Catalytic ozonation of reverse osmosis concentrate from coking wastewater reuse by surface oxidation over Mn-Ce/γ-Al2O3: Effluent organic matter transformation and its catalytic mechanism

Degradation of organics in high-salinity wastewater is beneficial to meeting the requirement of zero liquid discharge for coking wastewater treatment. Creating efficient and stable performance catalysts for high-salinity wastewater treatment is vital in catalytic ozonation process. Compared with ozonation alone, Mn and Ce co-doped γ-Al2O3 could remarkably enhance activities of catalytic ozonation for chemical oxygen demand (COD) removal (38.9%) of brine derived from a two-stage reverse osmosis treatment. Experimental and theoretical calculation results indicate that introducing Mn could increase the active points of catalyst surface, and introducing Ce could optimize d-band electronic structures and promote the electron transport capacity, enhancing HO• bound to the catalyst surface ([HO•]ads) generation. [HO•]ads plays key roles for degrading the intermediates and transfer them into low molecular weight organics, and further decrease COD, molecular weights and number of organics in reverse osmosis concentrate. Under the same reaction conditions, the presence of Mn/γ-Al2O3 catalyst can reduce ΔO3/ΔCOD by at least 37.6% compared to ozonation alone. Furthermore, Mn-Ce/γ-Al2O3 catalytic ozonation can reduce the ΔO3/ΔCOD from 2.6 of Mn/γ-Al2O3 catalytic ozonation to 0.9 in the case of achieving similar COD removal. Catalytic ozonation has the potential to treat reverse osmosis concentrate derived from bio-treated coking wastewater reclamation. The reverse osmosis concentrate (ROC) of coking wastewater reuse has the characteristics of complex organic pollutant composition, high salinity and refractory to biodegradation, and then its treatment is a big challenge in achieving zero liquid discharge of wastewater. We synthesized Mn and Ce co-doped catalysts by simple impregnation, which exhibited excellent performance for COD, UV254 and color removal during ROC treatment. The catalytic mechanism and organic transformation are systematically elaborated based on the experimental results and theoretical calculations. This work demonstrates the potential of catalytic ozonation in the practical application of ROC treatment for coking wastewater reclamation.