Industrial chlor-alkali electrolysis processes

Castner, Hamilton Young — (Sep. 11, 1858, Brooklyn, New York, USA - Oct. 11,1899, Saranac Lake, New York, USA) Castner studied at the Brooklyn Polytechnic Institute and at the School of Mines of Columbia University. He started as an analytical chemist, however, later he devoted himself to the design and the improvement of industrial chemical processes. He worked on the production of charcoal, and it led him to investigate the Devilles aluminum process. He discovered an efficient way to produce sodium in 1886 which made also the production of aluminum much cheaper. He could make aluminum on a substantial industrial scale at the Oldbury plant of The Aluminium Company Limited founded in England. However, - Hall and - Heroult invented their electrochemical process which could manufacture aluminum at an even lower price, and the chemical process became obsolete. Castner also started to use electricity, which became available and cheap after the invention of the dynamo by - Siemens in 1866, and elaborated the - chlor-alkali electrolysis process by using a mercury cathode. Since Karl Kellner (1851-1905) also patented an almost identical procedure, the process became known as Castner-Kellner process. Cast-... 

Chlorine and sodium hydroxide are the main products of the industrial chlor-alkali electrolysis that is described as a process example in Section 6.19. Hydrochloric acid is produced by reaction from the elements H2 and CI2 or by the reaction of chloride salts such as, for example, NaCl or CaCl2, with sulfuric acid. Other important sources of HCl are industrial chlorination processes using CI2 as chlorination agent (e.g., chlorination of benzene to form chlorobenzene and HCl or the chlorination of methane to give chloromethane and HCl) or industrial dehydrochlorination processes (e.g., production of vinyl chloride and HCl from 1,2-dichloroethane). The main uses of hydrochloric acid are addition reactions to unsaturated compounds (by hydrochlorination or oxychlorination), formation of chlorine in the Deacon process, production of chloride salts from amines and other organic bases, dissolution of metals, regeneration of ion exchange resins, and the neutralization of alkaline products. 

The effect of the cost of the ion exchange membrane on the total cost of electrodialysis or electrolysis is large because the membrane is relatively expensive. The lifetime of the membrane depends on the purpose and conditions of electrodialysis or electrolysis. A membrane for the electrodialytic concentration of seawater to produce sodium chloride has a lifetime of over 10 years, and that in the chlor-alkali membrane process, which is operated at ten times or more higher current density than that of seawater concentration, is over 5 years. However, in applications for food industries, the lifetime of the membrane is relatively short due to periodical sanitary cleaning of the electrodialyzer by acid or alkali solution, and sometimes oxidizing agents. 

Waste or by-product streams rich in hydrogen occur in several petrochemical and electrochemical processes, such as chlor-alkali electrolysis and electroplating. When no chemical use for the hydrogen is possible, its conversion to electricity can be performed in an MCFC the good co-generation opportunities typically found in industrial environments should make MCFCs preferable to other FC technologies. 

Chlorine, which is produced by chlor-alkali electrolysis, is a fundamental building block of the chemical industry and is used in over 50% of all industrial chemical processes. 

Schwabe felt committed to yet another field of technical electrochemistry, chlor-alkali electrolysis, perhaps because of the brief period he spent at IG Farben in Bitterfeld from 1928 to 1929 and because a number of his pupils also had gone to work at Bitterfeld as industrial chemists. This led to several papers on the development of amalgam and diaphragm electrode processes. 

You have already seen that chlorine gas can be made by the electrolysis of molten sodium chloride. In industry, some chlorine is produced in this way using the Downs cell described earlier. However, more chlorine is produced in Canada using a different method, called the chlor-alkali process. In this process, brine is electrolyzed in a cell like the one shown in Figure 11.32. Brine is a saturated solution of sodium chloride. 

In the last twenty-five years a new process has been developed in the chlor-alkali industry that uses a membrane to separate the anode and cathode compartments in brine electrolysis cells. The membrane is superior to the diaphragm used in diaphragm cells because the membrane is impermeable to anions. Only cations can flow through the membrane. Because neither Cl- nor OH- ions can... 

Industrial applications of perfluorinated ionomer membranes such as the electrolysis of sodium chloride solution to produce chlorine and sodium hydroxide often involve the use of highly concentrated solutions at elevated temperatures. The optimization of these systems depends upon a sound characterization of membrane transport processes under such conditions. Sodium ion is the major current-carrying species through the membrane in a chlor-alkali cell, and... 

Energy Consumption. Electric power consumption of electrolysis is the major part of the energy consumption in a chlor-alkali process. The power consumption of the membrane process has recently been greatly reduced by various improvements. The latest performance of Asahi Chemical s membrane process realized at a commercial plant and also in an industrial scale cell is shown in relation to current density in Figure 13 (82). 

Chlorine gas, CI2, is prepared industrially by the electrolysis of molten NaCl (see Section 19.8) or by the chlor-alkali process, the electrolysis of a concentrated aqueous NaCl solution (called brine). Chlor denotes chlorine and alkali denotes an alkali metal, snch as sodium.) Two of the common cells nsed in the chlor-alkali process are the mercnry cell and the diaphragm cell. In both cells the overall reaction is... 

In practice, we remain far from meeting these apparently trivial requirements so-called inert electrodes have a finite lifetime due to corrosion and physical wear while it is common, even normal, to accept an overpotential of several hundred millivolts. Only in the chlor-alkali process and, to a lesser extent, in water electrolysis has significant progress towards improved electrode materials been made. Generalizations concerning electrode materials are probably unwise and the choice of electrodes for particular industrial processes will be discussed in... 

Natural salts are often processed to remove some of their impurities before sale. All food-grade and certain chemical applications require this. In the chlor-alkali industry, it is necessary at some point to convert crade salt as mined or produced into a material suitable for use in electrolysis. Whether this occurs at the salt producer s site or in the chlor-alkali plant is fundamentally irrelevant. For economic or technical reasons, the salt supplier often undertakes a certain amount of upgrading. The most important processes are salt washing, brine evaporation, and salt recrystallization. 

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