Evaluation of Iron (II) Oxidation Reactions in Chloride Leach Solutions

The presence of iron in base metal leach solutions complicates nickel and copper recovery processes. Leach solutions are commonly purified by precipitating iron as hematite, jarosite or goethite. Fast oxidation of ferrous to ferric is an important step to remove iron by precipitation at low pH values. This study reviews the ferrous oxidation mechanism and reaction rates in chloride media using molecular oxygen. This work contributes to the development of a better understanding of iron precipitation processing steps, which continues to be an important matter in hydrometallurgy. The specific objectives were to investigate (1) the effect of key process variables (acid concentration, copper concentration, and temperature) on the rate and extent of ferrous oxidation by dissolved oxygen and (2) the oxidation mechanism by varying chloride and hydrogen ion concentrations separately. Batch oxidation tests were performed using synthetic chloride solutions containing 45 g/L Fe and 3 g/L Ni at 50 and 80°C, dissolved Cu concentrations (0.3 to 3 g/L) and HCl concentrations (2 to 4.6 M). Regression analysis indicated that the significance of the effect of different variables on the extent of oxidation achieved after five hours decreased in the following order: HCl concentration > Cu concentration > temperature. Increasing the HCl concentration from 4 M to 4.6 M caused the degree of oxidation achieved after two hours to increase from 58.3% to 98.1%. The catalytic effect of dissolved copper on ferrous oxidation was more significant at low acid concentrations. Experimental data suggest that rapid oxidation of ferrous is possible at high HCl concentrations for two main reasons. First, the formation of ferrous chloride complexes allows ferrous oxidation to proceed without the formation of superoxide as an intermediate product (the rate limiting step in dilute acid solutions). Second, the formation of ferric chloride complexes stabilises the oxidation product.