Journal of Membrane Science 335 (2009) 96102

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Journal of Membrane Science

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Use of pervaporation for the separation of phenol from dilute aqueous solutions
Xiaogang Hao, Mark Pritzker, Xianshe Feng
Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, Canada N2L 3G1

a r t i c l e

i n f o

Article history:
Received 19 January 2009
Received in revised form 23 February 2009
Accepted 28 February 2009
Available online 14 March 2009
Keywords:
Pervaporation
Phenol
Preferential sorption
Solubility selectivity

a b s t r a c t
Separation of phenol from dilute aqueous solutions by pervaporation using poly(ether block amide) (PEBA
2533) membranes was investigated as a means of recovering phenol from wastewater streams. The effects
of feed concentration (up to 1 wt%) and operating temperature (5080 C) on the separation performance
were studied in terms of permeation ux and selectivity. Although the phenol ux increased as its feed
concentration rose, the rate at which it increased diminished at higher concentration, resulting in a
decrease in the enrichment factor. It was also shown that an increase in temperature increased both the
phenol ux and selectivity. Experiments conducted to study the preferential sorption of the permeant
in the membrane with respect to the membrane permselectivity found that the phenol concentration in
the sorbed phase could reach as high as 8090 wt% at a phenol concentration of 2 wt% in the aqueous
solution. The high permselectivity of the membrane to phenol was primarily due to its high solubility
selectivity. It should be noted that this high permselectivity can cause the concentration of phenol in
the permeate to become high enough for it to precipitate. This is of particular interest from an industrial
point of view because the enriched phenol permeate can be easily recovered upon phase separation.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Phenols constitute a family of hydroxy aromatic compounds in
which the aromatic rings are bonded directly to hydroxyl groups.
Phenol concerned in this study is the simplest member of this family. It has a high boiling point (181.8 C) and limited solubility in
water (8.7 wt% at 25 C). Phenols are important raw materials
in the petrochemical, pharmaceutical, plastic and pesticide industries. They are also common pollutants often found in wastewater
streams from petroleum reneries, coal conversion processes, as
well as the production of phenolic resins, dyes and pesticides [1].
Phenols are highly toxic and are not easily degraded biologically
at high concentrations (>200 mg/L). The separation and recovery
of phenolic substances from industrial wastewater streams are of
signicant interest from an environmental perspective.
Conventional methods for phenol recovery from wastewater
include solvent extraction [2,3], adsorption with activated carbon and polymers [4,5] and precipitation [6]. Unfortunately, these
approaches are usually uneconomical to use when the phenol components are present at low concentrations. Recently, membrane
processes have attracted attention as an alternative technique for
the removal of low volatile organic compounds from wastewater [79]. Pervaporation is considered to hold great promise for
such applications [9]. Pervaporation separation has many advan-

Corresponding author. Fax: +1 519 746 4979.

E-mail address: xfeng@uwaterloo.ca (X. Feng).
0376-7388/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2009.02.036

tages: minimal energy consumption, no regeneration needed,

no addition of an entrainer and thus no secondary contamination.
There has been signicant interest in applying pervaporation for
recovering phenol from wastewater. For such applications, membranes based on siloxane polymers (especially poly(dimethyl siloxane) [1016] and urethane polymers [1721] have been used extensively. Since phenol has a relatively low vapor pressure (0.055 kPa at
25 C), the driving force for phenol transport in pervaporation is low,
and thus the mass transfer rate is generally low. Alternative membranes with good phenol permeability have also been pursued,
including poly(ether block amide) (PEBA) [15,16,22], a glassy polymer of intrinsic microporosity [23], and ethanepropenediene terpolymer (EPDM) [24]. Among these membranes, PEBA has shown
excellent permselectivity to phenol [15,16]. Boddeker et al. [22] prepared membranes using three different grades of PEBA polymers
(Shore D hardness 35, 40 and 55) for pervaporation separation of
phenol from low feed concentrations (below 1000 ppm). The use
of a PEBA membrane (Shore D hardness 40) was further tested by
Kujawski et al. [15,16] over a wider range of phenol concentrations
(08 wt%) in the feed. However, the effects of temperature, which
is an important operating parameter, on the pervaporation performance of the PEBA membranes were not investigated in either
study. At present, no commercial membrane is, to our knowledge,
available for phenol separation by pervaporation.
PEBA is a family of copolymers with micro-biphasic structures
consisting of hard polyamide and soft polyether segments in the
polymer chains. They exhibit many properties that are not readily

X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

97

available in either constituent polymer alone. The properties of

a specic PEBA polymer depend on the nature and contents of
the polyamide and polyether segments. In comparison to the
aforementioned grades of PEBA membranes, PEBA 2533 (Shore D
hardness 25) has a higher polyether content (80 wt%), which is
expected to yield a better permselectivity for phenol separation
due to its good afnity to phenol. In the present work, PEBA 2533
was chosen as the membrane material to investigate the pervaporative separation of phenol from aqueous solutions. The effects
of temperature and feed concentration on the membrane performance were evaluated. To help better understand the permeation
behavior, sorption studies were also conducted to determine the
solubility of phenol in the membrane.

permeate sample collected over a given period of time. The compositions of the feed and permeate mixtures were determined using
a Shimazu TOC-500 total organic carbon analyzer with a standard
deviation in measurements of 1%. To determine the membrane
permselectivity at a given feed concentration, the quantity of permeate removed by the membrane during each pervaporation run
was kept below 0.1% of the initial feed loading so that the feed composition remained essentially constant during a pervaporation run.
The membrane performance was measured in terms of permeation
ux (J) and separation factor () or enrichment factor (), which
are dened as

2. Experimental

Yp /Yw
Xp /Xw

(2)

Yp
Xp

(3)

J=

2.1. Material
Phenol with a purity of over 99.5 wt% was purchased from
Aldrich Chemical. The feed solutions of various compositions used
in the pervaporation and sorption experiments were prepared by
dissolving a pre-determined amount of phenol in de-ionized water.
PEBA polymer (grade 2533) was kindly supplied by Arkema Inc. It
comprises of 20 wt% nylon 12 as the amide segments and 80 wt%
poly(tetramethylene oxide) as the ether segments. Reagent grade
N,N-dimethyl acetamide supplied by Aldrich was used to dissolve
PEBA during membrane preparation.
2.2. Membrane preparation
The membrane was prepared by the solution casting technique.
Briey, PEBA 2533 was dissolved in N,N-dimethyl acetamide to form
a homogeneous solution of 15 wt%. The dissolution was facilitated
by heating the mixture to 70 C under vigorous agitation. The polymer solution was allowed to stand without disturbance for at least
1 day to remove entrapped gas bubbles. To prepare the membranes,
the polymer solution was cast onto a glass plate kept at 70 C, followed by evaporation of the solvent at 70 C in an oven for 1 day.
The membrane was then completely dried in a vacuum oven at
50 C for about 24 h to remove any residual solvent. The thickness of
the membranes used for pervaporation experiments was measured
by a Mitutoyo micrometer to be 30 m. Thicker membranes (ca.
120 m) were also prepared for use in the sorption and desorption
experiments.
2.3. Pervaporation
Pervaporation experiments were carried out in a laboratoryscale pervaporation system described elsewhere [25]. It consisted
of a feed tank, circulation pump, membrane cell, two cold traps and
a vacuum pump. The membrane was housed in a pervaporation
cell comprised of two detachable stainless steel parts set in proper
alignment. Rubber O-rings were used to provide a pressure tight
seal between the membrane and the permeation cell. The effective
area of the membrane for permeation was 20.4 cm2 . The apparatus
was also equipped with temperature and vacuum regulators to control and monitor the operating temperature and pressure. The feed
tank was thermostated by means of a microcomputer-controlled
heating system. After being installed in the cell, the membrane was
conditioned by pumping the feed solution across it for 3 h prior to
pervaporation tests. In all the experiments, the feed was circulated
through the membrane cell at 1.6 L/min, while keeping the permeate pressure below 1 mbar. The permeate vapor was condensed and
collected in a Pyrex glass cold trap immersed in liquid nitrogen. The
permeation rate was determined gravimetrically by weighing the

m
A t

(1)

where m is the weight of permeate sample collected over a period

of time t and A is the effective membrane area. X and Y are feed
and permeate concentrations (expressed as weight fraction), and
subscripts p and w denote the phenol and water component, respectively. In dilute systems, Xw 1 and so the separation factor will be
close in value to the enrichment factor unless the permeate is substantially enriched with phenol. The pervaporation data reported
represent an average of at least two measurements obtained from
replicate membrane samples. The experimental error was estimated to be within 5%.
In order to demonstrate the efciency of pervaporation for phenol removal from wastewater, batch pervaporation experiments
were also performed. The quantity and composition of the retentate
and permeate were determined at different times.
2.4. Sorption and desorption experiments
Sorption experiments were conducted by immersing membrane
(weight, Wo ) samples into aqueous solutions of phenol for at least
48 h at various concentrations (ranging from 0.05 to 2 wt%) maintained at different temperatures. The sorption was considered to
have reached equilibrium when no further increase in liquid uptake
with time was observed. To determine the total sorption uptake of
water and phenol in the membrane, the membrane sample was
taken from the solution, blotted quickly with Kimwipes to remove
excess liquid on the surfaces and then weighed to yield the wet mass
Wt . Immediately afterward, the wet membrane was dried under
reduced pressure at room temperature to remove water and the
sample re-weighed to yield the dry mass Wd . The sorption uptake
can be calculated using the following equations:
sorption uptake of phenol (g/g-membrane) =
sorption uptake of water (g/g-membrane) =

Wd Wo
Wo

Wt Wd
Wo

(4)

(5)

The phenol concentration in the sorbed phase is given by

phenol concentration in membrane (wt%) =

Wd Wo
100
Wt Wo

(6)

It may be mentioned that in the sorption experiments, relatively

thick membranes (120 m) were used in order to obtain enough
sorbate inside the membrane and more accurate measurements.
The sorption data reported are the average of at least two replicate
measurements.

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X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

Fig. 2. Effect of phenol concentration in the feed on the partial permeation uxes
of phenol and water at various temperatures.
Fig. 1. Effect of phenol concentration in the feed on permeation ux and permeate
phenol concentration at various temperatures.

3. Results and discussion

3.1. Effects of feed concentration and temperature on membrane
permselectivity
Fig. 1 shows the effects of feed concentration on the permeation
ux and the phenol concentration in permeate at different temperatures (5080 C). At a given temperature, the permeate phenol
concentration was found to increase signicantly with an increase
in the feed phenol concentration. A permeate phenol concentration
as high as 19.7 wt% was obtained at 80 C with a feed containing 0.86 wt% phenol. On the other hand, the total permeation ux
tended to increase only slightly with an increase in feed phenol
concentration before decreasing when the phenol content in the
feed reached above about 0.6 wt%. These results are understandable
on the basis of the solution-diffusion mechanism. A higher phenol content in the feed will lead to a higher sorption uptake in the
membrane, which causes membrane swelling and a more loosened
structure of the polymer matrix. In a swollen polymer, the mobility
of the polymer segments is enhanced and the free volume available
for diffusion is increased. As a result, membrane swelling caused by
permeating species generally leads to increased diffusivity through
the membrane. On the other hand, from the perspective of the driving force, a rise in phenol concentration in the feed increases the
driving force for permeation. For dilute solutions, with an increase
in the phenol concentration in the feed, both the driving force and
the membrane permeability for the permeation of phenol increase.
For water permeation, however, the driving force tends to decrease
with an increase in the feed phenol concentration, but the decrease
is relatively insignicant because phenol is the minor component
over the feed concentration range studied in which phenol content
remained below 1.04 wt%. The feed concentration is thus expected
to affect phenol permeation more signicantly than that of water.

This is conrmed in Fig. 2 showing the variation in the partial permeation uxes of phenol and water with feed concentration at
different temperatures. It is also evident that such a trend becomes
more signicant at elevated temperatures. However, when the phenol concentration becomes too high, clustering of phenol molecules
due to hydrogen bonding will occur, which tends to reduce their diffusivity and permeability. The effect of feed concentration on the
enrichment factor is shown in Fig. 3. As with many other pervaporation systems for organic removal from water, the enrichment
factor is high at low feed concentrations and decreases as the feed
concentration increases.

Fig. 3. Effect of phenol concentration in the feed on the separation factor at various
temperatures.

X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

99

Table 1
Pervaporation performance of phenolwater separation with different membranes.
Membranea

Feed phenol conc. (wt%)

Temp. ( C)

Membrane thickness (m)

Total

Phenol

PDMS
PDMSI
PIM-1
PUU

2
3
1
3

70
60
70
70

50
100
40
150

0.37
0.147
0.21
0.019

0.07
0.057

Polyurethane

80

PEBA 4033

80
70
60

PEBA 2533

0.60.8

80
70

30

80

Permeation ux (kg/(m2 h))

Separation factor

Reference

0.0125

21
20
16
64

[10]
[12]
[23]
[17]

0.62
0.4
0.225

0.15
0.1
0.075

35
40
30

[19]

1.6
1.1

0.26
0.16

28
23

This work

[22]

a
PDMS: polydimethylsiloxane; PDMSI: polydimethylsiloxaneimide: PIM-1: A polydioxane polymer with intrinsic microporosity; PUU: polyurethaneurea; PEBA 4033:
poly(ether block amide) (Shore D hardness 40).

Depending on feed concentration and operating temperature,

the phenol concentration in the phenol-enriched permeate can be
substantially higher than its solubility limit at ambient temperature and thus phase separation will occur. At 25 C, the solubility of
phenol in water is 8.7 wt%, while that of water in phenol is 28.7 wt%
[26]. The permeate composition data in Fig. 1 represent the overall
phenol concentration; the permeate sample was diluted with water
to ensure a homogeneous aqueous phase for the purposes of composition analysis. Thus, from an industrial application point of view,
if the phenol concentration is above its solubility limit, the phenolenriched permeate can be easily separated in a decanter into two
liquid phases: an aqueous phase containing 8.7 wt% phenol and an
organic phase containing 71.3 wt% phenol. The two phases can be
easily separated for further recovery and purication: The aqueous phase can be recycled to the process for enhanced recovery,
while the phenol phase can be puried by, for example, crystallization. It is worth mentioning that some phenol crystals were
obtained on the wall of the permeate cold traps during the experiment due to vapor deposition at sub-atmospheric pressures. This
phenomenon could also be exploited in practical applications for
phenol purication because of the vacuum available in the cold trap
during pervaporation.
The PEBA membrane in general compares favorably with other
membranes in terms of permselectivity for phenol separation.
Table 1 summarizes the performance data reported in the literature for other membranes used to remove phenol from aqueous
solutions at concentrations ranging from 1 to 3 wt%. Although it
is difcult to make a direct comparison because the experimental conditions were not always the same, the permeation ux
obtained with this PEBA membrane is quite high as compared to
those obtained with other membranes. This ux could be further
improved by using ultrathin PEBA membranes fabricated by solution casting on a water surface [27]. It should be pointed out that
the polyurethaneurea membrane of Gupta et al. [17] (who used
BrO3 /Br redox titration for composition analysis) seems to have
the greatest selectivity among all the membranes shown in Table 1.
However, there appear to be signicant discrepancies and contradictions in the performance data reported for the polyurethaneurea
membranes in these studies. For example, at a given feed phenol
concentration, the permeate phenol concentration was shown in
Ref. [17] to decrease with an increase in temperature, whereas the
opposite trend was reported in Ref. [18] for the same membrane.
It was even shown more recently [20] that a higher pervaporation
selectivity would be obtained when the membranes became highly
porous (with pore diameters 34 m!). While the intention of the
present study is not to evaluate the validity of the performance
data of the polyurethaneurea membranes, it appears clear that one
should be very cautious in assessing their excellent reported permselectivities.

At a given feed concentration, the temperature dependence of

the partial permeation of phenol and water was found to follow
an Arrehnius type of relation, as shown in Fig. 4. Pervaporation is
considered to occur as a solution-diffusion process. An increase in
temperature will make the permeating molecules more energetic
and thus increase their permeation ux due to increased diffusivity.
At the same time, an increase in temperature facilitates the thermal
motion of the polymer chains in the membrane, making it easier
for permeating molecules to move in the membrane. In addition,
the driving force for permeation through the membrane increases
with temperature because of the increased saturated vapor pressure on the feed side. All these aspects contribute to the enhanced
permeation ux. However, as will be discussed later, the solubility of the permeant in the membrane generally decreases with an
increase in temperature, which affects the permeation ux negatively. The data shown in Fig. 4 represent the observed overall
temperature dependency of permeation ux, which can be characterized by the apparent activation energy for permeation. Fig. 5
shows the effect of feed phenol concentration on the activation
energies for phenol and water permeation. In general, the activation energy for phenol permeation is higher than the activation

Fig. 4. Semilog plot of permeation ux versus reciprocal temperature illustrating

the Arrhenius type of temperature dependence of the permeation ux.

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X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

Fig. 5. Effect of phenol concentration in the feed on the apparent activation energies
for permeation of water and phenol through the PEBA membrane.

energy for water permeation, except at very low feed concentrations (below 800 ppm).
It is interesting to note that the effect of the feed concentration on the activation energy of permeation is different for phenol
and water. With an increase in phenol concentration in the feed,
the activation energy for water permeation tends to decrease in
a linear fashion, while the activation energy for phenol permeation initially increases and then decreases when the feed phenol
concentration is sufciently high (>0.9 wt%). The permeation of
phenol through the PEBA 2533 membrane is thus more temperature
sensitive than water permeation over a broad range of the feed concentrations studied. The apparent activation energy has accounted
for the heat of evaporation of the permeant [28]. In consideration
of the heats of evaporation of phenol and water (which are 45.6
and 41.2 kJ/mol, respectively [29]), it appears clear that the true
activation energy for the permeation of phenol molecules is greater
than the permeation activation energy of water molecules. This is
in agreement with physical reasoning. The activation energy for
permeation represents an energy barrier to be overcome by the permeating molecules. Because of the smaller size of water molecules,
the energy barrier for water to permeate through the membrane is
relatively low. Due to the good afnity between phenol molecules
and the membrane to be discussed later, an increase in the feed phenol concentration will lead to a more exible and loose membrane
structure because of membrane plasticization and swelling, which
should therefore lower the activation energy for water permeation.
On the other hand, phenol is the minor species in the feed solutions
in this study. Due to the proximity of the hydrophobic aromatic ring
and hydrophilic OH group, phenol molecules tend to form complexes with surrounding water molecules by phenol insertion in
water clusters [30,31], resulting in a higher activation energy for
permeation. As the phenol concentration is raised, complex formation should become more signicant and so lead to the rise in
activation energy shown in Fig. 5. In addition to phenolwater clusters, phenol molecules can also interact with each other to form
hydrogen-bonded clusters [32]. It is expected that the feed phenol
concentration will affect both the number and the sizes of the clusters and consequently inuence the activation energy for phenol
permeation as well.
3.2. Preferential sorption with respect to selective permeation
In consideration that phenol is larger (0.51 nm) than water
(0.26 nm) [33], the preferential permeation of phenol over water is
thus believed to derive from the solubility selectivity. To gain assess

Fig. 6. Variation of the equilibrium sorption uptake of phenol and water in the PEBA
membrane with equilibrium phenol concentration in solution at various temperatures.

whether the high permselectivity of phenol in the PEBA membrane

is due to the preferential sorption, we conducted sorption experiments to measure the solubility of the permeants in the membrane.
Fig. 6 shows the equilibrium sorption uptake of phenol and water
over a concentration range of 02 wt% at various temperatures. In
spite of the fact that phenol is a minor component in the solution
over the concentration range investigated, the experimental data
shown in Fig. 6 indicate that phenol is substantially more soluble in
the PEBA membrane than water. For example, at a phenol concentration of 1 wt% in the solution, the phenol uptake in the membrane
at 80 C reaches 0.18 g/g-polymer, which is nearly eight times that
of water uptake. At a given temperature, the sorption uptakes of
both phenol and water in the PEBA membrane increase almost linearly with the phenol concentration in the solution. It should also
be noted that the phenol sorption uptake is more strongly inuenced by the phenol concentration in the solution than is the water
sorption uptake. This can be attributed to the strong interactions
between the permeating components. If no phenolwater interactions occurred, an increase in the phenol concentration would
decrease the sorption uptake of water because of a decrease of its
activity. However, the phenolwater clustering due to their strong
hydrogen bonding helps drag water molecules into the membrane
when phenol molecules enter the membrane.
Fig. 6 further shows that at a given concentration of phenol
in solution, the sorption uptake decreases as the temperature
increases, indicating the sorption process is exothermic. Analogous to the temperature dependence of permeation ux, replotting
the sorption uptake versus reciprocal temperature on a semilogarithmic scale also yields a straight line (Fig. 7). The heat of
sorption for water on the membrane is shown to be about twice
the heat of sorption for phenol. Thus, although a lower temperature favors the permeation due to increased solubility, an increase
in temperature will favor preferential sorption of phenol over
water in the membrane. The high sorption selectivity for phenol
is demonstrated in Fig. 8, which shows the variation of the phenol concentration in the sorbed phase with its concentration in
the solution. In the solution concentration range of 0.12.0 wt%
phenol, the sorbate in the membrane reaches a phenol concentration of 8090 wt% at 353 K, corresponding to a solubility separation
factor of 4504000. The high solubility of phenol in the membrane is attributed to the excellent afnity between phenol and
the PEBA material. It appears clear that the high permselectivity of
the membrane derives primarily from its high solubility selectivity.
This preferential sorption of phenol in the membrane presum-

X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

101

Fig. 9. Variation of phenol composition in the feed solution as a function of time

during batch pervaporation. Symbols represent the experimental data, while the
solid lines represent the behavior obtained by tting the model given in Eqs. (7) and
(8).

the diffusivity selectivity that favors water permeation. This agrees

with the experimental observation that phenol concentration in
the permeate is lower than the corresponding concentration in the
sorbed phase at a given feed concentration and temperature (see
Figs. 1 and 8).
Fig. 7. Semilog plot of sorption uptake versus reciprocal temperature.

ably forms the basis for pervaporative separation of phenol from

aqueous solution. This is consistent with the general observation
that in the separation of organic compounds from dilute aqueous solutions by pervaporation using organophilic membranes, the
selective permeation of the organic compounds often results from
their preferential sorption in the membrane [3436]. According
to the solution-diffusion model, the mass transport from the feed
side to the permeate side is controlled not only by the sorption
step but also inuenced by the diffusion through the membrane.
Water molecules, which are smaller than phenol molecules, are
expected to have a larger diffusivity in the membrane and so the
diffusivity step should be less favorable for the preferential permeation of phenol. Thus, the sorption selectivity must compensate for

3.3. Batch pervaporation

The performance of the PEBA 2533 membrane for the removal
of phenol from wastewater was further investigated by batch
pervaporation. In a batch process, the permeate stream is continuously removed while the retentate stream is recycled back to
the system. Fig. 9 shows that the phenol concentration in the feed
tank decreases as pervaporation proceeds. The experimental data
demonstrate the high efciency of the PEBA membrane for the
recovery of phenol. For an initial feed loading (F0 ) per membrane
area (A) of 50 kg/m2 , over 80% of phenol can be removed in 3 h at
80 C when the initial feed concentration is 1000 ppm. As expected,
the time required to reach a given degree of phenol removal was
signicantly inuenced by the F0 /A ratio and temperature. While
temperature affects the membrane permselectivity, F0 /A represents
the processing capacity per membrane area.
Based on material balances, a mathematical model has been
developed to analyze the effects of the process parameters during
batch pervaporation [37]. For a special case where the instantaneous partial ux Jo of the organic compound is proportional to
its concentration X in the feed (i.e., Jo = mX) and the total ux Jt is
approximately constant (i.e., Jt = ) (which is often approximately
true for dilute solutions), the mathematical treatment can be simplied substantially to yield the following equations:

t=

F0
1
A

Ym =

Fig. 8. Variation of the equilibrium phenol concentration in the sorbed phase with
equilibrium phenol concentration in solution, demonstrating preferential sorption
of phenol in the membrane.

 X /(m) 
X0

X0

m/(m)

X m/(m)

/(m)
X0

X /(m)

(7)

(8)

where t is the processing time required to bring down the feed

concentration from an initial value of X0 to a target value of X and Ym
is the concentration of the accumulated permeate. For the phenol
separation system studied here, Eqs. (7) and (8) should apply for
a low phenol concentration range (below 0.5 wt%). The values of
m and obtained by data tting are listed in Table 2. This model
was therefore tted to the experimental data presented in Fig. 9 and

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X. Hao et al. / Journal of Membrane Science 335 (2009) 96102

Table 2
Empirical parameters m and (in kg/(m2 h)) for phenol and water permeation.
Temperature ( C)

60
70
80

0.72
1.01
1.31

9.93
18.5
30.0

found to be in good agreement. With this model, the membrane area

required for a given batch time or the batch time required for a given
membrane system to remove a specied amount of phenol from
a solution using a PEBA membrane can be determined, which is
important for process design and scale-up. In addition, the quantity
and concentration of the phenol-enriched permeate product can
also be predicted by the model.
4. Conclusions
The pervaporative separation of phenol from dilute aqueous
solutions using PEBA 2533 membrane was studied. It was shown
that the good permeation separation factor of the membrane for
phenol/water separation was derived from the solubility separation factor. The membrane exhibited excellent preferential sorption
to phenol over water. At a solution concentration of 0.12.0 wt%
phenol, the phenol concentration in the sorbed phase could reach
8090 wt%. The membrane performance was affected by phenol
concentration in the feed, especially at elevated temperatures. The
partial permeation ux of phenol rose with an increase in feed phenol concentration, while water ux was not signicantly affected. At
80 C and over feed concentrations from 300 to 8000 ppm, phenol
uxes from 0.017 to 0.26 kg/(m2 h), permeate phenol concentrations from 1.7 to 19.7 wt% and enrichment factors in the range
of 2060 were achieved. Depending on operating conditions (i.e.,
temperature and feed concentration), phenol concentration in the
permeate could be high enough to induce phase separation (or even
precipitation) at ambient conditions; the aqueous phase that is saturated with phenol could then be recycled back to the system for
enhanced recovery.
Acknowledgements
Research support from the Natural Sciences and Engineering
Research Council (NSERC) of Canada is acknowledged. Dr. Xiaogang
Hao gratefully acknowledges support provided by the Shanxi Scholarship Council of China for a research leave at the University of
Waterloo. The PEBA polymer was generously supplied by Arkema
Inc.
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