Abstract
A new chlorine resistant anion exchange membrane enables innovative possibilities for hydrochloric acid electrolysis for recovery of chlorine. This is of interest for hydrochloric acid that is neutralized in the chemical industry because purity and concentration are not sufficiently high for recycling. In the common electrolysis process hydrochloric acid is fed into the anode compartment and needs a satisfactory HCl concentration for supplying the anode with chloride ions. Using an anion exchange membrane as a cell separator the feed flows into the cathode chamber where a low HCl concentration is acceptable because Cl− ions at the anode can be supplied by addition of a salt which is not consumed. Experimental data of the membrane and the process are presented: membrane permselectivity improved up to above 97% using CaCl2 as added salt, chlorine current efficiency up to 98% and oxygen content as low as 0.5 vol%, cell voltage at 4 kA m−2 2.3 V, equivalent to 1740 kWh per t produced chlorine, even at low HCl concentrations. Thus, the power consumption is comparable with the common process. A problem of the new process is the high water transport through the membrane. Therefore, experiments for two process alternatives were carried out. Disadvantages of water transport can be avoided by using a high concentrated CaCl2 solution as anolyte and catholyte and as absorption medium for diluted HCl gas streams. Additionally, a cell design was investigated where the anode is directly connected to the membrane in an empty (gas filled) anode compartment.
Similar content being viewed by others
References
Information received from ‘Verband der Chemischen Industrie’ (VCI), (Frankfurt am Main, Germany, 2002)
Chlorine, Electrolysis of Hydrochloric Acid, in Ullmann’s Encyclopedia of Industrial Chemistry, 7th ed., (WILEY-VCH, Weinheim, Electronic Release 2005)
3. Hölemann H., (1962). Chem.-Ing.-Tech. 34:371
H. Isfort and W.-J. Stockmans, DECHEMA-Monographs 98 (1985) 141, VCH, Weinheim 1985
S. Motupally, A.J. Becker and J.W. Weidner, J. Electrochem. Soc. 149 (2002), Nr. 5, D63
US 4,107,005, ‘Process for electrolysing sodium chloride or hydrochloric acid, an and electrolytic cell, employing trifluorostyrene sulfonic acid membrane’, Hooker Chemicals & Plastics Corporation (Inv.: V.F. D’Agostino, J.Y. Lee and E.H. Cook, Jr.), Aug. 15, 1978
US 4,210,501, ‘Generation of halogens by electrolysis of hydrogen halides in a cell having catalytic electrodes bonded to a solid polymer electrolyte’, General Electric Co. (Inv.: R.M. Dempsey, T.G. Coker and A.B. La Conti), July 01, 1980
US 6,066,248, ‘Process for aqueous HCl electrolysis with thin film electrodes’, E.I. du Pont de Nemours and Company (Inv.: S.E.␣Lyke and P. Tatapudi), May 23, 2000
DE 100 48 004 A1, ‘Verfahren zur Elektrolyse wässriger Salzsäurelösungen’, Degussa AG, (Inv.: will be specified later), Apr. 11, 2002
US 5,411,641, ‘Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a cation-transporting membrane’, E.I.␣Du Pont de Nemours and Company (Inv.: J.A. Trainham, III, C.G. Law, Jr., J.S. Newman, K.B. Keating and D.J. Eames), May 02, 1995
US 5,798,036, ‘Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a membrane-electrode assembly or gas diffusion electrodes’, E. I. Du Pont de Nemours and Company (Inv.: W.H. Zimmerman, T.F. Saturno, J.S. Artysiewicz, J.A.␣Trainham, C.G. Law, Jr., J.S. Newman and D.J. Eames), Aug. 25, 1998
EP 0 785 294, ‘Improved method for the electrolysis of aqueous solutions of hydrochloric acid’, De Nora S.P.A. (Inv.: G.N. Faita), Sep. 04, 1997
EP 0 931 857, ‘Catalysts for gas diffusion electrodes’, De Nora S.P.A. (Inv.: R.J. Allen, D. Czerwiec, J.R. Giallombardo and K.␣Skaikh), Sep. 02, 1999
EP 1 313 893, ‘Process for the electrolysis of technical-grade hydrochloric acid contaminated with organic substances using oxygen-consuming cathodes’, Bayer AG, De Nora Elettrodi S.p.A., (Inv.: R.J. Allen, R.J. Giallombardo, D. Czerwiec, S. De Castro, K. Skaikh, F. Gestermann, H.-D. Pinter, and G. Speer), July 03, 2003
US 6,368,490, ‘Method for electrochemically processing HCl gas into highly pure chlorine’, Bayer AG, (Inv.: F. Gestermann), Apr. 09, 2002
G. Corti and M.B. Borghesi, Future technology based on GDE (Gas diffusion electrodes) for sodium chloride and HCl electrolysis, 7th Asian Chlor-Alkali Conference, Singapore, June 27–28, 2002
Bayer AG, (http://www.research.bayer.de/medien/pages/2867/Ele ktrolyse.pdf)
EP 0 518 075 B1, ‘Process and device for reprocessing contaminated water containing hydrochloric acid’, Sigri Great Lakes Carbon GmbH, (Inv. G. Härtel, W. Meissner and J. Künzel), May 5, 1992
19. Kreysa G., (1990). Chem.-Ing.-Tech. 62:357
J. Jörissen, Report AiF-Nr. 12774 N, University of Dortmund, 2003
DE 1 671 422, ‘Elektrode zur Verwendung in elektrolytischen Prozessen und Verfahren zu deren Herstellung’, Chemnor AG, (Inv.: H.B. Beer), June 16, 1971, (example 1 has been used)
Acknowledgements
The authors acknowledge financial support from the Arbeitsgemeinschaft industrieller Forschungsvereinigungen (AiF, funds of the Ministerium für Wirtschaft of the Federal Republic of Germany, AiF-No. 12774 N). They thank the DECHEMA e.V., Frankfurt am Main, for organizational help, and the Fumatech GmbH, St. Ingbert for membrane samples and preparation of membrane electrode units.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
BARMASHENKO, V., JÖRISSEN, J. Recovery of chlorine from dilute hydrochloric acid by electrolysis using a chlorine resistant anion exchange membrane. J Appl Electrochem 35, 1311–1319 (2005). https://doi.org/10.1007/s10800-005-9063-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-005-9063-1