The lead thus obtained contains several other metals, especially silver, copper, arsenic, antimony, iron, zinc, bismuth, and tin. Lead containing silver (work-lead) is next de-silverised, after which follows refining to get rid of the other impurities. For de-silverising work-lead rich in silver (containing about 10 per cent.) cupellation is practised, in which the silver lead is melted and oxidised so that the lead is converted into litharge, metallic silver remaining behind. In a cupellation furnace the flame strikes on the top of the lead bath, and at the same time air under slight pressure is driven in; the litharge which forms is removed through suitable openings. The litharge that is first formed contains silver and is treated again; the remainder is ready for market. After the litharge has run off silver appears, containing still 5-10 per cent. of lead, and it is again submitted to an analogous refining process. Work-lead which does not contain enough silver to be cupelled at once is generally treated first by either the Pattinson or the Parkes’ process.
In the Pattinson crystallising process work-lead is melted in open semi-circular pots: as the pots cool crystals of lead poor in silver form on the surface and are transferred by a perforated ladle into the next pot: the silver collects in the small amount of molten lead remaining behind. Lead that has become enriched by repeated crystallisation contains a high percentage of silver and is cupelled. The Parkes’ process or zinc de-silverisation depends on the formation of a lead-zinc alloy which is less fusible than lead. Work-lead is melted and agitated with addition of pure zinc. The crust which first rises on cooling contains gold, copper, zinc, and lead, and is removed. Further addition of zinc is then made: the rich silver crust which separates is subsequently freed from lead by gradual heating in a reverberatory furnace, and from zinc, in a zinc distilling retort. Other impurities are got rid of by oxidising in reverberatory or other furnaces. Small quantities of antimony and arsenic are removed by stirring with fresh green sticks.
Zinc is obtained principally from blende (sulphide of zinc) and from calamine (carbonate of zinc). The process of zinc recovery depends on the production of zinc oxide and reduction of this by carbon to metallic zinc.
Conversion of the ore to zinc oxide is effected by roasting. Since the temperature at which reduction takes place is higher than the melting-point of zinc the latter is volatilised (distilled) and must be condensed in suitable condensers.
Calamine is calcined in a blast furnace. Blende was formerly roasted in reverberatory furnaces, but such nuisance arose to the neighbourhood from sulphur dioxide vapour that now Hasenclever-Helbig calcining furnaces are used. These furnaces furnish a gas so rich in sulphur dioxide that they serve at once for the production of sulphuric acid. The Hasenclever furnaces consist of muffles placed one above another: the finely ground ore is charged through hoppers above and then raked down from muffle to muffle.
Reduction is carried out in the Belgian or Silesian process by strongly heating calcined matte with coal in retorts. The zinc as it distils is caught in special condensing receptacles (prolongs). After distillation is complete the residue is raked out of the muffle and the furnace charged afresh. As zinc ores generally contain much lead, the work-zinc is therefore refined by remelting in a reverberatory furnace, during which process the impurities collect on the zinc as dross and are removed by agitation with sal-ammoniac or magnesium chloride.
Fig. 28.—Arrangement of Spelter Furnace showing Ventilating Hood.
Risk of Poisoning in Lead, Silver, and Zinc Smelting.—As the description of the manipulations in smelting processes shows, all involve risk of lead poisoning. As a matter of fact in lead smelting much lead passes into the atmosphere. In the smelting works at Tarnowitz yearly some 36,000 kilos of oxidised lead escape.
Estimations[4] of the amount of lead in air samples collected in lead smelting works have been made. Thus in a cubic metre of air immediately over the slag run from 0·0029 to 0·0056 g. of lead were found, so that a worker in a ten-hour day would inhale from 0·013 to 0·025 g. of lead. In a cubic metre of air immediately above the Parkes’ melting-pot from 0·0056 to 0·0090 g. were found, so that a worker would inhale daily from 0·0252 to 0·0405 g. if he kept constantly close to the pot. On the handles of a de-silveriser 0·112 g. were found. In Hungarian lead-smelting works the water in which the hands had been washed was found to contain 1·27 g. of lead per litre. The hands of litharge grinders and sifters showed the highest amounts.