind. Eng. Chem. Res., Vol. 42, No. 2, 2003 391
(13) Raghunath, B.; Hwang, S. T. General Treatment of liquid-
phase boundary layer resistance in the pervaporation of dilute
aqueous organics through tubular membranes. J. Membr. Sci.
1992, 75, 29.
(14) Heintz, A.; Stephan, W. A generalized solution-diffusion
model to the pervaporation process through composite membranes.
Part II. Concentration polarization, couple diffusion and the
influence of the porous support layer. J. Membr. Sci. 1994, 89,
153.
(15) Krishna, R.; Wesseling, J. A. The Maxwell-Stefan ap-
proach to mass transfer. Chem. Eng. Sci. 1997, 52, 861.
(16) Fleming, H. L.; Slater, C. S. Applications and Economics.
In Membrane Handbook; Ho, W. S. W., Winston, W. S., Eds.;
Chapman and Hall: New York, 1992; Chapter 10.
(17) Park, H. C.; Meertens, R. M.; Mulder, M. H. V.; Smolders,
C. A. Pervaporation of alcohol-toluene mixtures through polymer
blend membranes of poly(acrylic acid) and poly(vinyl alcohol). J.
Membr. Sci. 1994, 90, 265.
(18) Park, H. C.; Meertens, R. M.; Mulder, M. H. V. Sorption
of alcohol-toluene mixtures in poly(acrylic acid) and poly(vinyl
alcohol) blend membranes and its role on pervaporation. Ind. Eng.
Chem. Res. 1998, 37, 4408.
(19) Duval, J.-M.; Folkers, B.; Mulder, M. H. V.; Desgrand-
champs, G.; Smolders, C. A. Separation of a toluene/ethanol
mixture by pervaporation using active carbon-filled polymeric
membranes. Sep. Sci. Technol. 1994, 29, 357.
(20) Zhou, M.; Persin, M.; Sarrazin, J. Methanol removal from
organics mixtures by pervaporation using polypyrrole membranes.
J. Membr. Sci. 1996, 117, 303.
(21) Huang, R. Y. M.; Moon, G. Y.; Pal, R. N-Acetylated chitosan
membranes for the pervaporation separation of alcohol/toluene
mixtures. J. Membr. Sci. 2000, 176, 223.
(22) Bhat, A. A.; Pangarkar, V. G. Methanol-selective mem-
branes for the pervaporation separation of methanol-toluene
mixtures. J. Membr. Sci. 2000, 167, 187.
(23) Mandal, S.; Pangarkar, V. G. Separation of methanol-
benzene and methanol-toluene mixtures by pervaporation: effects
of thermodynamics and structural phenomenon. J. Membr. Sci.
2002, 201, 175.
(24) Villaluenga, J. P. G.; Seoane, B. Experimental estimation
of gas-transport properties of linear low-density polyethylene
membranes by an integral permeation method. J. Appl. Polym.
Sci. 2001, 82, 3013.
(25) Van Krevelen, D. W. Properties of Polymers; Elsevier:
Amsterdam, The Netherlands, 1990; Chapter 7.
(26) Flory, P. J. Principles of Polymer Chemistry; Cornell
University Press: Ithaca, NY, 1953; Chapter 13.
(27) Dewan, A. K.; Tao, L. C.; Weber, J. H. Correlation of Wilson
parameters with number of carbon atoms for primary alcohol-
aromatic systems. Ind. Eng. Chem. Process Des. Dev. 1978, 17,
371.
(28) Lee, M. Y.; Bougeois, D.; Belfort, G. Sorption, diffusion and
pervaporation of organics in polymer membranes. J. Membr. Sci.
1989, 44, 161.
Received for review August 4, 2002
Accepted November 27, 2002
IE020603E