Electrolysis of sodium chloride using composite poly(styrene-co-divinylbenzene) cation exchange membranes

Abstract Composite cation exchange membranes are prepared from cross-linked styrene-divinylbenzene copolymers for the electrolysis of sodium chloride to produce sodium hydroxide and chlorine by selective removal of sodium ions. It is prepared from a syrup of the polymer using dual initiating system and is modified with chloroacetic acid to introduce acid functional groups (COO − ) on its surface. The effect of the modification is confirmed by FTIR, SEM, contact angle, water content, and ion exchange capacity measurements. The performance of the membrane has been evaluated in terms of current efficiency and power consumption and the effect of current density, salt concentration and flow rate on efficiency has been studied. Our membrane has an ion exchange capacity of 0.833 meq./g which is close to that of the commercially available Nafion-117 membrane having an ion exchange capacity 0.9 meq./g. The Nafion-117 used for electrodialysis of sodium sulfate has a current efficiency of around 90% and specific energy consumption of 0.1 kW/mol at 2N concentration of the salt at 1000 A/m 2 . Our membrane used for electrodialysis of sodium chloride has a current efficiency of 93% and a power consumption of around 0.3122 kW/mol at the same concentration of salt and at a current density of 254 A/m 2 . The two-dimensional space-charge model in cylindrical coordinates has been solved semi-analytically to obtain the effective wall potential and pore size of the membrane which are difficult to measure directly. The experimentally obtained solute flux and current density have been fitted to the model and optimum values of effective wall potential and pore diameter have been determined to be 98.5 mV and 0.8 nm, respectively.

[1]  Anilesh Kumar,et al.  Analysis of separation of chromic acid by zeolite–clay composite membrane using space-charge model , 2004 .

[2]  Helmut Schmieder,et al.  Electrochemical approaches to environmental problems in the process industry , 2000 .

[3]  V. Shahi Highly charged proton-exchange membrane : Sulfonated poly(ether sulfone)-silica polyelectrolyte composite membranes for fuel cells , 2007 .

[4]  José A. Manzanares,et al.  On the introduction of the pore wall charge in the space-charge model for microporous membranes , 1990 .

[5]  Matthias Wessling,et al.  Cation permeable membranes from blends of sulfonated poly(ether ether ketone) and poly(ether sulfone) , 2002 .

[6]  J. F. Osterle,et al.  Membrane transport characteristics of ultrafine capillaries. , 1968, The Journal of chemical physics.

[7]  K. Scott,et al.  Salt splitting with radiation grafted PVDF anion-exchange membrane , 2003 .

[8]  Jiujun Zhang,et al.  A review of polymer electrolyte membranes for direct methanol fuel cells , 2007 .

[9]  Matthias Wessling,et al.  Electro-catalytic membrane reactors and the development of bipolar membrane technology , 2004 .

[10]  J. Selman,et al.  Electrochemical chromic acid regeneration process: fitting of membrane transport properties , 2002 .

[11]  Soteris A. Kalogirou,et al.  Seawater desalination using renewable energy sources , 2005 .

[12]  Manoj Kumar,et al.  Preparation and characterization of iron salt embedded electrodialysis Analcime-C zeolite clay composite membrane , 2006 .

[13]  M. D. Exter,et al.  Synthesis and characterization of zeolite (MFI) membranes on porous ceramic supports , 1992 .

[14]  C. Kruissink The effect of electro-osmotic water transport on current efficiency and cell performance in chlor-alkali membrane electrolysis , 1983 .

[15]  P. Pintauro,et al.  Coion exclusion properties of polyphosphazene ion-exchange membranes , 1999 .

[16]  Anilesh Kumar,et al.  Separation of Cr(VI) by zeolite–clay composite membranes modified by reaction with NOx , 2007 .

[17]  K. Bouzek,et al.  A mathematical model of multiple ion transport across an ion-selective membrane under current load conditions , 2003 .

[18]  Laurent Bazinet,et al.  Electrodialytic Phenomena and Their Applications in the Dairy Industry: A Review , 2005, Critical reviews in food science and nutrition.

[19]  F. Faverjon,et al.  Regeneration of hydrochloric acid and sodium hydroxide from purified sodium chloride by membrane electrolysis using a hydrogen diffusion anode-membrane assembly , 2006 .

[20]  A. Szymczyk,et al.  Electrolyte conductivity in charged capillaries , 2003 .

[21]  A. Samui,et al.  All-solid-supercapacitor based on polyaniline and sulfonated polymers , 2006 .

[22]  M. Ersoz The electrochemical properties of polysulfone ion-exchange membranes , 2001 .

[23]  T. Xu,et al.  Application of electrodialysis to the production of organic acids: State-of-the-art and recent developments , 2007 .

[24]  Xu Tongwen,et al.  Electrodialysis processes with bipolar membranes (EDBM) in environmental protection—a review , 2002 .

[25]  Mukul M. Sharma,et al.  An improved Space-Charge model for flow through charged microporous membranes , 1997 .

[26]  Frédéric Lebon,et al.  Polarization phenomena at the interfaces between an electrolyte solution and an ion exchange membrane: Part I. Ion transfer with a cation exchange membrane , 1992 .

[27]  M. Kariduraganavar,et al.  Ion-exchange membranes: preparative methods for electrodialysis and fuel cell applications , 2006 .

[28]  James A. Kent,et al.  Riegel's handbook of industrial chemistry , 1933 .

[29]  M. Zeni,et al.  Study of ion-selective membranes from electrodialysis removal of industrial effluent metals II: Zn and Ni , 2002 .

[30]  W. G. Grot Perfluorierte Ionenaustauscher‐Membrane von hoher chemischer und thermischer Stabilität , 1972 .

[31]  T. Hyeon,et al.  Fabrication of novel mesoporous dimethylsiloxane-incorporated silicas , 2000 .

[32]  N. Yamazoe,et al.  Development of FET-type CO2 sensor operative at room temperature , 2004 .

[33]  Application of the Maxwell–Stefan theory to the membrane electrolysis process. Model development and simulations , 2001 .

[34]  Anilesh Kumar,et al.  Effect of gas phase modification of analcime zeolite composite membrane on separation of surfactant by ultrafiltration , 2002 .

[35]  J. Smit,et al.  The application of the space-charge model to the permeability properties of charged microporous membranes , 1985 .

[36]  J. Ross Ullman's encyclopedia of industrial chemistry , 1986 .

[37]  G. Dennis,et al.  Catalyst–accelerator method for the preparation of wood–polymer composites at ambient temperature , 1995 .

[38]  Eli Ruckenstein,et al.  Electrolyte osmosis through capillaries , 1981 .

[39]  Barragán,et al.  Current-Voltage Curves for Ion-Exchange Membranes: A Method for Determining the Limiting Current Density. , 1998, Journal of colloid and interface science.

[40]  K. Oyaizu,et al.  Cationic polysulfonium membrane as separator in zinc–air cell , 2003 .

[41]  J. C. Fair,et al.  Reverse Electrodialysis in Charged Capillary Membranes , 1971 .