States, England, France, Spain and Austria have been fairly
constant producers Germany produced 155,799 tons in 1900, and
198,208 in 1905, Belgium, 120,000 in 1900 and 143,165 in 1905;
the United States, 111,000 in 1900 and 183,014 in 1905. The world's
supply was 445,438 tons in 1900, and 654,367 in 1905.
Metallurgy
The principles underlying the extraction of zinc may be summarized as (1) the ore is first converted into zinc oxide, (2) the oxide is distilled with carbon and the distillate of metallic zinc condensed. Oxide of zinc, like most heavy metallic oxides, is easily reduced to the metallic state by heating it to redness with charcoal; pure red zinc ore may be treated directly; and the same might be done with pure calamine of any kind, because the carbon dioxide of the zinc carbonate goes off below redness and the silica of zinc silicate only retards, but does not prevent, the reducing action of the charcoal. Zinc blende, however, being zinc sulphide, is not directly reducible by charcoal, but it is easy to convert it into oxide by roasting: the sulphur goes off as sulphur dioxide whilst the zinc remains in the (infusible) form of oxide, ZnO. In practice, however, we never have to deal with pure zinc minerals, but with complex mixtures, which must first of all be subjected to mechanical operations, to remove at least part of the gangue, and if possible also of the heavy metallic impurities (see Ore-Dressing).
As ores of zinc are usually shipped before smelting from widely separated places—Sweden, Spain, Algiers, Italy, Greece, Australia and the Rocky Mountains region of North America—it is important that they be separated from their mixtures at the mines. The difficulty in separating zinc blende from iron pyrites is well known, and probably the most elaborate ore-dressing works ever built have been designed with this end in view. The Wetherill system of magnetic concentration has been remarkably successful in separating the minerals contained in the well-known deposit in Sussex county, N.J. Here, very clean non-magnetic concentrate of willemite, which is an anhydrous zinc silicate and a very high-grade zinc ore, is separated from an intimate mixture of willemite, zincite and franklinites, with calcite and some manganese silicates. The magnetic concentrates contain enough zinc to be well adapted to the manufacture of zinc oxide. Magnetic concentration is also applied in the removal of an excess of iron from partially roasted blende. Neither mechanical non-magnetic concentration can effect much in the way of separation when, as in many complex ores, carbonates of iron, calcium and magnesium replace the isomorphous zinc carbonate, when some iron sulphide containing less sulphur than pyrites replaces zinc sulphide, and when gold and silver are contained in the zinc ore itself. Hence only in exceptional circumstances is it possible to utilize a large class of widely distributed ores, carrying from 10 to 35 per cent. of zinc, in which the zinc alone, estimated at 2d. a pound, is worth from about £2 to £7 per ton of ore. The ores of the Joplin district, in the Ozark uplift in the Mississippi Valley, are remarkable in that they are specially adapted to mechanical concentration. The material as mined will probably not average over 10 per cent. of zinc, but the dressed zinc ore as sold ranges from 45 to 62 per cent. of zinc. This region now furnishes the bulk of the ore required by the smelters of Illinois, Missouri and Kansas.
The ore, even if it is not blende, must be roasted or calcined in order to remove all volatile components as completely as possible, because these, if allowed to remain, would carry away a large proportion of the zinc vapour during the distillation. If the zinc is present as blende, this operation offers considerable difficulties, because in the roasting process the zinc sulphide passes in the first instance into sulphate, which demands a high temperature for its conversion into oxide. Another point to be considered in this connexion is that the masses of sulphur dioxide evolved, being destructive of vegetable life, are an intolerable nuisance to the neighbourhood in which the operations take place. For the desulphurization of zinc blende where it is not intended to collect and save the sulphur there are many mechanical kilns, generally classified as straight-line, horse-shoe, turret and shaft kilns; all of these may be made to do good work on moderately clean ores which do not melt at the temperature of desulphurization. But the problem of saving the sulphur is yearly becoming more important. In roasting a ton of rich blende containing 60 per cent. of zinc enough sulphur is liberated to produce one ton of strong sulphuric acid, and unless this is collected not only are poisonous gases discharged, but the waste is considerable. When sulphuric or sulphurous acid is to be collected, it is important to keep the fuel gas from admixture with the sulphur gases, and kilns for this purpose require some modification. If hot air is introduced into the kiln, the additional heat developed by the oxidation of the zinc and the sulphur is sufficient to keep up a part of the reaction but for the complete expulsion of the sulphur an externally-fired muffle through which the ore is passed is found to be essential.
Distillation of the Oxide with Charcoal.—The distillation process in former limes, especially in England, used to be carried out “per descensum.” The bottom of a crucible is perforated by a pipe which projects into the crucible to about two-thirds of its height. The mixture of ore and charcoal is put into the crucible around the pipe, the crucible closed by a luted-on lid, and placed in a furnace constructed so as to permit of the lower end of the pipe projecting into the ash-pit. The zinc vapour produced descends through the pipe and condenses into liquid zinc, which is collected in a ladle held under the outlet end of the pipe. For manufacturing purposes a furnace similar to that used for the making of glass was employed to heat a circular row of crucibles standing on a shelf along the wall of the furnace. This system, however, has long been abandoned.
The modern processes may be primarily divided into two groups according to the nature of the vessel in which the operation is effected. These distilling vessels are called retorts if they are supported only at the ends, and the furnace using them is termed a Belgian furnace. If they are supported at intervals along a flat side, they are called muffles, and the furnace is known as a Silesian furnace. Various combinations and modifications of these two types of furnace have given rise to distinctive names, and as each system has its advantages and disadvantages local conditions determine which is the better.
In the Belgian process the reduction and distillation are carried
out in cylindrical or elliptical retorts of fire-clay, from 3 ft. 3 in.
to 4 ft 9 in long and 6 to 10 in internal diameter. Some forty-six
or more retorts, arranged in parallel horizontal rows, are heated
in one furnace. The furnaces are square and open in front, to
allow the outlet ends of the retorts to project: they are grouped
together by fours, and their several chimneys are within the same
enclosure. Each retort is provided with two adapters, namely,
a conical pipe of fire-clay, about 15 in. long, which fits into the
retort end, and a conical tube of sheet iron, which fits over the
end of the fire-clay pipe, and which at its outlet end is only about
an inch wide. To start a new furnace, the front side is closed
provisionally by a brick wall, a fire lighted inside, and the temperature
raised very gradually to a white heat. After four days' heating
the provisional front wall is removed piecemeal, and the retorts,
after having been heated to redness, are inserted in corresponding
sets. The charge of the retorts consists of a mixture of 1100 l℔
of roasted calamine and 550 ℔ of dry powdered coal per furnace.
A newly started furnace, however, is used for a time with smaller
charges. Supposing the last of these preliminary distillations to
have been completed, the residues left in the retorts are removed,
and the retorts, as they lie in the hot furnace, are charged by means
of semi-cylindrical shovels, and their adapters put on. The charging
operation being completed, the temperature is raised, and as a
consequence an evolution of carbon monoxide soon begins, and
becomes visible by the gas bursting out into the characteristic
blue flame. After a time the flame becomes dazzling white, showing
that zinc vapour is beginning to escape. The iron adapters are
now slipped on, and left on for two hours, when, as a matter of
experience, a considerable amount of zinc has gone out of the
retort, the greater part into the fire-clay adapter, the rest into the
iron cone. The former contains a mixture of semi-solid and molten
metal, which is raked out into iron ladles and cast into plates of
66 to 77 ℔ weight, to be sold as “spelter.” The contents of the
iron recipient consist of a powdery mixture of oxide and metal,
which is added to the next charge, except what is put aside to he
sold as “zinc dust.” This dust may amount to 10 per cent. of the
total production. As soon as the adapters have been cleareed of
their contents, they are replaced, and again left to themselves for
two hours, to be once more emptied and replaced, &c. The complete
exhaustion of the charge of a furnace takes about eleven
hours.
In the Silesian process the distillation is conducted in specially constructed muffles of a prismatic shape arched above, which are arranged in two parallel rows within a low-vaulted furnace, similar to the pots in a glass furnace. As a rule every furnace accommodates ten muffles. Through an orifice in the outlet pipe (which is closed during the distillation by a loose plug) a hot iron rod can be introduced from time to time to clear away any solid zinc that may threaten to obstruct it. As soon as the outlet pipe has become sufficiently hot the zinc flows through it and collects in conveniently placed receptacles. About six or eight hours after starting the distillation is in full swing, and in twenty-four hours it is completed. A fresh charge is then put in at once, the muffles being cleared only after three successive distillations. The distillate consists of a conglomerate of drops (“drop zinc”). It is fused up in iron basins lined with clay, and cast out into the customary form of cakes.
The chief improvements in the plant of these processes are concerned with the manufacture of the retorts or muffles, and especially with the introduction of gas-firing. Even a machine of simple type, like the ordinary drain-pipe machine, in which the retorts are made by forcing the plastic clay mixture through a die, may result in greater economy and uniformity than is possible when retorts are made by hand When hydraulic pressure to the amount of 2000 to 3000 ℔ per square inch is applied, the saving is unquestioned, since less time is required to dry the pressed retort, its life in the furnaces is longer, its absorption of zinc is less, and the loss of zinc by passage through its walls in the form of vapour is reduced.
