Selenium Reduction Via Conventional Water Treatment

For some time, selenate has eluded water treatment by conven­tional means such as precipitation and clarification. This has been due to the nearly universal solubility of all oxidized sele­nium species, the low levels required for surface discharge, and almost identical chemical behavior to all forms of oxidized sul­fur. The last characteristic makes selenate particularly difficult to deal with in acid mine waters where sulfate can easily be on the order of one gram per liter. Approaches such as ion exchange or reverse osmosis often tum into total demineraliza­tion schemes for the sake of removing a "trace" selenium species that may be present on the order of 108 sulfate/selenate. Reduction of selenate to selenite or elemental selenium by chemical means has been relatively unresearched. Some limit­ed success has been reported (Murphy, 1988) using ferrous hydroxide as a reducing agent; however, the reaction time as reported is too slow to be useful in a practical plant design. One significant difference between selenate and sulfate is that selenate has been discovered to be reducible in acid solution by elemental iron when catalyzed by soluble copper. Since the +4 or zero valence states of selenium are rather easy to deal with by coprecipitation with iron salts or alum, the elemental iron dis­solved in the process contributes to the overall process by pro­viding sludge upon raising the pH that can be separated by con­ventional clarification. Commercial production of selenium using copper catalyzed reduction of selenite to selenium metal via sulfur dioxide is well established, however, at the < 5 ppb requirements for surface discharge this reduction process equili­brates at levels far too high to be useful to low level selenate removal criteria. The reaction reported herein uses elemental iron for reduction of selenate with copper acting either as a cata­lyst or as a coprecipitation agent. This method, employed with conventional sludging, clarification and filtration can provide an economic method to achieve non detectable selenium (< 0.005 mg/I). Iron consumptions for the conditions tested have been on the order of 3 lbs/1,000 gallons treated. This represents as little as $0.06 or $2.00 per 1,000 gallons based on using a scrap source of iron or the purchase of electrolytic iron for the process.