During my practical activity (1879-1891) I had prepared barium peroxide and lead peroxide in large quantities on a manufacturing scale, the last-mentioned through the intermediate formation of plumbites and plumbates:
2NaOH + PbO + O = Na2PbO3 + H2O
or:
4NaOH + PbO + O = Na4PbO4 + 2H2O.
An experiment made in this connection showed that calcium plumbate is formed just as readily from slaked lime and litharge as the sodium plumbates above. Litharge is an intermediate product, produced in large quantities in lead works, and must in any case be brought back into the process. If, then, the litharge is roasted at a low temperature with slaked lime, the roasting of the galena could perhaps be entirely avoided by introducing that ore together with calcium plumbate into the converter, after the latter had once been heated up. Mr. Huppertz undertook the further development of this process, but I have no information on the later experimental results, as he placed himself in communication with neighboring lead works for the purpose of continuing his investigation, and has not since then given me any precise data. I will therefore confine myself to the statement that the fundamental idea for the experiments, which Mr. Huppertz undertook at my suggestion, was the following:
To dispense with the roasting of the galena, which is necessary according to Huntington and Heberlein; in other words, to convert the galena by direct blast, with the addition of calcium plumbate, the latter being produced from the litharge which is an unavoidable intermediate product in the metallurgy of lead and silver. (Borchers, “Elektrometallurgie,” 3d edition, 1902-1903, p. 467.)
This alone would, of course, have meant a considerable simplification of the roast, but the problem of the roasting of galena has been solved in a better way by A. Savelsberg, of Ramsbeck, Westphalia, who has determined the conditions for directly converting the galena with the addition of limestone and water and without previous roasting. He has communicated the following information regarding these conditions:
In order that, in blowing the air through the mixture of ore and limestone, an alteration of the mixture may not take place owing to the lighter particles of the limestone being carried away, it is necessary (quite at variance with the processes in use hitherto, in which for the sake of economy stress is laid on the precaution of charging the ore as dry as possible into the apparatus) to add a considerable quantity of water to the charge before introducing it into the converter. The water serves this purpose perfectly, also preventing any change in the mixture of ore and limestone, which invariably occurs if the ore is used dry. The water, moreover, exerts a very beneficial action in the process, inasmuch as it aids materially in the formation and temporary retention of sulphuric acid, which latter then, by its oxidizing action, greatly enhances the reaction and consequently the desulphurization of the ore. Furthermore, the water tends to moderate the temperature in the charge by absorbing heat in its volatilization.
In carrying out the process the converter must not be filled entirely all at once, but first only in part, additional layers being charged in gradually in the course of the operation. In this way a uniform progress of the reaction in the mass is secured.
The following mode of procedure is advantageously adopted: A small quantity of glowing fuel (coal, coke, etc.) is introduced into the converter, which is provided at the bottom with a grate (perforated sheet iron), the grate being first covered with a thin layer of crushed limestone in order to protect it from the action of the red-hot coals and ore. Upon this red-hot fuel a uniform layer of the wetted mixture of crude ore and limestone is placed. When the surface of the first layer has acquired a uniform red heat, a fresh layer is charged on, and this is continued, layer by layer, until the converter is quite full. While the layers are still being put on, the blast is passed in at quite a low pressure, and only when the converter is entirely filled is the whole force of the blast, at a rather greater pressure, turned on. There then sets in a kind of slag formation, which, however, is preceded by a very vigorous desulphurization. After the termination of the process, which can be recognized by the fact that vapors cease to be evolved, and that the surface of the ore becomes hard, the converter is tipped over, and the desulphurized mass drops out as a solid cone of slag, which is then suitably broken up for the subsequent smelting in the shaft furnace.