The losses and difficulties in “black-copper smelting” are, however, of interest in so far as they apply to certain analogous problems in modern work. These difficulties in reduction smelting arose largely from three causes:—
- (a) Losses of copper in the slag.
- (b) Simultaneous reduction of iron with the copper.
- (c) Chilling in the furnace hearth.
(a) In the case of reduction smelting where sulphides are not present in any appreciable quantity, the losses of copper may be either
- (i.) As silicate, or
- (ii.) As metal.
(i.) Sulphur is the natural protector of the copper in the furnace charge, as, owing to their powerful affinity, a fusible, fluid and dense product is formed, which is very slightly soluble in slag; and on this account, a ready separation of the copper from the earthy materials can be effected. So long as sulphur is present in moderate quantity there is little chance of copper entering the slag as silicate.
In reduction smelting, however, and especially in black-copper smelting where sulphur is lacking, such losses are liable to occur, since copper oxide is itself strongly basic, and readily fluxes off with silica at high temperatures, yielding silicates. These products are less dense, and are markedly soluble in the other silicates which constitute the slag; moreover, the copper oxides themselves are likewise partly soluble in, and are readily carried in suspension by, the silicate slags.
In order to prevent such losses as much as possible, the reducing conditions in the furnace must be increased by the employment of more coke, so as to ensure the reduction of the copper oxides and silicates. These reducing conditions must not, however, be too drastic, especially if the temperature of working be high, on account of the great tendency to cause (b) a reduction of metallic iron, which results in the formation of bears and scaffolds, with their attendant difficulties of removal and their interference with working.
Between these opposing causes of loss and difficulty, a careful balance has to be observed in the smelting operations. (In modern practice, losses of copper as silicate and oxide, for reasons such as those detailed above, occur to a marked extent in those operations where the sulphur is present in small proportions only, and particularly where the reactions are intensely oxidising, as in the furnace-refining operations and the later stages in the converter process. The slags in such cases usually carry considerable quantities of copper in the form of silicate and oxide, not infrequently to the extent of 20 to 30 per cent., or even more. The quantity of this slag is, however, kept as small as possible, and copper in the material is readily recovered by the addition of these slags to the blast-furnace charge.)
(ii.) Losses of copper as metal also, were formerly serious in black-copper smelting, the metallic copper held in suspension in the slag being indeed the chief source of loss in this method. The efficient separation of copper from slag, especially in the small quantities formerly operated, was therefore of importance. Satisfactory settling was, however, difficult of application, since the behaviour of metallic copper is very different from that of sulphides. It is much less fusible, much less fluid, and the small globules, as reduced, do not readily coalesce, whilst the high temperatures favourable to good fluidity of the products and to good settling, promote copper losses from the other causes noted above.
Moreover, the high melting point of the metal and its great conductivity added to the difficulties in providing suitable arrangements for settling, since the copper not only tended to chill readily in any external settler, but it was also very liable to do so in the crucible of the ordinary form of water-jacketed blast furnace, such masses being exceedingly difficult to remove, whilst the working of the furnace was necessarily much interfered with.