Cobalt electrowinning – A systematic investigation for high quality electrolytic cobalt production

Abstract

The process of Minera y Metalúrgica del Boleo recovers cobalt from a complex oxide and sulfide ore by solvent extraction and electrowinning after the recovery of copper and zinc (as copper cathode and zinc sulfate monohydrate). As part of the process development, cobalt electrowinning was systematically studied with respect to temperature, pH, pitting behavior, deposit morphology, deposition stress and interfacial tension. Electrowinning test work was conducted in a bench scale diaphragm cell in a sulfate medium with control of the catholyte pH. Cobalt was deposited on a coated stainless-steel mandrel cathode with exposed circles to allow plating of disk shaped deposits over the surface of the cathode that could be easily stripped after 5–7 days of deposition. Limiting the area of plating prevents the detachment of the cobalt deposit from the cathode due to high deposition stress. The morphology and pitting behaviour varied for different commercial cobalt raw materials used for making cobalt sulfate solution as they contained different impurities or additives. The deposition behaviour changed after the solutions had an activation carbon treatment as some impurities (mainly organic compounds) were removed. In the temperature range from 50 to 65 °C, a higher temperature resulted in a brighter deposit with more pits and smaller lateral dendrites. The cobalt deposition current efficiency was around 98% at pH 3.0 and was not sensitive to temperature. With decreasing catholyte pH from 3.5 to 2.0, the cobalt current efficiency decreased from 99 to 88% and the growth of lateral dendrites were significantly suppressed. The formation of pits resulted from the adhesion of hydrogen bubbles on the cobalt deposit. The adhesion of hydrogen bubbles was determined by the prevailing surface and interfacial tensions. Anti-pitting agents were used to change the interfacial and surface tensions in such a way that the detachment of bubbles was facilitated, resulting in a pit-free cobalt deposit. The anti-pitting agents affected the deposit morphology and internal stress. The impact of the anti-pitting agents on the disengagement of organic and aqueous phases during cobalt solvent extraction was also investigated. The internal stress of the cobalt deposit as a function of temperature and anti-pitting agent dosage and the conductivities of the CoSO4-Na2SO4-H2SO4 system are reported.