Methanol and formic acid oxidising anodes in zinc electrowinning

Abstract: Electrowinning is an energy demanding process, in which the electrolysis accounts for the major part of the energy consumption. The anodic reaction in the electrolysis of zinc from sulphate based electrolytes is oxygen evolution, which has a standard potential of 1.23 V at 25 ºC. The lead anodes used in zinc electrowinning today have a high overpotential for oxygen evolution and the operating anode potential is as high as 2 V vs NHE. Since the lead anodes are not stable some of the lead can dissolve and incorporate in the zinc metal on the cathode. The lead anodes are also undesired because of health concerns. By introducing formic acid or methanol oxidation as anode reaction, the anode potential could be lowered significantly. This would reduce the energy consumption and also enable the use of new types of electrodes.The general aim of this thesis was to investigate how depolarised anodes for methanol and formic acid oxidation can be used in electrowinning processes.Several electrodes were shown to be suitable as anodes in zinc electrowinning. A high activity was obtained with porous electrodes, whereas a platinum coated titanium was the most stable electrode. The choice of electrode will however always be a compromise between activity, stability and costs. All electrodes were deactivated with time and the best method for reactivation tested in this study, was periodic current reversal (PCR).An operating procedure was established for methanol and formic acid oxidation on high surface area electrodes, Pt-TySAR®. With the use of PCR at process current density, a potential lower than 0.7 V vs NHE could be maintained for 36 hour in synthetic electrolyte. The use of formic acid oxidation resulted in lower potentials than the use of methanol oxidation.The activities for methanol and formic acid oxidation in industrial electrolyte were very low and chloride impurities were shown to cause the major part of the activity reduction. Even small amounts of chloride (10-6-10-5 M) affected the activity of the electrodes. The chloride impurities are considered as the main problem to overcome in order to introduce the oxidation of formic acid or methanol in the zinc electrowinning process.