Abstract
Chlorine and its coproduct, sodium hydroxide (caustic soda), are significant factors in the world economy. They are indispensable intermediates for the chemical industry, and also possess important uses in a variety of other industries. Chlorine is second to aluminum as a consumer of electricity among the electrolytic processes. Direct current (dc) power for chlorine cells accounts for nearly 2% of all electric power generated in the United States.(1)
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References
T. R. Beck, in Proceedings of the Workshop on Energy Conservation in Industrial Electrochemical Processes, Argonne National Laboratory Report No. ANL/OEPM-77–1, August 1976, pp. 37–82.
J. J. Leddy, I. C. Jones, Jr., B. S. Lowry, F. W. Spillers, R. E. Wing, and C. D. Binger, Alkali and Chlorine Products, in Encyclopedia of Chemical Technology, 3rd ed., Vol. 1, John Wiley and Sons, New York (1978), pp. 799–865.
Y-C. Yen, Chlorine, Process Economic Program Report No. 61B, Stanford Research Institute, Menlo Park, California, November 1978, p. 3.
J. Renner and K. E. Woodard, Jr., Report of the electrolytic industries, presented at the Electrochemical Society Meeting, Boston, Massachusetts, May 1979, p. 4.
Chemical Origins and Markets, Stanford Research Institute, Menlo Park, California, 1967.
L. R. Belohlav and E. T. McBee, in Chlorine—Its Manufacture, Properties and Uses, A.C.S. Monograph 154, J. S. Sconce, ed., Reinhold, New York (1962), Chap. 1, pp. 1–9.
H. W. Schultze, The chlorine industry—past, present and future, in Chlorine Bicentennial Symposium, Electrochemical Society, Princeton, New Jersey (1974), pp. 1–19.
M. S. Kircher, in Chlorine—Its Manufacture, Properties and Uses, A.C.S. Monograph 154, J. S. Sconce, ed., Reinhold, New York (1962), Chap. 5, pp. 81–126.
W. C. Gardiner, Castner, a pioneer inventor in alkali-chlorine, in Chlorine Bicentennial Symposium, Electrochemical Society, Princeton, New Jersey (1974), pp. 35–43.
K. E. Stuart, U.S. Patent 1,865, 152 (1932).
R. B. MacMullin, in Chlorine—Its Manufacture, Properties and Uses, A.C.S. Monograph 154, J. S. Sconce, ed., Reinhold, New York (1962), Chap. 6, pp. 127–199.
D. W. F. Hardie, Electrolytic Manufacture of Chemicals from Salt, 2nd ed., The Chlorine Institute, New York (1975), pp. 77–78.
G. Faita, P. Longhi, and T. Mussini, Standard potentials of the Cl2/C1- electrode at various temperatures with related thermodynamic functions, J. Electrochem. Soc. 114, 340–343 (1967).
R. B. MacMullin, Algorithms for the vapor pressure of water over aqueous solutions of salt and caustic soda, J. Electrochem. Soc. 116, 416–419 (1969).
J. E. Currey and G. G. Pumplin, Chloralkali, in Encyclopedia of Chemical Processing and Design, Vol. 7, Marcel Dekker, New York (1978), pp. 305–450.
R. E. De La Rue and C. W. Tobias, On the conductivity of dispersions, J. Electrochem. Soc. 106, 827–833 (1959).
F. Hine and K. Murakami, Bubble effects on the solution it-drop in a vertical electrolyzer under free and forced convection flow conditions, presented at the Electrochemical Society Meeting, Boston, Massachusetts, May 1978, Abstract No. 281.
D. Dobos, Electrochemical Data, Elsevier, Amsterdam (1975), p. 85.
L. I. Kheifets and A. B. Gol’dberg, The rate of anolyte circulation in diaphragm-type electrolysis cells, Soy. Electrochem. (Engl. Transi.) 10, 1140–1147 (1974).
F. Hine and M. Yasuda, Studies on the deposited asbestos diaphragm with a miniature diaphragm-type chlorine cell, J. Electrochem. Soc. 118, 166–173 (1971).
F. Hine, M. Yasuda, and T. Tanaka, Mass transfer through the deposited asbestos diaphragm in chlor-alkali cells, Electrochem. Acta 22, 429–437 (1977).
Z. Nagy, A mechanistic model for the calculation of material balance for a diaphragm type chlorine caustic cell, J. Electrochem. Soc. 124, 91–95 (1977).
F. Hine and M. Yasuda, Studies on the cathodic reaction in the diaphragm-type chlorine cell, J. Electrochem. Soc. 118, 170–173 (1971).
I. E. Veselovskaya, E. M. Kuchinskii, and L. V. Morochko, The cathodic reduction of chlorate, J. Appl. Chem. USSR (Engl. Transi.) 37, 85–91 (1964).
J. M. McIntyre, Thermal temperature coefficients of the hydrogen electrode, presented at the Electrochemical Society Meeting, Seattle, Washington, May 1978, Abstract No. 541.
L. I. Krishtalik, G. L. Melikova, and E. G. Kalinina, Investigation of the effect of electrolysis conditions on the stability of graphite anodes in the chlorine cell, J. Appl. Chem. USSR (Engl. Transl.) 34, 1464–1469 (1961).
L. E. Vaaler, Graphite anodes in brine electrolysis, J. Electrochem. Soc. 107, 691–698 (1960).
L. E. Vaaler, Graphite-electrolytic anodes, Electrochem. Technol. 5, 170–174 (1967).
F. Hine, M. Yasuda, I. Sugiura, and T. Noda, Effects of the active chlorine and the pH on consumption of graphite anode in chlor-alkali cells, J. Electrochem. Soc. 121, 220–225 (1974).
Chem. Eng. (N. Y) 86, 45 (December 18, 1978 ).
R. H. Stevens, U.S. Patent 1,077, 894 (1913).
J. B. Cotton, E. C. Williams, and A. H. Barber, U.K. Provisional Patent Spec. 22619 (1957); U.K. Patent 877, 901 (1961).
H. B. Beer, Neth. Patent Appl. 216,199 (1957); U.S. Patent 3,236, 756 (1966).
D. B. Rogers, R. D. Shannon, A. W. Sleight, and J. L. Gillson, Crystal chemistry of metal dioxides with rutile-related structures, Inorg. Chem. 8, 841–849 (1969).
H. B. Beer, Living from invention, Chem. Ind. (London), 491–496 (July 15, 1978 ).
H. B. Beer, S. African Patent 2667 /66 (1967).
H. B. Beer, U.S. Patents 3,711,385 (1973), 3,632, 498 (1972).
K. J. O’Leary, U.S. Patent 3,776,834 (1973).
V. deNora, Ion selective electrodes, presented at the Electrochemical Society Meeting, Seattle, Washington, May 1978, Abstract No. 458.
S. Pizzini and G. Bianchi, Oxides with metallic conductivity, in The Science of Materials Used in Advanced Technology, John Wiley and Sons, New York (1973), Chap. 10, pp. 229–241.
D. C. Cronemeyer, Electrical and optical properties of rutile single crystals, Phys. Rev. 87, 876–886 (1952).
H. P. R. Frederikse, Recent studies on rutile (TiO2), J. Appl. Phys. Suppl. 32 (10), 2211–2215 (1961).
J. Riga, C. Tenret-Noël, J. J. Pireaux, R. Caudano, and J. J. Verbist, Electronic structure of rutile oxides TiO2, RuO2 and IrO2 studied by x-ray photoelectron spectroscopy, Phys. Scr. 16, 351–354 (1977).
G. Lodi, E. Sivieri, A. DeBattisti, and S. Trasatti, Ruthenium dioxide-based film electrodes, J. Appl. Electrochem. 8, 135–143 (1978).
F. Hine, M. Yasuda, and T. Yoshida, Studies on the oxide-coated metal anodes for chlor-alkali cells, J. Electrochem. Soc. 124, 500–505 (1977).
L. J. J. Janssen, L. M. C. Starmans, J. G. Visser, and E. Barendrecht, Mechanism of the chlorine evolution on a ruthenium oxide/titanium oxide electrode and on a ruthenium electrode, Electrochem. Acta 22, 1093–1100 (1977).
G. Faita and G. Fiori, Anodic discharge of chloride ions on oxide electrodes, J. Appl. Electrochem. 2, 31–35 (1972).
A. T. Kuhn and P. M. Wright, in Industrial Electrochemical Processes, A. T. Kuhn, ed., Elsevier, Amsterdam (1971), p. 533.
T. Matsumura, R. Itai, M. Shibuya, and G. Ishi, Electrolytic manufacture of sodium chlorate with magnetite anodes, Electrochem. Technol. 6, 402–404 (1968).
P. P. Anthony, U.S. Patent 3,711, 382 (1973).
A. Martinsons, U.S. Patent 3,711, 397 (1973).
G. N. Kokhanov, R. A. Agapova, F. I. Mulina, V. V. Avksent’ev, V. L. Kubasov, Yu. V. Dobrov, N. G. Baranova, S. A. Avdeeva, R. I. Kuznetsova, F. V. Kupovich, and Yu. M. Filimonov, USSR Patent 492, 301 (1975).
M. B. Konovalov, V. I. Bystrov, and V. L. Kubasov, A probe method for the study of the electrochemical characteristics of cobalt oxide anodes, Soy. Electrochem. (Engl. Transl.) 11, 218–220 (1975).
M. B. Konovalov, V. I. Bystrov, and V. L. Kubasov, Titanium-base cobalt oxide electrodes, Soy. Electrochem. (Engl. Transi.) 12, 1160–1162 (1976).
R. A. Agapova and G. N. Kokhanov, Electrochemical properties of cobalt oxide anodes, Soy. Electrochem. (Engl. Transi.) 12, 1505–1508 (1976).
D. L. Caldwell and R. J. Fuchs, U.S. Patent 3,977, 958 (1976).
D. L. Caldwell and M. J. Hazelrigg, U.S. Patent 4,142, 005 (1979).
M. J. Hazelrigg and D. L. Caldwell, Cobalt oxide based chlorine cell anodes, presented at the Electrochemical Society Meeting, Seattle, Washington, May 1978, Abstract No. 457.
M. J. Hazelrigg and D. L. Caldwell, U.S. Patent 4,061, 549 (1977).
M. D. Zholudev and V. V. Stender, Overvoltage in the evolution of hydrogen from alkaline solutions, J. Appl. Chem. USSR (Engl. Transi.) 31, 711–715 (1958).
N. P. Fedom’ev, N. V. Berezina, and E. G. Kruglova, Cathodes with positive potential of hydrogen formation, Zh. Prikl. Khim. 21, 317–328 (1948).
K. Sasaki and R. Matsui, Japan. Patent 31–6611 (1956).
Hooker Chemicals and Plastics Corp., Neth. Patent Appl. 75–07550 (1976).
J. R. Brannan and I. Malkin, U.S. Patent 4,024, 044 (1977).
R. B. MacMullin, German Patent Appl. 2, 704, 213 (1977).
J. R. Brannan, I. Malkin, and C. M. Brown, U.S. Patent 4,104, 133 (1978).
J. R. Hall and J. T. Van Gemert, U.S. Patent 3,291, 714 (1966).
S. D. Gokhale, U.S. Patent 3,974, 058 (1976).
H. H. Hoekje, H. B. Johnson, and R. D. Chamberlin, U.S. Patent 3,990, 957 (1976).
W. W. Carlin, U.S. Patent 4,010, 085 (1977).
H. C. Kuo, R. L. Dotson, and K. E. Woodard, U.S. Patent 4,033, 837 (1977).
A. Martinsons and H. B. Johnson, U.S. Patent 4,105, 516 (1978).
D. W. Carnell and C. R. S. Needes, Energy-saving catalytically active cathodes for caustic-chlorine production, presented at the Electrochemical Society Meeting, Boston, Massachusetts, May 1979, Abstract No. 260.
W. W. Carlin and W. B. Darlington, Activated cathodes for reduced power consumption in electrolytic cells, presented at the Electrochemical Society Meeting, Boston, Massachusetts, May 1979, Abstract No. 261.
I. Malkin and J. R. Brannan, Reduction of hydrogen overpotential in a chlorine cell, presented at the Electrochemical Society Meeting, Boston, Massachusetts, May 1979, Abstract No. 262.
G. Gritzner, U.S. Patents 4,035,254 and 4,035, 255 (1977).
Internat. Electrochem. Progr. 7(73), 9 (January 1978).
R. L. Dotson, Modern electrochemical technology, Chem. Eng. (N. Y.) 85, 106–118 (July 17, 1978 ).
J. S. Newman, Electrochemical Systems, Prentice-Hall, Englewood Cliffs, New Jersey (1973), p. 9.
T. Mukaibo, Technical analysis of diaphragm cells for the electrolysis of NaC1 solution, Denki Kagaku 20, 482–489 (1952).
V. V. Stender, O. S. Ksenzhek, and V. N. Lazarev, Alkali transfer and current efficiency in electrolysis of solutions of chlorides in diaphragm cells, J. Appl. Chem. USSR (Engl. Transi.) 40, 1245–1249 (1967).
O. S. Ksenzhek and V. M. Serebrit-skii, Theory of current efficiency in the electrolytic preparation of chlorine and alkali by the diaphragm method, Soy. Electrochem. (Engl. Transi.) 4, 1294–1300 (1968).
V. M. Serebrit-skii and O. S. Ksenzhek, Measurement of transport numbers of hydroxyl ions in mixed highly concentrated solutions of alkali and sodium chloride, J. Appl. Chem. USSR (Engl. Trans].) 43, 69–71 (1970).
V. M. Serebrit-skii and O. S. Ksenzhek, Theory of current yield during the electrolytic production of chlorine and alkali by the diaphragm method. II, Soy. Electrochem. (Engl. Transi.) 7, 1592–1596 (1971).
I. S. Stepanyan, Checking the theory of the unsteady condition for electrolysis of a sodium chloride solution in industrial cells with vertical filtering diaphragms, Soy. Electrochem. (Engl. Transi.) 9, 810–812 (1973).
V. L. Kubasov, Estimation of the thickness of the filtering diaphragm of electrolysis vessels for the preparation of chlorine and alkali, Sou. Electrochem. (Engl. Transi.) 12, 72–75 (1976).
L. I. Kheifets and A. B. Gol’dberg, Macrokinetics and chlorine cells with filter-action diaphragms. I. The effect of secondary processes on the current yield, Soy. Electrochem. (Engl. Transi.) 12, 1525–1528 (1976).
A. B. Gol’dberg and L. I. Kheifets, Macrokinetics chlorine cells with filter action diaphragm. II. Temperature dependence on the current yield, and the limits of the effect of anolyte resaturation, Soy. Electrochem. (Engl. Trans].) 12, 1555–1558 (1976).
H. Kaden and A. Pohl, Concerning porosity and pore structure of asbestos diaphragms, Chem. Tech. (Leipzig) 30, 25–28 (1978).
J.-A. Leduc, U.S. Patent 3,694, 281 (1972).
W. B. Darlington and R. T. Foster, U.S. Patent 3,853, 721 (1974).
R. N. Beaver and C. W. Becker, U.S. Patent 4,093, 533 (1978).
R. Goldsmith, U.S. Patent 3,281, 511 (1966).
W. G. Grot, U.S. Patent 3,702, 267 (1972).
C. Valiance, U.S. Patent 3,930, 979 (1976).
H. Shibata, Y. Kokubu, and I. Okazaki, The Nobel diaphragm cell: a flexible design for high currents and its performance characteristics at 330 kA, in Diaphragm Cells for Chlorine Production, Society of Chemical Industry, London (1977), pp. 53–65.
J. E. Currey and J. W. Ahern, Hooker’s membrane cell at Reed Paper Ltd.’s Dryden, Ontario plant, presented at the 19th Chlorine Institute Chlorine Plant Manager’s Seminar, Montreal, Quebec, February 1976.
K. J. O’Leary, Membrane chlorine cell design and operation, in Diaphragm Cells for Chlorine Production, Society of Chemical Industry, London (1977), pp. 103–115.
Symposium on Fluorocarbon Ion Exchange Membranes, Electrochemical Society Meeting, Atlanta, Georgia, October 1977, Abstract Nos. 436–443.
E. H. Price and D. E. Maloney, Nafion perfluorosulfonic acid membranes for the production of chlorine and caustic soda, presented at the 21st Chlorine Institute Chlorine Plant Manager’s Seminar, Houston, Texas, February 1978.
D. R. Pulver, The Commercial use of membrane cells in chlorine-caustic plants, presented at the 21st Chlorine Institute Chlorine Plant Manager’s Seminar, Houston, Texas, February 1978.
Y. Oda, M. Suhura, and E. Endo, U.S. Patent 4,065, 366 (1977).
H. Ukihashi and T. Asawa, Ion exchange membrane for chlor-alkali process, presented at the Electrochemical Society Meeting, Philadelphia, Pennsylvania, May 1977, Abstract No. 247.
M. Seko, The ion-exchange membrane chlor-alkali process, Ind. Eng. Chem. Prod. Res. Dey. 15, 286–292 (1976).
M. P. Grotheer and C. J. Harke, The development of Hooker’s H-2A and H-4 cells, in Chlorine Bicentennial Symposium, Electrochemical Society, Princeton, New Jersey (1974), pp. 209–217.
J. E. Currey, Recent advances in Hooker chlor-alkali cell technology, in Diaphragm Cells for Chlorine Production, Society of Chemical Industry, London (1977), pp. 79–91.
R. E. Loftfield and H. W. Laub, U.S. Patent 3,591, 483 (1971).
E. I. Fogelman U.S. Patent 3, 674, 676 (1972).
T. A. Liederbach, Technical advances in diaphragm chlorine cells, in Diaphragm Cells for Chlorine Production, Society of Chemical Industry, London (1977), pp. 41–52.
R. M. Hunter, L. B. Otis, and R. D. Blue, U.S. Patent 2,282, 058 (1942).
V. deNora, Chlorine production using Glanor cells, Chem. Ing. Tech. 47, 141 (1975).
Internat. Electrochem. Progr. 7 (82), 7. October 1978.
S. A. Dahl, Chlor-alkali cell features new ion-exchange membrane, Chem. Eng. (N.Y) 82, 60–61 (August 18, 1975 ).
R. E. Hulme, U.S. Patent 2,765, 873 (1956).
T. Hooker and R. H. Miller, U.S. Patent 2,750, 002 (1956).
D. L. Caldwell and R. J. Fuchs, U.S. Patent 4,073, 873 (1978).
T. G. Coker, SPE brine electrolyzers, presented at the Oronzio deNora Symposium on Chlorine Technology, Venice Lido, Italy, May 1979.
S. Ogawa, Asahi Chemical membrane chlor-alkali process, presented at the Seminar on Developments in Chlor-Alkali Industry, Indian Institute of Chemical Engineers, New Delhi, India, March 1980.
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Caldwell, D.L. (1981). Production of Chlorine. In: Bockris, J.O., Conway, B.E., Yeager, E., White, R.E. (eds) Comprehensive Treatise of Electrochemistry. Comprehensive Treatise of Electrochemistry, vol 2. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-3785-0_2
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