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Vacuum 79 (2005) 215–220


www.elsevier.com/locate/vacuum

Pervaporation separation of ethylacetate–water mixtures


through a crosslinked poly(vinylalcohol) membrane
Yavuz Salt, Ayc- a Hasanoğlu, İnci Salt, Sevinc- Keles-er,
Semra Özkan, Salih Dinc- er
Chemical Engineering Department, Yıldız Technical University, Davutpas- a Campus, 34210 Esenler-Istanbul, Turkey
Received 20 September 2004; received in revised form 14 March 2005; accepted 24 March 2005

Abstract

The pervaporation separation of ethylacetate–water mixtures was carried out using poly(vinyl alcohol) membranes
prepared by crosslinking with tartaric acid. Pervaporation experiments were conducted for 1–2.5 wt% water containing
ethylacetate–water binary mixtures at 30 1C, 40 1C and 50 1C. It is observed that permeation rates increased and
selectivity decreased with increasing content of water in the feed. As a result of variations in fluxes, with an increase in
temperature, the selectivity increased for the 2 and 2.5 wt% water containing mixture, but decreased for the 1 wt%
water content. However, the selectivity of the 1.5 wt% water containing mixture decreased slightly. The ethylacetate
and water fluxes showed almost the same trend with both temperature and water concentration changes in the feed.
Meanwhile, the variation amount between fluxes of ethylacetate at 40 1C and 50 1C was evidently less than those of
fluxes at 30 1C and 40 1C.
r 2005 Elsevier Ltd. All rights reserved.

Keywords: Pervaporation; Ethylacetate–water mixture; Crosslinked poly(vinylalcohol); Membranes

1. Introduction water and the separation of organic mixtures, and


provides several advantages: easy process design,
Pervaporation as a membrane separation pro- high selectivity, low energy consumption and
cess is today considered a basic unit operation with moderate cost to performance ratio etc[1–4]. In
significant potential in a wide range of applica- the pervaporation process, the feed mixture is
tions, such as the dehydration of organic com- maintained in contact with one side of a mem-
pounds, the recovery of organic compounds from brane which selectively permeates one of the feed
components. As the component passes through the
Corresponding author. Tel.: +90 212 449 1925; membrane its partial pressure drops below its
Fax: +90 212 449 1895. equilibrium vapour pressure, and therefore it
E-mail address: dincer@yildiz.edu.tr (S. Dinc- er). leaves the membrane as a vapour by application

0042-207X/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2005.03.010
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216 Y. Salt et al. / Vacuum 79 (2005) 215–220

of vacuum. The separation achieved is propor- The mixture of ethylacetate and water is
tional to the rate of permeation of the components azeotropic, and miscible phases occur at composi-
of the mixture through the membrane [5,6]. tions of approximatelyo7 wt% ethylacetate
Pervaporation, therefore, offers the possibility of and497 wt% ethylacetate. The investigation in
separating liquid mixtures whose components have this work was concentrated on removing water in
close boiling points, or azeotropes that are difficult the higher ethylacetate concentration phase by
to separate by distillation or other means [7]. using the PVOH membrane crosslinked with Tac.
However, it must be emphasized that vacuum
application is one of the crucial parts of perva-
poration process. 2. Experimental
In the published literature there are no sorption
data, and very few data reported on the perva- 2.1. Membrane preparation
poration of the ethylacetate (EAc)-water system.
Clément et al. [8] reported data on the batch-type PVOH was purchased from Fluka Co. The
pervaporation separation of ethylacetate–water PVOH was 99% hydrolyzed, and the molecular
mixtures at 30 1C with the silicone composite weight was 72 kg/mol. Tac used as crosslinking
membrane manufactured by the Gesellschaft für agent for PVOH was purchased from Riedel-de
Trenntechnik (G.F.T.) Corp. On the other hand, Häen Co. PVOH flakes were dissolved in pure
Shaban [9,10] undertook a pervaporation study in water at 95 1C at a low mixing speed for 6 h to
the hydrolysis of ethylacetate for the initial feed produce 10 wt% PVOH solution. Also, aqueous
composition of the ternary mixture with 10 wt% Tac solution of 10 wt% was prepared at room
water, 40 wt% ethylacetate and 50 wt% acetic acid temperature by mixing for 1/2 h. Then, for cross-
where ethanol forms as a product at 35 1C, 50 1C, linking PVOH, calculated amounts of two solu-
65 1C and 80 1C, using a standard PVOH mem- tions were mixed together at room temperature for
brane with a thickness of 2 mm supplied by G.F.T. 1 h to obtain 20 wt% crosslinking agent in the
of Germany. In a previous work, we reported data membrane. The determination of the amount of
for ethylacetate–water mixture at only 30 1C with 2 crosslinking agent and sorption behaviour of
and 2.5 wt% content [11]. membranes have been described in our previous
A membrane should have good selectivity work [11].
accompanied by an acceptable flux of water for After membranes were cast on to a plexiglass
the dehydration of organic-water mixtures by plate, they were placed in an oven at 50 1C
pervaporation. Hydrophilic polymers are generally overnight. Completely dried membranes were then
used as dehydration membrane materials because peeled off, and the membranes were subjected to
both the solubility and diffusivity of water in them thermal treatment at 150 1C for 1 h. Crosslinked
are higher than the organics. Poly (vinyl alcohol) membranes were kept in pure water at room
(PVOH), which is a suitable membrane for this temperature overnight, and then the membranes
purpose, can be used for the dehydration of were dried at 105 1C for 2 h. The resulting
ethylacetate by pervaporation, but it is known membranes were stored in the same solution
that the PVOH membrane has to be crosslinked to compositions as the pervaporation feed [11].
reduce its solubility [12].
In the present work, a study of the pervapora- 2.2. Pervaporation studies
tion separation of ethylacetate–water mixtures of
low percentages of water has been carried out The apparatus used for pervaporation is illu-
using PVOH membranes crosslinked with tartaric strated in Fig. 1 [11]. The feed tank and
acid (Tac) at different temperatures. The cross- pervaporation cell were maintained at a constant
linking reaction between PVOH and Tac takes temperature by a water bath. The effective
place between hydroxyl groups of PVOH and membrane area was 23 cm2, and the glass feed
carboxylic groups of Tac [11]. tank had a volume of 4 L. After steady state was
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Y. Salt et al. / Vacuum 79 (2005) 215–220 217

Digital thermometer 70
TI Membrane
Heater cell
60
1 wt% water
1.5 wt% water
50
Feed PI Vacuum gauge 2 wt% water

Water flux (g/m2h)


tank 2.5 wt% water
Water 40
bath
Liquid 30
nitrogen
dewar
20

Feed Collection
10
pump bottle Vacuum
pump
0
Fig. 1. Schematic presentation of pervaporation apparatus. 20 30 40 50 60
Temperature ( oC)

Fig. 2. Variation of water flux with temperature for the


attained, the permeate was collected in traps
mixtures containing 1, 1.5, 2 and 2.5 wt% water in PVOH
immersed in liquid nitrogen. Product samples were membrane crosslinked with 20 wt% Tac.
collected every hour, and weighed accurately. The
permeate composition was determined using Schi-
madzu GC-9A with a Porapak T column, and 12000
helium as the carrier gas. Pervaporation experi- 1 wt% water
ments for mixtures containing 1, 1.5, 2 and 2.5 wt 1.5 wt% water
10000
% water were conducted at 30 1C, 40 1C and 50 1C. 2 wt% water
The downstream pressure was maintained at 2.5 wt% water
p 4 mbar vacuum in all experiments. 8000
Selectivity, α

6000
3. Results and discussion
4000
The selectivity, awater=EAc , was calculated from
the following equation [13];
  2000
awater=EAc ¼ Y water =Y EAc = X water =X EAc , (1)
where Y is the weight fraction of the permeate and 0
X is the weight fraction of the feed. 20 30 40 50 60
The experimental data for the variation of flux o
Temperature ( C)
and selectivity with temperature and weight
fraction of water in feed mixture at 30 1C, 40 1C Fig. 3. Variation of selectivity with temperature for the
mixtures containing 1, 1.5, 2 and 2.5 wt% water in PVOH
and 50 1C are given in Figs. 2–5, respectively. Fig. membrane crosslinked with 20 wt% Tac.
2 shows that the amount of flux increases with
increasing content of water, but it decreases with
increasing temperature, except for 1 wt% water It is well known that the sorption of water in
content. However, for the experiments with PVOH occurs by the interaction between the
1.5 wt% water content, no appreciable change is hydroxyl group of PVOH and water, and the
observed. sorption of a solute in PVOH depends on its
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218 Y. Salt et al. / Vacuum 79 (2005) 215–220

70 3 Table 1
30 ˚C The calculated binary interaction parameters
60 40 ˚C
2.5 Temperature (1C) v1p w1p v2p w2p
50 ˚C
50 30 0.997 4.908 0.5762 0.850

Ethylacetate flux (g/m 2 h)


2
Water flux (g/m2h)

40 0.980 3.066 0.4251 0.711


40 50 0.964 2.535 0.3047 0.632
1.5
1: ethylacetate, 2: water, p: polymer.
30
1
20

10 0.5 strength of interactions existing between the solute


molecules and the polymer. The binary interaction
0 0 parameters w1p and w2p given in Table 1 are
1 1.5 2 2.5 calculated as follows [13]
Water concentration in feed (wt%) 
1n 1  vip þ vip
Fig. 4. Variation of fluxes of water and ethylacetate with wip ¼  ,
weight fraction of water in the feed at different temperatures. v2ip
i ¼ 1; 2 ð1 : ethylacetate; 2 : waterÞ, ð2Þ
12000 where vip ¼ 1  vi is the volume fraction of
30 ˚C polymer, and vi is the volume fraction of pure
40 ˚C component in membrane, which are calculated
10000
50 ˚C from sorption experiments.
As can be seen from Table 1, by increasing the
8000 temperature, the interaction between ethylacetate
and polymer increases (binary interaction para-
Selectivity,α

meter decreases) more than that of between water


6000
and polymer. Thus, ethylacetate impedes the
sorption and diffusion of water and the permea-
4000 tion of water becomes slower, and the flux
decreases except for 1 wt% water containing
mixture. Furthermore, this effect becomes domi-
2000
nant with the increasing content of water due to
low chemical affinity between ethylacetate and
0 water, and thus the flux drop increases with
0.5 1 1.5 2 2.5 3 increasing content of water due to approach to
Water concentration in feed (wt%) miscibility limit. Also, the amount of ethylacetate
in permeation is low because of the chemical
Fig. 5. Variation of selectivity with weight fraction of water in
affinity between PVOH and water as well as an
the feed at different temperatures.
inherently stronger interaction among water mo-
lecules, and the smaller molecular size of water
[12]. These effects are less effective for 1 wt% water
polarity and molecular size. Thus, with an increase containing mixture, and therefore flux increases
in the content of water, flux increases due to with increasing temperature.
chemical affinity between PVOH and water. The Fig. 3 illustrates the effect of temperature on
mobilities of molecules differ greatly from one selectivities with respect to water. It can be seen
another, as mobility depends on the relative that as a result of variations in fluxes, selectivity
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Y. Salt et al. / Vacuum 79 (2005) 215–220 219

increases with the temperature for the contents of 4. Conclusions


2 and 2.5 wt% water, but decreases for the 1 wt%
water content. However, the selectivity of the In the present study, permeation of ethylaceta-
1.5 wt% water containing mixture decreased te–water binary mixtures has been carried out
slightly. Meanwhile, the selectivity increases using a PVOH membrane crosslinked by Tac.
slightly from 40 1C to 50 1C for 2.5 wt% water, Both water and ethylacetate fluxes increase with
while it increases evidently from 30 1C to 40 1C the increasing water content in feed due to the
because of the variations in fluxes. internal plasticization and coupling effect, but
The effects of feed water composition on the amount of ethylacetate permeating through the
ethylacetate and water fluxes are shown in Fig. 4. membrane is lower due to larger molecular size
Both the fluxes of water and ethylacetate increase and low chemical affinity to the PVOH membrane.
with the increasing water content in the feed, with The trend observed for ethylacetate flux with the
ethylacetate and water showing the same trend increasing water content at 30 1C is similar to the
with both temperature and water concentration in trends of water flux at 30 1C, 40 1C and 50 1C.
the feed. This is a result of the cross-plasticization However, at 40 1C and 50 1C a similar trend for
indicating that the sorption of one component is ethylacetate flux is not observed as the ethylace-
affected by the sorption of the other component tate–water mixture has a negative temperature
[14], and the coupling effect occurring between the coefficient of solubilitiy. Meanwhile, the water flux
transport of different migrant species. In addition, decreases except for 1 wt% water containing
both ethylacetate and water permeation trends mixture with the increasing temperature as the
change evidently with temperature going from 2 to interaction between ethylacetate and polymer
2.5 wt% water containing mixture as the binary increases more than that between water and
interaction parameter between ethylacetate and polymer by increasing the temperature. This effect
polymer decreases more than that between water becomes dominant with the increasing content of
and polymer with an increase in temperature water due to approach to miscibility limit.
which results in increased water fluxes due to It could be concluded that the membrane
increased sorption of the membrane. prepared by crosslinking PVOH with 20 wt%
The trend of ethylacetate flux change with water Tac is effective in separation of ethylacetate-water
concentration in feed at 30 1C is similar to that of binary mixture, and will be a good alternative to
water flux. However, at 40 1C and 50 1C a similar membranes currently available.
trend is not observed because, as the temperature
increases, ethylacetate solubility in water slightly
decreases due to the negative temperature coeffi- Acknowledgement
cient of solubility of the ethylacetate–water mix-
ture. The interaction between ethylacetate and The financial supports of YTÜAF (23-07-01-02,
water is due to weak hydrogen bonds, and with an 25-07-01-06) and DPT (98-07-01-01) are appre-
increase in temperature, the hydrogen bonds ciated.
between unlike molecules become weaker than
the forces between the pure components [15]. As a
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