England have patented processes by which jets of the electrolyte are caused to impinge with considerable force upon the surface of the cathode, so that the renewal of the liquid at this point takes place very rapidly, and current-densities per sq. ft. of 50 to 100 amperes are recommended by the former, and of 300 amperes by the latter. Graham has described experiments in this direction, using a jet of electrolyte forced (beneath the surface of the bath) through a hole in the anode upon the surface of the cathode. Whilst the jet was playing, a good deposit was formed with so high a current-density as 280 amperes per sq. ft., but if the jet was checked, the deposit (now in a still liquid) was instantaneously ruined. When two or more jets were used side by side the deposit was good opposite the centre of each, but bad at the point where two currents met, because the rate of flow was reduced. By introducing perforated shields of ebonite between the electrodes, so that the full current-density was only attained at the centres of the jets, these ill effects could be prevented. One of the chief troubles met with was the formation of arborescent growths around the edges of the cathode, due to the greater current-density in this region; this, however, was also obviated by the use of screens. By means of a very brisk rotation of cathode, combined with a rapid current of electrolyte, J. W. Swan has succeeded in depositing excellent copper at current-densities exceeding 1000 amperes per sq. ft. The methods by which such results are to be obtained cannot, however, as yet be practised economically on a working scale; one great difficulty in applying them to the refining of metals is that the jets of liquid would be liable to carry with them articles of anode mud, and Swan has shown that the presence of solid particles in the electrolyte is one of the most fruitful causes of the well-known nodular growths on electro-deposited copper. Experiments on a working scale with one of the jet processes in America have, it is reported, been given up after a full trial.
In copper-refining practice, the current-density commonly ranges from 7.5 to 12 or 15, and occasionally to 18, amperes per sq. ft. The electrical pressure required to force a current of this intensity through the solution, and to overcome a certain opposing electromotive force arising from the more electro-negative impurities of the anode, depends upon the composition of the bath and of the anodes, the distance between the electrodes, and the temperature, but under the usual working conditions averages 0.3 volt for every pair of electrodes in series. In nearly all the processes now used, the solution contains about 1½ to 2 ℔ of copper sulphate and from 5 to 10 oz. of sulphuric acid per gallon of water, and the space between the electrodes is from 1½ to 2 in., whilst the total area of cathode surface in each tank may be 200 sq. ft., more or less. The anodes are usually cast copper plates about (say) 3 ft. by 2 ft. by ¾ or 1 in. The cathodes are frequently of electro-deposited copper, deposited to a thickness of about 132 in. on black-leaded copper plates, from which they are stripped before use. The tanks are commonly constructed of wood lined with lead, or tarred inside, and are placed in terrace fashion each a little higher than the next in series, to facilitate the flow of solution through them all from a cistern at one end to a well at the other. Gangways are left between adjoining rows of tanks, and an overhead travelling-crane facilitates the removal of the electrodes. The arrangement of the tanks depends largely upon the voltage available from the electric generator selected; commonly they are divided into groups, all the baths in each group being in series. In the huge Anaconda plant, for example, in which 150 tons of refined copper can be produced daily by the Thofehrn multiple system (not the jet system alluded to above), there are 600 tanks about 8¼ ft. by 4½ ft. by 3¼ ft. deep, arranged in three groups of 200 tanks in series. The connexions are made by copper rods, each of which, in length, is twice the width of the tank, with a bayonet-bend in the middle, and serves to support the cathodes in the one and the anodes in the next tank. Self-registering voltmeters indicate at any moment the potential difference in every tank, and therefore give notice of short circuits occurring at any part of the installation. The chief differences between the commercial systems of refining lie in the arrangement of the baths, in the disposition and manner of supporting the electrodes in each, in the method of circulating the solution, and in the current-density employed. The various systems are often classed in two groups, known respectively as the Multiple and Series systems, depending upon the arrangement of the electrodes in each tank. Under the multiple system anodes and cathodes are placed alternately, all the anodes in one tank being connected to one rod, and all the cathodes to another, and the potential difference between the terminals of each tank is that between a single pair of plates. Under the series system only the first anode and the last cathode are connected to the conductors; between these are suspended, isolated from one another, a number of intermediate bi-polar electrode plates of raw copper, each of these plates acting on one side as a cathode, receiving a deposit of copper, and on the other as an anode, passing into solution; the voltage between the terminals of the tank will be as many times as great as that between a single pair of plates as there are spaces between electrodes in the tank. In time the original impure copper of the plates becomes replaced by refined copper, but if the plates are initially very impure and dissolve irregularly, it may happen that much residual scrap may have to be remelted, or that some of the metal may be twice refined, thus involving a waste of energy. Moreover, the high potential difference between the terminals of the series tank introduces a greater danger of short-circuiting through scraps of metal at the bottom of the bath; for this reason, also, lead-lined vats are inadmissible, and tarred slate tanks are often used instead. A valuable comparison of the multiple and series systems has been published by E. Keller (see The Mineral Industry, New York, 1899, vol. vii. p. 229). G. Kroupa has calculated that the cost of refining is 8s. per ton of copper higher under the series than it is under the multiple system; but against this, it must be remembered that the new works of the Baltimore Copper Smelting and Rolling Company, which are as large as those of the Anaconda Copper Mining Company, are using the Hayden process, which is the chief representative of the several series systems. In this system rolled copper anodes are used; these, being purer than many cast anodes, having flat surfaces, and being held in place by guides, dissolve with great regularity and require a space of only 58 in. between the electrodes, so that the potential difference between each pair of plates may be reduced to 0.15–0.2 volt.
J. A. W. Borchers, in Germany, and A. E. Schneider and O. Szontagh, in America, have introduced a method of circulating the solution in each vat by forcing air into a vertical pipe communicating between the bottom and top of a tank, with the result that the bubbling of the air upward aspirates solution through the vertical pipe from below, at the same time aërating it, and causing it to overflow into the top of the tank. Obviously this slow circulation has but little effect on the rate at which the copper may be deposited. The electrolyte, when too impure for further use, is commonly recrystallized, or electrolysed with insoluble anodes to recover the copper.
The yield of copper per ampere (in round numbers, 1 oz. of copper per ampere per diem) by Faraday’s law is never attained in practice; and although 98% may with care be obtained, from 94 to 96% represents the more usual current-efficiency. With 100% current-efficiency and a potential difference of 0.3 volt between the electrodes, 1 ℔ of copper should require about 0.154 electrical horse-power hours as the amount of energy to be expended in the tank for its production. In practice the expenditure is somewhat greater than this; in large works the gross horse-power required for the refining itself and for power and lighting in the factory may not exceed 0.19 to 0.2 (or in smaller works 0.25) horse-power hours per pound of copper refined.
Many attempts have been made to use crude sulphide of copper or matte as an anode, and recover the copper at the cathode, the sulphur and other insoluble constituents being left at the anode. The best known of these is the Marchese process, which was tested on a working scale at Genoa and Stolberg in Rhenish Prussia. As the operation proceeded, it was found that the voltage had to be raised until it became prohibitive, while the anodes rapidly became honeycombed through and, crumbling away, filled up the space at the bottom of the vat. The process was abandoned, but in a modified form appears to be now in use in Nijni-Novgorod in Russia. Siemens and Halske introduced a combined process in which the ore, after being part-roasted, is leached by solutions from a previous electrolytic operation, and the resulting copper solution electrolysed. In this process the anode solution had to be kept separate from the cathode solution, and the membrane which had in consequence to be used, was liable to become torn, and so to cause trouble by permitting the two solutions to mix. Modifications of the process have therefore been tried.
Modern methods in copper smelting and refining have effected enormous economy in time, space, and labour, and have consequently increased the world’s output. With pyritic smelting a sulphuretted copper ore, fed into a cupola in the morning, can be passed directly to the converter, blown up to metal, and shipped as 99% bars by evening—an operation which formerly, with heap roasting of the ore and repeated roasting of the mattes in stalls, would have occupied not less than four months. A large furnace and a Bessemer converter, the pair capable of making a million pounds of copper a month from a low-grade sulphuretted ore, will not occupy a space of more than 25ft. by 100ft.; and whereas, in making metallic copper out of a low-grade sulphuretted ore, one day’s labour used to be expended on every ton of ore treated, to-day one day’s labour will carry at least four tons of ore through the different mechanical and metallurgical processes necessary to reduce them to metal. About 70% of the world’s annual copper output is refined electrolytically, and from the 461,583 tons refined in the United States in 1907, there were recovered 13,995,436 oz. of silver and 272,150 oz. of gold. The recovery of these valuable metals has contributed in no small degree to the expansion of electrolytic refining.
Production.—The sources of copper, its applications and its metallurgy, have undergone great changes. Chile was the largest producer in 1869 with 54,867 tons; but in 1899 her
