Lowering the Energy Consumption of Zinc Electrowinning By Electrocatalysis of Oxygen Evolution Reaction Using Manganese Oxides

Zinc has a wide range of commercial applications including but not limited to galvanizing iron and steel and production of various metal alloys such as brass and bronze. In hydrometallurgical processes, zinc electrowinning from sulfate-based electrolytes is the last step of zinc extraction in which high purity metallic zinc is electrodeposited from a highly acidic solution on an aluminum cathode. The electrowinning stage is very energy-intensive and responsible for approximately 80% of the power requirement of a zinc refinery (1). Thus, improving the energy efficiency and lowering the operating costs of zinc electrowinning are of primary significance. The oxygen evolution reaction (OER) overpotential on conventional lead-silver (Pb-Ag) anodes contributes to nearly 25% of the total electrowinning cell potential (2). Therefore, the high anodic OER overpotential places a heavy financial burden on zinc refining plants. The present study aims to evaluate novel anodic electrocatalysts incorporating MnO x in order to lower the anodic OER overpotential of the zinc electrowinning process. Anodically electrodeposited MnO x catalysts on Pb-Ag electrodes were prepared using galvanostatic and potentiodynamic polarizations. The OER catalytic activity and stability of MnOx electrodeposited Pb-Ag electrodes were evaluated in 160 g/L sulphuric acid solution with 3 g/L of manganese (II) and in the absence and presence of 0.3 g/L of chloride ion at 35°C, using a standard three-electrode setup. The electrolyte composition and operating conditions were selected such that to be directly applicable to the industrial zinc electrowinning process. The OER activity of the MnOx electrodeposited electrodes was investigated through potentiodynamic polarization and 72-hour galvanostatic electrolysis at 50 mA/cm2 superficial current density. Finally, the activity of MnOx electrodeposited Pb-Ag electrodes was explored in a full zinc electrowinning cell through 24-hour galvanostatic electrolysis at 50 mA/cm2 superficial current density. The OER potential variations of the bare Pb-Ag and MnO x electrodeposited Pb-Ag anodes during the 72-hour galvanostatic polarization are shown in Fig. 1. In the absence and presence of chloride ions, the three MnO x electrodeposited Pb-Ag electrodes are observed to reduce the anodic potential by maximum of 150 mV and 90 mV, respectively. Investigation of these novel electrodes in the full-cell zinc electrowinning operation corroborated the half-cell experiments, revealing a maximum of 80 mV reduction in cell potential at 50 mA/cm2 superficial current density and in the presence of 0.3 g/L of chloride ion. Thus, this work demonstrates that MnO x electrodeposited Pb-Ag anodes have great capacity to lower the power consumption of the zinc electrowinning process. Fig. 1. OER activity and stability comparison under galvanostatic polarization for four anodes: bare Pb-Ag (baseline) and three MnOx electrodeposited Pb-Ag anodes prepared via linear scan voltammetry (LSV), constant current density (CCD), and cyclic voltammetry (CV). Superficial current density: 50 mA/cm2. Electrolyte:160 g/L H2SO4 with 3 g/L Mn2+ and 0.3 g/L Cl- at 35°C. References 1. A. C. Scott, R. M. Pitbaldo, G.W. Barton, A. R. Ault, J. Appl Electrochem, 18, 120–127 (1988). 2. S. Schmachtel, M. Toiminen, K. Kontturi, O. Forsen, M. H. Barker, J. Appl Electrochem, 39, 1835–1848 (2009). Figure 1

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