Fabrication and Characterization of Chitosan/Alginate Multilayer Composite Membrane Supported by a Porous Poly (Acrylonitrile) Substrate for Pervaporation Dehydration of Alcohol

Document Type: Research Paper


Zhejiang Sci-Tech University


Chitosan (CS) and alginate (Alg) are complementary in their membrane performance, but the combination of them is normally difcult to use due to their different solubilities. Layer-by-Layer deposition appears to be an effective method for improving the separation efciency of a composite membrane. In this work, the polyelectrolyte multilayer composite membranes (PEMCMs) were fabricated by depositing CS and Alg solutions alternatively onto a hydrolyzed porous poly(acrylonitrile) (PAN) substrate under a reduced pressure, as evidenced by Attenuated total reflectance Fourier transform infrared spectroscopy, contact angle and zeta potential measurement. Pervaporation results showed that the water selectivity increased while the flux decreased with the growth of CS/Alg-based polyelectrolyte layer. It was interesting that the sorption process dominated the pervaporation process when the numbers of polyelectrolyte layers were less than 7. However, the diffusion effect was more profound than the sorption effect as more than 8 polyelectrolyte layers were deposited on the PAN substrate. In particular, the prepared CS/Alg PEMCMs exhibited highly improved water selectivities towards alcohol/water mixtures, and a good compromise between flux and separation factor was observed when compared to other polyelectrolyte-based membranes. For separating 90% IPA/water mixtures at 60 ºC, the (CS/Alg)4 composite membrane displayed a separation factor of 4491 and a flux of 596 g/m2.h, respectively. These results indicate that the fabricated CS/Alg composite membranes are excellent waterpermselective ones for alcohol dehydration.

Graphical Abstract

Fabrication and Characterization of Chitosan/Alginate Multilayer Composite Membrane Supported by a Porous Poly (Acrylonitrile) Substrate for Pervaporation Dehydration of Alcohol


-Chitosan/sodium alginate composite membrane was fabricated by a press-driven process.

-The prepared polyelectrolyte composite membrane was employed for alcohol dehydration.

-Microporous poly (acrylonitrile) substrate was hydrolyzed for the subsequent deposition.

-The separation mechanism was dependent on the number of deposition layer.

-The prepared composite membrane exhibited desirable pervaporation performance.


Main Subjects

[1]  X. Feng, R. Y. M. Huang, Liquid separation by membrane pervaporation: a review, Ind. Eng. Chem. Res. 36 (1997) 1048-1066.

[2] P. Shao, R. Y. M. Huang, Polymeric membrane pervaporation, J. Membr. Sci. 287 (2007) 162-179.

[3] Q. Zhao, Q. F. An, Y. Ji, J. Qian, C. Gao, Polyelectrolyte complex membranes for pervaporation, nanofiltration and fuel cell applications, J. Membr. Sci. 379 (2011) 19-45.

[4] P. S. Rachipudi, A. A. Kittur, S. K. Choudhari, J. G. Varghese, M. Y. Kariduraganavar, Development of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes for dehydration of isopropanol,Eur. Polym. J.45 (2009) 3116-3126.

[5] Y. Li, H. Jia, Q. Cheng, F. Pan, Z. Jiang, Sodium alginate-gelatin polyelectrolyte complex membranes with both high water vapor permeance and high permselectivity, J. Membr. Sci.  375 (2011) 304-312.

[6] L. Krasemann, A. Toutianoush, B. Tieke, Self-assembled polyelectrolyte multilayer membranes with highly imporved pervaporation separation of ethanol/water mixtures, J.  Membr. Sci. 181 (2001) 221-228.

[7] D. M. Sullivan, M. L. Bruening, Ultrathin, cross-linked polyimide pervaporation membranes prepared from polyelectrolyte multilayers, J. Membr. Sci. 248 (2005) 161-170.

[8] G. Zhang, W. Gu, S. Ji, Z. Liu, Y. Peng, Z. Wang, Preparation of polyelectrolyte multilayer membranes by dynamic layer-by-layer process for pervaporation separation of alcohol/water mixtures, J. Membr. Sci. 280 (2006) 727-733.

[9] S. Ji, G. Zhang, Z. Liu, Y. Peng, Z. Wang, Evaluations of polyelectrolyte multilayer membranes assembled by a dynamic layer-by-layer technique, Desalination 234 (2008) 300-306.

[10] G. Zhang, X. Gao, S. Ji, Z. Liu, Electric field-enhanced assembly of polyelectrolyte composite membranes, J. Membr. Sci. 307 (2008) 151-155.

[11] P. Zhang, J. Qian, Y. Yang, Q. F. An, X. Liu, Z, Gui, Polyelectrolyte layer-by-layer self-assembly enhanced by electric field and their multilayer membranes for separating isopropanol-water mixtures, J. Membr. Sci. 320 (2008) 73-77.

[12] M. Yin, J. Qian, Q. F. An, Q. Zhao, Z. Gui, J. Li, Polyelectrolyte layer-by-layer self-assembly at vibration condition and the pervaporation performance of assembly multilayer films in dehydration of isopropanol, J. Membr. Sci. 358 (2010) 43-50.

[13] P. D. Chapman, T. Oliveira, A. G. Livingston, K. Li, Membranes for the dehydration of solvents by pervaporation, J. Membr. Sci. 318 (2008) 5-37.

[14] S. Kalyani, B. Smitha, S. Sridhar, A. Krishnaiah, Separation of ethanol-water mixtures by pervaporation using sodium alginate/poly (vinyl pyrrolidone) blend membrane crosslinked with phosphoric acid, Ind. Eng. Chem. Res. 45 (2006) 9088-9095.

[15] R.Y.M. Huang, R. Pal, G. Y. Moon, Characteristics of sodium alginate membranes for the pervaporation dehydration of ethanol-water and isopropanol-water mixtures, J. Membr. Sci. 160 (1999) 101-103.

[16] T. Uragami, M. Nanno, T. Miyata, Dehydration of an ethanol/water azeotrope through alginate-DNA membranes cross-linked with metal ions by pervaporation, Carbohydr. Polym. 134 (2015) 38-45.

[17] K. Rao, M. C.S. Subha, M. Sairam, N. N. Mallikarjuna, T. M. Aminabhavi, Blend membranes of chitosan and poly (vinyl alcohol) in pervaporation dehydration of isopropanol and tetrahydrofuran, J. Appl. Polym. Sci. 103 (2007) 1918-1926.

[18] M. N. Hyder, P. Chen, Pervaporation dehydration of ethylene glycol with chitosan-poly (vinyl alcohol) blend membranes: Effect of CS-PVA blending ratios, J. Membr. Sci. 340 (2009) 171-180.

[19] R. Jiraratananon, A. Chanachai, R. Y. M. Huang, D. Uttapap, Pervaporation dehydration of ethanol-water mixtures with chitosan/hydroxyethylcellulose (CS/HEC) composite membranes. I. Effect of operation conditions, J. Membr. Sci. 195 (2002)143-151.

[20] R. Jiraratananon, A. Chanachai, R. Y. M. Huang, Pervaporation dehydration of ethanol-water mixtures with chitosan/hydroxyethylcellulose (CS/HEC) composite membranes. II. Analysis of mass transport, J. Membr. Sci. 199 (2002) 211-222.

[21] J.-J. Shieh, R. Y. M. Huang, Pervaporation with chitosan membranes. II. Blend membranes of chitosan and polyacrylic acid and comparasion of homogeneous and composite membrane based on olyelectrolyte complexes of chitosan and polyacrylic acid for the separation of ethanol-water mixtures, J. Membr. Sci. 127  (1997) 185-202.

[22] S. Y. Nam, Y. M. Lee, Pervaporation and properties of chitosan-poly (acrylic acid) complex membranes, J. Membr. Sci. 135 (1997) 161-171.

[23] P. Kanti, K. Srigowri, J. Madhuri, B. Smitha, S. Sridhar, Dehydration of ethanol through blend membranes of chitosan and sodium alginate by pervaporation, Sep. Purif. Technol. 40 (2004) 259-266.

[24] J. Meier-Haack, W. Lenk, D. Lehmann, K. Lunkwitz, Pervaporation separation of water/alcohol mixtures using composite membranes based on polyelectrolyte multilayer assemblies, J. Membr. Sci. 184 (2001) 233-243.

[25] S.-G. Kim, G.-T. Lim, J. Jegal, K.-H. Lee, Pervaporation separation of MTBE (methyl tert-butyl ether) and methanol mixtures through polyion complex composite membranes consisting of sodium alginate/chitosan, J. Membr. Sci. 174 (2000) 1-15.

[26] A. M. Sajjan, B. K. Jeevan Kumar, A. A. Kittur, M. Y. Kariduraganavar, Novel approach for the development of pervaporation membranes using sodium alginate and chitosan-wrapped multiwalled carbon nanotubes for the dehydration of isopropanol, J. Membr. Sci. 425-426 (2013) 77-88.

[27] H. Lv, Z. Chen, X. Yang, L. Cen, X. Zhang, P. Gao, Layer-by-layer self-assembly of minocycline-loaded chitosan/alginate multilayer on titanium substrates to inhibit biofilm formation, J. Dent. 42 (2014) 1464-1472.

[28] M. G. Sankalia, R. C. Mashru, J. M. Sankalia, V. B. Sutariya, Reversed chitosan-alginate polyelectrolyte complex for stability improvement of alpha-amylase: Optimization and physicochemical characterization, Eur. J. Pharm. Biopharm. 65 (2007) 215-232.

[29] G. Y. Moon, R. Pal, R. Y. M. Huang, Novel two-ply composite membranes of chitosan and sodium alginate for the pervaporation dehydration of isopropanol and ethanol, J. Membr. Sci. 156 (1999) 17-27.

[30] R. Y. M. Huang, R. Pal, G. Y. Moon, Pervaporation dehydration of aqueous ethanol and isopropanol mixtures through alginate/chitosan two ply composite membranes supported by poly (vinylidene fluoride) porous membrane, J. Membr. Sci. 167 (2000) 275-289.

[31] W. Zhang, Z. Yu, Q. Qian, Z. Zhang, X. Wang, Improving the pervaporation performance of the glutaraldehyde crosslinked chitosan membrane by simultaneously changing its surface and bulk structure, J. Membr. Sci. 348  (2010) 213-223.

[32] X. Wang, N. Li, W. Wang, Pervaporation properties of novel alginate composite membranes for dehydration of organic solvents, J. Membr. Sci. 193 (2001) 85-95.

[33] T. Zhou, Y. Luo, Y. Lin, Q. Li, P. Yu, M. Zeng, Study of pervaporation for dehydration of caprolactam though blend NaAlg-poly (vinyl pyrrolidone) membranes on PAN supports, Sep. Purif. Technol. 74 (2010) 242-252.

[34] C. Qiu, S. Qi, C. Y. Tang, Synthesis of high flux forward osmosis membranes by chemically crosslinked layer-by-layer polyelectrolytes, J. Membr. Sci. 381 (2011) 74-80.

[35] G. Zhang, H. Yan, S. Ji, Z. Liu, Self-assembly of polyelectrolyte multilayer pervaporation membranes by a dynamic layer-by-layer technique on a hydrolyzed polyacrylonitrile ultrafiltration membrane, J. Membr. Sci. 292 (2007) 1-8.

[36] W. Zhang, G. Li, Y. Fang, X. Wang, Maleic anhydride surface-modification of crosslinked chitosan membrane and its pervaporation performance, J. Membr. Sci. 295 (2007) 130-138.

[37] M. Muller, M. Brissova, T. Rieser, A. C. Powers, K. Lunkwitz, Deposition and properties of polyelectrolyte multilayers studied by ATR-FTIR spectroscopy, Mater. Sci. Eng. C 8-9 (1999) 163-169.

[38] V. Tangpasuthadol, N. Pongchaisirikul, V. P. Hoven, Surface modification of chitosan films. Effects of hydrophobicity on protein adsorption, Carbohydr. Res. 338 (2003) 937-942.

[39] C. Gao, M. Zhang, J. Ding, F. Pan, Z. Jiang, Y. Li, J. Zhao, Pervaporation dehydration of ethanol by hyaluronic acid/sodium alginate two-active-layer composite membranes, Carbohydr. Polym. 99 (2014) 158-165.

[40] E.J. Flynn, D. Keane, J. D. Holmes, M. A. Morris, Unusual trend of increasing selectivity and decreasing flux with decreasing thickness in pervaporation separation of ethanol/water mixtures using sodium alginate blend membranes, J. Colloid Interface Sci. 370 (2012) 176-182

[41] X. Liu, Y. Sun, X. Deng, Studies on the pervaporation membrane of permeation water from methanol/water mixture, J. Membr. Sci. 325 (2008) 192-198.

[42] Q. Zhao, J. Qian, Q. F. An, M. Zhu, M. Yin, Z. Sun, Poly (vinyl alcohol)/polyelectrolyte complex blend membrane for pervaporation dehydration of isopropanol, J. Membr. Sci. 343 (2009) 53-61.

[43] S. G. Adoor, M. Sairam, L. S. Manjeshwar, K. V. S. N. Raju, T. M. Aminabhavi, Sodium montmorillonite clay loaded novel mixed matrix membranes of poly (vinyl alcohol) for pervaporation dehydration of aqueous mixtures of isopropanol and 1,4-dioxane, J. Membr. Sci. 285 (2006) 182-195.

[44] W. Zhang, Y. Xu, Z. Yu, S. Lu, X. Wang, Separation of acetic acid/water mixtures by pervaporation with composite membranes of sodium alginate active layer and microporous polypropylene substrate, J. Membr. Sci. 451 (2014) 135-147.

[45] C.-Y. Tu, Y.-L. Liu, K.-R. Lee, J.-Y. Lai, Hydrophilic surface-grafted poly (tetrafluoroethylene) membranes using in pervaporation dehydration process, J. Membr. Sci. 274 (2006) 47-55.

[46] M. C. Burshe, S. B. Sawant, J. B. Joshi, V. G. Pangarkar, Sorption and permeation of binary water-alcohol systems through PVA membranes crosslinked with multifunctional crosslinking agents, Sep. Purif. Technol. 12 (1997) 145-156.

[47] X. Liu, Y. Sun, X. Deng, Studies on the pervaporation membrane of permeation water from methanol/water mixture, J. Membr. Sci. 325 (2008) 192-198.

[48] A. Toutianoush, L. Krasemann, B. Tieke, Polyelectrolyte multilayer membranes for pervaporation separation of alcohol/water mixtures, Colloid Surf. A: Physicochem. Eng. Asp. 198-200 (2002) 881-889.