Catalytic activity comparison of natural ferrous minerals in photo-Fenton oxidation for tertiary treatment of dyeing wastewater.

Abstract

Natural ferrous minerals are readily available and recyclable catalysts in photo-Fenton-like oxidation for wastewater treatment. In this work, typical ferrous oxide and sulfide minerals including magnetite, chalcopyrite, and pyrrhotite were exploited as catalysts in heterogeneous photo-Fenton oxidation for purification of biological effluent of dyeing wastewater. In a wide initial pH range (3.0~7.5), ferrous mineral-based heterogeneous photo-Fenton-like reactions were proven to be effective on the oxidation of recalcitrant pollutants. COD removals achieved 60.57%, 58.83%, and 57.41% using pyrrhotite, chalcopyrite, and magnetite, respectively, as catalyst under ultraviolet irradiation of 220~275 nm at H2O2 concentration of 9.8 mM. The corresponding COD removals were 51.75% and 34.09% with or without ferrous sulfate additions in UV/H2O2 systems. Minerals exhibited excellent stability and reusability with photo-catalytic activity reduction of less than 10% in the reuse of 5 cycles. Dissolved iron concentrations were determined to be 1.86 mg L-1, 4.62 mg L-1, and 7.53 mg L-1 for magnetite, chalcopyrite, and pyrrhotite, respectively, at pH 3 and decreased to zero in neutral pH environment, which were much lower than those required for homogenous Fenton reaction. It was deduced that oxidation of recalcitrant pollutants was mainly catalyzed by Fe(II) on the mineral surface. The more reactive oxygen species such as hydroxyl radicals were resulted from the reaction of surface Fe (II) with H2O2, H2O2 photolysis, and charge separation of minerals under UV irradiation.