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Pervaporation Dehydration of Ethyl Acetateethanolwater Azeotrope Using Chitosanpoly (Vinyl Pyrrolidone) Blend Membranes
Pervaporation Dehydration of Ethyl Acetateethanolwater Azeotrope Using Chitosanpoly (Vinyl Pyrrolidone) Blend Membranes
Pervaporation Dehydration of Ethyl Acetateethanolwater Azeotrope Using Chitosanpoly (Vinyl Pyrrolidone) Blend Membranes
a r t i c l e i n f o a b s t r a c t
Article history: In this paper, chitosan (CS)/poly (vinyl pyrrolidone) (PVP) blend membranes crosslinked by glutaralde-
Received 18 July 2008 hyde (GA) were prepared for the separation of ethyl acetate/ethanol/water azeotrope by pervaporation
Received in revised form (PV). Their chemical and physical characteristics were studied by Fourier transform infrared (FTIR),
19 November 2008
environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), differential scanning
Accepted 19 November 2008
calorimeter (DSC), thermogravimetric analysis (TGA), and contact angle measurement. The PV properties
Available online 27 November 2008
of the membranes were investigated through dehydration of the azeotrope. Permeation flux increased
with increasing feed temperature and PVP content, while separation factor decreased. However, the sep-
Keywords:
Ethyl acetate/ethanol/water azeotrope
aration factor increased with increasing GA content, whereas the flux decreased. The results showed that
Chitosan/PVP blend the membranes with PVP content of 10 wt% exhibited excellent PV properties with a flux of 953 g m−2 h−1
Pervaporation and separation factor of 746 at 35 ◦ C.
Membranes © 2008 Elsevier B.V. All rights reserved.
0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.11.034
X.H. Zhang et al. / Journal of Membrane Science 327 (2009) 274–280 275
efficiency, it is of great significance to design membranes with both CS and PVP were mixed uniformly in the membrane. The accu-
high permeation flux and separation factor. rately weighed samples (5 mg) were placed into aluminum cups
The affinity between membranes and feed components plays and then were heated from 30 to 320 ◦ C at a constant heating rate
an important role in pervaporation efficiency. Chitosan (CS), of 10 ◦ C min−1 under constant nitrogen purging at 10 ml min−1 . The
with many reactive amino and hydroxyl groups, is a promis- thermal stability of the membranes were analyzed using a TG209F1
ing hydrophilic membrane material and has been widely used (Netzsch, Germany) system. It was conducted by heating from 30
in pervaporation [8,24]. Poly (vinyl pyrrolidone) (PVP) is also an to 990 ◦ C at a constant heating rate of 10 ◦ C min−1 under a nitrogen
idea hydrophilic membrane material and can easily blend with atmosphere.
other organic or inorganic compounds. Currently, the relationship
between the structures of polymer membranes and their perms- 2.4. Pervaporation experiments
electivity has been intensively studied. Some groups reported
that polymer blending, crosslinking and annealing can all strongly Pervaporation experiments were carried out on a laboratory
influence permeability or selectivity [9,23]. In the present work, chi- scale apparatus. The azeotrope of 82.6 wt% ethyl acetate, 8.4 wt%
tosan/poly (vinyl pyrrolidone) blend membranes crosslinked with ethanol and 9 wt% water was used as feed solution. A vacuum pump
GA were prepared, characterized and used for pervaporation dehy- was used to maintain the permeate side pressure at 650 Pa. The
dration of ethyl acetate/ethanol/water azeotrope. CS/PVP blend permeate was collected using a liquid nitrogen cold trap and was
membranes had ever been prepared for direct methanol fuel cell analyzed by a gas chromatography (GC-950) for its concentration.
applications, and were found to be effective methanol barriers and The total permeation flux (J) including all components in the per-
to possess sufficient thermal stability [25]. meate and the separation factor (˛) are calculated from Eqs. (1) and
(2), respectively
2. Experimental G
J= (1)
A × t
2.1. Materials yi /(1 − yi )
␣= (2)
xi /(1 − xi )
Chitosan, with 95% deacetylation and an average molecular
weight of 2 × 105 g mol−1 , was provided by Chekiang Golden-shell where G refers to the amount of the permeate (g) including water,
Biochemical Co., Ltd. Poly (vinyl pyrrolidone) K-30, glutaralde- ethanol and ethyl acetate, A refers to the effective area (m2 ) of the
hyde (GA) 25 wt%, ethanol and ethyl acetate were all purchased membrane used in pervaporation and t is the time (h) used to col-
from Sinopharm Chemical Reagent Co., Ltd. Both ethanol and ethyl lect the permeate. In Eq. (2), yi is the mass fraction of component i
acetate used were of analytical grade. in the permeate, xi is the mass fraction of component i in the feed
solution. The subscript i represents the component in the solution
such as 1 referring to water, 2 ethanol and 3 ethyl acetate. In the
2.2. Membrane preparation
present work, water was named one component, both ethanol and
ethyl acetate another pseudo-component, in the calculation of sep-
1.5 g CS and PVP in range of 0–0.35 g was dissolved in 100 ml
aration factor, sorption selectivity and diffusion selectivity. In this
0.8 wt% acetic acid solution under stirring at 25 ◦ C for 2 h, where-
paper all the separation factor, sorption selectivity and diffusion
after a certain amount of 1 wt% GA was added into the solution and
selectivity discussed are referred to water.
the mixture was then stirred for 0.5 h. The insoluble impurities were
removed from the solution by pumping filtration. After deaeration
2.5. Sorption and desorption
for 24 h, the resulting solution was cast onto a clean glass plate,
dried in an oven at 35 ◦ C for 8 h and then the obtained membranes
Before each swelling test, the CS/PVP blend membranes were
were annealed in vacuum at 100 ◦ C for 4 h.
completely dried in vacuum at 80 ◦ C to evacuate the moisture
and weighed immediately. Whereafter, they were immersed into
2.3. Membrane characterization ethyl acetate/ethanol/water azeotrope until an equilibrium was
achieved. The membranes were taken out, wiped quickly with fil-
Water static contact angles of the membranes were measured ter paper and weighed. This process was repeated for several times
by the pendant drop method using a contact angle meter (SL200B, until the weight of the membrane was maintained a constant value.
SOLON TECH, Shanghai, China) at 26 ± 1 ◦ C with 67 ± 2% relative The degree of swelling (DS) is calculated from Eq. (3).
humidity. The density of the membranes was measured to inves- Desorption was performed to estimate the concentration of the
tigate the variation of the free volume of the membranes with sorbed solution. The sorbed solution was completely desorbed from
different composition [26] using a digital microbalance (Mettler the membrane at 90 ◦ C under vacuum and collected in a liquid nitro-
Toledo, AB204-S) with density kit. The density was determined by gen cold trap. The concentration of the collected solution was also
measuring the weights of the membranes in air and cyclohexane determined by gas chromatography (GC-950). The sorption selec-
at 26 ± 0.5 ◦ C. The IR spectra of the membranes were recorded by tivity ˛s and the diffusion selectivity ˛d are calculated from Eqs. (4)
Fourier transform infrared (FTIR) 740SX (Nicolet, USA) to analyze and (5), respectively
the composition of the membranes. Crystal structure characteriza-
Ww − Wd
tion was carried out by using X-ray diffraction (XRD) (Panalytical DS = (3)
Wd
X’pert Philip, Holland) with Cu K␣ radiation. The diffraction was
operated at 40 kV and 30 mA at a 2 range of 5–35◦ , using a step Ci /(1 − Ci )
˛s = (4)
size of 0.0167◦ and a counting time of 10 s per step. Environmen- xi /(1 − xi )
tal scanning electron microscopy (ESEM) (XL30ESEM-TMP, Philips, ˛d = ˛/˛s (5)
Holland) was used to characterize the surface and cross-section of
the membranes. The sample used to characterize the cross-section where Ww is the weight of the wet membrane(g), Wd is the weight
was quenched by immersing the membrane in liquid nitrogen. of the dry membrane(g), Ci is the mass fraction of component i in
The membranes were also characterized by a differential scan- the sorbed solution, and xi is the mass fraction of component i in
ning calorimeter (Netzsch DSC 204 Phoenix) to analyze whether the azeotrope. The subscript i is the same as that in Eq. (2).
276 X.H. Zhang et al. / Journal of Membrane Science 327 (2009) 274–280
Fig. 1. IR spectra of the membranes of CS (a), CS/GA (b), CS/PVP (c) and CS/PVP/GA Fig. 3. XRD spectra of the CS membranes crosslinked by GA with various amounts.
(d).
Fig. 2. The SEM image of the GA crosslinked CS/PVP blend membranes: the surface (a) and cross-section view (b).
X.H. Zhang et al. / Journal of Membrane Science 327 (2009) 274–280 277
Fig. 4. DSC (a) and DTG (b) curves of CS membrane, PVP membrane, and CS/PVP10 blend membrane.
crosslinking by GA can enhance the thermal stability of the CS/PVP meation flux. PVP, an amorphous hydrophilic polymer with amide
blend membranes. groups and carbonyl groups, was introduced into CS to prepare
CS/PVP blend membranes to solve the inherent decrease in per-
3.2. Effect of composition on pervaporation performance meation flux arising from crosslinking.
It is found that the membranes demonstrate quite good PV per-
Chitosan is a strong hydrophilic membrane material since it formance. The permeation flux was high. In the meanwhile, the
contains many reactive amino and hydroxyl groups. However, mass fraction of ethanol and ethyl acetate in the permeate was
the pristine chitosan membranes swell excessively in the ethyl below 3.5 and 0.5%, respectively, due in part to their bigger molec-
acetate/ethanol/water azeotrope, resulting in a low permselectiv- ular size.
ity, or even worse, the destruction of structure of the membranes.
Therefore it is necessary to control the swelling of the pris- 3.2.1. Effect of PVP content on pervaporation performance
tine chitosan membranes. Crosslinking could remarkably depress Polymer blending is an efficient method for membrane mod-
the mobility of the polymer chains. However, it was found that ification. In this paper, PVP was introduced to modify the CS
crosslinking could not effectively control the swelling of the mem- membranes. Fig. 5 reflects the effect of PVP content on the per-
branes just dried at 35 ◦ C, as the membranes might still broken after meation flux and selectivity. It was obvious that the permeation
a short time when applying in separation of the azeotrope. Anneal- flux increased with increasing the PVP content, whereas the sepa-
ing is reported to be an efficient method for controlling the swelling ration factor decreased. On the one hand, introduction of PVP into
of a membrane since it not only can enhance the crosslinking [27] CS can disorder the arrangement of the CS chains, resulting in a
but also lead to condensation of the polymers which will form net- decrease in the compactness of the membranes and an increase in
works and reduce the polymer chain flexibility. In this work, the the swelling degree of the membranes, reflected by the variation
membranes were annealed at 100 ◦ C. of the density of the membranes with introducing the PVP (Fig. 6).
Although crosslinking and annealing can depress the swelling As a result, the degree of the crystallinity of the CS decreased, and
of membranes, it will also simultaneously lead to a decrease in per- the free volume of the membranes increased with increasing the
PVP loading. All these lead to a decrease in the density of the mem-
branes, as shown in Fig. 6. On the other hand, introduction of PVP
could significantly enhance the hydrophilicity of the membranes
because it has strong polarity and hydrophilic groups. The forma-
tion of hydrogen bonding between the membranes and water was
hence promoted. Therefore the affinity between water and mem-
branes increased accordingly, which was confirmed by the contact
angle measurement, as shown in Table 1. All these will cause an
increase in the sorption of water. The decrease of sorption selectiv-
ity is unusual when the hydrophilicity of the membranes increased
with increasing the PVP content (Fig. 7). Examination of the sorp-
tion selectivity and diffusion selectivity for the liquid pairs reveals
Table 1
Water contact angle of the membranes.
CS 69.91 ± 0.94
CS/GA0.33 72.75 ± 0.76
CS/PVP10 65.60 ± 0.82
CS/PVP10 /GA0.33 70.29 ± 0.59
Fig. 5. Effect of PVP content on the PV performance of the CS/PVP blend membranes
at 25 ◦ C. Subscript 0.33 is the weight fraction of GA, and 10 is that of PVP.
278 X.H. Zhang et al. / Journal of Membrane Science 327 (2009) 274–280
Fig. 6. Density of CS/PVP10 /GA membranes with different GA content (a) and CS/PVP/GA0.33 membranes with different PVP content (b).
that the diffusion selectivity contributes significantly to the separa- 3.2.2. Effect of GA content on pervaporation performance
tion factor. This can be explained by that increasing swelling degree The performance of membranes is closely related to their struc-
leads to an increase in the free volume of the membranes, result- ture. Crosslinking is an efficient way to modify the structure of
ing in an increase in the diffusion of all components, especially in membranes. Fig. 8 shows the effect of GA content on pervapo-
favor of ethanol and ethyl acetate owing to their high feed con- ration properties. Permeation flux decreased with increasing GA
centration. And the free volume played a dominant role over the content in the range of 0.25–0.50 wt%, whereas separation factor
affinity possibly because of the plasticization (or synergy) effects increased. Networks formed in the blend of CS/PVP crosslinked
for such kind of polymers. The effect of the free volume was even by GA can restrain the mobility of the polymer chains, and hence
more remarkable with increasing PVP content. The diffusion selec- make the structure of the membranes more compact, and result
tivity decreased slowly in the range of PVP content below 15%, and in a decrease in the free volume of the membranes. Therefore the
then decreased remarkably with increasing the PVP content. The density of the membranes increases (Fig. 6). In addition, the crys-
sorption selectivity always decreased possibly because the blend tallinity decreased due to the disorder of the polymer chains arising
membranes were readily plasticized by ethanol and ethyl acetate from the crosslinking (Fig. 3). The depression of the mobility of
and that their “plasticization” might be a significant contributor the polymer chains led to a decrease in the swelling degree. And
to their enhancement in liquid sorption with increasing PVP con- the free volume of the membranes crosslinked by GA was also
tent. As a result, separation factor decreased and permeation flux reduced. Furthermore, the hydrophilic groups of the membranes
increased with increasing PVP content arising from both the affinity reduced after crosslinking with GA. As a result, the affinity between
and high swelling degree. the membranes and water decreased, which was confirmed by the
Fig. 7. Effect of PVP content on the DS, ˛s and ˛d of the CS/PVP blend membranes at Fig. 8. Effect of the amount of GA on the PV performance of the CS/PVP blend
25 ◦ C. membranes at 25 ◦ C.
X.H. Zhang et al. / Journal of Membrane Science 327 (2009) 274–280 279
Fig. 12. Effect of temperature on the ˛s and ˛d of the CS/PVP blend membranes.
4. Conclusion
[8] B.K. Zhu, X.Z. Tian, Y.Y. Xu, Recovering ethyl acetate from aqueous solution
Nomenclature using P (VDF-co-HFP) membrane based pervaporation, Desalination 184 (2005)
71–78.
[9] A. Sharma, S.P. Thampi, S.V. Suggala, P.K. Bhattacharya, Pervaporation from a
A effective area of membranes (m2 )
dense membrane: roles of permeant–membrane interactions, Kelvin effect, and
Ci the mass fraction of component i in the sorbed solu- membrane swelling, Langmuir 20 (2004) 4708–4714.
tions [10] B.V. Bruggen, J.C. Jansen, A. Figoli, J. Geens, Determination of parameters affect-
DS the degree of swelling ing transport in polymeric membrane: parallels between pervaporation and
nanofiltration, J. Phys. Chem. B 108 (2004) 13273–13279.
G mass of the permeate (g) [11] T. Miyata, H. Yamada, T. Uragami, Surface modification of microphase-separated
J total permeation flux (g m−2 h−1 ) membranes by fluorine-containing polymer additive and removal of dilute
t time used to collect the permeate (h) benzene in water through these membranes, Macromolecules 34 (2001)
8026–8033.
Ww the weight of the wet membrane (g) [12] T.A. Peters, N.E. Benes, J.T.F. Keurentjes, Zeolite-coated ceramic pervaporation
Wd the weight of the dry membrane (g) membranes; pervaporation–esterification coupling and reactor evaluation, Ind.
xi the mass fraction of component i in the feed solution Eng. Chem. Res. 44 (2005) 9490–9496.
[13] T. Uragami, K. Tsukamoto, T. Miyata, Performance of butyrylcellulose
yi the mass fraction of component i in the permeate membranes for benzene/cyclohexane mixtures containing a low benzene con-
centration by pervaporation, Biomacromolecules 5 (2004) 2116–2121.
Greek symbols [14] T. Uragami, H. Matsugi, T. Miyata, Pervaporation characteristics of
organic–inorganic hybrid membranes composed of poly (vinyl alcohol-
˛ separation factor
co-acrylic acid) and tetraethoxysilane for water/ethanol separation,
˛s sorption selectivity Macromolecules 38 (2005) 8440–8446.
˛d diffusion selectivity [15] A. Hasanoglu, Y. Salt, S. Keleser, S.O.S. Dincer, Pervaporation separation of
ethyl acetate–ethanol binary mixtures using polydimethylsiloxane membranes,
Chem. Eng. Process. 44 (2005) 375–381.
Subscript [16] A. Arpornwichayop, U. Sahapatsombud, Y. Patcharavorachot, F. Assabum-
i referring to component, 1 water, 2 ethanol, and 3 rungrat, Hybrid process of reactive distillation and pervaporation for the
ethyl acetate production of tert-amyl ethyl ether, Chin. J. Chem. Eng. 16 (1) (2008) 100–103.
[17] M.T.D. Gomez, A. Klein, J.U. Repke, G. Wozny, A new energy-integrated perva-
poration distillation approach, Desalination 224 (2008) 28–33.
[18] A. Verhoef, J. Degreve, B. Huybrechs, H. Veen, P. Pex, B. Bruggen, Simulation
of a hybrid pervaporation–distillation process, Comput. Chem. Eng. 32 (2008)
the CS/PVP10 /GA0.33 membrane was the best one since it exhibited 1135–1146.
both high permeation flux and separation factor. [19] X.Z. Tian, X. Jiang, Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP)
membranes for ethyl acetate removal from water, J. Hazard. Mater. 153 (2008)
128–135.
Acknowledgements [20] Y. Salt, A. Hasanoglu, I. Salt, S. Keleser, et al., Pervaporation separation of
ethylacetate–water mixtures through a crosslinked poly(vinylalcohol) mem-
The support of National Nature Science Foundation of China brane, Vacuum 79 (2005) 215–220.
[21] D. Panek, K. Konieczny, Pervaporation of toluene and toluene/acetone/ethyl
Grant No. 50573063, the Program for New Century Excellent Tal-
acetate aqueous mixtures through dense composite polydimethylsiloxane
ents in University and the research fund for the Doctoral Program membranes, Desalination 200 (2006) 367–373.
of Higher Education (No. 2005038401) in preparation of this article [22] A. Hasanoglu, Y. Salt, S. Keleser, S. Ozkan, S. Dincer, Pervaporation separation
of organics from multicomponent aqueous mixtures, Chem. Eng. Process. 46
is gratefully acknowledged.
(2007) 300–306.
[23] T. Uragami, K. Okazaki, H. Matsugi, T. Miyata, Structure and permeation charac-
References teristics of an aqueous ethanol solution of organic–inorganic hybrid membranes
composed of poly (vinyl alcohol) and tetraethoxysilane, Macromolecules 35
(2002) 9156–9163.
[1] G.R. Christoph, J.F. Hansen, H.W. Leung, Subchronic inhalation neurotoxicity
[24] L. Gales, A. Mendes, C. Costa, Removal of acetone, ethyl acetate and ethanol
studies of ethyl acetate in rats, Neuro Toxicol. 24 (2003) 861–874.
vapors from air using a hollow fiber PDMS membrane module, J. Membr. Sci.
[2] K. Inui, T. Kurabayashi, S. Sato, Direct synthesis of ethyl acetate from ethanol
197 (2002) 211–222.
over Cu–Zn–Zr–Al–O catalyst, Appl. Catal. A 237 (2002) 53–61.
[25] B. Smitha, S. Sridhar, A.A. Khan, Chitosan–poly(vinyl pyrrolidone) blends as
[3] J.A. Monick, Alcohols, vol. 19, Reinhold Book Corporation, New York, 1968, p.
membranes for direct methanol fuel cell applications, J. Power Sources 159
45.
(2006) 846–854.
[4] J. McMurry, Organic Chemistry, 5th Edition, Brooks/Cole, 2000, p. 855.
[26] C.L. Staiger, S.J. Pas, A.J. Hill, C.J. Comelius, Gas separation, free volume distribu-
[5] Nieuwoudt, Izak, V.D. Braam, Separation of ethanol mixtures by extractive dis-
tion, and physical aging of a highly microporous spirobisindane polymer, Chem.
tillation, U.S. Patent 6375807 (2002–2004).
Mater. 20 (2008) 2606–2608.
[6] J.P.G. Villaluenga, A.T. Mohammadi, A review on the separation of ben-
[27] T. Kai, T. Yamaguchi, S. Nakao, Preparation of organic/inorganic composite
zene/cyclohexane mixtures by pervaporation processes, J. Membr. Sci. 169
membranes by plasma-graft filling polymerization technique for organic-liquid
(2000) 159–174.
separation, Ind. Eng. Chem. Res. 39 (2000) 3284–3290.
[7] P. Shao, R.Y.M. Huang, Polymeric membrane pervaporation, J. Membr. Sci. 287
(2007) 162–179.