Catalytic ozonation of phenolic acids over a Mn-Ce-O catalyst

Abstract

Catalytic ozonation of a simulated phenolic wastewater composed by six acids: syringic, vanillic, 3,4,5-trimethoxybenzoic, veratric, protocatechuic and 4-hydroxybenzoic normally present in olive mill wastewaters was studied over a Mn-Ce-O laboratorial catalyst under different operating conditions. A high improvement in total organic carbon (TOC) degradation was observed even when low catalyst concentrations were used when compared with single ozonation. The influence of the medium pH in the performance of both single and catalytic ozonation was assessed in a wide range of pH values. An inhibitory effect in TOC removal was observed in the catalytic process performance at high pH values. The use of radical scavengers proved that this catalytic system does not follow a free radical pathway. No differences were observed between fresh and used catalyst structure and morphology by SEM and XRD. Nevertheless, a decrease on BET surface area was detected. Leaching of Mn as well as carbon adsorption due to organic intermediates deposition at the catalyst surface was analyzed for the recovered catalyst at the end of the experiments. The role of the catalyst in the catalytic ozonation pathway was discussed being concluded that the main mechanism should be developed through surface reactions involving both pollutants and ozone adsorption. A series of feed-batch trials was performed to test Mn-Ce-O activity along the time. A slight decrease on TOC removal was observed from the first to the second use, remaining the catalyst performance constant after the third run