Influence of the Electro Crystallization Inhibitors during Copper Electrorefining: A New Experimental Approach

"The influence of the copper electro crystallization inhibitors (mainly thiourea, gelatin and chloride ions) is studied in a new fully automatic pilot plan. This paper describes the conception and the building of this plan. The new approach is to reproduce the experimental conditions observed in the industry with the three additives present simultaneously in the electrolyte and secondly to study the influence of a slight modification of the concentration of one inhibitor, the others being present in the electrolyte with their industrial nominalconcentrations.1. INTRODUCTIONDespite the fact that gelatine, thiourea and chloride ions have been used in copper electrorefining for a long time, precise knowledge concerning their influence on the cathode deposit, metallographic structure and associated properties is still lacking.Many authors studied the influence of each additive separately, or of two added at a time. Only a few authors studied the combined influence of the three additives added simultaneously. The general conclusion that can be drawn is that the combined influence is far from that forseen from the influence of each additive separately, or even from two additives used at a time. Moreover most of the experiments described in the literature were performed by adding all additives at once initially. It is however, well known that gelatine looses a great part of its activity during the first half hour due to degradation by sulfuric acid (as shown by the cathode overpotential drop). Thiourea is rapidly replaced by a number of degradation mole,cules and complex ions including cations from the solution, changing even the equilibrium between Cu, Cu(I) and Cu(II).Chloride ions are consumed by precipitation.A number of successive research projects [1-9] led pregressively to the concept that, in order to obtain reproducible results representative of industrial cathodes, it was necessary to simulate as far as possible industrial conditions. It was essential that all additives were added continuously during the electrolysis, with, as consequence, a continuous bleed.The purpose of this paper is to describe the concept of a new fully automatic pilot plan for copper electrorefining and to present the first results."