Sodium Hydroxide, with Lime, from Sulphate

Preparation. Industrially, cobalt is normally produced as a by-product from the production of copper, nickel and lead. The ore is roasted to form a mixture of metals and metal oxides. Treatment with sulphuric acid leaves metallic copper as a residue and dissolves out iron, cobalt and nickel as the sulphates. Iron is separated by precipitation with lime (CaO) while cobalt is produced as the hydroxide by precipitation with sodium hypochlorite. The trihydroxide Co(OH)3 is heated to form the oxide and then reduced with carbon (as charcoal) to form cobalt metal. 

The sulphate process consists in kiering pieces of wood in a solution composed of sodium hydroxide, sodium sulphide and sodium carbonate in a 65 15 20 ratio. The concentration of the solution is 10-12% of NaOH. Boiling at a temperature of 170-175°C under pressure lasts about 6 hr, of which 3 hr are required for heating, the other 3 hr being the kiering proper. Cellulose is then separated from the lye, washed with water, bleached, and subjected to final purification. The lye is condensed, evaporated to dryness, then sodium sulphate is added, and the whole is calcined. The sodium sulphate is thus reduced to sodium sulphide. Unchanged sulphate and the excess of carbonate are removed by addition of milk of lime. 

What became known as the Leblanc process was actually several interrelated processes. Salt was first reacted with sulphuric acid in a cast-iron pan, then in a reverberator furnace (in which heat was apphed from a flame blown from a separate chamber, not in direct contact with the salt), to produce saltcake (sodium sulphate), with hydrochloric acid released as a waste gas. Saltcake was used to make sodium carbonate, or roasted with limestone (calcium carbonate) and coal or coke to produce black ash. This mixture of sodium carbonate, calcium sulphide, sodium sulphide, hme, salt, carbon, and ash could be treated further with hot water to produce impure sodium carbonate in solution, evaporated into soda crystals (washing soda), or heated to yield anhydrous sodium carbonate. The latter, in turn, could be reacted with lime to made caustic soda (sodium hydroxide), the strongest commercial alkali then available. 

It is usual to take advantage of the alkali addition to separate off ferric iron and other metallic ions which precipitate at a lower pH than uranium. Furthermore, this can often be done with lime. This is normally the cheapest alkali and also has the advantage that it precipitates the sulphate ion impurity at the same time as the iron. A pH of 3 -6 is used for this impurity precipitation, followed by the first-stage filtration. Then the addition of extra alkali, e.g. ammonia, sodium hydroxide or magnesia, to pH 6 7 precipitates the uranium. The second-stage filtration finally removes the uranium from solution as ammonium, sodium or magnesium di-uranates. 

After filtration, addition of sodium sulphide to the clear solution effects the precipitation of the three metals, cobalt, nickel, and manganese, as sulphides. Digestion with the calculated quantity of ferric chloride oxidises the manganese sulphide to sulphate, which passes into solution. The residue consists of cobalt and nickel sulphides, which are washed and converted into their soluble sulphates by roasting. The sulphates are extracted with water, and converted into chlorides by addition of calcium chloride solution. Their separation is effected g.s follows The requisite fraction of the chloride solution is precipitated with milk of lime, and the insoluble hydroxides of nickel and cobalt thus obtained are oxidised to the black hydroxides by treatment with chlorine. The. washed precipitate is then introduced into the remainder of the chloride solution, and the whole is well stirred and heated, when the black hydrated oxide of nickel passes, into solution, displacing tlm Remainder of. the cobalt from the solution, into. the precipitate.. The final product is thus a suspension of hydrated peroxide.of cobalt,in p. solution of nickel chloride, from which idle cobalt precipitate is removed by filtration, washed, and ignited, to the black oxide. 

Potassium hydroxide, KOH.—The hydroxide can be prepared by methods similar to those employed for the corresponding sodium derivative. The chief processes are the electrolysis of the chloride, and the interaction of the carbonate or sulphate11 in aqueous solution with slaked lime. In the sulphate process, evaporation of the mother-liquid yields the anhydrous hydroxide, the monohydrate, or the di-hydrate, the formation of each product depending on the concentration.12 For laboratory use, the substance can be prepared free from carbonate by a method described by Jorissen and Filippo.13... 

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