Review on Membrane Materials for Ethanol/Water Separation by Pervaporation


  • Natthida Rakkapao ᵃFaculty of Science and Industrial Technology, Prince of Songkla University, Surat Thani Campus, Surat Thani 84000, Thailand ᵇCenter of Excellence in Membrane Science and Technology, Prince of Songkla University, Hat Yai, Songkhla 90110, Thailand
  • Sutida Marthosa ᵃFaculty of Science and Industrial Technology, Prince of Songkla University, Surat Thani Campus, Surat Thani 84000, Thailand ᵇCenter of Excellence in Membrane Science and Technology, Prince of Songkla University, Hat Yai, Songkhla 90110, Thailand
  • Ekasit Anancharoenwong Faculty of Science and Industrial Technology, Prince of Songkla University, Surat Thani Campus, Surat Thani 84000, Thailand



Ethanol, pervaporation, membrane, polymer, inorganic


Bioethanol is produced through the fermentation of biomass. It has garnered significant research attention due to its potential as the next generation of sustainable energy. The fermentation broth must be purified before it can be used. This article reviews membrane materials for the separation of ethanol and water using pervaporation membranes. It covers the pervaporation mechanism, membranes for ethanol dehydration, membranes for ethanol recovery, and the prospects of using membranes in this application.


N. Singh and R. Prasad. (2011). Fuel grade ethanol by diffusion distillation: An experimental study. Journal of Chemical Technology & Biotechnology, 86(5), 724-730. Doi: 10.1002/JCTB.2579.

S. Marthosa, W. Youravong, and E. Anancharoenwong. (2020). Influence of pretreatments on sustainability of bioethanol production from napier grass. International Journal of Integrated Engineering, 12(5). Doi: 10.30880/ijie.2020.12.05.024.

H. S. Samanta and S. K. Ray. (2015). Separation of ethanol from water by pervaporation using mixed matrix copolymer membranes. Sep Purif Technol, 146, 176-186. Doi: 10.1016/J.SEPPUR.2015.03.006.

N. L. Le and S. P. Nunes. (2016). Materials and membrane technologies for water and energy sustainability. Sustainable Materials and Technologies, 7, 1-28. Doi: 10.1016/J.SUSMAT.2016.02.001.

C. W. Cho and S. T. Hwang. 1991. Continuous membrane fermentor separator for ethanol fermentation. J Memb Sci, 57(1), 21-42. Doi: 10.1016/S0376-7388(00)81160-6.

D. J. O’Brien, L. H. Roth, and A. J. McAloon. (2000). Ethanol production by continuous fermentation–pervaporation: A preliminary economic analysis. J Memb Sci, 166(1), 105-111. Doi: 10.1016/S0376-7388(99)00255-0.

P. Peng, Y. Lan, L. Liang, and K. Jia. (2021). Membranes for bioethanol production by pervaporation. Biotechnology for Biofuels, 14(1), 1-33. Doi: 10.1186/S13068-020-01857-Y.

S. Marthosa, W. Youravong, C. Kongmanklang, and W. Khongnakorn. (2019). Applications and characterization of silicalite-1/polydimethylsiloxane composite membranes for the pervaporation of a model solution and fermentation broth. Journal of Polymer Engineering, 39(2), 152-160. Doi: 10.1515/POLYENG-2018-0138/MACHINEREADABLECITATION/RIS.

M. Alberto et al. (2017). Enhanced organophilic separations with mixed matrix membranes of polymers of intrinsic microporosity and graphene-like fillers. J Memb Sci, 526, 437-449. Doi: 10.1016/J.MEMSCI.2016.12.06.

K.-Y. Law. (2015). Definitions for Hydrophilicity, Hydrophobicity, and Superhydrophobicity: Getting the Basics Right. Journal Pure and Applied Chemistry, 87(8), 759-765. Doi: 10.1021/jz402762h.

C. Fu et al. (2016). Ethanol fermentation integrated with PDMS composite membrane: An effective process. Bioresour Technol, 200, 648-657. Doi: 10.1016/J.BIORTECH.2015.09.117.

J. Kujawski, A. Rozicka, M. Bryjak, and W. Kujawski. (2014). Pervaporative removal of acetone, butanol and ethanol from binary and multicomponent aqueous mixtures. Sep Purif Technol, 132, 422-429. Doi: 10.1016/J.SEPPUR.2014.05.047.

L. M. Vane. (2008). Separation technologies for the recovery and dehydration of alcohols from fermentation broths. Biofuels, Bioproducts and Biorefining, 2(6), 553-588. Doi: 10.1002/BBB.108.

X. Zhan, R. Ge, Z. Gao, T. Gao, L. Wang, and J. Li. (2022). PVA-based MMMs for ethanol dehydration via pervaporation: A comparison study between graphene and graphene oxide. Separations, 9(2). Doi: 10.3390/SEPARATIONS9020026/S1.

H. Tong et al. (2023). Efficient pervaporation for ethanol dehydration: ultrasonic spraying

Preparation of Polyvinyl Alcohol (PVA)/Ti3C2Tx Nanosheet Mixed Matrix Membranes. Membranes (Basel), 13(4), 430. Doi: 10.3390/MEMBRANES13040430/S1.

I. Aranaz et al. (2021). Chitosan: An overview of its properties and applications. Polymers (Basel), 13(19). Doi: 10.3390/POLYM13193256.

M. N. Fini, S. Soroush, and M. M. Montazer-Rahmati. (2018). Synthesis and optimization of chitosan ceramic-supported membranes in pervaporation ethanol dehydration. Membranes, 8(4), 119. Doi: 10.3390/MEMBRANES8040119.

S. P. Dharupaneedi, R. V. Anjanapura, J. M. Han, and T. M. Aminabhavi. (2014). Functionalized graphene sheets embedded in chitosan nanocomposite membranes for ethanol and isopropanol dehydration via pervaporation. Ind Eng Chem Res, 53(37), 14474-14484. Doi: 10.1021/IE502751H/SUPPL_FILE/IE502751H_SI_001.PDF.

D. Xu, L. S. Loo, and K. Wang. (2010). Pervaporation performance of novel chitosan-POSS hybrid membranes: Effects of POSS and operating conditions. J Polym Sci B Polym Phys, 48(21), 2185-2192. Doi: 10.1002/POLB.22100.

M. N. Fini, S. Soroush, and M. M. Montazer-Rahmati. (2018). Synthesis and optimization of chitosan ceramic-supported membranes in pervaporation ethanol dehydration. Membranes, 8(4), 119. Doi: 10.3390/MEMBRANES8040119

H. Sun, L. Lu, X. Chen, and Z. Jiang. (2008). Pervaporation dehydration of aqueous ethanol solution using H-ZSM-5 filled chitosan membranes. Sep Purif Technol, 58(3), 429-436.

B. Bolto, M. Hoang, and Z. Xie. (2011). A review of membrane selection for the dehydration of aqueous ethanol by pervaporation. Chemical Engineering and Processing: Process Intensification, 50(3), 227-235. Doi: 10.1016/J.CEP.2011.01.003.

R. Y. M. Huang, R. Pal, and G. Y. Moon. (1999). Characteristics of sodium alginate membranes for the pervaporation dehydration of ethanol–water and isopropanol–water mixtures. J Memb Sci, 160(1), 101-113. Doi: 10.1016/S0376-7388(99)00071-X.

G. Dudek and R. Turczyn. (2018). New type of alginate/chitosan microparticle membranes for highly efficient pervaporative dehydration of ethanol. RSC Adv, 8(69), 39567, Doi: 10.1039/C8RA07868H.

P. Grzybek et al. (2022). Composite alginate membranes with dispersed MQFP hard magnet network as a new concept for highly efficient pervaporative dehydration of ethanol/water mixture. Sep Purif Technol, 303. Doi: 10.1016/j.seppur.2022.122183.

L. Y. Jiang, Y. Wang, T. S. Chung, X. Y. Qiao, and J. Y. Lai. (2009). Polyimides membranes for pervaporation and biofuels separation. Prog Polym Sci, 34(11), 1135-1160. Doi: 10.1016/J.PROGPOLYMSCI.2009.06.001.

L. W. McKeen. (2014). The Effect of Long Term Thermal Exposure on Plastics and Elastomers. Polyimidepp, 117-137. Doi: 10.1016/B978-0-323-22108-5.00006-0.

Y. Wang, L. Jiang, T. Matsuura, T. S. Chung, and S. H. Goh. (2008). Investigation of the fundamental differences between polyamide-imide (PAI) and polyetherimide (PEI) membranes for isopropanol dehydration via pervaporation. J Memb Sci, 318(1-2), 217-226. Doi: 10.1016/J.MEMSCI.2008.02.033

K. S. Burts, T. V. Plisko, V. G. Prozorovich, G. B. Melnikova, A. I. Ivanets, and A. V. Bildyukevich. (2022). Modification of thin film composite PVA/PAN membranes for pervaporation using aluminosilicate nanoparticles. Int J Mol Sci, 23(13). Doi: 10.3390/IJMS23137215.

Q. G. Zhang, Q. L. Liu, A. M. Zhu, Y. Xiong, and L. Ren. (2009). Pervaporation performance of quaternized poly(vinyl alcohol) and its crosslinked membranes for the dehydration of ethanol. J Memb Sci, 335(1-2), 68-75.

J.-W. Ji-Won Rhim, C.-K. Yeom, and S.-W. Kim. (1998). Modification of poly(vinyl alcohol) membranes using sulfur-succinic acid and its application to pervaporation separation of water–alcohol mixtures. J Appl Polym Sci, 68, 1717-1723,

J. W. Rhim, S. W. Lee, and Y. K. Kim. (2002). Pervaporation separation of water–ethanol mixtures using metal-ion-exchanged poly(vinyl alcohol) (PVA)/sulfosuccinic acid (SSA) membranes. J Appl Polym Sci, 85(9), 1867-1873. Doi: 10.1002/APP.10735.

V. S. Praptowidodo. (2005). Influence of swelling on water transport through PVA-based membrane. Journal of Molecular Structure, 739(1-3), 207-212.

B. Sun and J. Zou. (2003). Poly(vinyl alcohol)-based polyelectrolyte pervaporation membranes. Ann N Y Acad Sci, 984, 386-400. Doi: 10.1111/J.1749-6632.2003.TB06014.X.

M. Rafik, A. Mas, M. F. Guimon, C. Guimon, A. Elharfi, and F. Schué. (2003). Plasma-modified poly(vinyl alcohol) membranes for the dehydrationof ethanol. Polym Int, 52(7), 1222-1229. Doi: 10.1002/PI.1260.

M. L. Gimenes, L. Liu, and X. Feng. (2007). Sericin/poly(vinyl alcohol) blend membranes for pervaporation separation of ethanol/water mixtures. J Memb Sci, 295(1-2), 71-79. Doi: 10.1016/J.MEMSCI.2007.02.036

P. Grzybek et al. (2022). “Robust and high selective chitosan asymmetric Membranes: Relation between microporous structure and pervaporative efficiency in ethanol dehydration. Sep Purif Technol, 281, 119897. Doi: 10.1016/J.SEPPUR.2021.119897

V. Dubey, L. K. Pandey, and C. Saxena. (2005). Pervaporative separation of ethanol/water azeotrope using a novel chitosan-impregnated bacterial cellulose membrane and chitosan–poly(vinyl alcohol) blends. J Memb Sci, 251(1-2), 131-136,

A. Mochizuki, S. Amiya, Y. Sato, H. Ogawara, and S. Yamashita. (1990). Pervaporation separation of water/ethanol mixtures through polysaccharide membranes. IV.

The relationships between the permselectivity of alginic acid membrane and its solid state structure. J Appl Polym Sci, 40, 385-400.

Y. Q. Dong, L. Zhang, J. N. Shen, M. Y. Song, and H. L. Chen. (2006). Preparation of poly(vinyl alcohol)-sodium alginate hollow-fiber composite membranes and pervaporation dehydration characterization of aqueous alcohol mixtures,” Desalination, 193(1-3), 202-210. Doi: 10.1016/J.DESAL.2005.08.023.

S. Li et al. (2020). Highly selective sodium alginate mixed-matrix membrane incorporating multi-layered MXene for ethanol dehydration. Sep Purif Technol, 235, 116206. Doi: 10.1016/J.SEPPUR.2019.116206

J. H. Kim, K. H. Lee, and S. Y. Kim. (2000). Pervaporation separation of water from ethanol through polyimide composite membranes. J Memb Sci, 169(1), 81-93. Doi: 10.1016/S0376-7388(99)00335-X.

H. Yanagishita et al. (2001). Separation performance of polyimide composite membrane prepared by dip coating process. J Memb Sci, 188(2), 165-172. Doi: 10.1016/S0376-7388(01)00337-4.

A. Kudasheva, S. Sorribas, B. Zornoza, C. Téllez, and J. Coronas. (2015). Pervaporation of water/ethanol mixtures through polyimide based mixed matrix membranes containing ZIF-8, ordered mesoporous silica and ZIF-8-silica core-shell spheres. Journal of Chemical Technology & Biotechnology. 90(4), 669-677. Doi: 10.1002/JCTB.4352.

J. M. Zhu, G. Li, and L. Y. Jiang. 2016. Fabrication and structural tuning of novel composite hollow fiber membranes for pervaporation. J Appl Polym Sci, 133(16). Doi: 10.1002/APP.43324.

L. M. Vane, V. V. Namboodiri, and T. C. Bowen. (2008). Hydrophobic zeolite–silicone rubber mixed matrix membranes for ethanol–water separation: Effect of zeolite and silicone component selection on pervaporation performance. J Memb Sci, 308(1-2), 230-241. Doi: 10.1016/J.MEMSCI.2007.10.00.

F. Xiangli, Y. Chen, W. Jin, and N. Xu. (2007). Polydimethylsiloxane (PDMS)/Ceramic Composite Membrane with High Flux for Pervaporation of Ethanol−Water Mixtures. Ind Eng Chem Res, 46(7), 2224-2230.

X. Zhan, J. Lu, T. Tan, and J. Li. (2012). Mixed matrix membranes with HF acid etched ZSM-5 for ethanol/water separation: Preparation and pervaporation performance. Appl Surf Sci, 259, 547-556. Doi: 10.1016/J.APSUSC.2012.05.167.

S. L. Schmidt, M. D. Myers, S. S. Kelley, J. D. McMillan, and N. Padukone. (1997). Evaluation of PTMSP membranes in achieving enhanced ethanol removal from fermentations by pervaporation. Applied Biochemistry and Biotechnology - Part A Enzyme Engineering and Biotechnology, 63-65(1), 469-482. Doi: 10.1007/BF02920447/METRICS

H. S. Samanta and S. K. Ray. (2015). Separation of ethanol from water by pervaporation using mixed matrix copolymer membranes. Sep Purif Technol, 146, 176-186. Doi: 10.1016/J.SEPPUR.2015.03.006.

N. L. Le, Y. Wang, and T. S. Chung. (2011). Pebax/POSS mixed matrix membranes for ethanol recovery from aqueous solutions via pervaporation. J Memb Sci, 379(1-2), 174-183. Doi: 10.1016/J.MEMSCI.2011.05.060.

K. Ishihara and K. Matsui. (1987). Pervaporation of ethanol-water mixture through composite membranes composed of styrene-fluoroalkyl acrylate graft copolymers and cross-linked polydimethylsiloxane membrane. J Appl Polym Sci, 34(1), 437-440. Doi: 10.1002/APP.1987.070340135.

A. Ghofar and T. Kokugan. (2004). The pervaporation mechanism of dilute ethanol solution by hydrophobic porous membranes. Biochem Eng J, 18(3), 235-238. Doi: 10.1016/J.BEJ.2003.09.002.

S. Yi, Y. Su, and Y. Wan. (2010). Preparation and characterization of vinyltriethoxysilane (VTES) modified silicalite-1/PDMS hybrid pervaporation membrane and its application in ethanol separation from dilute aqueous solution. J Memb Sci, 360(1-2), 341-351. Doi: 10.1016/J.MEMSCI.2010.05.02.

X. Liu et al. (2015). Preparation and characterization of Silicalite-1/PDMS surface sieving pervaporation membrane for separation of ethanol/water mixture. J Appl Polym Sci, 132(34), Doi: 10.1002/APP.42460.

P. V. Naik, S. Kerkhofs, J. A. Martens, and I. F. J. Vankelecom. (2016). PDMS mixed matrix membranes containing hollow silicalite sphere for ethanol / water separation by pervaporation. J Memb Sci, 502, 48-56. Doi: 10.1016/J.MEMSCI.2015.12.02.

Z. Zhu et al. (2017). Three-component mixed matrix organic/inorganic hybrid membranes for pervaporation separation of ethanol–water mixture. J Appl Polym Sci, 134(17). Doi: 10.1002/APP.44753.

H. Yin et al. (2017). Free-standing ZIF-71/PDMS nanocomposite membranes for the recovery of ethanol and 1-butanol from water through pervaporation. J Memb Sci, 529, 286-292. Doi: 10.1016/J.MEMSCI.2017.02.00.

X. Zhan, M. Wang, T. Gao, J. Lu, Y. He, and J. Li. (2020). A highly selective sorption process in POSS-g-PDMS mixed matrix membranes for ethanol recovery via pervaporation. Sep Purif Technol, 236, 116238. Doi: 10.1016/J.SEPPUR.2019.11623.

X. Q. Cheng et al. (2017). Organic microporous nanofillers with unique alcohol affinity for superior ethanol recovery toward sustainable biofuels. ChemSusChem, 10(9), 1887-1891. Doi: 10.1002/CSSC.201700362.

J. Gu, X. Shi, Y. Bai, H. Zhang, L. Zhang, and H. Huang. (2009). Silicalite-filled PEBA membranes for recovering ethanol from aqueous solution by pervaporation, Chem Eng Technol, 32(1), 155-160. Doi: 10.1002/CEAT.200800252.

X. Zhan et al. (2022). Breakthroughs on tailoring membrane materials for ethanol recovery by pervaporation. Chin J Chem Eng, 52, 19-36. Doi: 10.1016/j.cjche.2021.12.010.

C. Conde-Mejía and A. Jiménez-Gutiérrez. (2020). Analysis of ethanol dehydration using membrane separation processes. Open Life Sci, 15(1), 122. Doi: 10.1515/BIOL-2020-0013.

J. Sekulić, J. E. Ten Elshof, and D. H. A. Blank. (2005). Separation mechanism in dehydration of water/organic binary liquids by pervaporation through microporous silica. J Memb Sci, 254(1-2), 267-274. Doi: 10.1016/J.MEMSCI.2005.01.01.

L. Peng, Z. Wu, B. Wang, H. Liu, C. Zhang, and X. Gu. (2022). Fabrication of high-stability W-MFI zeolite membranes for ethanol/water mixture separation. J Memb Sci, 659, 120729. Doi: 10.1016/J.MEMSCI.2022.120729.




How to Cite

Rakkapao, N., Marthosa, S., & Anancharoenwong, E. (2023). Review on Membrane Materials for Ethanol/Water Separation by Pervaporation. Journal of Applied Membrane Science & Technology, 27(3), 1–18.