State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Helanshan Rd. 539, Yinchuan, 750021, China.
Environ Sci Pollut Res Int. 2021 Aug;28(30):41504-41515. doi: 10.1007/s11356-021-13629-8. Epub 2021 Mar 30.
A composite Mn-Cu-Ce tri-metal oxide supported on γ-AlO (Mn-Cu-Ce/AlO) 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 AlO surface and the catalyst maintained a large surface area and a high pore volume compared with the pristine AlO. 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/AlO 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/AlO catalytic ozonation process, and its biodegradability has also been significantly improved. The experimental results of ∙OH scavengers revealed that the mechanism of Mn-Cu-Ce/AlO catalytic ozonation was to promote the generation of ∙OH radicals. The catalytic activity of Mn-Cu-Ce/AlO was only a slight decrease in six consecutive catalytic ozonation treatments, showing good stability. Therefore, Mn-Cu-Ce/AlO can be used as a candidate catalyst for the advanced treatment of refractory organic wastewaters upon catalytic ozonation.
一种复合 Mn-Cu-Ce 三金属氧化物负载在γ-AlO（Mn-Cu-Ce/AlO）催化剂上，通过浸渍-煅烧法制备，并在实际煤化工废水（CCW）的催化臭氧化处理中进行了研究。催化剂采用 XRD、SEM、TEM、XRF、BET 和 XPS 技术进行了表征。结果表明，Mn、Cu 和 Ce 金属氧化物均匀分布在 AlO 表面，与原始 AlO 相比，催化剂保持了较大的表面积和较高的孔体积。Mn、Cu 和 Ce 氧化物之间的协同作用极大地丰富了催化活性位，增强了臭氧化性能。与单独臭氧化相比，Mn-Cu-Ce/AlO 的催化臭氧化过程使总有机碳（TOC）的去除率提高了 31.6%。Mn-Cu-Ce/AlO 催化臭氧化过程有效地降解和矿化了 CCW 中的酮类、芳香族化合物、酚类和含氮杂环化合物，其生物降解性也得到了显著提高。•OH 清除剂的实验结果表明，Mn-Cu-Ce/AlO 催化臭氧化的机制是促进•OH 自由基的生成。Mn-Cu-Ce/AlO 的催化活性在六次连续的催化臭氧化处理中仅略有下降，表现出良好的稳定性。因此，Mn-Cu-Ce/AlO 可以作为催化臭氧化后难处理有机废水深度处理的候选催化剂。
