Chemical Engineering and Processing 50 (2011) 227–235

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Review

A review of membrane selection for the dehydration of aqueous ethanol by

pervaporation
Brian Bolto ∗ , Manh Hoang, Zongli Xie
CSIRO Materials Science and Engineering, Private Bag 33, Clayton South MDC, Victoria 3169, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Four broad types of membranes are categorised: organic polymers generally, crosslinked poly(vinyl alco-
Received 12 July 2010 hol), organic–inorganic hybrids and charged polymers. The best performers in terms of flux, which reaches
Received in revised form a maximum of 5 kg/m2 h, are anionic or cationic polymers, including polysalts. Polyanion and polysalt
19 December 2010
membranes are superior. Two examples are thin layers of the active polysalt membrane on a support-
Accepted 11 January 2011
ing membrane. The best combination for flux and selectivity is a polyethyleneimine/poly (acrylic acid)
Available online 28 January 2011
polysalt deposited on a reverse osmosis membrane, at 4 kg/m2 h and 1075 respectively. It is noticeable
that hybrid poly(vinyl alcohol)/inorganic membranes do not show enhanced fluxes. Very high separation
Keywords:
Pervaporation
factors were observed, covering a range of polymers, of neutral, anionic or cationic character. The top
Polar polymers results (>10,000) were for charged membranes, either cationic or anionic, but not polysalts. The fluxes
Polyanions encountered here were miniscule, the best being caesium alginate at about 1 kg/m2 h. The ideal structure
Polycations for high fluxes would appear to be one containing discrete domains of oppositely charged species of
Polysalts optimal size. Fresh approaches are being actively studied, such as layer-by-layer deposition of oppositely
charged polyelectrolytes, with due attention to appropriate separation of the sites of opposite character.

Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
2. Pervaporation membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.1. Membranes based on organic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.2. Crosslinked PVA membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2.3. Hybrid PVA/inorganic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.4. Modified chitosan membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2.5. Other polymers containing charged groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
2.6. Membranes formed from polysalts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3. Best performing membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234

1. Introduction
tion on one side, while permeate is removed as a vapour from the
Membranes can be used for the selective removal of water from other side [1]. Transport through the membrane is driven by the
aqueous organic mixtures. The knowledge gained from this area vapour pressure difference between the feed solution and the per-
can influence the design of membranes for other water treatment meate vapour. The vapour pressure difference can be maintained
processes. Pervaporation (PV), aimed at the separation of liquid by applying a vacuum on the permeate side, or by cooling the per-
mixtures, involves a membrane that is in contact with the feed solu- meate vapour so that it condenses, thus creating a partial vacuum.
Commercial systems for the dehydration of concentrated alcohol
and other solutions have been developed since the 1980s, much of
∗ Corresponding author. Tel.: +61 3 9545 2037; fax: +61 3 9545 1128. the push coming from interest in the production of pure ethanol
E-mail address: brian.bolto@csiro.au (B. Bolto). as an alternative liquid fuel, where PV can be used to dehydrate

0255-2701/$ – see front matter. Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2011.01.003
228 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235

Table 1
PV dehydration of ethanol through various polymeric membranes [4,5].

Polymer Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

Regenerated cellulose 50 45 5.0 2060 [4,47]

Cellulose acetate 4 60 5.9 200 [4]
Teflon-g-polyvinylpyrrolidone 4 25 2.9 2200 [50]
Perfluorinated polymer on PAN support 1.3 50 387 1650 [5]
Nafion-H+ 4 70 2.5 5000 [36]
Polyacrylonitrile-polyvinylpyrrolidone 4 20 3.2 2200 [51]
Poly(maleimide-co-acrylonitrile) 15 15 33 8 [52]
Poly(acrylic acid-co-acrylonitrile) 18 15 877 13 [53]
Polystyrene 4 40 101 5 [54]
Poly(vinyl chloride) 4 40 63 3 [55]
Alginic acid 4 40 8.8 48 [56]
5 60 13 2800 [37]

Chitosan 4 40 2208 4 [16]

Chitosan acetate salt 4 40 2556 2 [21]
Chitosan/glutaraldehyde 4 40 202 7 [21]
PVA/25% TEOS, annealed at 160 ◦ C 15 40 329 5 [4]
PVA/25% TEOS, annealed at 130 ◦ C 15 40 893 4 [4]

azeotropic ethanol/water mixtures [2]. The 200–500-fold separa-
tion achieved is due entirely to the selectivity of the membranes
used, which are much more permeable to water than to ethanol.
More than 100 plants for the dehydration of ethanol have been
installed, the largest processing 5000 kg/h [1].
PV data can be expressed in a number of ways [1]. The bulk
of the literature expresses them in terms of the total flux through
the membrane and a separation factor. The flux of a component i
through a PV membrane can be expressed in terms of the partial
vapour pressures pio and pit on either side of the membrane by
PG
i there are no data to tell whether any nanoporosity or the like is
Ji = (pio − pit )
l present in the membranes mentioned so far. It may be that the
where Ji is the flux, l is the membrane thickness and PG
i is the
gas separation permeability coefficient.
The separation factor ˛sep can be defined for a two-component
liquid system as the ratio of the two components on the permeate
side divided by the ratio of the two components on the feed side of
the membrane. Thus
PH2 O /PEtOH
˛sep =
FH2 O /FEtOH
these membranes may be highly crosslinked. This survey of the
different polymer types is somewhat crude as there are crucial
variables that are not taken into account. Only one publication
has been found where further variables are addressed, with the
data being normalised by the authors to remove the effects of
different membrane thicknesses and an applied pressure or vac-
uum [6]. Crosslinked membranes exhibited less swelling, had a
higher separation factor, but lower water permeability, measured
as g␮m/m2 h kPa. The results are included in Table 2 and will be
discussed further under the heading of charged polymers.
Of course the physical format of the membranes is crucial, but
different heat treatment on crosslinking PVA results in enhanced
crystallinity, with more pronounced channels on the molecular
scale being formed between the crystalline regions, thus facilitat-
ing transport. In the choice of appropriate membranes, crosslinked
PVA is pertinent because of its very hydrophilic nature [7]. A wide
range of crosslinking agents has been employed in the fabrication
of PVA membranes.

where PH2 O and PEtOH are the mass fractions of water and ethanol
in the permeate, and FH2 O and FEtOH are the mass fractions of water
and ethanol in the feed [3].
2. Pervaporation membranes
2.1. Membranes based on organic polymers
A general survey of the permeation characteristics of a variety
of organic polymers in the treatment of aqueous ethanol solutions
of low water content was published by an early reviewer in the
field, and is given in Table 1 [4]. It is difficult to get a consis-
tent picture, but it would seem that the non-polar polystyrene and
poly(vinyl chloride) membranes are responsible for moderate sep-
aration factors and low fluxes. A recent example of a hydrophobic
active layer of a commercial amorphous perfluorinated polymer on
a polyacrylonitrile (PAN) supporting membrane gives, a moderate
separation factor, but with a much higher flux [5]. However, the
very hydrophilic poly(vinyl alcohol)/tetraethoxysilane (PVA/TEOS)
and chitosan products also show low flux behaviour. The highest
fluxes are those for the hydrophilic membranes based on cellulose
and Nafion, and grafts of hydrophilic poly(vinyl pyrrolidone) on
Teflon and polyacrylonitrile. The PVA/TEOS membranes are excep-
tions in that they are hydrophilic, but exhibit low fluxes. However,
2.2. Crosslinked PVA membranes
An amic acid has been used as a crosslinker for PVA [8].
Imidisation at 150 ◦ C gave an improved membrane for the PV of
aqueous ethanol when there was 12 wt% crosslinker present. More
crosslinker showed the reverse effect because of the dispersion
of unreacted crosslinker within the membrane. Separation factors
ranged from 70 to 380 and permeation rates from 30 to 1600 g/m2 h
at 30–75 ◦ C, depending on the operating temperature and feed
mixture composition. At 45 ◦ C the separation factor was 100 and
the permeation rate 200 g/m2 h when the feed contained 30 wt%
water (Table 3). As the water concentration increased, the separa-
tion factor decreased and the permeation rate increased. This was
explained by the plasticising effect of water, making the amorphous
regions of the PVA membrane more swollen, as the polymer chains
become more flexible. At 75 ◦ C the permeation rate was 500 g/m2 h,
with the separation factor little changed.
Crosslinking of PVA with maleic acid or citric acid has been
used to prepare membranes for permeation studies of water and
lower aliphatic alcohol mixtures [9]. Citric acid gave more selec-
tive behaviour than maleic acid, with the selectivity being highest
for water–isopropanol and water–isobutanol systems. For the
water–ethanol system the selectivity was 80 and the flux 495 g/m2 h
for a 30% aqueous solution at 30 ◦ C.
 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235 229

Table 2
Normalised separation data for PV dehydration of ethanol with modified PVA membranes [6].

Membrane synthesis Feed, wt% Temp., ◦ C Water permeability, Permselectivity Reference

water g␮m/m2 h kPa

Poly(ethylene glycol) blend and TEOS 15 50 0.17 218 [17]

Poly(acrylic acid) 15 40 18 17* [16]
copolymer and TEOS 250
Sulphated zirconia crosslinker 10 50 5.6 80 [7]
Acrylic acid graft 4.4 60 3.0 3.5 [8]
␥-aminopropyl-triethoxysilane 15 50 3.0 63 [3]
Quaternised PVA uncrosslinked 15 50 13 58 [6]
Quaternised PVA and glutaraldeyde 15 50 8.0 75 [6]
*
No poly(ethylene glycol).

Table 3
PV dehydration of ethanol as a function of PVA crosslinking agent.

Crosslinker Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

None 4.6 75 721 247 [32]

Amic acid to imide 30 45 100 200 [8]
30 75 95 500 [8]

Citric acid 30 30 80 495 [9]

PAA 50 75 60 2800 [11]
PVA/GA containing PAA/EG IPNs 5 50 50 260 [12]
Fumaric acid 20 100 211 1511 [13]
20 80 411 771 [13]
20 60 779 217 [13]

Glutaraldehyde 10 30 180 50 [14]

20 30 150 130 [15]
10 40 104 280 [15]
20 30 – 93 [34]

PVA (MW 50 kDa) has been crosslinked with poly(acrylic acid) or
PAA (MW 2 kDa) by heat treatment at 150 ◦ C for 1 h [10]. The prod-
ucts have been used for the PV of methanol/methyl tert-butyl ether
mixtures, and later ethanol–water mixtures [11]. For 50 wt% water
ethanol solutions the separation factor was 60 at 75 ◦ C and the flux
2800 g/m2 h. Interpenetrating networks (IPNs) of PVA crosslinked
with glutaraldehyde (GA) containing PAA crosslinked with ethy-
lene glycol (EG) have similarly low permeation rates to PVA/GA
membranes, with semi-IPNs giving the better results [12].
Fumaric acid, trans-HO2 C CH CH CO2 H, has been employed
as the crosslinking agent at 0.05 mole per mole of PVA in multilayer
membranes formed on a polyacrylonitrile support membrane [13].
In the PV of 20 wt% water in ethanol, the separation factors varied
from 779 to 211 over the temperature range 60–100 ◦ C, and fluxes
from 217 to 1511 g/m2 h.
The dehydration of ethanol and other alcohol/water mixtures
has been explored with PVA membranes crosslinked with GA [14].
At 30 ◦ C the flux was 50 g/m2 h for ethanol of 10 wt% water content,
and 130 g/m2 h when the water content was 20 wt%. The corre-
sponding separation factors were 180 and 150. The flux increased
with increasing water content, while the reverse was the case with
the separation factor. The flux also increased with the feed temper-
ature, but the separation factor was lowered.
From the summary of the results obtained for variously
crosslinked PVA membranes given in Table 3 it can be seen that
the highest fluxes are obtained when the crosslinking agent is a
carboxylic acid, which could arise from the ionic component in the
polymer network. The charge is dependent on the pH of the sys-
tem, so it would be illuminating to see how performance varies with
pH. There is no comparable performance with alginic acid though
PV of 10 wt% water in ethanol at 40 ◦ C, the fluxes ranging from
249 to 313 g/m2 h and the separation factors from 69 to 108. The
details are given in Table 4. The more crosslinked membranes are
less hydrophilic as OH groups are consumed in the crosslinking
reaction, and the membranes are more rigid, making for greater
obstruction to diffusion within.
2.3. Hybrid PVA/inorganic polymers
Membranes made from PVA crosslinked with 25 wt% of TEOS
have been prepared for the PV of aqueous ethanol, with the aim
of minimising the swelling of the PVA [4]. Annealing of the mem-
branes under nitrogen at temperatures of 100, 130 and 160 ◦ C was
needed to complete the condensation reaction that introduced
bridging and crosslinking, when higher selectivity resulted. As
shown in Table 5, the best result, for a 15 wt% water mix in ethanol
at 40 ◦ C, was a separation factor of 893 and a flux of 40 g/m2 h when
the annealing temperature was 130 ◦ C, versus 329 and 50 g/m2 h
respectively when annealing was at 160 ◦ C. It was postulated that
the crosslinking reaction took place in the non-crystalline parts of
the PVA membrane, forming denser non-crystalline regions.
Annealing also improved the selectivity of similar membranes
made from poly(vinyl alcohol-co-acrylic acid) [16]. In one example
the separation factor was 250 for a 15 wt% aqueous ethanol at 40 ◦ C,
and a flux of 18 g/m2 h. Blends of PVA and poly(ethylene glycol) or
PEG have been crosslinked with TEOS and annealed at 130 ◦ C to
Table 4
Influence of degree of GA crosslinking of PVA on PV of 10% aqueous ethanol at 40 ◦ C
[15].

(Table 1). Likewise with the ethylenediamine salt of Nafion, or chi- Swelling degree, % Flux, g/m2 h Water selectivity
tosan, except for the GA crosslinked material, the latter having a 28.4 313 69
high flux. 27.9 302 84
Similar GA crosslinked membranes have been reported and 27.1 289 93
their swelling properties explored [15]. The more crosslinked, less 26.5 279 107
24.8 249 108
swollen membranes had lower fluxes but higher selectivities in the
230 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235

Table 5
PV dehydration of ethanol using PVA/inorganic hybrid membranes.

Crosslinker Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference
◦
TEOS (160 C) 15 40 329 50 [4]
TEOS (130 ◦ C) 15 40 893 40 [4]
PEG blend and TEOS 15 50 300 46 [17]
No PEG 15 50 160 500 [17]
Poly(acrylic acid) copolymer and TEOS 15 40 250 18 [16]
␥-aminopropyl-triethoxysilane 5 50 537 36 [3]
Sulphated zirconia 5 50 263 10 [18]
10 50 142 105 [18]
20 50 86 183 [18]
30 50 61 1036 [18]

produce a membrane with a separation factor of 300 for a 15 wt%
water mix in ethanol at 50 ◦ C [17]. The presence of PEG decreased
the flux from 500 to 46 g/m2 h, but almost doubled the separation
factor (Table 5).
When ␥-aminopropyltriethoxysilane was used for crosslink-
ing PVA, the hydrophilicity of the membranes increased when the
silane content was <5%, and the permeation increased remarkably
while the selectivity increased at the same time, thus breaking the
trade-off between the two [3]. With a feed containing 5 wt% water
the separation factor was 537 and the flux 36 g/m2 h at 50 ◦ C.
PVA has been crosslinked with the solid acid of sulphated zir-
conia by an acid-catalysed reaction which affected the degree of
swelling and the crosslinking density of the membrane [18]. For the
same duty, both flux and selectivity were lower than for the silane
products (Table 5). The flux increased with feed water content,
while the selectivity decreased.
Overall, by comparison with the results for organically
crosslinked PVA membranes (Table 4), the data in Table 5 show
that there is no advantage in introducing inorganic particulates into
PVA. The story is quite different for totally inorganic membranes
such as those based on zeolites, which have been reviewed recently
[19]. They are beyond the scope of the present paper. An LTA zeo-
lite membrane can give extremely high fluxes of 12, 15, 18 and
22 kg/m2 h at 100,110, 120 and 130 ◦ C respectively in dehydrating
a 93 wt% ethanol mixture.
2.4. Modified chitosan membranes
Another highly hydroxylated polymer, chitosan, or poly(2-
amino-2-deoxy-d-glucose), has been used to make PV membranes.
It has a cationic charge when the amino group is protonated. At neu-
tral pH levels it is slightly charged with 17% of the amino groups
being protonated [20]. A chitosan acetate membrane has more
than 10 times the separation factor of chitosan itself, as does a GA
crosslinked chitosan [21], as detailed in Table 6. Very low flux lev-
els were obtained with all these membranes for feeds of low water
contents.
Chemical modification of chitosan has been carried out by
carboxylation, sulphonation or phosphorylation to produce PV
membranes [22]. The phosphorylated products [23] gave the high-
est flux in dehydrating ethanol, with a selectivity of 541 and a flux
of 180 g/m2 h for mixtures containing 10 wt% water at 70 ◦ C. Other
variants such a sulphonation or carboxymethylation had much
higher selectivities, but lower fluxes. It was proposed that phos-
phorylation formed phosphates at the C-6 position in the glucose
units, reducing the chain relaxation markedly because of the bulky
side chain and crosslinking. A less packed structure would make the
membrane more relaxed and mobile, allowing passage of ethanol
and resulting in a lower selectivity.
Blends of chitosan with hydroxyethylcellulose that have been
crosslinked with a urea–formaldehyde–sulphuric acid mixture pro-
duce PV membranes with the very high selectivity of 10,491 when
the hydroxyethylcellulose content is 50 wt% [24]. The addition of
the blending agent increases the hydrophilicity of the membranes,
and since the hydroxyethyl group is larger than the amino group in
chitosan, there is an increased flexibility and openness in the poly-
mer network. The fluxes measured were many times those of the
unmodified chitosan membranes.
Likewise, in the preparation of PV membranes for
ethanol dehydration, chitosan has been crosslinked with 3-
aminopropyltriethoxysilane to form chitosan–silica hybrid
membranes [25]. The hydrophilicity of the membranes increased
with increasing amounts of the crosslinker, reaching a maximum
when the content was 10 wt%. The flux and separation factor
increased as a result, compared to the unmodified chitosan mem-
brane. The crosslinking limited the swelling of the polymer. It was
claimed that there were strong hydrogen bonds as well as covalent
bonds formed, along with a lowering of crystallinity. Thus the
FTIR spectrum showed an intense absorption band at ∼1072 cm−1 ,
indicating that esterification took place between the OH groups
in the polymer and the silanol groups in the crosslinker, to form
C O Si bonds. If the second ethoxy group reacts with the OH
in another chain, bridges can occur. The crosslinking makes the
polymer chains in the amorphous regions more compact, resulting

Table 6
PV dehydration of ethanol using chitosan-based membranes.

Chitosan product Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

GA crosslinked 4 40 2208 4 [21]

Uncrosslinked 202 7 [21]
Acetate salt 2556 2 [21]
Phosphorylated 10 70 541 180 [22,23]
Acetate salt 242 142 [22,23]
Sulphonated & GA 1560 52 [22,23]
Carboxymethylated 1294 36 [22,23]
Carboxyethylated 301 30 [22,23]
Cyanoethylated 52 80 [22,23]
Hydroxyethylcellulose 50% blend 10 60 10,491 112 [24]
10% 3-aminopropyl-triethoxysilane 15 50 597 887 [25]
Uncrosslinked 15 50 200 275 [25]
 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235 231

Table 7
PV dehydration of aqueous ethanol with chitosan membranes in various forms [26].

Chitosan format Feed, wt% water Temp., ◦ C Sepn. Factor Flux, g/m2 h

99% deacetylated 5 70 5.4 840

99% deacetylated 4.4 40 17 65
73% deacetylated 8 35 1240 6
Crosslinked with GA 10–50 40 >2000 –
98% deacetylated-HOAc 10 60 123 400
98% deacetylated-HCl 10 60 593 210
98% deacetylated-H2 SO4 10 60 1040 160
98% deacetylated-non-ionised 10 60 36 350

Table 8
PV dehydration of 20% aqueous ethanol at 70 ◦ C using graft polymer membranes having different charges [27].

Host polymer Grafted polymer Graft site charge Separation factor Flux, g/m2 h

Polyvinylidene fluoride 4-vinylpyridine Neutral 9 200

Polyvinylidene fluoride N-vinyl-imidazole Neutral 10 1600
Polyvinyl fluoride N-vinylmethyl- acetamide Neutral 4 2900
Polyvinyl fluoride N-vinyl-pyrrolidone Neutral 7 1000
Polyacrylonitrile Acrylic acid Neutral 10 1800
Polyacrylonitrile K+ acrylate Anionic 500 3000
Polyvinyl fluoride K+ acrylate Anionic 156 4700
Polyvinylidene fluoride Quaternised 4-vinylpyridine Cationic 175 400
Polyvinylidene fluoride Quaternised N-vinylimidazole Cationic 61 1800
Polyvinylidene fluoride 4-vinylpyridine/BrCH2 COOH Zwitterionic 76 200
Polyvinyl fluoride Vinylimidazole/BrCH2 COOH Zwitterionic 63 1250

in less space for species to permeate through the membrane and
making the resistance to flow higher for the larger species.
Research into various forms of chitosan has shown that a lighter
level of deacetylation of the original chitin is beneficial as regards
the separation factor, as is crosslinking of chitosan with GA, or hav-
ing the amino groups in the salt form when the anion involved is
divalent, as shown in Table 7 [26]. However, the fluxes obtained
were all low.
2.5. Other polymers containing charged groups
The use of hydrophilic membranes for the dehydration of
organic solvents in general by PV has been the subject of compre-
hensive reviews [27,28]. The emphasis is on selectivity, postulated
to be determined by selective sorption and selective diffusion.
Selective sorption is governed by the presence in the membrane
of active centres such as charged sites which are capable of spe-
cific interaction with water, while selective diffusion is governed
by the rigidity and regularity of the polymer structure and the
nature of the polymer interspace, exemplified by the degree of
swelling and the frequency of the crosslinks. The results for a series
of membranes made by grafting neutral or charged polymers onto
supporting membranes are given in Table 8. A neutral amide graft
and an anionic acrylate graft produced the highest moderate fluxes.
Charged membranes formed by crosslinking PVA with 7 wt% of
a sulphosuccinic acid yields membranes that in the separation of
10/90 wt% water/ethanol at 60 ◦ C have a separation factor of 240
and a flux of 180 g/m2 h [29]. At 70 ◦ C the results are 175 and
300 g/m2 h respectively. When the lithium salt of the crosslinker
was prepared, it showed lower results of 44 and 59 g/m2 h, but at
50 ◦ C and with 5 wt% crosslinker, as shown in Table 9 [30].
Quaternised poly(acrylonitrile-co-3-N ,N -dimethylaminopro-
pylacrylamide) has been used as a PV membrane for dehydrating
ethanol [31]. The selectivity factor increased with decreasing lev-
els of water in the feed solution, reaching over 15,000 for the fully
quaternised polymer at 30 ◦ C when the water content was 10 wt%.
However, the flux was then only 10 g/m2 h.
Cationic and anionic PVA membranes have been
made by reacting PVA with a catalyst and 3-chloro-2-
hydroxypropyltrimethylammonium chloride or phosphoric
acid [32]. Performance depended on the degree of substitution
(DS), the separation factor increasing with an increase in the DS for
the cationic membrane, to 1540 for the higher DS, but decreasing
in the case of the anionic membrane. For the cationic membrane
both selectivity and flux were improved by a higher DS, which
is unusual. The highest flux was still not impressive though, and
levels were higher for the anionic than the cationic membrane.
Cationic and anionic PVA membranes have been made also via
copolymers with acrylamidopropyltrimethylammonium chloride
or with itaconic acid [15]. The degree of swelling decreased from
neutral to cationic to anionic PVA with values of 26.5%, 15.7% and
14.0% respectively. Here the anionic PVA gave better performance
than the cationic derivative, in contrast with the other examples in
Table 9. The anionic membrane had 2.5 times the separation factor
of the neutral PVA, at 837 versus 335 for one duty. The flux was
correspondingly lower (86 g/m2 h versus 189 g/m2 h).
The plasma modification of GA crosslinked PVA membranes
by grafting acrylic acid onto them gave membranes which had
enhanced hydrophilicity [33]. The fluxes ranged from 122 to
144 g/m2 h for 96 wt% ethanol at 25–60 ◦ C, and the separation fac-
tors from 23 to 8. The respective results for unmodified membranes
were 75–120 g/m2 h and 19–10. Other work on PVA crosslinked
with GA reports fluxes of up to 93 g/m2 h for the PV of ethanol
containing 20 wt% water at 30 ◦ C [34]. Incorporating sericin, the
gelatinous protein that binds the fibres in silk, into PVA that is
crosslinked with dimethylolurea gives a membrane that is only
moderately selective to water [35]. The crosslinker reacts with the
OH groups of the polymers leaving the amino groups in sericin free
to interact with water.
As shown in Table 2, a quaternised PVA, made by grafting
2,3-epoxypropyltrimethylammmonium chloride onto the polymer
and then crosslinking with GA has been tested [6]. The quater-
nary ammonium groups reduced the crystallinity of the polymer
and enhanced the hydrophilicity and water permselectivity. The
results are still modest: a membrane with 4% quaternisation
had a water permselectivity of 58 and a water permeability of
13 g␮m/m2 h kPa for 15% aqueous ethanol at 50 ◦ C. The data here
have been normalised by the authors to remove the effects of
different membrane thickness and applied pressure or vacuum.
Crosslinked membranes exhibited less swelling, and had a higher
232 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235

Table 9
PV dehydration of ethanol with membranes containing charged groups.

Polymer and charged species Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

PVA/7 wt% sulphosuccinic acid 10 70 175 300 [29]

10 60 240 180 [29]

PVA/5 wt% Li+ sulphosuccinate 10 50 44 59 [30]

Quaternised poly(acrylo-nitrile-co-3-N ,N - 10 30 >15,000 10 [31]
dimethyl-aminopropyl
acrylamide)
Cationic PVA* 4.6 75 424a 216 [32]
4.6 75 1540b 249 [32]

Anionic PVA* 4.6 75 398c 632 [32]

4.6 75 72d 407 [32]

Unmodified PVA 4.6 75 721 247 [32]

Cationic PVA/GA† 4 40 709(216) 89(123) [15]
Anionic PVA/GA† 4 40 837(228) 86(119) [15]
PVA/GA† 4 40 335(107) 189(279) [15]
PVA/GA acrylic acid 4 40 14 135 [33]
Plasma graft 4 60 8.4 144 [33]
Unmodified PVA 4 40 15 91 [33]
4 60 10 120 [33]

PVA/9% acrylic acid graft 10 15 800 7 [27]

20 15 700 10 [27]

PVA/sericin blend 8.5 50 90 70 [35]

*
DS: a, 2.9%; b, 5.2%; c, 2.3%; d, 5.0%.
†
The data in parentheses are for a down stream pressure of 0.4 kPa; the rest are for a down stream pressure of 1.4 kPa.

water permselectivity of 75, but a lower water permeability of
8.0 g␮m/m2 h kPa.
Nafion sulphonic acid membranes have been tested for the influ-
ence of the counterion on PV performance [36]. The data (Table 10)
show that the acid form has a much greater flux than the various salt
forms, no doubt because of the less space occupied by the proton
versus the cations studied.
Alginic acid has been tested for PV behaviour [37]. It was found
that the selectivity factor increased enormously when the acid
was neutralised with alkali, from 19 to over 10,000, while the
flux decreased markedly, with the acid form again exhibiting by
far the highest flux. The counter ion influenced the flux in the
order Na+ < K+ < Rb+ < Cs+ < H+ , which was ascribed to a change in
the conformation of the alginate molecule so that its mobility was
increased, as was the mobility of the ion hydration shell and the
crystallinity of the membrane. The conformational change was ver-
ified by 13 C NMR. A blend of sodium alginate with PVA crosslinked
with 1.5 wt% maleic acid had a lower separation factor than the
membrane without the PVA [38].
Ion exchange membranes in the form of styrene-based qua-
ternary ammonium and sulphonated polyethylene containing
different counter ions have been tested, to give the results shown in
Table 10 [2]. The sulphonic acid membrane had a much higher flux
than the sodium salt, by a factor of several hundred, somewhat sim-
ilar to the Nafion and alginic acid experiences. The selectivity was
correspondingly lower. Diffusion of liquid water through the con-
tinuous pathway of water shells around charged groups is claimed
to be faster than diffusion through clusters of free water in the
membrane [39].
Membranes have been made by modifying poly(vinyl
chloride) or PVC membranes by reacting them with
sodium N-methyldithiocarbamate or sodium N-methyl-N-
carboxydithiocarbamate, and then with metal ions such as Li+ , Ca++
and Cu++ [40]. The Cu++ complex showed an extremely high selec-
tivity of >5000 in the dehydration of ethanol at high water contents
(80 wt%). Various salt forms of sulphonated polyamide membranes
have been tested [41]. There was little variation in selectivity, but
the flux decreased in the order PEI+ > K+ > NEt4 + > Cs+ > Na+ , where
PEI is polyethyleneimine, which had by far the greatest influence
on selectivity (Table 10). Mixing two polymers of opposite charge
like this forms a polysalt.
2.6. Membranes formed from polysalts
It has been speculated that polysalts, formed from anionic and
cationic polyelectrolytes, would be appropriate for obtaining both
highly permeable and highly selective membranes [27]. Earlier
work on PV with membranes formed from sodium polyacrylate and
various cationic polyelectrolytes [42,43] is summarised in Table 11.
Having a quaternary ammonium structure in the backbone
of the cationic polymer appears to be advantageous as regards
selectivity, but less so for the epichlorohydrin/dimethylamine
(ECH/DMA) polymer, where the presence of an OH group may
be a handicap. The flux levels are again not impressive. Several
membranes based on polysalts have been explored, as detailed in
Table 12. The highest flux results were from structures based on
cellulose sulphate as the polyanion [44], plus one based on sodium
carboxymethyl cellulose, or Na+ CMC, and chitosan [45] or poly(N-
ethyl-4-vinylpyridinium bromide) [46].
Other physical structures affecting membrane behaviour have
been examined as ways to enhance the flux. Thus a porous poly-
sulphone membrane has been coated with a polysalt formed from
chitosan and poly(acrylic acid), and the composite membrane
tested for PV of aqueous ethanol [47]. For dehydration of 5 wt%
aqueous ethanol at 30 ◦ C, when compared with the dense homoge-
neous membrane that is unsupported, the composite version had a
flux of 132 g/m2 h versus 33 g/m2 h and a separation factor of 1008
versus 2216 (Table 12). The composite membrane was only supe-
rior for solutions of high ethanol content. For all membranes both
parameters increased with heating for feeds of high water con-
tent (>30 wt%), which is unusual. This was ascribed to the strong
sorption contribution to the activation energy for PV with these
membranes. For optimal performance the ratio of membrane thick-
ness to the permeation characteristics of the dense layer and the
porous supporting membrane had to be appropriate. One way of
achieving this is to use a layer-by-layer deposition method, which
allows one to choose which thickness of active membrane skin is
the best.
 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235 233

Table 10
Effect of counter ion on PV dehydration of ethanol with membranes containing charged groups.

Polymer and charged species Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference
+
Nafion-H 4 70 2.5 5000 [36]
Nafion-Na+ 4 70 5.0 500 [36]
Nafion-K+ 4 70 9.8 200 [36]
Nafion-N(CH3 )3 + 4 70 10.5 340 [36]
Alginic acid 10 60 19 1300 [37]
Li+ alginate 10 60 11,400 100 [37]
Na+ alginate 10 60 11,600 210 [37]
K+ alginate 10 60 11,600 550 [37]
Rb+ alginate 10 60 11,600 750 [37]
Cs+ alginate 10 60 10,000 1030 [37]
Na+ alginate-PVA blend 10 45 380 380 [38]
Anion exchanger-SCN− 15 60 38 470 [2]
Sulphonated PE-H+ 16 26 2.6 1360 [2]
Sulphonated PE-Na+ 16 26 671 80 [2]
PVC/dithiocarbamate-Cu++ 40 25 63 20 [40]
80 25 >5000 103 [40]

Polyamide sulphonate-Na+ 20 60 1.3 160 [41]

Polyamide sulphonate-K+ 20 60 2.1 230 [41]
Polyamide sulphonate-Cs+ 20 60 1.4 11 [41]
Polyamide sulphonate-NEt4 + 20 60 1.5 18 [41]
Polyamide sulphonate-PEI+ 20 60 11 14 [41]

Table 11
PV dehydration of 5% aqueous ethanol at 70 ◦ C with membranes based on polysalts where the polyanion is sodium polyacrylate [42,43].

Polycation Carbon backbone Charged group Charged site Separation factor Flux, g/m2 h
+
Polyethyleneimine –CH2 CH2 – –NH2 – Backbone 220 830
Polyallylamine –CH2 CH2 – –CH2 NH3 + Pendant 750 510
Ethylene/phenylene dimethylammonium Ditto & –CH2 C6 H4 CH2 – –N+ (CH3 )2 – Backbone 1710 790
Propylenedimethyl-ammonium –(CH2 )3 – –N+ (CH3 )2 – Backbone 1940 820
ECH/DMA polymer –CH2 CH(OH)CH2 – –N+ (CH3 )2 – Backbone 830 340
Trimethylammoniumethyl methacrylate –CH2 C(CH3 )– –N+ (CH3 )3 Pendant 380 220

Table 12
PV dehydration of aqueous ethanol with membranes based on various polysalts.

Polyanion Polycation Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

Poly(acrylonitrile-co-acrylic acid) Poly(acrylonitrile-co-vinyl pyridine) 10 – 5000 400 [44]

Cellulose-SO3 − Na+ Polyethyleneimine 16 50 295 1900 [45]
Cellulose-SO3 − Na+ PolyDADMAC, linear 16 50 140 3200 [45]
Cellulose-SO3 − Na+ Same, but branched 16 50 123 4900 [45]
Cellulose-SO3 − Na+ Poly-N,N-dimethyl-3,5- 16 50 123 2700 [45]
dimethylenepiperidine
chloride
Aromatic polyamide sulphonate Polyethyleneimine 20 60 15 300 [41]
Poly(acrylic acid) Chitosan
On polysulphone Supporting membrane 5 30 1008 132 [47]
No supporting Membrane 5 30 2216 33 [47]

Na+ polystyrene sulphonate Polyallylamine.HCl 6.2 70 70 230 [57]

Na+ CMC Chitosan 10 70 1062 1140 [45]
Na+ CMC N-ethyl-4-vinyl-pyridinium bromide 10 70 782 1320 [46]
Anionic PVA, Cationic PVA,
DS 2.3% DS 2.9% 4.6 75 2250 378 [32]
DS 5.0% DS 5.2% 4.6 75 1910 284 [32]

3. Best performing membranes
The best performers in terms of flux, which at a maximum of
5 kg/m2 h never achieve high values, are charged polymers of one
type or another, including polysalts. Table 13 shows that anionic
and polysalt membranes are superior. For anionic polymers, the
proton form has a significantly higher flux than the metal or qua-
ternary ammonium salt versions, owing to the greater free space
within the polymer network. Two of the polysalt examples involve
thin layers of the active membrane on an RO or UF supporting mem-
brane. They also exhibit the highest separation factors. The best
combination for flux and selectivity is PEI/PAA on an RO membrane,
at 4 kg/m2 h and 1075 respectively. It is interesting to note that
hybrid PVA/inorganic membranes do not show enhanced fluxes,
the best being PVA/sulphated zirconia, at just over 1 kg/m2 h, so
there is no great advantage in incorporating inorganic fillers within
the membrane. External factors enhancing the flux include heat-
ing, and an increased water content, which follows from greater
swelling and a low level of crosslinking. However, crosslinking can
occur while maintaining the swollen state. It is very difficult to com-
pare different membranes in terms of fluxes and separation factors
as these parameters are not only a function of the intrinsic proper-
ties of the membranes themselves, but rely also on the operating
conditions such as temperature permeate pressure and the feed
concentration [48,49]. So for membranes tested under different
conditions, caution needs to be applied in attempting comparisons.
234 B. Bolto et al. / Chemical Engineering and Processing 50 (2011) 227–235

Table 13
Highest fluxes for PV dehydration of aqueous ethanol.

Membrane polymer Mem. type Feed, wt% water Temp., ◦ C Flux, g/m2 h Separation factor Reference
+
Nafion-H Anionic 4 70 5000 2.5 [36]
Cellulose-SO3 − Na+ and polyDADMAC, branched Polysalt 16 50 4900 125 [44]
K+ acrylate graft on poly(vinyl fluoride) Anionic 20 70 4700 156 [27]
PEI/PAA on RO membrane Polysalt 10* 70 4050 1075 [58]
Cellulose-SO3 − Na+ and polyDADMAC, linear Polysalt 16 50 3200 140 [44]
K+ acrylate graft on PAN Anionic 20 70 3000 500 [27]
PolyDADMAC/Na+ CMC on UF membrane Polysalt 10* 75 3000 960 [59]
*
Aqueous isopropanol, not ethanol.

Table 14
Highest separation factors for PV dehydration of aqueous ethanol.

Membrane polymer Mem. type Feed, wt% water Temp., ◦ C Separation factor Flux, g/m2 h Reference

Quaternised poly(acrylo-nitrile-co-3-N ,N - Cationic amide 10 30 >15,000 10 [31]

dimethyl-aminopropyl
acrylamide)
Metal alginate salts (Na+ , K+ , Rb+ , Li+ or Cs+ ) Anionic 10 60 11,600–10,000 100–1030 [37]
Chitosan/50% blend with hydroxyethylcellulose Cationic 10 60 10,491 112 [24]
PVC/dithiocarbamate-Cu++ Anionic 80 25 >5000 103 [40]
Chitosan acetate Cationic 4 40 2556 2 [57]
PVA crosslinked with GA Neutral 10–50 40 >2000 – [26]

A range of very high separation factors is shown in Table 14
for the top selective performers. A variety of polymer types are
included, of neutral, anionic or cationic character. The top results
(>10,000) are for charged membranes again, either cationic or
anionic, but not polysalts. The fluxes encountered here are minis-
cule, the best being caesium alginate at about 1 kg/m2 h. External
factors that improve the flux, such as heating and increased water
content, have detrimental effects on the separation factor.
4. Conclusions
The ideal structure for good fluxes would appear to be one
containing discrete domains of oppositely charged species of opti-
mal size, such that internal neutralisation is minimised. Possible
solutions could be a tightly crosslinked non-polar host polymer
containing charged nanoparticles, or a crosslinked block copolymer
that has dual substitution. The influence of a number of parameters
needs to be determined, such as the minimum desirable size of the
charge domain, the distance between oppositely charged sites, and
the role of counter ions. Fresh approaches are needed; one such
could be layer-by-layer deposition of oppositely charged polyelec-
trolytes, with due attention to appropriate separation of the sites of
opposite character. Imperfect matching of the oppositely charged
centres would create an open structure. A greater understanding of
the free volume within charge mosaic membranes, as provided for
example by positron annihilation lifetime spectroscopy, is needed.
Better insight into the detailed crosslinked structure of the mem-
branes could be provided by using a synchrotron light source.
As well as the water content of the aqueous ethanol feed, tem-
perature is a crucial parameter, the benefit of which is attributed
to the increase in diffusivity and reduction in flow viscosity that
occurs on heating. Mechanical energy in the form of extra applied
pressure or vacuum can likewise be called upon to enhance the flux.
The thickness of the membrane is another vital factor: the active
layer should be as thin as possible. The inherent permeability of the
membrane polymer is similarly important. The main parameters
for better water flux are therefore
• Higher feed water temperature
• Increased pressure/vacuum
• [10] J.-W. Rhim, Y.-K. Kim, Pervaporation separation of MTBE-methanol mixtures
Thinner membranes
• Improved membrane permeability
Hence expenditure on thermal energy will improve the water
flux. Cheaper thermal sources that could be exploited are solar,
geothermal and industrial waste heat.
A related process is vapour permeation, which employs a poly-
meric a membrane as a semi-permeable barrier between a feed
side under high pressure and a permeate side under low pressure
[60]. It differs from PV in that the feed is a vapour and not a liq-
uid, so that there is no phase change or significant temperature
difference across the membrane. The membranes work according
to a solution–diffusion mechanism. Separation is achieved by the
different degrees to which components are dissolved in and dif-
fuse through the membrane. The material used in the membrane
will hence depend on the types of compounds being separated – a
variety of organic and inorganic membranes can be used [61,62].
The driving force can be approximated to the difference in partial
pressures of the components in the feed.
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