Refractory organic compounds in coal chemical wastewater treatment by catalytic ozonation using Mn-Cu-Ce/Al2O3

A composite Mn-Cu-Ce tri-metal oxide supported on gamma-Al2O3 (Mn-Cu-Ce/Al2O3) catalyst was prepared by an impregnation-calcination method and investigated in the catalytic ozonation treatment of real coal chemical wastewater (CCW). The catalyst was characterized by XRD, SEM, TEM, XRF, BET, and XPS techniques. The results showed that Mn, Cu, and Ce metal oxides were evenly distributed on the Al2O3 surface and the catalyst maintained a large surface area and a high pore volume compared with the pristine Al2O3. The synergy between Mn, Cu, and Ce oxides greatly enriched the catalytic active sites and enhanced the ozonation performance. The catalytic ozonation process with Mn-Cu-Ce/Al2O3 increased the removal rate of total organic carbon (TOC) by 31.6% compared with ozonation alone. The ketones, aromatic compounds, phenols, and nitrogen-containing heterocyclic compounds in CCW have been effectively degraded and mineralized by Mn-Cu-Ce/Al2O3 catalytic ozonation process, and its biodegradability has also been significantly improved. The experimental results of center dot OH scavengers revealed that the mechanism of Mn-Cu-Ce/Al2O3 catalytic ozonation was to promote the generation of center dot OH radicals. The catalytic activity of Mn-Cu-Ce/Al2O3 was only a slight decrease in six consecutive catalytic ozonation treatments, showing good stability. Therefore, Mn-Cu-Ce/Al2O3 can be used as a candidate catalyst for the advanced treatment of refractory organic wastewaters upon catalytic ozonation.

Automated summary

The Mn-Cu-Ce tri-metal oxide supported on gamma-Al2O3 catalyst showed improved catalytic ozonation performance in treating coal chemical wastewater, significantly enhancing removal of TOC and improving biodegradability. The synergy between Mn, Cu, and Ce oxides enriched catalytic active sites and promoted the generation of center dot OH radicals, leading to effective degradation and mineralization of pollutants in the wastewater. Additionally, the catalyst exhibited good stability over multiple treatments, making it a promising candidate for advanced treatment of organic wastewaters through catalytic ozonation.