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Sodium molybdate - a possible alternate additive for sodium dichromate in the electrolytic production of sodium chlorate

机译:钼酸钠-电解生产氯酸钠中重铬酸钠的替代添加剂

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摘要

Sodium dichromate is commonly used in sodium chlorate production to maintain high current efficiency; however, it is also a well documented carcinogen. To reduce the environmental impact, identification of a suitable alternative with similar buffering characteristics to dichromate and without adverse effect on the electrolytic performance of sodium chlorate production is important; sodium molybdate is a good candidate. Molybdate ion and its conjugated acid work as a buffer pair at pH 5-6, a lower and slightly narrower pH window than the typical buffer region of dichromate. Nonetheless, the molybdate buffer works effectively during the electrolytic process by maintaining pH at similar to 5.9. Although the use of molybdate buffer will lower the overpotential of hydrogen evolution reaction (HER) by similar to 100 mV, the average off-gas oxygen content is noticeably compromised at 3.6-4.6%, measured using a pilot cell operated at 3 kA m(-2) and 80 degrees C during a 3-day trial. The resulting current efficiency of 91 similar to 92% is significantly lower than when dichromate is employed as the process additive (> 96%). Mixtures of different dichromate and molybdate ratio were also investigated in terms of the resulting cathode surface potential.
机译:重铬酸钠常用于氯酸钠生产中,以保持高电流效率。但是,它也是有据可查的致癌物。为了减少对环境的影响,重要的是找到一种具有与重铬酸盐相似的缓冲特性并且对氯酸钠生产的电解性能没有不利影响的合适替代品;钼酸钠是一个很好的候选人。钼酸根离子及其共轭酸在pH 5-6时作为缓冲液对,比重铬酸盐的典型缓冲液区域的pH窗口低且稍窄。尽管如此,钼酸盐缓冲液在pH值保持在5.9左右的过程中仍能有效地发挥作用。尽管使用钼酸盐缓冲液会使氢释放反应(HER)的过电势降低约100 mV,但使用在3 kA m下运行的中试池测得的平均废气氧含量显着降低至3.6-4.6%。 -2)并在80天的温度下进行了3天的试用。与使用重铬酸盐作为加工助剂时(> 96%)相比,所得的91的电流效率(约92%)要低得多。还根据所得的阴极表面电势研究了不同重铬酸盐和钼酸盐比例的混合物。

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