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Cu2+强化UV活化过氧乙酸降解水中的双氯芬酸
引用本文:张李,付永胜,刘义青.Cu2+强化UV活化过氧乙酸降解水中的双氯芬酸[J].中国环境科学,2021,40(12):5260-5269.
作者姓名:张李  付永胜  刘义青
作者单位:西南交通大学地球科学与环境工程学院, 四川 成都 611756
基金项目:四川省科技厅重点研发项目(2017SZ0175);重大科技专项(2018SZDZX0026);中央高校基本科研业务费科技创新项目(2682018CX32)
摘    要:研究了Cu2+强化UV活化过氧乙酸(Cu2+/UV/PAA)对水中双氯芬酸(DCF)的降解,考察了pH值、PAA投加量、Cu2+投加量、无机阴离子(Cl-、SO42-、NO3-和CO32-)和溶解有机物(DOM)对DCF去除的影响;探讨了DCF在该体系中的降解产物和转化机理.结果表明:UV和Cu2+都能活化PAA产生活性自由基促进DCF降解.DCF在Cu2+/UV/PAA中的降解遵循准一级动力学,其降解可能归因于直接光解、HO·氧化和CH3COO·、CH3COOO·等其它自由基氧化.在pH=3~11范围内,DCF降解的最佳pH=8.5.DCF的降解效率随着PAA投加量的增大而逐渐增高,过量的PAA能与DCF竞争HO·.Cu2+用量的提高也能促进DCF的去除,但是过量的Cu2+可生成Cu(OH)2导致其催化能力下降.由于NO3-在UV照射下可以产生HO·,其对DCF降解有促进作用,且NO3-浓度越高,促进作用越明显.不同浓度的Cl-、SO42-、CO32-和DOM对DCF降解影响较小.在Cu2+/UV/PAA降解DCF的过程中,共检测出13种降解产物.根据这些降解产物,提出了DCF可能的转化机理,包括8种不同的反应路径.

关 键 词:双氯芬酸  UV  过氧乙酸  Cu2+  羟基自由基  转化机理  

Degradation of diclofenac in water by Cu2+ enhanced UV activation of peracetic acid
ZHANG Li,FU Yong-sheng,LIU Yi-qing.Degradation of diclofenac in water by Cu2+ enhanced UV activation of peracetic acid[J].China Environmental Science,2021,40(12):5260-5269.
Authors:ZHANG Li  FU Yong-sheng  LIU Yi-qing
Institution:Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu 611756, China
Abstract:The degradation of diclofenac (DCF) by Cu2+ enhanced UV activation of peracetic acid (Cu2+/UV/PAA) was investigated. The effects of pH, PAA dose, Cu2+ dose, inorganic anions (such as Cl-, SO42-, NO3- and CO32-) and dissolved organic matter (DOM) on DCF removal by Cu2+/UV/PAA were also evaluated. The degradation products and transformation mechanism of DCF by Cu2+/UV/PAA were studied. Both UV and Cu2+ could activate PAA to produce active radicals, which could promote DCF removal. The degradation of DCF by Cu2+/UV/PAA followed the pseudo first-order kinetics and its degradation was probably attributed to direct photolysis, HO· oxidation and other radicals oxidation such as CH3COO· and CH3COOO·. In the pH range of 3-11, DCF had the best degradation efficiency at pH 8.5. When PAA dose increased, the degradation efficiency of DCF was enhanced gradually, but excessive PAA could compete with DCF for HO·. The increase of Cu2+ dose could also promote DCF removal, while excessive Cu2+ could form Cu(OH)2, which might lead to the reduction of its catalytic ability. Since NO3- can generate HO· under UV irradiation, its existence promoted the degradation of DCF, and the enhancement effect increased with the increase in its concentration. The presence of Cl-, SO42-, CO32- and DOM in different concentrations had little effect on DCF removal. Thirteen degradation products were detected in the degradation of DCF by Cu2+/UV/PAA. According to these degradation products, the probable transformation mechanism of DCF was proposed exhibiting eight reaction pathways.
Keywords:diclofenac  UV  peracetic acid  Cu2+  hydroxyl radical  transformation mechanism  
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