Influencing factors of microwave degradation of 2,2’,4,4’-tetrabromodiphenyl ether in aqueous solution

doi:10.3969/j.issn.1000-1565.2017.01.005

摘要/Abstract

摘要： 采用微波辐射技术降解典型溴代阻燃剂2,2’,4,4’-四溴联苯醚(BDE-47),以固相微萃取(SPME)结合气相色谱(GC)技术作为分析检测手段,研究了微波技术降解水溶液中BDE-47的影响因素及降解规律,通过自由基猝灭剂实验证明了Fe³⁺对BDE-47微波降解影响遵循自由基反应机理.对影响BDE-47降解率的反应时间、反应温度、样品浓度、搅拌方式、微波功率等因素进行了考察和优化.实验结果表明,在反应温度为60 ℃、反应时间为120 min、充分搅拌的条件下,溶液中BDE-47的降解率可达80%以上.水溶液中不同质量浓度的BDE-47微波降解符合准一级反应动力学方程.Fe³⁺对BDE-47微波降解具有双重作用,低浓度促进,高浓度抑制.

关键词: 2, 2’, 4, 4’-四溴联苯醚(BDE-47), 微波降解, 影响因素, 自由基

Abstract: 2,2’,4,4’-tetrabromodiphenyl ether(BDE-47)as a typical kind of brominated flame retardants was degraded by microwave irradiation and determined by solid-phase micro-extraction(SPME)combined with chromatography(GC).The influence factors and degradation laws of BDE-47 degradation by microwave in aqueous solution were studied.The influencing of Fe³⁺ on BDE-47 degradation followed the free-radical reaction mechanism,which was proved by adding free radical quencher during microwave degradation with Fe³⁺.The influencing factors on degradation rate of BDE-47,such as reaction time,reaction temperature,sample concentration,stirring method,microwave power,were investigated and optimized.The results indicated that the degradation rate of BDE-47 was more than 80% when the reaction temperature was 60 ℃,the reaction time was 120 min,and the solution was fully stirred.The microwave degradation of BDE-47 in aqueous solution with different concentration conformed to the first order kinetic equation.Fe³⁺ had a dual role in the microwave degradation of BDE-47,Fe³⁺ with low concentration promoted the BDE-47 degradation and Fe³⁺ with high concentration inhibited the BDE-47 degradation.- DOI:10.3969/j.issn.1000-1565.2017.01.005水相中2,2’,4,4’-四溴联苯醚微波降解的影响因素刘芃岩,杨金新,王永慧,张彦娜,田润(河北大学化学与环境科学学院分析科学重点实验室,河北保定 071002)摘要:采用微波辐射技术降解典型溴代阻燃剂2,2’,4,4’-四溴联苯醚(BDE-47),以固相微萃取(SPME)结合气相色谱(GC)技术作为分析检测手段,研究了微波技术降解水溶液中BDE-47的影响因素及降解规律,通过自由基猝灭剂实验证明了Fe³⁺对BDE-47微波降解影响遵循自由基反应机理.对影响BDE-47降解率的反应时间、反应温度、样品浓度、搅拌方式、微波功率等因素进行了考察和优化.实验结果表明,在反应温度为60 ℃、反应时间为120 min、充分搅拌的条件下,溶液中BDE-47的降解率可达80%以上.水溶液中不同质量浓度的BDE-47微波降解符合准一级反应动力学方程.Fe³⁺对BDE-47微波降解具有双重作用,低浓度促进,高浓度抑制.关键词:2,2’,4,4’-四溴联苯醚(BDE-47);微波降解; 影响因素;自由基中图分类号:X13 文献标志码:A 【additional_page=38】文章编号:1000-1565(2017)01-0024-07Influencing factors of microwave degradation of 2,2’,4,4’-tetrabromodiphenyl ether in aqueous solutionLIU Pengyan,YANG Jinxin,WANG Yonghui,ZHANG Yanna,TIAN Run(Key Laboratory of Analytical Science,College of Chemistry and Environmental Science,Hebei University,Baoding 071002,China)Abstract: 2,2’,4,4’-tetrabromodiphenyl ether(BDE-47)as a typical kind of brominated flame retardants was degraded by microwave irradiation and determined by solid-phase micro-extraction(SPME)combined with chromatography(GC).The influence factors and degradation laws of BDE-47 degradation by microwave in aqueous solution were studied.The influencing of Fe³⁺ on BDE-47 degradation followed the free-radical reaction mechanism,which was proved by adding free radical quencher during microwave degradation with Fe³⁺.The influencing factors on degradation rate of BDE-47,such as reaction time,reaction temperature,sample concentration,stirring method,microwave power,were investigated and optimized.The results indicated that the degradation rate of BDE-47 was more than 80% when the reaction temperature was 60 ℃,the reaction time was 120 min,and the solution was fully stirred.The microwave degradation of BDE-47 in aqueous solution with different concentration conformed to the first order kinetic equation.Fe³⁺ had a dual role in the microwave degradation of BDE-47,Fe³⁺ with low concentration promoted the BDE-47 degradation and Fe³⁺ with high concentration inhibited the BDE-47 degradation.- 收稿日期:2016-10-24 基金项目:国家自然科学基金资助项目(21377033);河北省教育厅重点资助项目(ZD20131046) 第一作者:刘芃岩(1964—),女,河北保定人,河北大学教授,博士,主要从事环境中典型污染物的生成降解与迁移转化研究以及食品污染检测方法研究.E-mail:hbupyliu@163.com第1期刘芃岩等:水相中2,2’,4,4’-四溴联苯醚微波降解的影响因素

Key words: 2,2’,4,4’-tetrabromodiphenyl ether(BDE-47), microwave degradation, influencing factors, free radical

中图分类号:

刘芃岩,杨金新,王永慧,张彦娜,田润. [J]. 河北大学学报(自然科学版), 2017, 37(1): 24-30.

LIU Pengyan,YANG Jinxin,WANG Yonghui,ZHANG Yanna,TIAN Run. Influencing factors of microwave degradation of 2,2’,4,4’-tetrabromodiphenyl ether in aqueous solution[J]. Journal of Hebei University (Natural Science Edition), 2017, 37(1): 24-30.

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