An electrochemical investigation of the formation of CoSx and its effect on the anodic dissolution of iron in ammoniacal-carbonate solutions

Abstract

It has been found that the co-presence of cobalt (II) and thiosulphate ions in ammoniacal-carbonate solutions promotes the passivation of iron, under conditions in which it would otherwise continue to dissolve anodically. Electrochemical experiments have shown a relationship between the immersion time required for passivation and the formation of a solid species on the iron surface, which is thought to be implicated in the mechanism of passivation, whilst not being itself the protective species. Based on a combination of electrochemical, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and grazing incidence X-ray diffraction (GIXRD) characterisation techniques, the said species has been identified as CoSx, resulting from the interaction of cobalt (II) and thiosulphate ions. It is thought to form as a product of the cathodic reactions taking place on the iron surface during its active dissolution.These findings are particularly relevant to the Caron process, in which the ammoniacal-carbonate solutions containing dissolved cobalt and thiosulphate ions are used to leach nickel and cobalt from pre-reduced laterite ores rich in metallic iron. Both the loss of cobalt into the CoSx layer and the passivation of iron and of its alloys with nickel and cobalt, are potential contributing factors to the low cobalt and nickel recoveries, which are typical of the Caron process. This study provides a better understanding of the conditions under which the CoSx layer forms and promotes the passivation of iron, and may therefore provide useful information to help minimise the effect this may have on the extraction efficiency of the process. In particular, at the cobalt and thiosulphate ion concentrations usually encountered at a Caron plant, the passivation of iron was found to be prevented by maintaining a high enough concentration of ammonia.