Electrochemical characterization of anode passivation mechanisms in copper electrorefining

Anode passivation can decrease productivity and quality while increasing costs in modern copper electrorefineries. This investigation utilized electrochemical techniques to characterize the passivation behavior of anode samples from ten different operating companies. It is believed that this collection of anodes is the most diverse set ever to be assembled to study the effect of anode composition on passivation. Chronopotentiometry was the main electrochemical technique, employing a current density of 3820 A m⁻². From statistical analysis of the passivation characteristics, increasing selenium, tellurium, silver, lead and nickel were shown to accelerate passivation. Arsenic was the only anode impurity that inhibited passivation. Oxygen was shown to accelerate passivation when increased from 500 to 1500 ppm, but further increases did not adversely affect passivation. Nine electrolyte variables were also examined. Increasing the copper, sulfuric acid or sulfate concentration of the electrolyte accelerated passivation. Arsenic in the electrolyte had no effect on passivation. Chloride and optimal concentrations of thiourea and glue delayed passivation. Linear sweep voltammetry, cyclic voltammetry, and impedance spectroscopy provided complementary information. Analysis of the electrochemical results led to the development of a unified passivation mechanism. Anode passivation results from the formation of inhibiting films. Careful examination of the potential details, especially those found in the oscillations just prior to passivation, demonstrated the importance of slimes, copper sulfate and copper oxide. Slimes confine dissolution to their pores and inhibit diffusion. This can lead to copper sulfate precipitation, which blocks more of the surface area. Copper oxide forms because of the resulting increase in potential at the interface between the copper sulfate and anode. Ultimate passivation occurs when the anode potential is high enough to stabilize the oxide film in the bulk electrolyte. The effect of anode impurities or electrolyte concentrations can be related to the formation of one of these films. Reactions occurring after passivation have also been examined. Post-passivation reactions are believed to include silver dissolution, transformation of lead sulfate to lead oxide, and oxygen evolution. Following the sharp potential increase caused by the passivation, silver that has accumulated on the anode surface will dissolve into the electrolyte at a potential between 1.0 and 1.3 V. After the silver has dissolved, the potential increases again at which point the oxidation of lead sulfate to lead oxide occurs. The formation of lead oxide provides a surface with a lower oxygen evolution overpotential. The presence of kupferglimmer also results in a stable lower oxygen evolution potential occurring at approximately 2.0 V