Electrolytic sodium, commercial production

Sir Humphry Davy first isolated metallic sodium ia 1807 by the electrolytic decomposition of sodium hydroxide. Later, the metal was produced experimentally by thermal reduction of the hydroxide with iron. In 1855, commercial production was started usiag the DeviUe process, ia which sodium carbonate was reduced with carbon at 1100°C. In 1886 a process for the thermal reduction of sodium hydroxide with carbon was developed. Later sodium was made on a commercial scale by the electrolysis of sodium hydroxide (1,2). The process for the electrolytic decomposition of fused sodium chloride, patented ia 1924 (2,3), has been the preferred process siace iastallation of the first electrolysis cells at Niagara Falls ia 1925. Sodium chloride decomposition is widely used throughout the world (see Sodium compounds). 

Alcohol sulfates commonly have free alcohol and electrolytes as impurities. Other hydrophobic impurities can also be present. A method suitable for the purification of surfactants has been proposed by Rosen [120]. Consequently, commercial products have CMCs that deviate from the accepted reference values. This was demonstrated by Vijayendran [121] who studied several commercial sodium lauryl sulfates of high purity. The CMC was determined both by the conductimetric method and by the surface tension method. The values found were similar for both methods but while three samples gave CMC values of 7.9, 7.8, and 7.4 mM, close to the standard range of 8.0-8.2 mM, three other samples gave values of 4.1, 3.1, and 1.7 mM. The sample with a CMC of 7.9 mM was found to have a CMC of 8.0 mM with no detectable surface tension minima after purification and recrystallization. This procedure failed in all other cases. 

The first production of aluminum was by the chemical reduction of aluminum chloride with sodium. The electrolytic process, based on the fused salt electrolysis of alumina dissolved in cryolite, was independently developed in 1886 by C. M. Hall in America and P. L. Heroult in France. Soon afterwards a chemical process for producing pure alumina from bauxite, the commercial source of aluminum, was developed by Bayer and this led to the commercial production of aluminum by a combination of the Bayer and the Hall-Heroult processes. At present this is the main method which supplies all the world s needs in primary aluminum. However, a few other processes also have been developed for the production of the metal. On account of problems still waiting to be solved none of these alternative methods has seen commercial exploitation. 

The phase Na2Sx is sodium polysulfide, a material with a sulfur content of between 3 and 5. The anode reaction takes place at the liquid sodium - (3"-alununa interface. Here sodium atoms lose an electron and the Na+ ions formed enter the conduction planes in the electrolyte. The cathode reaction, which occurs at the interface between the (3"-alumina and the liquid sulfur forms sodium polysulfides. Despite the desirable properties of the cell, technical and economic considerations have acted so as to curtail large-scale commercial production. 

These reactions of lead metal and lead alloys with alkyl esters are conducted at elevated temperatures (usually above 80 °C) and at elevated pressure (autogenous pressure of RX), and in the presence of a suitable catalyst, such as ethers, amines, iodides, dependent on the particular system involved. Despite the large number of systems which have been investigated, none has been found to be as economical for the commercial production of tetramethyllead and tetraethyllead as the sodium-lead alloy reaction, with the possible exception of the electrolytic process developed by Nalco Chemical Company for tetramethyllead. Electrolytic processes are discussed in Section 6. 

The ore is first treated with caustic soda under pressure. The aluminium largely dissolves as the aluminate, the iron oxide is insoluble and the silica also remains in the form of a sodium aluminium silicate, which leads to a loss of aluminium. Hence the best bauxites are those low in silica. After filtration, the hydrated aluminium oxide is reprecipitated by seeding and the caustic soda solution may be re-used. The alumina is washed and then heated at 1200°C to remove water. The final step in the production of aluminium metal has to be electrolytic since the reduction of alumina with carbon is only possible at very high temperatures and the reverse reaction occurs on cooling. Moreover, because of the chemistry of aluminium, the electrolysis medium cannot be water in fact almost all commercial production of aluminium during the last ninety years has used an electrolysis in molten cryolite (Na3AlF5). 

Possible surface treatment mechanisms include anodization [32-34], plasma and flame treatment [35], solution oxidation [36,37], gas phase oxidation, and high temperature oxidation. Some of these treatments have been reviewed 1 Donnet and coworkers [18,38]. The most practical surface treatment for commercial production of carbon fibers is anodization. This is because anodization (electrolytic oxidation) can be performed continuously on carbon fibers. Typical anodizations have been performed in aqueous acidic or basic solutions. Electrolytes include sodium hydroxide, potassium hydroxide, sulfuric add, nitric add, and solutions of amine salts. Amine salts have an added advantage in that, after treatment, excess electrolyte can be removed simply by heating the fiber to high temperatures (250 C). 

The addition of such electrolytes as KCl and BaCl2 in quantities not exceeding 0.1 mole/liter to solutions of propyl, ethyl, and methyl alcohols leads to an increased adhesion. We noted something rather similar (Fig. IV.18) when studying adhesion in solutions of surface-active substances (commercial products containing small quantities of electrolytes). The fact that the adhesive forces in solutions of T Duomin, NT Armak, and sodium oleate exceed the expected values may clearly be attributed to the presence of such electrolytes. 

Salt that is substantially free of sulfate and other impurities is the cell feed. This grade may be purchased from commercial salt suppHers or made on site by purification of cmde sea or rock salt. Dried calcium chloride or cell bath from dismanded cells is added to the bath periodically as needed to replenish calcium coproduced with the sodium. The heat required to maintain the bath ia the molten condition is suppHed by the electrolysis current. Other electrolyte compositions have been proposed ia which part or all of the calcium chloride is replaced by other salts (61—64). Such baths offer improved current efficiencies and production of cmde sodium containing relatively Htde calcium. 

Commercially, hydrogen chloride is obtained either as a by-product in the manufacture of salt cake from sodium chloride, or by allowing chlorine produced as a by-product in electrolytic processes to react with hydrogen in the presence of activated charcoal. It is also formed as a byproduct in the manufacture of phenol. 

The term chlor-alkali refers to those products obtained from the commercial electrolysis of aqueous sodium chloride. These are chlorine, sodium hydroxide, and sodium carbonate. The first two are produced simultaneously during the electrolysis while the latter is included because it is also produced in small quantities and shares many of the end uses of sodium hydroxide. Perfluorinated ionomer membranes are permeable to sodium ions but not the chloride ions, and hence they are useful for these electrolytic cells. The arrangement of a typical membrane cell is shown in Figure 10.2. 

The starting material for all industrial chlorine chemistry is sodium chloride, obtained primarily by evaporation of seawater. The chloride ion is highly stable and must be oxidized electrolytically to produce chlorine gas. This is carried out on an industrial scale using the chlor-alkali process, which is shown schematically in Figure 21-15. The electrochemistry involved in the chlor-alkali process is discussed in Section 19-. As with all electrolytic processes, the energy costs are very high, but the process is economically feasible because it generates three commercially valuable products H2 gas, aqueous NaOH, and CI2 gas. 

The original process used aqueous tetraethylammonium ethylsulfate as the electrolyte, a lead cathode, and a lead-silver alloy anode. The Mark II process, commercialized in the mid-1970s, uses an emulsion of acrylonitrile in aqueous sodium phosphate containing a salt of the hexamethylene-bis-(ethyldibutylammonium) cation. The process was invented in 1959 by M. M. Baizer at Monsanto Corporation, St. Louis, MO. It was commercialized in 1965 and has been continuously improved ever since. The process is also operated in Japan by Asahi Chemical Industry Company. In 1990, the world production of adiponitrile by this process was over 200,000 tonnes per year. 

Only a small number of compounds are produced directly by electrolysis. To illustrate this type of process, the electrolytic production of sodium hydroxide is described in detail. Then it is shown how this process may be modified to permit the formation of two other valuable commercial chemicals. 

Substantial quantities of commercial and captive HF are used in the production of aluminum trifluoride and sodium cryolite, both used by the aluminum industry. The electrolytic process for the production of aluminum involves fused A1203, A1F3, and Na3AlF6. About 8-10% of the world production of HF is consumed by aluminum industry which serves the World s two largest industries automotive and building construction. Due to the recent economic upturn, there is a large demand for aluminum metal in the market. As a result, the aluminum industry has opted for the least expensive source of fluoride ions such as hexafluorosilicic acid. 

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