Investigating the Effects of Thiourea and Selenium on the Electroreduction of Cupric Ions in Acidic Sulphate Solutions

"Selenium removal and platinum group metal (PGM) recovery from copper sulfate leach solutions form an integral part of platinum producers’ base metal refinery operations. Recent studies found that substantially higher PGM recoveries can be achieved if excess thiourea instead of sulfurous acid is used as precipitation reagent; however, the impact of the proposed process on downstream processes was unknown. The objective of the current study was therefore to investigate the effects that excess thiourea and residual selenium present in the rich copper sulfate electrolyte have on copper electrowinning. This was achieved by performing cyclic voltammetry tests using a platinum rotating disk as working electrode, a graphite auxiliary electrode and a saturated calomel reference electrode. A synthetic copper sulfate electrolyte containing 0.01 M Cu2+, 1 M H2SO4 and varying amounts of selenium (20 – 150 mg/L) and thiourea (10 mg/L and 100 – 300 % excess) was used. The results obtained have shown that both thiourea and selenium interact with the cupric ion cathodic reduction reaction. Thiourea polarized the working electrode and lowered the efficiency of the cupric reduction reaction. Tests on the solutions with high selenium concentration showed simultaneous reduction of copper and selenium, which led to copper selenide formation. Nodule formation on the deposit surface also became significant at higher selenium concentrations. Based on these results, it was concluded that precipitation of PGMs from the copper sulfate solution with excess thiourea is not feasible due to the detrimental effect on downstream electrowinning operations.INTRODUCTION During the high pressure oxidative leaching stage in a typical base metal refinery (BMR) circuit, selenium, tellurium and some platinum group metals (PGMs) are dissolved along with the desired copper ions. The impurities (selenium and tellurium) may pass to the copper electrowinning circuit where it can result in the formation of nodular copper electrodeposits or reduced current efficiency. The presence of PGMs in solution, on the other hand, increases the precious metal inventory and potential losses of the operation. Currently, sulfurous acid is widely used for selenium and tellurium precipitation from copper sulfate leach solutions. Sulfurous acid is capable of reducing cupric ions to cuprous ions; the generated cuprous ions then react with Se4+ and Se6+ to precipitate selenium as a copper selenide (Bello, Dorfling, 2014). Recent studies have, however, proposed the use of excess thiourea as a precipitating agent for the removal of selenium and tellurium; it has the advantage of improved PGM recovery in the Se/Te precipitation step (Lottering, Eksteen et al., 2012; Mulwanda, Dorfling, 2015)."