Cathodic current efficiency in the chlorate process

Sodium chlorate is produced in undivided electrolysis cells. Hydrogen is evolved on the cathodes, usually made of steel, while chloride ions are oxidised to chlorine on the anodes, usually DSA (R) s. Parasitic cathodic reactions, lowering the cathodic current efficiency (CE), are the reduction of hypochlorite and chlorate ions. These reactions are suppressed by the addition of Cr(VI) to the electrolyte. In this work the effects that time of the electrolysis, chromate concentration and interruption of the electrolysis process have on CE has been investigated. New steel, as well as steel samples cut from cathodes used in a chlorate plant, were used as cathode material. Laboratory experiments in a divided cell were made to determine the rate of hydrogen production, and thereby indirectly CE, at varying operating conditions. It was found that the chromate concentration is important for the CE in the range 0.5-6 g l(-1) Na2Cr2O7. The CE was higher on new steel than on the used steel, which had a more corroded and inhomogeneous surface. When starting the electrolysis the CE was initially low, at a value depending on the operating conditions, but increased with time of polarisation. The time to reach an approximate steady CE was generally in the order of hours. Electrolysis shut downs in the presence of hypochlorite (<= 3 g l(-1) NaClO) resulted in corrosion of iron and a low CE when restarting the process. After one such corrosion shut down the new steel showed as low CE as the used steel. When restarting the electrolysis after a shut down without hypochlorite the CE was higher than before the shut down. Current densities of a simulated bipolar plate during a shut down were measured to 50-150 A m(-2), resulting from oxidation of steel and reduction of oxy chlorides on the catalytic DSA (R) electrode.