A Mineralogical Study Of The Deportment Of Impurities During The Electrorefining Of Secondary Copper Anodes

Secondary copper anodes are generally rich in Sn, Pb, Ni and Sb, but are notably deficient in Se, Te and Ag. In the secondary copper anodes, most of the Ni, virtually all of the Ag, slightly more than one-fifth of the Pb, about one-third of the As and Sb, and approximately one-tenth of the Sn are in solid solution in the copper. The remaining impurity contents occur as 1-5 µm grain-boundary inclusions in the anodes, and these are mainly Cu2O, SnO2, Cu-Pb-As-Sb-Bi oxide, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide, Cu-Sb-Ni oxide (Kupferglimmer) and trace Cu2(Se,Te). Barium sulphate, which originates from the mold wash used in casting, is also present in the anodes. During electrorefining, the BaSO4, SnO2, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide and Cu- Sb-Ni oxide inclusions are liberated and accumulate in the slimes layer. Solid solution Ni dissolves and the Ni accumulates in the electrolyte. Solid solution Sn and Pb dissolve, but partly reprecipitate as Sn arsenate and PbSO4, respectively. Solid solution Ag dissolves but rapidly reacts to form Ag2(Se,Te), Ag powder, Ag-bearing Cu2O, (Cu,Ag)SO4 or a complex oxidate phase. Partial dissolution of the Cu-Pb-As-Sb-Bi oxide particles takes place; the Pb component is converted to PbSO4, whereas Cu, As, Sb and Bi dissolve. The reacted particles retain the morphology of the original Cu-Pb-As- Sb-Bi oxide phase. Some of the solubilized As, Sb and Bi remains in solution, but much reprecipitates as SbAsO4, As-Sb-Bi oxide, and as a poorly defined oxidate phase which consists mostly of Cu-Ag-Pb arsenate-sulphate. The high Sn contents of secondary copper anodes do not seem to affect the behaviour of the anodes during electrorefining.