亚铁改性沸石活化过氧乙酸降解水中双氯芬酸的研究

史鸿乐; 汪诗翔; 刘义青; 付永胜

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中国环境科学 ›› 2020, Vol. 40 ›› Issue (5) : 2116-2123.

水污染与控制

亚铁改性沸石活化过氧乙酸降解水中双氯芬酸的研究

史鸿乐, 汪诗翔, 刘义青, 付永胜

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Enhanced degradation of diclofenac by catalytic peracetic acid using Fe²⁺ modified zeolite

SHI Hong-Le, WANG Shi-Xiang, LIU Yi-Qing, FU Yong-Sheng

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摘要

采用亚铁改性沸石-过氧乙酸（FMZ/PAA）新型高级氧化体系降解水中双氯芬酸（DCF）.考察了初始pH、药剂投加量、共存干扰离子（CO₃^2-，NO₃^-，Cl^-，SO₄^2-，Fe³⁺，Cu²⁺，Ca²⁺，Mg²⁺）及天然有机物（NOM）对DCF去除效果的影响，通过自由基清除实验探讨了反应过程中的关键活性物种.结果表明，DCF在FMZ/PAA体系中的降解符合一级反应动力学方程，在常温常压、初始pH值为7.0、FMZ投加量为0.2g/L、PAA投加量为80 μmol/L的条件下，1 μmol/L的DCF在40min内得到完全去除.共存Cl^-、CO₃^2-和NOM由于自由基竞争反应明显抑制DCF的降解，而Cu²⁺则参与了PAA的活化，有助于DCF的去除.碳中心自由基是FMZ/PAA体系降解DCF反应中的主要活性物种.基于DCF降解过程中检出的3种产物，提出了其在FMZ/PAA体系中的3种转化途径，即C-N键断裂、脱羧反应和甲酰化反应.

Abstract

A novel heterogeneous advanced oxidation system (Fe²⁺ modified zeolite/PAA) capable of generating several radicals was developed to remove diclofenac (DCF) from the contaminated water. The influences of various operational parameters including the initial pH, dosages of Fe²⁺ modified zeolite (FMZ) and PAA, as well as the water matrix on the removal of DCF were investigated. Meanwhile, the main reactive species in this system were elucidated by radical scavenging experiments. Results indicated that the DCF degradation by FMZ/PAA could be described by first-order kinetic model. DCF was completely removed in 40min under the conditions of pH 7.0, FMZ dosage of 0.2g/L, PAA dosage of 80μmol/L, initial DCF concentration of 1μmol/L and temperature of 25^oC. The presence of Cl^-, CO₃^2- and NOM had negative effects on DCF degradation through radical competition, whereas Cu²⁺ could promote obviously the DCF degradation by accelerating the activation of PAA to generate more radicals. Carbon-centered radical was proved to be mainly responsible for DCF oxidation. According to three identified products, the degradation pathway of DCF by FMZ/PAA was proposed including C-N bond cleavage, decarboxylation and formylation.

导出引用

史鸿乐, 汪诗翔, 刘义青, 付永胜. 亚铁改性沸石活化过氧乙酸降解水中双氯芬酸的研究[J]. 中国环境科学. 2020, 40(5): 2116-2123

SHI Hong-Le, WANG Shi-Xiang, LIU Yi-Qing, FU Yong-Sheng. Enhanced degradation of diclofenac by catalytic peracetic acid using Fe²⁺ modified zeolite[J]. China Environmental Science. 2020, 40(5): 2116-2123

中图分类号： X522

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