Development of Green Rust/Ferrite Process for Treating Selenium Contaminated Groundwater

"A novel selenium removal process called Recycled Green rust/Ferrite Process is developed by MMC. In this process, a mixed Fe2+-Fe3+ hydroxide compound, green rust (GR), reduces selenate to elemental selenium, while GR is consequently oxidized to magnetite Fe3O4. Sequencing batch-mode experiment showed that the residual selenium concentration gradually decreased with the number of batch test increased. Stable selenium removal was achieved when the number of batch test exceed 15 times. Optimum selenium removal ratio reached 99.95% where initial Se concentration 2.1mg/L decreased to 0.001mg/L. Furthermore, the continuous feeding test carried out through a pilot-scale plant with a feeding capacity 600 L/hr. Approximately 860-hour-feeding test was carried out for the selenium-contaminated groundwater which had an averaged selenium concentration of 0.88 mg/L. Selenium concentration in the effluent from thickener maintained less than 0.01 mg/L (selenium removal rate of 99%) until a net operating time reached 800 hours.IntroductionJapan is one of the largest producers of selenium, and thus there are potential environmental impacts of selenium on soil and aquatic environments. The Mitsubishi Material Corporation (MMC) owns some real estate properties whose soil and groundwater was polluted by selenium and other heavy metals. These sites include former industrial plants: a smelter for nonferrous metal and a fabricating semiconductors and pigments. Selenium in aquatic environment commonly exists in four oxidation states, namely, VI, IV, 0 and -II. Selenate ion (SeO4 2-), the most oxidized form of selenium, and selenite ion (SeO3 2-) are highly soluble and mobile. Elemental selenium (Se0) is insoluble in water and therefore has much lower toxicity. Because selenium is carcinogenic and teratogenic at high concentration, the national effluent standard in Japan is fixed at 0.1 mg/L and the environmental standard at 0.01 mg/L. Although there are several selenium removal techniques, the most conventional process is coprecipitation with a ferric hydroxide because of its simplicity and low cost. It is known that selenite is adsorbed strongly on the surface of ferric hydroxide, but selenate is not. The low affinity of selenate on oxide mineral surfaces was demonstrated by the fact that selenate could be easily displaced by adding competing anions, particularly sulfate ion. Selenate removal from polluted water is one of the most difficult techniques, and more effective methods are desired. MMC developed a novel selenium removal process [1]. In this process, the concentrated slurry that contains Fe(II)-Fe(III) hydroxyl-salts known as Green Rusts (GRs) contributes to selenate removal. The main components of the iron precipitate in the reactor are GRs and their oxidation product, magnetite (Fe3O4)."