リサイクルした低品位銅をアノードに用いた銅電解精製におけるアノードの不動態化挙動

Abstract

Cu electrolysis was performed using low-grade copper anode with purity 78.7 mass% at a anode current density of 200 A・m-2 in an unagitated sulfate solution containing 0.596 mol・dm-3 of Ni2+ ions as impurity at 60 ℃, and the structure of anode slime before and after passivation was analyzed. The highly-concentrated Sb, Pb and Ag were dispersed in copper anode before electrolysis. The passivation occurred at short time of 17.7 hours in the case of low-grade copper anode, and it occurred at shorter time of 11.4 hours in the solution containing Ni2+ ions as impurity. At normal dissolution of copper anode, copper parent phase dissolved in the form of dendrite and the framework of anode slime was composed of remained Cu-Ni-Sb-Sn-As compound. Cu2S and single phase of Ag and Pb were observed around this framework. At passivation, Cu, Ni and Sn dissolved from the slime framework composed of Cu-Ni-Sb-Sn-As compound, resulting in formation of Sb condensed phase. These Cu-Ni-Sb-Sn-As compound, Sb condensed phase, Cu2S compound around the slime framework, Ag and needle-shaped PbO dotted in the whole slime suppressed the diffusion of Cu2+ ions, as a result, CuSO4 was formed at interface between the slime and copper substrate. The passivation occurred at slime thickness of approximately 500μm in Ni2+-free solution, while it occurred at slime thickness of approximately 300μm in solution containing Ni2+ ions. This indicates that the passivation do not depend on only the thickness of slime. The thickness of CuSO4 formed at passivation in Ni2+-free solution was almost identical with that from the solution containing Ni2+ ions. In solution containing Ni2+ ions, the passivation occurred at less thickness of slime, showing that CuSO4 is easy to be formed in the vicinity of copper substrate due to decrease in solubility of CuSO4 and diffusion coefficient of Cu2+ ions.