Anolyte

Small amounts of propionitrile and bis(cyanoethyl) ether are formed as by-products. The hydrogen ions are formed from water at the anode and pass to the cathode through a membrane. The catholyte that is continuously recirculated in the cell consists of a mixture of acrylonitrile, water, and a tetraalkylammonium salt the anolyte is recirculated aqueous sulfuric acid. A quantity of catholyte is continuously removed for recovery of adiponitrile and unreacted acrylonitrile the latter is fed back to the catholyte with fresh acrylonitrile. Oxygen that is produced at the anodes is vented and water is added to the circulating anolyte to replace the water that is lost through electrolysis. The operating temperature of the cell is ca 50—60°C. Current densities are 0.25-1.5 A/cm (see Electrochemical processing). 

Separation of the anode and cathode products in diaphragm cells is achieved by using asbestos [1332-21 -4] or polymer-modified asbestos composite, or Polyramix deposited on a foraminous cathode. In membrane cells, on the other hand, an ion-exchange membrane is used as a separator. Anolyte—catholyte separation is realized in the diaphragm and membrane cells using separators and ion-exchange membranes, respectively. The mercury cells contain no diaphragm the mercury [7439-97-6] itself acts as a separator. 

Current Efficiency. Current efficiency for caustic production in diaphragm and membrane cells can be estimated from collection of a known amount of caustic over a period of time and from a knowledge of the number of coulombs of electricity passed during that time period. An alternative method involves analysis of the gases evolved during electrolysis and determining the anolyte composition. Material balance considerations (7) show the expression for the caustic efficiency for membrane cells to be... 

Fig. 25. OxyTech MGC electroly2er a, membrane b, anode assembly c, manifold spacer d, anolyte outlet e, catholyte outlet f, bulkhead g, brine inlet h, NaOH inlet i, insulating channel j, bulkhead insulator k, interface material 1, cathode assembly m, interceU bus n, tie rod o, current distributor p,...

The brine feed to the electroly2ers of all the processes is usually acidified with hydrochloric acid to reduce oxygen and chlorate formation in the anolyte. Table 14 gives the specifications of the feed brines requited for the membrane and diaphragm cell process to reali2e optimal performance. 

Nickel. Most nickel is also refined by electrolysis. Both copper and nickel dissolve at the potential required for anodic dissolution. To prevent plating of the dissolved copper at the cathode, a diaphragm cell is used, and the anolyte is circulated through a purification circuit before entering the cathodic compartment (see Nickel and nickel alloys). 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

Selectivity of propylene oxide from propylene has been reported as high as 97% (222). Use of a gas cathode where oxygen is the gas, reduces required voltage and eliminates the formation of hydrogen (223). Addition of carbonate and bicarbonate salts to the electrolyte enhances ceU performance and product selectivity (224). Reference 225 shows that use of alternating current results in reduced current efficiencies, especiaHy as the frequency is increased. Electrochemical epoxidation of propylene is also accompHshed by using anolyte-containing silver—pyridine complexes (226) or thallium acetate complexes (227,228). 

Ohio, high carbon ferrochromium is leached with a hot solution of reduced anolyte plus chrome alum mother Hquor and makeup sulfuric acid. The slurry is then cooled to 80°C by the addition of cold mother Hquor from the ferrous ammonium sulfate circuit, and the undissolved soHds, mostiy siHca, are separated by filtration. The chromium in the filtrate is then converted to the nonalum form by conditioning treatment for several hours at elevated temperature. 

A newer technology for the manufacture of chromic acid uses ion-exchange (qv) membranes, similar to those used in the production of chlorine and caustic soda from brine (76) (see Alkali and cm ORiNE products Chemicals frombrine Mep rane technology). Sodium dichromate crystals obtained from the carbon dioxide option of Figure 2 are redissolved and sent to the anolyte compartment of the electrolytic ceU. Water is loaded into the catholyte compartment, and the ion-exchange membrane separates the catholyte from the anolyte (see Electrochemical processing). 

When a potential is appHed across the ceU, the sodum and other cations are transported across the membrane to the catholyte compartment. Sodium hydroxide is formed in the catholyte compartment, because of the rise in pH caused by the reduction of water. Any polyvalent cations are precipitated and removed. The purified NaOH may be combined with the sodium bicarbonate from the sodium dichromate process to produce soda ash for the roasting operation. In the anolyte compartment, the pH falls because of the oxidation of water. The increase in acidity results in the formation of chromic acid. When an appropriate concentration of the acid is obtained, the Hquid from the anolyte is sent to the crystallizer, the crystals are removed, and the mother Hquor is recycled to the anolyte compartment of the ceU. The electrolysis is not allowed to completely convert sodium dichromate to chromic acid (76). Patents have been granted for more electrolytic membrane processes for chromic acid and dichromates manufacture (86). 

The distribution of species as a function of anolyte pH is shown in Eigure 8 (21). Chlorine is the primary product at pH < 4. Hypochlorous acid [7790-92-3] HOCl, is the dorninant species from pH 4 to pH 6. Above pH 6 combinations of HOCl and hypochlorite ion, C10 , exist but react to produce CIO- (22) ... 

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