haemoglobin, and of a species of Limulus; in straw, hay, eggs,
cheese, meat, and other food-stuffs; in the liver and kidneys,
and, in traces, in the blood of man and other animals (as an entirely
adventitious constituent, however); it has also been shown
by A. H. Church to exist to the extent of 5.9% in turacin, the
colouring-matter of the wing-feathers of the Turaco.
Native copper, sometimes termed by miners malleable or virgin copper, occurs as a mineral having all the properties of the smelted metal. It crystallizes in the cubic system, but the crystals are often flattened, elongated, rounded or otherwise distorted. Twins are common. Usually the metal is arborescent, dendritic, filiform, moss-like or laminar. Native copper is found in most copper-mines, usually in the upper workings, where the deposit has been exposed to atmospheric influences. The metal seems to have been reduced from solutions of its salts, and deposits may be formed around mine-timber or on iron objects. It often fills cracks and fissures in the rock. It is not infrequently found in serpentine, and in basic eruptive rocks, where it occurs as veins and in amygdales. The largest known deposits are those in the Lake Superior region, near Keweenaw Point, Michigan, where masses upwards of 400 tons in weight have been discovered. The metal was formerly worked by the Indians for implements and ornaments. It occurs in a series of amygdaloidal dolerites or diabases, and in the associated sandstones and conglomerates. Native silver occurs with the copper, in some cases embedded in it, like crystals in a porphyry. The copper is also accompanied by epidote, calcite, prehnite, analcite and other zeolitic minerals. Pseudomorphs after calcite are known; and it is notable that native copper occurs pseudomorphous after aragonite at Corocoro, in Bolivia, where the copper is disseminated through sandstone.
Ores.—The principal ores of copper are the oxides cuprite and melaconite, the carbonates malachite and chessylite, the basic chloride atacamite, the silicate chrysocolla, the sulphides chalcocite, chalcopyrite, erubescite and tetrahedrite. Cuprite (q.v.) occurs in most cupriferous mines, but never by itself in large quantities. Melaconite (q.v.) was formerly largely worked in the Lake Superior region, and is abundant in some of the mines of Tennessee and the Mississippi valley. Malachite is a valuable ore containing about 56% of the metal; it is obtained in very large quantities from South Australia, Siberia and other localities. Frequently intermixed with the green malachite is the blue carbonate chessylite or azurite (q.v.), an ore containing when pure 55.16% of the metal. Atacamite (q.v.) occurs chiefly in Chile and Peru. Chrysocolla (q.v.) contains in the pure state 30% of the metal; it is an abundant ore in Chile, Wisconsin and Missouri. The sulphur compounds of copper are, however, the most valuable from the economic point of view. Chalcocite, redruthite, copper-glance (q.v.) or vitreous copper (Cu2S) contains about 80% of copper. Copper pyrites, or chalcopyrite, contains 34.6% of copper when pure; but many of the ores, such as those worked specially by wet processes on account of the presence of a large proportion of iron sulphide, contain less than 5% of copper. Cornish ores are almost entirely pyritic; and indeed it is from such ores that by far the largest proportion of copper is extracted throughout the world. In Cornwall copper lodes usually run east and west. They occur both in the “killas” or clay-slate, and in the “growan” or granite. Erubescite (q.v.), bornite, or horseflesh ore is much richer in copper than the ordinary pyrites, and contains 56 or 57% of copper. Tetrahedrite (q.v.), fahlerz, or grey copper, contains from 30 to 48% of copper, with arsenic, antimony, iron and sometimes zinc, silver or mercury. Other copper minerals are percylite (PbCuCl2(OH)2), boleite (3PbCuCl2(OH)2, AgCl), stromeyerite {(Cu, Ag)2S}, cubanite (CuS, Fe2S3), stannite (Cu2S, FeSnS3), tennantite (3Cu2S, As2S3), emplectite (Cu2S, Bi2S3), wolfsbergite (Cu2S, Sb2S3), famatinite (3Cu2S, Sb2S5) and enargite (3Cu2S, As2S5). For other minerals, see Compounds of Copper below.
Metallurgy.—Copper is obtained from its ores by three principal methods, which may be denominated—(1) the pyro-metallurgical or dry method, (2) the hydro-metallurgical or wet method, and (3) the electro-metallurgical method.
The methods of working vary according to the nature of the ores treated and local circumstances. The dry method, or ordinary smelting, cannot be profitably practised with ores containing less than 4% of copper, for which and for still poorer ores the wet process is preferred.
Copper Smelting.—We shall first give the general principles which underlie the methods for the dry extraction of copper, and then proceed to a more detailed discussion of the plant used. Since all sulphuretted copper ores (and these are of the most economic importance) are invariably contaminated with arsenic and antimony, it is necessary to eliminate these impurities, as far as possible, at a very early stage. This is effected by calcination or roasting. The roasted ore is then smelted to a mixture of copper and iron sulphides, known as copper “matte” or “coarse-metal,” which contains little or no arsenic, antimony or silica. The coarse-metal is now smelted, with coke and siliceous fluxes (in order to slag off the iron), and the product, consisting of an impure copper sulphide, is variously known as “blue-metal,” when more or less iron is still present, “pimple-metal,” when free copper and more or less copper oxide is present, or “fine” or “white-metal,” which is a fairly pure copper sulphide, containing about 75% of the metal. This product is re-smelted to form “coarse-copper,” containing about 95% of the metal, which is then refined. Roasted ores may be smelted in reverberatory furnaces (English process), or in blast-furnaces (German or Swedish process). The matte is treated either in reverberatory furnaces (English process), in blast furnaces (German process), or in converters (Bessemer process). The “American process” or “Pyritic smelting” consists in the direct smelting of raw ores to matte in blast furnaces. The plant in which the operations are conducted varies in different countries. But though this or that process takes its name from the country in which it has been mainly developed, this does not mean that only that process is there followed.
The “English process” is made up of the following operations: (1) calcination; (2) smelting in reverberatory furnaces to form the matte; (3) roasting the matte; and (4) subsequent smelting in reverberatory furnaces to fine- or white-metal; (5) treating the fine-metal in reverberatory furnaces to coarse- or blister-copper, either with or without previous calcination; (6) refining of the coarse-copper. A shorter process (the so-called “direct process”) converts the fine-metal into refined copper directly. The “Welsh process” closely resembles the English method; the main difference consists in the enrichment of the matte by smelting with the rich copper-bearing slags obtained in subsequent operations. The “German or Swedish process” is characterized by the introduction of blast-furnaces. It is made up of the following operations: (1) calcination, (2) smelting in blast-furnaces to form the matte, (3) roasting the matte, (4) smelting in blast-furnaces with coke and fluxes to “black-” or “coarse-metal,” (5) refining the coarse-metal. The “Anglo-German Process” is a combination of the two preceding, and consists in smelting the calcined ores in shaft furnaces, concentrating the matte in reverberatory furnaces, and smelting to coarse-metal in either.
The impurities contained in coarse-copper are mainly iron, lead, zinc, cobalt, nickel, bismuth, arsenic, antimony, sulphur, selenium and tellurium. These can be eliminated by an oxidizing fusion, and slagging or volatilizing the products resulting from this operation, or by electrolysis (see below). In the process of oxidation, a certain amount of cuprous oxide is always formed, which melts in with the copper and diminishes its softness and tenacity. It is, therefore, necessary to reconvert the oxide into the metal. This is effected by stirring the molten metal with a pole of green wood (“poling”); the products which arise from the combustion and distillation of the wood reduce the oxide to metal, and if the operation be properly conducted “tough-pitch” copper, soft, malleable and exhibiting a lustrous silky fracture, is obtained. The surface of the molten metal is protected from oxidation by a layer of anthracite or charcoal. “Bean-shot” copper is obtained by throwing the molten metal into hot water; if cold water be used, “feathered-shot” copper is formed.
