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铜基钙钛矿作为一种用于石油炼制废水处理的新型催化湿式过氧化氢氧化催化剂:性能、毒性及作用机制

Cu-based perovskite as a novel CWPO catalyst for petroleum refining wastewater treatment: Performance, toxicity and mechanism.

作者信息

Ma Wencheng, Zhang Shaobo, Deng Liming, Zhong Dan, Li Kefei, Liu Xiaotong, Li Jinxin, Zhang Jingna, Ma Jun

机构信息

State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, PR China; Harbin Institute of Technology, National Engineer Research Center of Urban Water Resources, Harbin 150090, PR China.

State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, PR China.

出版信息

J Hazard Mater. 2023 Apr 15;448:130824. doi: 10.1016/j.jhazmat.2023.130824. Epub 2023 Jan 18.

Abstract

For the first time, Cu-based perovskite oxides were used as catalysts to treat highly toxic and refractory petroleum refining wastewater based on catalytic wet peroxide oxidation (CWPO) technology. Perovskite LaCuO was synthesized by sol-gel method. A series of characterizations showed that the synthesized catalyst particles are tetragonal phase perovskite structure. The experimental results showed that under the conditions of catalyst dosage of 0.75 g, temperature of 100 ℃ and reaction time of 30 min, the COD removal rate was 89.58 %, the TOC removal rate was 87.38 %. The morphology and structure of the catalyst before and after the reaction proved that the catalyst has strong stability and catalytic activity. The components of raw water, Wet Air Oxidation (WAO) effluent and CWPO effluent were compared and analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), and the possible mechanism and path of WAO and CWPO degradation of petroleum refining wastewater were further explored. The changes of Cu components in LaCuO before and after CWPO reaction and the transformation of lattice oxygen and adsorbed oxygen were analyzed by X-ray Photoelectron Spectroscopy (XPS). The involvement of Cu (Ⅱ) /Cu (Ⅰ) in the activation of HO was speculated. Finally, the biotoxicity of raw water, WAO effluent and CWPO effluent was predicted. The results provide reference value for the application of catalyst LaCuO in various petrochemical wastewater.

摘要

首次将铜基钙钛矿氧化物用作催化剂,基于催化湿式过氧化氢氧化(CWPO)技术处理高毒性和难处理的炼油废水。采用溶胶-凝胶法合成了钙钛矿型LaCuO。一系列表征表明,合成的催化剂颗粒为四方相钙钛矿结构。实验结果表明,在催化剂用量为0.75 g、温度为100℃、反应时间为30 min的条件下,COD去除率为89.58%,TOC去除率为87.38%。反应前后催化剂的形貌和结构证明了该催化剂具有较强的稳定性和催化活性。采用气相色谱-质谱联用仪(GC-MS)对原水、湿式空气氧化(WAO)出水和CWPO出水的成分进行了比较分析,进一步探讨了WAO和CWPO降解炼油废水的可能机理和途径。通过X射线光电子能谱(XPS)分析了CWPO反应前后LaCuO中Cu组分的变化以及晶格氧和吸附氧的转化。推测了Cu(Ⅱ)/Cu(Ⅰ)参与HO的活化过程。最后,预测了原水、WAO出水和CWPO出水的生物毒性。研究结果为催化剂LaCuO在各类石化废水处理中的应用提供了参考价值。

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