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The economic viability of the electrochemical chlorate process depends on toxic chromate to induce cathodic selectivity to hydrogen and mitigate reduction of hypochlorite or chlorate. In this study, it is shown that performance of a pilot plant for chlorate production can be sustained when a 1000-fold reduction in chromate concentration is compensated by addition of molybdate. Laboratory measurements employing a Quartz Crystal Microbalance suggest growth of a nanometre-thick hybrid Mo–Cr-oxide film to induce cathodic selectivity. An optimized energy efficiency for pilot plant operation was obtained using 0.8 mM molybdate and 27 μM chromate, balancing formation of an effective oxide layer and undesired Mo-induced decomposition of hypochlorite to oxygen in solution. Refinement at the pilot scale level is expected to further optimize the energy consumption, thereby increasing safety aspects and the economic viability of chlorate production. Graphical Abstract

Mixed Chromate and Molybdate Additives for Cathodic Enhancement in the Chlorate Process