The Effects of Glue and Thiourea on the Electrodepostion of Bismuth and Copper from Acidic Sulfate Solutions

"The effects of commercial copper electrorefining additives (glue and thiourea) on the electrochemical removal of bismuth are of importance in copper production. It was found that Bi(III) electrodeposition occurs readily from acidic sulfate solution via a diffusion-controlled quasi-reversible reduction. The diffusion coefficient of Bi(III) was measured and found to be less than reported values of copper in similar solutions. The presence of thiourea and/or glue was found to accelerate or de-polarize Bi(III) reduction on stainless steel as compared to the inhibition or polarization of Cu(II) reduction. The additives also inhibited the dissolution of the Bi-Cu co-deposit during cyclic voltammetry. During short term deposition studies, the additives increased the concentration of Bi in co-deposited Cu-Bi products from solutions with low concentrations of Cu (<2 g/L). Bi deposition was significantly suppressed by increasing the Cu(II) concentration in the solution. The formation of a copper layer on the stainless steel electrode appeared to significantly suppress the reduction of Bi(III). This study demonstrates that glue and thiourea depolarize the deposition of bismuth on stainless steel. Therefore, the additives could be used to improve Bi impurity removal during third stage liberation.INTRODUCTIONThe production of high purity copper has been steadily increasing due to the wide application of the metal and its alloys in electrical and electronic products, infrastructure construction, industrial machinery and equipment, general products and transportation (Moskalyk et al., 2003). Most high purity copper is manufactured from copper sulfide mineral concentrates and/or scrap via a pyrometallurgical process followed by electrorefining (Navarro et al., 1999). During the electrorefining process, cast anodes of 99-99.5% purity are electrochemically dissolved into an acidified copper sulfate solution while high purity copper (>99.99%) is plated on stainless steel blanks or copper starter sheets (Davenport et al., 2002). The control of cathode deposit growth (purity and morphology) while maintaining a high current efficiency is of significant importance for copper refining (Ilkhchi et al., 2007). At typically applied current densities for industrial copper electrorefining, mass and charge transfer play important roles in the quality of cathodic products (Hiskey et al., 1998). If the real current density at some surface points is substantially higher owing to uneven current distribution, then rough spots can and will grow faster leading to nodules (Suarez et al., 1992). Nodulated deposits tend to capture solution and anode impurities (slimes) resulting in unacceptable cathode quality (Afifi et al., 1987). Furthermore, these nodules can grow until they eventually contact the anode leading to short circuits and current efficiency reduction (Ilkhchi et al. 2007)."