Achieving Sub-Ppb End-Of-Pipe Selenium Targets and Stable Solids Residues Using Selen-Ix™: Combining Ion Exchange and Electro-Reduction

"Recent changes in regulations and scientific advances concerning selenium bioaccumulation have placed greater importance on non-biological treatment systems for selenium control. Mining wastewater contains hexavalent selenium (selenate) as the predominant aqueous species and possibly small amounts of tetravalent selenium (selenite). Non-biological removal of selenite is accomplished readily and cost effectively by ferric co-precipitation and adsorption using ferric oxyhydroxides sourced from ferric salts or iron anodes in electrocoagulation cells. Selenate on the other hand is difficult to remove. It is often incorrectly assumed that electrocoagulation is suitable for removing both selenite and selenate. Selenate removal efficiency by electrocoagulation is low and the amount of waste residue produced high. In contrast, BioteQ’s Selen-IX™ process removes selenate very efficiently and produces a much smaller amount of stable residue. The process combines selective ion exchange with electro-reduction of selenate in electrocells that physically resemble electrocoagulation cells but are designed and operated differently. This paper summarizes four years of pilot scale demonstration on a wide range of mine waters and discusses the key benefits and limitations of Selen-IX™. The pros and cons of combining ion exchange with electro-reduction in comparison to direct electro-reduction of selenate are also reviewed.INTRODUCTION Selenium in Mining and Mineral Processing Effluents Similar to sulphate and metals, selenium presence in mining and mineral processing wastewater originates from minerals contained in the mined deposits. Therefore, no organoselenium species are typically present in these kinds of waters and inorganic species including selenite (SeO32-), selenate (SeO42) and elemental selenium account for the majority, if not all, selenium present in these streams. Elemental selenium is not always present in mine water but is often contained in smelter wastewater. To comply with new environmental regulations, a successful water treatment plant must remove selenium from all these forms effectively and economically without generating by-products that are difficult to dispose of or manage. Elemental selenium can be dealt with using filtration or gravity separation in clarifiers often assisted by flocculants and/or coagulants. Mine impacted waters typically contain other forms of suspended solids which are removed from water in this way. Once the solids are removed, the selenium species that remain untreated are the dissolved forms. In mining waters this is mostly selenate with small fraction of selenite. In smelter wastewater, the majority could be selenite. It is well established that tetravalent selenium is readily removed from water by using ferric iron co-precipitation at pH > 4 (NAMC SWG, 2010). Ferric hydroxide/ferrihydrite solids act as the adsorbent for tetravalent selenium when it is in one of the ionic forms of biselenite or selenite. This treatment for tetravalent selenium is highly efficient. Therefore, tetravalent selenium removal is generally not an issue and is often easily incorporated into lime neutralization or unit operations such as electrocoagulation used for removing other metals present in mine impacted waters. Another option of dealing with tetravalent selenium is sulphide precipitation in acidic pH which produces SeS2 and can separate selenite from other metals and/or sludge produced at neutral to alkali pH."