• Bismuth: extraction
  • Bismuth is extracted from its ores by dry, wet, or electro-metallurgical methods, the choice depending upon the composition of the ore and economic conditions.
  • The dry process is more frequently practised, due to the easy reducibility of the oxide and sulphide, together with the low melting-point of the metal, which renders it possible to effect a ready separation of the metal from the gangue and impurities. The extraction from ores in which the bismuth is present in the metallic condition may be accomplished by a simple liquation, or melting, in which the temperature is just sufficient to melt the bismuth, or by a complete fusion of the ore. The first process never extracts all the bismuth, as much as one third being retained in the matte or speiss.
  • The second is more satisfactory, since the extraction is more complete, and also allows the addition of reducing agents to decompose any admixed bismuth oxide or sulphide. In the liquation process the ore is heated in inclined cylindrical retorts, and the molten metal is tapped at the lower end; the residues being removed from the upper end. The fusion process is preferably carried out in crucible furnaces; shaft furnaces are unsatisfactory on account of the disintegrating action of the molten bismuth on the furnace linings.
  • Sulphuretted ores are smelted, either with or without a preliminary calcination, with metallic iron; calcined ores may be smelted with carbon (coal). The reactions are strictly analogous to those which occur in the smelting of galena, the carbon reducing any oxide, either present originally in the ore or produced in the calcination, and the iron combining with the sulphur of the bismutite. A certain amount of bismuth sulphate is always formed during the calcination; this is subsequently reduced to the sulphide and ultimately to the metal in the fusion. Calcination in reverberatory furnaces and a subsequent smelting in the same type of furnace with the addition of about 3% of coal, lime, soda and fluorspar, has been adopted for treating the Bolivian ores, which generally contain the sulphides of bismuth, copper, iron, antimony, lead and a little silver. The lowest layer of the molten mass is principally metallic bismuth; the succeeding layers are a bismuth copper matte, which is subsequently worked up, and a slag. Ores containing the oxide and carbonate are treated either by smelting with carbon or by a wet process.
  • In the wet process the ores, in which the bismuth is present as oxide or carbonate, are dissolved out with hydrochloric acid, or, if the bismuth is to be extracted from a matte or alloy, the solvent employed is aqua regia or strong sulphuric acid. The solution of metallic chlorides or sulphates so obtained is precipitated by iron, the metallic bismuth filtered, washed with water, pressed in canvas bags, and finally fused in graphite crucibles, the surface being protected by a layer of charcoal. Another process consists in adding water to the solution and so precipitating the bismuth as oxychloride, which is then converted into the metal.
  • The crude metal obtained by the preceding processes is generally contaminated by arsenic, sulphur, iron, nickel, cobalt and antimony, and sometimes with silver or gold. A dry method of purification consists in a liquation on a hearth of peculiar construction, which occasions the separation of the unreduced bismuth sulphide and the bulk of the other impurities. A better process is to remelt the metal in crucibles with the addition of certain refining agents. The details of this process vary very considerably, being conditioned by the composition of the impure metal and the practice of particular works. The wet refining process is more tedious and expensive, and is only exceptionally employed, as in the case of preparing the pure metal or its salts for pharmaceutical or chemical purposes. The basic nitrate is the salt generally prepared, and, in general outline, the process consists in dissolving the metal in nitric acid, adding water to the solution, boiling the precipitated basic nitrate with an alkali to remove the arsenic and lead, dissolving the residue in nitric acid, and reprecipitating as basic nitrate with water. J. F. W. Hampe prepared chemically pure bismuth by fusing the metal with sodium carbonate and sulphur, dissolving the bismuth sulphide so formed in nitric acid, precipitating the bismuth as the basic nitrate, redissolving this salt in nitric acid, and then precipitating with ammonia. The bismuth hydroxide so obtained is finally reduced by hydrogen.
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