Precipitation of Selenium from Zinc Plant Weak Acidic Solutions Using Sodium Dithionite and Sodium Sulphide

In the late 1990s, a chemical process to remove mercury and selenium from weak sulphuric acid solutions was patented and implemented in the CEZinc refinery in Valleyfield, Quebec. The CEZinc process comprises two stages. In the first one, sodium sulphide is added to the weak acid solution in order to precipitate the soluble mercury. The solution is then treated with sodium dithionite in order to reduce the selenium to elemental form. Because of recent changes in the composition of the industrial solution, a project to study the background chemical reactions was started. In this paper, a review of the background chemistry is presented on the basis of several eh-pH diagrams on one hand, while on the other experimental results are reported dealing with the reaction of selenium (IV) species with either dithionite, sulphide or a combination of the two. According to this work, elemental selenium enjoys a wide pH-eh range stability with selenium sulphide being metastable. Selenium (IV) in single metal synthetic solutions was found to be reduced - to elemental state - at ambient temperature down to ppb range with dithionite as long as the stoichiometric ratio (dithionite/selenium) was in excess of two and the pH < 1.7. Under these conditions the reaction was very fast reaching completion within one minute. Sodium sulphide proved equally effective in reducing selenium (this time as selenium sulphide) to ppb range from single metal solutions. However, in mixed Se-Hg solutions deviations from this "ideal" behaviour was observed resulting in higher levels of residual soluble selenium left in solution.