Mineralization of Riluzole by Heterogeneous Fenton Oxidation Using Natural Iron Catalysts

Abstract

Fenton (H2O2/Fe2+) system is a simple and efficient advanced oxidation technology (AOT) for the treatment of organic micropollutants in water and soil. However, it suffers from some drawbacks including high amount of the catalyst, acid pH requirement, sludge formation and slow regeneration of Fe2+ ions. If these drawbacks are surmounted, Fenton system can be the best choice AOT for the removal of persistent organics from water and soil. In this work, it was attempted to replace the homogeneous catalyst with a heterogeneous natural iron-based catalyst for the decomposition of H2O2 into oxidative radical species, mainly hydroxyl (HO•) and hydroperoxyl radicals (HO2•). The natural iron-based catalyst is hematite-rich (α-Fe2O3) and contains a nonnegligible amount of magnetite (Fe3O4) indicating the coexistence of Fe (III) and Fe(II) species. A pseudo-first order kinetics was determined for the decomposition of H2O2 by the iron-based solid catalyst with a rate constant increasing with the catalyst dose. The catalytic decomposition of H2O2 into hydroxyl radicals in the presence of the natural Fe-based catalyst was confirmed by the hydroxylation of benzoic acid into salicylic acid. The natural Fe-based catalyst/H2O2 system was applied for the degradation of riluzole in water. It was demonstrated that the smaller the particle size of the catalyst, the larger its surface area and the greater its catalytic activity towards H2O2 decomposition into hydroxyl radicals. The degradation of riluzole can occur at all pH levels in the range 3.0–12.0 with a rate and efficiency greater than H2O2 oxidation alone, indicating that the natural Fe-based catalyst can function at any pH without the need to control the pH by the addition of chemicals. An improvement in the efficiency and kinetics of the degradation of riluzole was observed under UV irradiation for both homogeneous and heterogeneous Fenton systems. The results chromatography analysis demonstrate that the degradation of riluzole starts by the opening of the triazole ring by releasing nitrate, sulfate, and fluoride ions. The reuse of the catalyst after heat treatment at 500 °C demonstrated that the heat-treated catalyst retained an efficiency >90% after five cycles. The results confirmed that the natural sources of iron, as a heterogeneous catalyst in a Fenton-like system, is an appropriate replacement of a Fe2+ homogeneous catalyst. The reuse of the heterogeneous catalyst after a heat-treatment represents an additional advantage of using a natural iron-based catalyst in Fenton-like systems.