Extractive Metallurgy Division - Recovery of Zinc by the Dithionate Sulphur-dioxide Leaching Process.

When manganese ores are leached with sulphur dioxide, a large part of any zinc in the ore usually is extracted with the manganese.1 In the dithionate process,2,3 in which the manganese ore is leached with dilute sulphur dioxide gas and the manganese is subsequently precipitated by adding lime to the pregnant solution, the zinc is precipitated with the manganese. These facts suggested the possibility of applying the dithionate process to the recovery of zinc from oxidized ores or calcined sulphide concentrates. Accordingly, an investigation was begun, and preliminary tests were made on several ores and concentrates. The results were encouraging, but the need to devote available funds and personnel to other projects made it necessary to drop the work before the various factors involved in the process could be studied in detail. A brief mention of the process,4 however, elicited a number of inquiries, so that it appeared desirable to report the results of the preliminary work. The dithionate process as applied to zinc may be summarized briefly as follows: The ore or calcined concentrate is leached with dilute SO2 gas to dissolve the zinc, largely as zinc sulphate, in accordance with the following equation in which [ZnO] represents the "oxide zinc" in the ore or calcine: [ZnO] + SO2(g) + 1/2 O2 = Zn++SO4— [1] If, in the leaching step, the ore or calcine is suspended in calcium dithionate solution, the sulphate ion, as it is formed, is precipitated immediately as calcium sulphate, which is subsequently filtered off with the insoluble ore residue: Zn++SO4— + Ca++S2O6— = CaSO4(s) + Zn++S2O6- [2] An alternative procedure is to suspend the ore in water, filter off the insoluble ore residue after leaching, add calcium dithionate to the resulting zinc sulphate solution, and then filter off the calcium sulphate precipitate. In either event the zinc is obtained in the form of a pregnant solution of zinc dithionate, from which it can be precipitated as relatively pure zinc hydroxide by adding milk of lime: Zn++S2O6— + Ca(OH), = Zn(OH)2(s) + Ca++S2O6- [3] The zinc hydroxide precipitate is calcined to form the final zinc oxide product: Zn(OH)2 = ZnO(s) + H2O(g) [4] Theoretically the process is completely cyclic with respect to dithionate ion, the calcium dithionate required for reaction 2 being replaced by that formed in reaction 3. In practice, of course, small amounts of dithionate would be lost in the various filter cakes, depending on the economic washing limits. In the leaching step, however, some of the SO2 is oxidized to dithionale instead of sulphate, accord- ing to the following overall reaction: ZnO + 2SO2(g) + 1/2 O2(g) = Zn++S2O6-, [5] so that the dithionate losses are made up, at least in part. Ores and Concentrates Tested The analyses of the ores and concentrates tested are summarized in Table 1, which also includes the analyses of the calcines produced from the concentrates. The concentrates were roasted in a laboratory muffle furnace at the temperatures indicated until evolution of SO2 could no longer be detected; shallow clay dishes ordinarily were used; but calcines 2a and 2c were prepared in iron dishes, with the result that these two calcines were badly contaminated with iron scale. The "complex" concentrate, sample 1, consisted essentially of sphalerite grains containing inclusions of pyrite and other sulphide minerals too minute to be liberated by grinding within economic limits. In the " marmatitic" concentrate, sample 2, the iron was present largely as marmatite (that is, as iron sulphide in solid solution in zinc sulphide) rather than as pyrite inclusions. The zinc was present largely as the carbonate in the two "oxidized" ores, samples 3 and 4, and as the silicate in the "willemite" ore, sample 5. Leaching Tests The leaching cell was a 3-liter glass beaker placed in an electrically heated water bath manually controlled to maintain a temperature of 35°C in the leach slurry. The slurry was agitated by means of a flat paddle-type stirrer