Mineralization of organic pollutants by anodic oxidation using reactive electrochemical membrane synthesized from carbothermal reduction of TiO2

Abstract

Reactive Electrochemical Membrane (REM) prepared from carbothermal reduction of TiO₂ is used for the mineralization of biorefractory pollutants during filtration operation. The mixture of Ti₄O₇ and Ti₅O₉ Magnéli phases ensures the high reactivity of the membrane for organic compound oxidation through ^•OH mediated oxidation and direct electron transfer. In cross-flow filtration mode, convection-enhanced mass transport of pollutants can be achieved from the high membrane permeability (3300 LMH bar^-1). Mineralization efficiency of oxalic acid, paracetamol and phenol was assessed as regards to current density, transmembrane pressure and feed concentration. Unprecedented high removal rates of total organic carbon and mineralization current efficiency were achieved after a single passage through the REM, e.g. 47 g m^-2 h^-1 - 72% and 6.7 g m^-2 h^-1 - 47% for oxalic acid and paracetamol, respectively, at 15 mA cm^-2. However, two mechanisms have to be considered for optimization of the process. When the TOC flux is too high with respect to the current density, aromatic compounds polymerize in the REM layer where only direct electron transfer occurs. This phenomenon decreases the oxidation efficiency and/or increases REM fouling. Besides, O₂ bubbles sweeping at high permeate flux promotes O₂ gas generation, with adverse effect on oxidation efficiency.

Keywords: Anodic oxidation; Electro-oxidation; Mineralization; Organic pollutants; Reactive electrochemical membrane; Sub-stoichiometric titanium oxide.