Journal ofMembrane Science, 68 (1992) 141-148 Elsevier Science Publishers B.V.

, Amsterdam

141

The separation of water and ethanol by pervaporation with PVA-PAN composite membranes
H. Ohya, K. Matsumoto*, Y. Negishi, T. Hinob and H.S. Choi
Department of Material Science and Chemical Engineering, Yokohama National University, 156, Tokiwadai, Hodokayaku, Yokohama 230 (Japan) bChiyoda Corporation, 12-1, Tsurumichuo P-chome, Tsurumi-ku, Yokohama 230 (Japan) Department of Industrial Chemistry, Kyungpook Sanup University, 55, Hyomokdong, Tong-ku, Taegu 701-702 (SouthKorea) (Received May 29,199l; accepted in revised form November 25,199l)

Abstract

Composite membranes witha thinpoly(vinylalcohol) [ PVA ] layer coated on poly (acrylonitrile ) [PAN] support membranes wereevaluated for pervaporation separation of a water-ethanol mixture. The permeabilityof purewaterthrough the PAN supportmembrane wasin therangefrom0.214 to 4.32 mm3/ ( m2set-Pa), and the molecular weight cut-off was in the range of 35 000 to 100 000. The PVA-PAN composite membranes as prepared were water permeable, and the maximum separation factor was 4800. From the experimental results, a separation model for the composite membrane for pervaporation is proposed. The function of the PAN support membrane is to restrict physically swelling of the PVA within the PAN pores at the PVA-PAN interface, thereby maintaining a dense PVA skin and desirable selectivity. Keywords: composite membrane; pervaporation; separation factor ultrafiltration; separation of ethanol-water mixture;

1. Introduction There has been much progress in the research and development of membranes and their use in pervaporation processes for the separation of various organic liquid mixtures and aqueous organic mixtures, especially ethanol-water solutions. Currently, much attention is being paid to pervaporation as an energy saving separation method for the replaceCorrespondence to: H. Ohya, Department of Material Science and Chemical Engineering, Yokohama National University, 156, Tokiwadai, Hodokaya-ku, Yokohama 240 (Japan).

ment of distillation of aqueous alcohol solutions and azeotropic mixtures [l-4]. The driving force in pervaporation is the concentration difference across the membrane resulting from a pressure difference; this offers substantial energy savings. In addition, it has the advantage of simplifying process plants. It also has the advantage of avoiding the pollutants used in distillation processes to breakup azeotropic mixtures. Sander [5] investigated a pilot plant combining pervaporation and extraction-distillation. He reported that the operating cost of his hybrid process was l/3 to l/4 less than that of a conventional extraction-distillation process.

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H. Ohya et al./J, Membrane Sci. 68 (1992) 141-148

In recent years, priority in pervaporation research has been given to the development of new polymer membranes which have a high selectivity, acceptable flux rate, and good stability and/or durability. For example, in the case of dehydration of a high-concentration ethanol solution, above 95 wt.%, a membrane which preferrentially allows the passage of water is needed. The pioneer membrane used ethanolwater separation by pervaporation is the GFTmembrane, which was developed by GFT (Germany) at the beginning of the 1980s. It is a composite membrane with a poly(viny1 alcohol) [PVA] coated on a poly (acrylonitrile) [PAN] ultrafiltration membrane [ 61. Recently, to improve further the performance of pervaporation, several researchers have investigated the performance of membranes made from other materials. In addition, during the past several years, pervaporation has been studied extensively with the aim of industrial applications. Wesslein et al. [7] studied the separation of binary mixtures with the GFTmembrane for 11 kinds of solvents. Huang and Yeom [B] reported on the effect of the concentration of a crosslinking agent (amic acid) for PVA membranes on membrane performance. Nobrega et al. [9] investigated the effect of chemical and thermal treatments on PVA membrane performance. Spitzen et al. [lO,ll] reported on the water permselectivity of PVA and PAN membranes used in pervaporation processes. Until now, the results of investigations on conventional PVA membranes indicate that both its water permselectivity and durability are relatively low. Still, the PVA-PAN composite membrane is now considered to be one of the best for aqueous-organic pervaporation processes because of its high water permselectivity and durability. However, the characteristics of PAN ultrafiltration membranes alone are not yet well understood. Therefore, this study was carried out to determine the effects of varying the PAN fabrication param-

eters on the membranes pure-water permeability and molecular weight cut-off. We also examined the effect of the PAN dope composition on the performance of the PVA-PAN composite membrane. The composite membranes were also evaluated for pervaporation separation of a water-ethanol mixture. 2. Experimental 2.1.Preparation of the membranes 2.1.1. Materials The polymers used in this study were poly (acrylonitrile ) , supplied by Aldrich Chemicals, and poly (vinyl alcohol) (degree of polymerization: 1700, degree of hydrolysis: 99.5 ? 0.1), supplied by the Kurare Company (Japan). The solvent used was analytical grade dimethylformamide (DMF ) from WAKO Chemicals (Japan). The non-woven fabrics of polyester used as a base in the fabrication of PAN membrane were supplied by the Kanai Juyo Ind. Co. (Japan). 2.1.2. Support membrane (PAN UFmembrane) The dope solution consisted of 5, 10 and 15 wt.% PAN in DMF. First a non-woven polyester fabric was fixed on a glass plate (with tape), and the polymer solution was cast onto the fabric. The solvent was then allowed to evaporate for a specific period of time at room temperature or at 60 C in an oven. The glass plate was subsequently immersed in water gelation bath (ice water at 2 C ) for a specific period of time. Table 1 shows the conditions for preparation of PAN support membrane. The membrane was rinsed in tap water for 24 hr, and immersed in an ethanol solution for 24 hr at room temperature to remove the residual solvent. The membrane was then dried under vacuum at room temperature.

H. Ohya et al.jJ. Membrane Sci. 68 (1992) 141-148

TABLE 1 Conditions of preparation of PAN support membranes Membrane Concentration of dope solution (wt.%) A B C D E 5 10 5 10 5 60 60 60 5 5 5 30 30 30 30 30 20 26 27 26 41 Predrying temperature (C) Predrying time (min) Gelation time (min) Thickness of top IayeP (w)

143

tran solutes used were T-10, T-40, T-70 and T-500 from Pharmacia Chem.; the solution was a multi-component mixture with 100 mg/l of each component. The permeate samples were taken after the flux had reached steady state. The determination of the solution concentration was carried out with a gel-permeation chromatograph (Shimadzu, model LC-64 system). The columns used were OH Pak B803/s, 804/s and 805 from Shodex. 2.3. Pervaporation The pervaporation separation of water (component i) and ethanol (component j) mixtures was carried out with the PVA-PAN composite membranes. The details of the pervaporation equipment are shown in Fig. 1. The membrane was placed on the porous stainless steel plate in the cell. The effective area of the membrane cell was 23.7 cm2. The feed solution was circulated with a flow rate of 200 ml/min from the feed reservoir, which was placed in a thermostatic bath. The operating temperature of the equipment was controlled at 25, 40, 50, or 60C. The concentrations of the feed solution were 20,40,60,80 or 95 wt.% ethanol. The permeate was condensed in a liquid nitrogen trap, and the flux was calculated directly by measuring the permeate weight per unit time. The down

by SEM observation.

2.1.3. PVA-PAN composite membrane PVA-PAN composite membranes were made by the procedure proposed by Brtischke [14]. The concentration of PVA in the coating solution was 7 wt.% in water, and the PVA was crosslinked by the addition of maleic acid. The amount of crosslinking agent was 1 unit of maleic acid per 20 units of vinyl alcohol monomer base, assuming 100% reaction. The composite membrane was made by thermally treating PVA dip-coated on the PAN UFsupport-membrane. The thermal treatment consisted of placing the membrane in an oven at 150 C for 2 hr. The degree of hydration of the crosslinked PVA layer was 45%. 2.2. Ultrafiltration testing of the support membrane The pure water flux of the PAN membrane was determined experimentally, and the molecular weight cut-off of the membrane was determined with the method reported in Ref. [ 121 using aqueous dextran solutions instead of PEG. In order to keep the levels of concentration polarization of dextran on the PAN membrane surface the same, the trans-membrane pressure was chosen to give a similar solution flux, i.e. 2.85 kPa for the loosest membranes A and C, 4.55 kPa for membranes B and D, and 35 kPa for the tightest membrane E. The dex-

FL
G I
A Pervapnatm
B C D Membrane Thermocouple Feed reservar balh

cell

F G

Feed Cold Prani

crculalng trap gauge

pump

I Vacuum pump

E Thermoset

Fig.

1. Apparatus used for the pervaporation experiments.

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stream vacuum pressure was maintained between 0.01 and 1.5 Torr and measured by a Pirani gauge (Okano, model Pg-25). The feed and permeate composition were measured by gaschromatography. The detectors used were TCD (Shimadzu, model GC-4C) for high concentrations of ethanol and FID (Shimadzu, model GC9A) for low concentrations. The selectivity of the membrane was determined by the separation factor, Lyi/j, defined for binary mixtures as follows:

3. Results and discussion Ultrafiltration testing of PAN support membrane The characteristics of the PAN support membrane are shown in Table 2. The permeability of pure water at 25 oC was in the range of 0.214 to 4.32 mm/ ( m2 set Pa), and the relative molecular weight cut-off was between 35 000 and 100 000.
3.1.

(listed in Table 2) is shown in Fig. 2 together with that for the GFT membrane [ 151. The UFmembrane A is known to be water permselective and the composite membrane (PVA-PANA) shows better behavior than the GFT membrane for the entire ethanol concentration range investigated in this study [ 21. The dependence of the separation factors and the permeation fluxes on the temperature for another PVA-PAN composite membrane is shown in Fig. 3. The permeation flux increased with increasing temperature, but the separation factor did not change. A linear relationship is observed between the permeation flux and the inverse of the absolute temperature. This suggests that the membrane structure did not change as a result of temperature changes. Membrane durability Pervaporation experiments were carried out in which the feed concentration of ethanol was continuously varied from high to low (H-L segment in Fig. 4) and low to high (L-H segment ). The change of the permeation flux and the separation factor with time for a PVA-PAN composite membrane with support membrane B is shown in Fig. 4. The numbers in the figure (data point labels) are the days at which the data were collected. In the H-L segment, the separation factor for an initial feed concentration of 95 wt.% was 4200, and 70 for 20 wt. % at
3.2.2.

3.2. Pervaporation 3.2.1. Permseparation of water-ethanol mixtures The measured separation for the composite membrane of PVA coated on UF-membrane A
TABLE 2 Characteristics of PAN Membrane

support membranes
Molecular weight cut-off (g/mol) 100 000 76 000 42 000 50 000 35 000

Pure water permeability (at 25C) [mm3/(m2-set-Pa)] 4.32 3.28 2.63 1.81 0.214

A B C D E

EtOHCont. in Feed Cwt./J Fig. 2. Pervaporation curve of composite membranes and vapor-liquid equilibria for water-ethanol mixtures.

H. Ohya et al./J. Membrane Sci. 68 (1992) 141-148

145

11 T X103CK-'I I 60 50 40

I 25'C

Fig. 3. Dependence of total flux and separation factor on temperature for a PVA-PAN composite membrane. (Membrane: PVA-B ) .

the turning point. The concentration of ethanol in all the permeates was in the range of 0.270.41 wt.% for the entire feed concentration range. Note that hysteresis was observed for both the separation factor and the flux; the final values did not return to their original levels. The final value of the separation factor in the L-H segment was approximately l/lOth the initial value in the H-L segment. The final flux value was 7.5 times the initial value. The changes of the permeation fluxes for both water and ethanol with time and varying feed concentration are shown in Fig. 5. The difference in initial value and final value in permeation flux for ethanol was larger than that for water. From these results, we believe that the PVA coating layer of the composite membrane swells as the ethanol concentration in the feed solution is decreased, resulting in a more extensive (more open) polymer network, which remains open as the ethanol concentration is raised to its original level. 3.2.3. Comparisons of various support membranes A comparison of the separation factors and permeate fluxes for PVA-PAN composite membranes with a different PAN support is

-1 k $ 10-lso-2 -

; (i lo-3 10-1v) "'0

20

40

60

80
CwtX3

100

EtOH Cont. in Feed

'o-50

20

40

60

80
CwW.1

11 1

EtOH Cone. in Feed

Fig. 4. Permeation flux and separation factor with of time for a PVA-PAN composite membrane. (Membrane: PVAB).

Fig. 5. Permeation fluxes for both water and ethanol with of time for a PVA-PAN composite membrane at 60C. (Membrane: PVA-B).

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H. Ohya et al/J. Membrane Sci. 68 (1992) 141-148

shown in Fig. 6 and 7. Also, the relationship between the separation factor and the pure water permeability of the PAN support membrane are shown in Fig. 8. It was found that the PVA-PAN composite membranes have higher separation factors than conventional non composite PVA membranes, and that the water

Feed Cont. CwlXl

60

- 0 _ (,

PVA-A PVA-B PVA-C

1 Pure Water Permeability

10-l

IO ~VII~/ITI~ spa3

Fig. 8. Separation factors of PVA-PAN membranes at 6OC, as a function of pure water permeability of PAN support membranes.

20 40 60 80 100 EtOH Cont. in Feed Cwt1.1

Fig. 6. A comparison of the separation factors for PVAPAN composite membranes with different PAN support membranes at 60C.

_ I3
1

PVA-D
8 I 1 1 ;O 40 60 60 100 EtOH Cont. in Feed Cwt%l

o-3;

Fig. 7. A comparison of the permeation fluxes for PVAPAN composite membranes with different PAN support membranes at 60 C.

permselectivity of PVA increases with the addition of a support PAN membrane. Unlike composite membranes, the PVA membrane swelled and broke up in a feed with a composition of less than 60 wt.% ethanol, as shown in Fig. 6. Furthermore, it was observed that the permeation flux decreased as the densification of the PAN support membrane increased. A homogeneous PAN membrane has been reported to be water permselectivity [ 10,ll 1. Therefore, it should be possible to increase the separation factor by increasing the densification of the PAN support membrane. However, our experimental results in Fig. 6 show that the opposite is true, i.e. the separation factor decreased with increasing densification of the PAN support membrane (i.e. from PVA-A to PVA-E). This difference between PVA-A and PVA-E is the largest at a high feed concentration. The separation factor has a maximum value in the vicinity of 80 wt.% ethanol and is lower for 95 wt.% ethanol. This fact suggests that the relative diffusion rates for ethanol and water through PVA are reversed between ethanol concentrations of 80 and 95 wt.% [lo].

H. Ohya et al./J. Membrane Sci. 68 (1992) 141-148

147

Feed Solution

Feed Solution

Permeate (4

Permeate (b)

Fig. 9. Models of PVA-PAN composite membrane during pervaporation.

That is, at 80 wt.% ethanol, the ethanol diffusion rate is higher. From the experimental results of this study, the model shown in Fig. 9 is proposed. (1) The feed solution dissolves into the PVA layer, diffuses through this layer, and subsequently desorbs, i.e. vaporizes toward the down stream side through the small pores of the support membrane. We suppose that a dense, nonswollen skin forms at the interface between the PVA coating and the PAN support membrane [ 131, and that this dense skin increases the selectivity of the composite membrane. (2) Swelling of the PVA skin layer is suppressed by the rigid PAN pore structure in which the PVA coating is partially imbedded. In the case of a small pore structure in the support membrane, the coating is probably not imbedded deeply, and thus the support only weakly suppresses swelling (Fig. 9b). This model is consistent with the selectivities shown in Fig. 8. The increase in selectivity (separation factor) with respect to the pure water permeability (pore size) is relatively large for high feed concentrations, but small for low feed concentrations. It may be so that at the lower ethanol concentrations, more of the PVA coating layer is swollen, resulting in a thinner skin. Furthermore, Figs. 6, 7 and 8 indicate that highly permeable membranes (PVA-A and PVA-B ) have relatively high separation factors at high ethanol concentration, but that their separation factors drop below those of the less permeable membranes at middle and low ethanol concentrations. Possibly, the larger pore structure of the more permeable mem-

branes does not have sufficient mechanical strength to suppress the swelling which occurs at low ethanol concentrations, resulting in the reduced separation factors discussed above. 4. Conclusions (1) The permeability of pure water through a PAN support membrane is in the range from 0.214 to 4.32 mm/ (m2-set-Pa) and the molecular weight cut-off is in the range from 35 000 to 100 000. (2 ) The PVA-PAN composite membrane as prepared is water permselective for the ethanol concentration range of 20 to 95 wt.% in the feed, and the separation factor exhibits a maximum value of 4800. (3 ) The dependence of the permeate flux on temperature is consistent with the Arrhenius relationship, and the separation factor hardly varied in the temperature range investigated. (4) It is verified that the permselectivity of the membrane is increased by the addition of the PAN support membrane, i.e. by making the PVA-PAN composite membrane. However, the separation factor decreases with excessively increasing densification of the support membrane. (5) A function of the PAN support membrane is to suppress the swelling of the PVA layer at the PVA-PAN interface and to create a dense skin, thereby improve the selectivity by allowing PVA to intrude into the micropores of the PAN support membrane. Therefore, the support membrane porosity is of great importance in the selection of a support, capable of

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H. Ohya et al./J. Membrane Sci. 68 (1992) 141-148 nary systems with complete and partial miscibility, J. Membrane Sci., 51 (1990) 169. R.Y.M. Huang and C.K. Yeom, Pervaporation separation of aqueous mixtures using crosslinked poly(viny1 alcohol) [ PVA]. II. Permeation of ethanolwater mixtures, J. Membrane Sci., 51 (1990) 273. R. Nobrega, A.C. Harbert, M.E.F. Garcia, R.J. Esposito and C.P. Borges, Separation of ethanol/water mixtures by pervaporation through poly(viny1 alcohol) [ PVA ] membranes, Proc. 3rd Int. Cong. on Pervaporation Processes in the Chem. Ind., Nancy, Sept. 19-22,1988, R. Bakish (Ed.), Bakish Materials Corp., Englewood, NJ, p. 326. J.W.F. Spitzen, E. Elsinghorst, M.H.V. Mulder and C.A. Smolders, Solution-diffusion aspects in the separation of ethanol/water mixtures with PVA membranes, Proc. 2nd Int. Cong. on Pervaporation Processes in the Chem. Ind., San Antonio, TX, March 811, 1987, R. Bakish (Ed.), Bakish Materials Corp., Englewood, NJ, p. 209. J.W.F.Spitzen,G.H.Koops,M.H.V.MulderandC.A. Smolders, The influence of membrane thickness on pervaporation performance, Proc. 3rd Int. Cong. on Pervaporation Processes in the Chem. Ind., Nancy, Sept. 19-22,1988, R. Bakish (Ed.), Bakish Materials Corp., Englewood, NJ, p. 252. H. Ohya, A. Haio, Y. Negishi and K. Matsumoto, Standardization method for molecular weight cut-off evaluation of ultrafiltration membrane II., Maku (Jpn.), 15 (1990) 62. T. Hirotsu, Swelling and permseparation of waterethanol in poly(viny1 alcohol) membranes, Bulletin of Research Institute for Polymers and Textiles (Jpn. ) , 156 (1987) 11. H.E.A. Briischke, German Patent DE 3 220 570A1, 1982. Y. Morigami, M. Kondo and A. Kidoguchi, Zero loss solvent recovery, Proc. 2nd Int. Cong. on Pervaporation Processes in the Chem. Ind., San Antonio, TX, March 8-l&1987, R. Bakish (Ed.), Bakish Materials Corp., Englewood, NJ, p. 200.

forming the dense (non-swollen) skin. The support membrane having a molecular weight cut-off of 100 000 (composite membrane A) to 76 000 (B ) might be the best choice. On the other hand a membrane having a lower pure water permeability (less than 1.8 mm/ ( m2-secPa) might not be good because it is not able to suppress the swelling of the PVA membrane on top. References
H. Ohya and K. Matsumoto, Membranes for separation of aqueous alcohol solutions, Sekiyu Gakkaishi (Jpn), 33 (1990) 127. U. Sander and P. Soukup, Design and operation of a pervaporation plant for ethanol dehydration, J. Membrane Sci., 36 (1988) 463. R. Rautenbach, C. Herion, M. Franke, A.A. Asfour, A. Bemqerer-Costa and E. Bo, Investigation of mass transport in asymmetric pervaporation membranes, J. Membrane Sci., 36 (1988) 445. K.W. Boddeker, Terminology in pervaporation, J. Membrane Sci., 51 (1990) 259. U. Sander, Experiences in design of a dehydration plant for ethanol-water mixtures spent liquor of a pulp and paper mill, Proc. 1st Int. Cong. on Pervaporation Process in the Chem. Ind., Atlanta, GA, Feb. 23-26, 1986, R. Bakish (Ed.), Bakish Materials Corp., Englewood, NJ, p. 163. H.E.A. Briischke and G.F. Tusel, Economics of industrial pervaporation processes, Proc. Europe-Japan Cong. on Membs. and Memb. Processes, Stresa, Italy, 1984, Plenum Press, New York, NY, 1986, p. 581. M. Wesslein, A. Heintz and R.N. Lichtenthaler, Pervaporation of liquid mixtures through poly(viny1 alcohol) membranes. I. Study of water containing bi-

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