Desalination 208 (2007) 146–158

Separation of furfural from aqueous solution by pervaporation

using HTPB-based hydrophobic polyurethaneurea membranes
Ujjal K. Ghosha, Narayan C. Pradhana*, Basudam Adhikarib
a
Department of Chemical Engineering, bMaterials Science Centre, Indian Institute of Technology,
Kharagpur 721302, India
Tel. +91 (3222) 283940; Fax: +91 (3222) 255303; email: ncp@che.iitkgp.ernet.in

Received 25 November 2005; Accepted 13 April 2006

Abstract
Hydroxyterminated polybutadiene (HTPB) was reacted with 2,4-toluylene diisocyanate (TDI) in THF medium
followed by the addition of a diamine chain extender, 4,4N-diaminodiphenyl sulfone (DADPS) to prepare
polyurethaneurea (PUU). The prepared viscous polyurethaneurea solution was cast over a glass Petri dish to obtain
polymer membrane. Pervaporative separation of furfural/water mixtures was performed by using prepared flat sheet
hydrophobic polyurethaneurea membranes. The effect of feed composition on the membrane performance was
described by the permeate flux of furfural and separation factor. The synthesized polyurethaneurea membrane was
found to permeate furfural selectively with high separation factor for the organic component.

Keywords: Pervaporation; Aqueous furfural; Polyurethaneurea; Separation factor; Activation energy; Solution–
diffusion model

1. Introduction
Pervaporation is a membrane separation pro-
cess in which a pure liquid or liquid mixture is in
contact with a dense membrane on the feed (or
upstream) side of the membrane at atmospheric
pressure, and the permeate (or downstream) side
of the membrane is a vapor phase caused by a
vacuum or sweeping gases. The mass transport
*Corresponding author.
through the membrane, which is generally
described by the solution–diffusion model [1],
involves three steps: sorption, diffusion, and
desorption. Additional resistances due to con-
centration polarization in the feed side and due to
the mass transfer toward the vacuum trap in the
permeate side are also considered. Compared to
other traditional processes, pervaporation appears
far more effective due to its simplicity and high
selectivity.

0011-9164/07/$– See front matter © 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.04.078
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158
Applications of pervaporation can be divided
into three general categories: dehydration of
organics [2,3], removal of organic pollutants from
dilute aqueous solutions [4,5], and separation of
organic/organic mixtures [6–9]. Separation of fur-
fural from aqueous solution is in the second
category.
Furfural is used as a solvent for extractive
refining of lubricating oils, as it is very effective
in removing compounds containing oxygen or
sulfur. Furfural is also a feedstock for producing
furfuryl alcohol, which is used for making resins
and tetrahydrofuran, an excellent solvent. Fur-
fural is one of the major components of concern
present in wastewater of petrochemical industry
and petroleum refineries. The separation of
furfural is an important field of study for the sake
of industrial safety and environmental protection.
A variety of different solvents have been tested
for the extraction of furfural from aqueous
solutions, including alcohol [10]. However, there
is no information in the literature on the sepa-
ration of furfural from dilute aqueous solution by
membrane pervaporation.
Pervaporation with polymeric membranes of
high permselectivity were used for effective
dehydration of alcohol, recovery of aromatic
compounds and separation of organic solvents.
Several organophilic membranes used in pervapo-
ration include polydimethylsiloxane (PDMS)
[11], poly (ether-block-amide), polyurethane [12],
and silicone polyurethane copolymer [13]. Poly-
urethane has a unique polymer chain structure
and morphology comprising of flexible soft
segment (polyol) and rigid hard segment
(diisocyanate and chain extender, viz. diol,
diamine). The affinity for organics can be
increased by the selection of a suitable polyol in
polyurethane. Polybutadiene-based polyurethane
membranes were used earlier for separation of
ethanol–water mixture [3], gas separation and
separation of phenol from aqueous solution [14].
It was thought that the higher hydrophobic nature
of polybutadiene might prove advantageous for
147
the selective permeation of furfural from dilute
aqueous solution.
In this work, hydroxyterminated poly-
butadiene (HTPB)-based diamine chain extended
polyurethaneurea (PUU) membranes were pre-
pared and used for the separation of aqueous
furfural solution by pervaporation. The perfor-
mance of the membranes was monitored with the
variation in soft segment of the synthesized
membrane and working temperature. The
influences of operating conditions such as the
feed mixture concentration and temperature on
the separation performance of the membranes
were also studied.
2. Solution–diffusion model for transport
through dense membrane
The solution–diffusion model assumes that the
pressure within a membrane is uniform at the
high pressure value and that the chemical poten-
tial gradient across the membrane is expressed
only as a concentration gradient. The flux of
components can be predicted by the solution–
diffusion model [1] from the estimation of per-
meation coefficient (Pi), provided the perva-
poration process is diffusion-controlled, as in the
present study. The general permeation equation
for flux of mediated transport processes like
membrane pervaporation is expressed according
to the solution–diffusion model as [15]
Di⎡ ⎧ −Vi ( pi1 − pi 2 ) ⎫⎤
Ji = ⎢ Ki1Ci1 − K i 2Ci 2 exp ⎨ ⎬⎥
l ⎣ ⎩ RT ⎭⎦
(1)
where subscript i denotes furfural, Ci1 and Ci2 are
concentrations of component i at feed and per-
meate side, respectively. pi1 and pi2 are the partial
pressures of component i at the membrane
boundary adjacent to the feed and permeate sides,
respectively. Ki1 and Ki2 are the partition coeffi-
cients for component i at the membrane boundary
148 U.K. Ghosh et al. / Desalination 208 (2007) 146–158

adjacent to the feed and permeate sides, respec- (DBTDL) (Fluka AG) was used as received.
tively. Di stands for diffusion coefficient of Tetrahydrofuran (THF) was purified before use
component i and l is the membrane thickness. Vi by first adding sodium and then refluxing for
is the molar volume of furfural. Eq. (1) can be 24 h.
rearranged as
3.2. Synthesis of polyurethaneurea and mem-
DK ⎡ 1 ⎧ −V ( p − pi 2 ) ⎫⎤ brane casting
J i = i i1 ⎢Ci1 − Ci 2 exp ⎨ i i1 ⎬⎥
l ⎣ β ⎩ RT ⎭⎦ Polyurethaneurea (PUU) was synthesized
(2) from the prepolyurethane (PU), which is a pre-
cursor material, prepared by reacting HTPB and
where β = Ki1/Ki2 (enrichment factor) and Ki1 = TDI in dry THF maintaining NCO:OH mole ratio
Ci3/Ci1, Ki2 = Ci3/Ci2. of 2:1 at 30oC in presence of 0.5 wt% DBTDL as
Using Pi = DiKi1, Eq. (2) can be rewritten as catalyst. PU was obtained as a viscous solution in
THF. The length of the PU chain was further
Pi ⎡ 1 ⎧ −Vi ( pi1 − pi 2 ) ⎫ ⎤ extended by reacting the terminal NCO groups of
Ji = ⎢Ci1 − Ci 2 exp ⎨ ⎬ ⎥ (3) PU with the amino groups of DADPS. For the
l ⎣ β ⎩ RT ⎭ ⎦ synthesis of PUU, diamine (DADPS) solution in
dry THF of required concentration was added
In the present study, the permeate side was slowly to the reaction mixture containing PU with
kept at sufficiently low pressure (0.67 kPa) and constant stirring after 55 min of reaction between
Ci2 was assumed to be zero. So, the above equa- HTPB and TDI, i.e., PU formation. The reaction
tion is simplified as was continued for further 30 min. The tempera-
ture during polymerization reaction was main-
Pi
Ji = Ci1 (4) tained at 30oC. A highly viscous solution of PUU
l in THF was obtained. Since the PUU is highly
reactive to moisture, it was kept in a closed con-
Ji can be calculated using Eq. (4) by knowing the dition. Before casting a membrane, the trapped air
values of Pi and l. bubbles from the viscous PUU solution was
removed by applying vacuum by which majority
of THF was also escaped. Then the viscous mass
3. Experimental of PUU with small amount of THF was quickly
poured on a flat base petridish. The liquid mass
3.1. Materials
on the petridish was kept exposed to laboratory
HTPB (functionality = 2.4, hydroxyl value = ambient conditions at a temperature of 30oC for
43.2 mg of KOH/g) with a number average 24 h to effect simultaneous evaporation of resi-
molecular weight of 2580 (Mn, in g/mol) was dual THF and crosslinking of the membrane by
received from VSSC (India) and was used as reacting with water molecules of the atmospheric
received. 2,4-Toluylene diisocyanate (TDI) moisture. The maximum and minimum value of
(Fluka AG) was used without further purification. relative humidity in the laboratory was 81% and
4,4N-Diaminodiphenylsulfone (DADPS) was first 46%, respectively. The cast films of PUU having
dehydrated under vacuum overnight and then was thickness of about 0.20 mm were thermally cured
sublimed. The catalyst dibutyltindilaurate in an oven at 80oC for 5 h.
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158
3.3. Degree of swelling
The degree of swelling of the membranes was
measured by immersing the membranes in
aqueous furfural solution for 48 h.
m − mo
Degree of swelling = × 100% (5)
mo
where m denotes the weight of the swelled mem-
brane and mo denotes the weight of the dry
membrane.
3.4. Measurement of diffusion coefficient
The diffusion coefficients of furfural and
water (Di and Dj) in polyurethaneurea were
measured at different temperatures and at
different furfural concentrations by keeping the
membranes immersed in aqueous furfural solu-
tion and noting the change in relative weight gain
(mt/mα) with time. Thicker membranes were pre-
ferred in order to nullify the error due to vapori-
zation of liquid from the film surface. The value
of average diffusion coefficient was calculated
from the slope of a plot of relative weight gain
(mt/mα) against t following the equation [16]:
⎛ m ⎞ π2D ⎛ 8 ⎞
ln ⎜ 1 − t ⎟ = − 2 i t + ln ⎜ 2 ⎟ (6)
⎝ m∞ ⎠ δM ⎝π ⎠
3.5. Pervaporation apparatus
Pervaporation of furfural–water mixture was
carried out in a pervaporation cell (Fig. 1). It is
assembled from two cylinderical half-cells made
of stainless steel fastened together by nuts and
bolts. The membrane was supported on a sintered
(perforated) stainless steel plate placed at the joint
of two cells. The feed liquid was circulated using
a peristaltic pump. The feed temperature was
maintained by circulating hot water through the
cell jacket. For all measurements, the downstream
149
pressure was maintained at 0.67 kPa by applying
vacuum. The permeate vapor was collected in a
glass condenser suspended inside a cryostat
whose temperature was maintained at !15oC. The
experiment was run for 6 h with no change in flux
with time, confirming the steady-state operation.
The effective membrane area was 28.3×10!4 m2.
The permeate material collected in glass con-
denser was weighed in a weighing balance along
with the glass condenser. The weight of the
permeate was obtained by subtracting empty
glass condenser weight from condenser weight
along with permeate.
3.6. Analysis of permeate
The permeate material collected in glass con-
denser was analyzed for furfural content by UV-
spectroscopic analysis at 224.5 nm wavelength.
The flux (J) (g/(m2 h)) of permeation was
calculated from the following expression:
Q
J= (7)
At
where Q is the weight of permeate (either furfural
or water or whole permeate) obtained at time t
and A is the effective membrane area.
3.7. Estimation of membrane boundary
parameters
The separation factor for permeation (αp) of
furfural is expressed as
Ci 2 C j1
αp = (8)
Ci1 C j 2
where Ci1 and Ci2 are the concentrations of fur-
fural in feed and permeate and Cj1 and Cj2 are the
concentrations of water in feed and permeate,
respectively. The separation factor for partition
(αk), as defined below, was estimated by vapori-
zation and condensation of absorbate from a
150 U.K. Ghosh et al. / Desalination 208 (2007) 146–158

Fig. 1. Sketch of the experimental set-up. 1: Feed inlet; 2: Stirrer; 3: Thermometer pocket; 4: Feed chamber; 5: Permeate
chamber; 6: Sintered SS disk; 7: Condenser-cum-collector; 8: Cryosta.

swelled piece of membrane. This was done by 4. Results and discussion

heating the swelled membrane at 70oC in a sealed
glass vessel and the vapor was collected in the
cold trap connected to vacuum.
Ci 3 C j1
αk =
Ci1 C j 3
where Ci3 and Cj3 are the concentrations of
furfural and water, respectively, inside the mem-
brane. The separation factor for diffusion (αd) was
calculated from αp and αk as follows:
αp
αd = (10)
αk
The partition constant (Ki1) is defined as the ratio
of concentrations at the membrane boundary and
adjacent phase solution as
Ci 3
K i1 = (11)
Ci1
The permeability constant of furfural (Pi) was
measured following the equation
Pi = Di Ki1 (12)
The pervaporation of furfural–water mixture
through a polyurethaneurea membrane consists of
three consecutive steps [1]. The sorption of com-
ponents from the feed solution onto membrane,
(9)
the permeation (diffusion) through the membrane
and finally desorption from the membrane on the
permeate side under low-pressure. As such, it is
necessary to know the behavior of the membrane
with respect to furfural–water mixture before any
study of pervaporative separation. All the experi-
mental data (swelling, measurement of diffusion
coefficient and pervaporation) were checked for
their reproducibility and were found to be repro-
ducible within ±3%.
4.1. Membrane characterization
The separation performance of an organic–
water mixture through PUU membrane depends
upon the membrane morphology, i.e., distribution
of hydrophobic (soft) and hydrophilic (hard)
domains contributed by HTPB and urethane-urea
linkages, respectively. Urethane groups formed
by the reaction of isocyanate groups of TDI and
hydroxyl groups of HTPB and urea groups
formed by the reaction of isocyanate groups and
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158 151

Table 1
Composition of polyurethaneurea membranes and their swelling in aqueous furfural solution

Membrane Diaminea Soft block content Degree of swelling in aqueous furfural solution (%)
(mole %) (wt fraction)
at 30EC with at 30EC with at 60EC with
1.0 wt% solution 2.0 wt% solution 2.0 wt% solution

PUU20 20 0.82 6.8 10.9 19.2

PUU50 50 0.75 5.6 9.8 16.8
PUU70 70 0.72 4.2 7.8 13.8
PUU100 100 0.67 2.7 4.9 9.2

a
With respect of Mn of HTPB.

amine groups of the diamine chain extender
(DADPS) form the hard segment in the mem-
brane. HTPB contributes to the soft segment.
Since the soluble PUU molecules in THF are
highly sensitive to undergo crosslinking in con-
tact with moisture, the measurement of its mole-
cular weight could not be done at this stage. On
exposure to atmospheric moisture after casting
the membrane on petri dish, the PUU molecules
were crosslinked through allophanate bond
formation [17]. However, with gradual curing in
presence of moisture, the PUU molecules in the
membrane were crosslinked to form a three-
dimensional network of polyurethaneurea mole-
cules. Ultimately after complete curing the mole-
cular weight of the PUU system in the membrane
becomes infinite. The membrane designations,
compositions and characteristics are shown in
Table 1.
4.2. Swelling of polyurethaneurea membranes in
aqueous furfural solution
The swelling data of polyurethaneurea mem-
branes in aqueous furfural solution at different
furfural concentrations and different temperatures
are given in Table 1. It is evident from this table
that the membrane swelling varies with soft
segment content of polyurethaneurea. The degree
of swelling is minimum for PUU100 membrane
with lowest soft segment content (corresponding
to highest amount of diamine chain extender used
in the preparation of the polyurethaneurea mem-
brane). The degree of swelling increases with
increase in temperature for each of the mem-
branes as the chain mobility increases at higher
temperature to provide more free space in
polymer matrix for penetration. In addition,
Table 1 shows that the degree of swelling
increases as furfural content in the feed solution
increases. The increase in the degree of swelling
is attributed to the increasing plasticizing effect of
furfural at increasingly higher concentrations.
4.3. Effect of feed composition on permeate flux
The effect of feed composition on permeate
flux (total as well as individual) was investigated
over the furfural concentration range 1.0–6.0 wt%
of furfural at 30oC for PUU20 membrane. The
total flux and the individual fluxes of furfural and
water (which were calculated by using both the
total flux and permeate composition data) are
plotted in Fig. 2 as a function of feed furfural
concentration. It can be seen from Fig. 2 that the
total flux as well as furfural flux increases with
increasing furfural concentration in the feed
solution. The increase in furfural flux is attributed
to the increase in furfural activity in the feed
mixture at increasingly higher concentrations. It
152 U.K. Ghosh et al. / Desalination 208 (2007) 146–158

Fig. 2. Variation of permeate flux (total, furfural and Fig. 3. Variation of furfural concentration in permeate
water) with feed furfural concentration at 30EC for with feed furfural concentration for PUU20 and PUU100
PUU20 membrane. membranes (pervaporation temperature 30EC).

is expected that water flux would decrease with

the increase in feed furfural concentration as
activity of water decreases. But water flux
increases slowly with increase in feed furfural
concentration. At higher feed furfural concen-
tration sorption of furfural is higher and hence,
penetration of furfural is higher. The enhanced
penetration of heavier furfural molecules induces
penetration of water molecules through the
hydrophobic polyurethaneurea membrane. The
increase in water flux is due to this contribution
from the so-called bulk flow.

4.4. Effect of feed composition on furfural

concentration in permeate
The effect of feed composition on the furfural
concentration in permeate as well as the sepa-
ration factor for furfural was investigated over the
furfural concentration range 1.0–6.0 wt% of fur-
fural at 30oC for PUU20 and PUU100 membranes
(Figs. 3 and 4). Polyurethaneurea membranes
being hydrophobic in nature are selective toward
Fig. 4. Variation of separation factor for furfural with
feed furfural concentration for PUU20 and PUU100
membranes (pervaporation temperature 30oC).
furfural. At higher furfural concentration in the
feed solution penetration of furfural molecules
into the membrane is higher; thereby diffusivity
of furfural is higher. Consequently, furfural
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158
Fig. 5. Variation of total permeate flux with feed tem-
perature for polyurethaneurea membranes (feed furfural
concentration 2.0 wt%).
concentration in permeate was observed to
increase at higher feed furfural concentration.
4.5. Effect of temperature on permeate flux
The effect of temperature on permeate flux
(total as well as individual) was investigated over
the temperature range 30–75oC for 2.0 wt%
aqueous furfural solution as feed for the poly-
urethaneurea membranes (Figs. 5 and 6). The
total flux as well as furfural flux was seen to
increase with increase in temperature for all poly-
urethaneurea membranes. It is quite expected that
the increase in temperature increases the diffu-
sivity of furfural through the polymer membrane,
thereby increasing the total and furfural permeate
fluxes.
As shown in Fig. 6, water flux also increases
slowly with temperature and only at 75oC a slight
fall is observed. Overall, it may be assumed to be
constant. A possible explanation for this type of
behaviour is that the contribution of molecular
diffusion to the water flux is expected to be very
153
Fig. 6. Variation of permeate fluxes (furfural and water)
with feed temperature for PUU20 and PUU100 mem-
branes (feed furfural concentration 2.0 wt%).
less due to hydrophobic nature of the membrane
and hence no effect of temperature could be
observed.
4.6. Effect of temperature on furfural con-
centration in permeate
The effect of temperature on the furfural
concentration in permeate as well as the separa-
tion factor for furfural was investigated over the
temperature range 30–75oC for 2.0 wt% aqueous
furfural solution as feed for the polyurethaneurea
membranes (Figs. 7 and 8). The increase in
furfural selectivity with temperature for all the
membranes is evident as the diffusion of furfural
increases more rapidly than that of water with
temperature. This is expected as hydrophobic
polybutadiene segment of polyurethaneurea inter-
acts more with furfural than that with water. In
the swelling experiment, the extent of swelling of
membranes was seen to increase with the increase
of pervaporation temperature (Table 1). This
explains the affinity of furfural towards hydro-
154 U.K. Ghosh et al. / Desalination 208 (2007) 146–158

Fig. 8. Variation of separation factor with pervaporation

Fig. 7. Variation of furfural concentration in permeate temperature for polyurethaneurea membranes (feed
with pervaporation temperature for polyurethaneurea furfural concentration 2.0 wt %).
membranes (feed furfural concentration 2.0 wt%).

phobic polybutadiene soft segment, which

governs the diffusion of furfural into the mem-
brane and overall pervaporation process.

4.7. Effect of soft segment content of membrane

on permeate flux
The effect of soft segment content on the
permeate flux was investigated. Fig. 9 shows the
permeate flux (total as well as individual) as a
function of soft segment content in polyurethane-
urea membrane. Soft segment content decreases
from PUU20 to PUU100 membranes as the
concentration of diamine chain extender used for
the synthesis of polyurethaneurea membranes
increases. The total flux as well as the furfural Fig. 9. Variation of total and individual fluxes with
flux decreases as the soft segment content weight fraction of soft blocks in polyurethanerea
membranes (feed furfural concentration 2.0 wt%, feed
decreases. temperature 45oC).
As the percentage of diamine used increases,
the cross-linking in the membrane also increases
through the formation of urea and allophanates diffusion of the molecules through the polymer
linkages by reaction of diamine and free NCO matrix. Minimum flux was, therefore, observed
groups of PU oligomers and TDI [17]. Increase in for PUU100 membrane with minimum soft seg-
cross-linking density increases resistance to ment content. Higher furfural flux compared to
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158
Table 2
Diffusion and permeation parameters of 2.0 wt% furfural solution at 30oC
Membrane Furfural in membrane Pi ×1010 Di ×1012
(wt%) (m2/s) (m2/s)
PUU20 82.4 1.17 2.84
PUU50 82.8 1.88 4.54
PUU70 84.3 2.07 4.90
PUU100 86.1 2.35 5.46
water found in the temperature range as well as
concentration range of study indicates that the
polyurethaneurea membranes used for the perva-
poration study are highly furfural selective.
4.8. Effect of soft segment content of membrane
on furfural concentration in permeate
The effect of soft segment content on the
furfural concentration in permeate as well as the
separation factor for furfural was investigated
over the temperature range 30–75oC for aqueous
furfural solution with two different feed furfural
concentrations (Figs. 7 and 8). At a particular
temperature, separation factor for furfural as well
as furfural concentration in permeate were found
to increase from PUU20 to PUU100. Variation of
separation factor for furfural as well as furfural
concentration in permeate with soft segment
content of the membranes can be explained by
considering the change in sorption selectivity of
furfural and water into the membrane. Permea-
bility increases as the soft segment content in the
membrane decreases (Table 2). Permeability
depends on sorption selectivity of the membrane
and the sorption selectivity depends on flexibility
of the membrane. The flexibility of the polymer
chain decreases with increase in cross-linking. As
cross-linking increases, the spacing between two
polymer chains becomes narrower. The pene-
tration of less interactive water molecules through
hydrophobic polymer chain becomes more dif-
ficult and, as a result, separation factor for
155
Dj ×1013 αp(i,j) αk(i,j) αd(i,j)
(m2/s)
2.05 88.7 229.4 0.39
1.91 96.5 235.8 0.41
1.74 103.6 263.1 0.39
1.58 113.2 303.5 0.37
furfural as well as furfural concentration in
permeate was found to increase as the soft seg-
ment content of the membrane decreases.
4.9. Applicability of solution-diffusion model for
pervaporation of furfural–water mixture through
polyurethaneurea membranes
A comparative study of experimentally
obtained furfural flux with that obtained using the
solution-diffusion model was made and reported
in Table 3. It is evident from the results that the
experimentally obtained furfural fluxes are lower
than that predicted by the model. The extent of
deviation from model behavior is expressed by
permeation ratio (ΘFlux) (Table 3). ΘFlux value
decreases with the extent of deviation. Moreover,
the deviation of furfural flux increases with
increase in hard segment content of the
membranes. According to solution-diffusion
model, the flux of a component increases linearly
with diffusion/sorption coefficient. It means, the
increase in diffusion coefficient of furfural with
hard segment is not reflected properly in the
experimental furfural flux. Although solution-
diffusion model could not predict furfural flux
properly, it could throw some light on the
interaction of the furfural molecule with hard
segment of the polyurethaneurea membrane.
According to solution-diffusion model, the
furfural flux should increase with increase in hard
segment content of the membrane. Here, the
opposite trend is observed. As it is more so with
156 U.K. Ghosh et al. / Desalination 208 (2007) 146–158

Table 3
Comparison of experimentally obtained furfural flux with that obtained using solution–diffusion model for pervaporation
of furfural–water solution

Membrane Temperature Feed concentration Furfural flux, g/m2 h Extent of

(oC) (wt%) deviation, θFlux
Experimental Theoretical

PUU20 30 1.0 3.9 6.7 0.58

60 2.0 24.0 59.8 0.40
PUU50 30 1.0 3.4 7.1 0.49
60 2.0 22.4 57.0 0.39
PUU70 30 1.0 3.1 8.4 0.37
60 2.0 20.6 57.3 0.36
PUU100 30 1.0 2.9 8.9 0.33
60 2.0 17.2 61.2 0.28

increased furfural concentration in the feed, the
deviation from solution–diffusion model may be
due to increase in cohesion between the hard
segment and permeating furfural molecules due
to polar-polar interaction inside polyurethane
matrix, which retards desorption of furfural. This
cohesive force would be maximum for PUU100
having highest hard segment content, which in
turn shows maximum deviation from flux pre-
dicted by solution–diffusion model. This obser-
vation indicates the necessity of introducing
parameters like cohesive energy density, which
will take into account the chemical interactive
nature of the membrane materials with diffusing
species in those theoretical models.
5. Conclusions
Tailor made polyurethaneurea membranes
were tested for pervaporation characteristics of
aqueous furfural solution. The membranes were
found to be highly furfural selective, with furfural
separation factor as high as 638 and a permeate
flux as high as 44.7 g m!2 h!1. The total flux was
found to increase with temperature and concen-
tration of furfural in the feed. The partial flux of
furfural increased with an increase in furfural
content in the feed and with an increase in feed
temperature. The furfural flux as well as sepa-
ration factor for furfural was seen to vary with
concentration of diamine chain extender used for
polyurethaneurea membrane synthesis. The high-
est separation factor for furfural is associated with
the membrane with lowest soft segment content.
The overall pervaporation process was observed
to be diffusion controlled. The membranes were
found to be highly suitable for the separation of
furfural from furfural-water mixtures, between
the experimental boundaries used in this study.
6. Symbols
A — Effective membrane area (m2)
C — Molar concentration (mol m!3)
Ci1 — Concentration of component i (fur-
fural) at feed side (g m!3)
Ci2 — Concentration of component i (fur-
fural) at permeate side (g m!3)
Cj1 — Concentration of component j (water)
at feed side (g m!3)
Cj2 — Concentration of component j (water)
at permeate side (g m!3)
Di — Diffusion coefficient of furfural
(m2 s!1)
 U.K. Ghosh et al. / Desalination 208 (2007) 146–158
Dj — Diffusion coefficient of water (m2 s!1)
J — Flux of furfural (g m!2 h!1)
Ki1 — Partition coefficient of component i
between feed and membrane
Ki2 — Partition coefficient of component i
between permeate and membrane
l — Thickness of membrane (m)
m — Mass of the swelled foil (g)
mo — Mass of the dry polymer foil (g)
mt — Fractional weight gain of membrane
at time t
mα — Fractional weight gain of membrane
at equilibrium swelling
Pi — Permeability constant of furfural
Pi1 — Partial pressures of component i at
membrane boundary of feed side
(J m!3)
Pi2 — Partial pressures of component i at
membrane boundary of permeate side
(J m!3)
Q — Weight of permeate (g)
R — Universal gas constant (J mol!1 K!1)
t — Time (h)
T — Temperature in absolute scale (K)
Vi — Molar volume of furfural (m3)
Greek
αd — Separation factor for diffusion
αk — Separation factor for partition
αp — Separation factor for permeation
ΘFlux — Permeation ratio
β — Enrichment factor
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