Low brominated diphenyl ethers and brominated dioxins with high toxicity were easily produced in the pyrolysis process of decabromodiphenyl ethers, Based on this, the pyrolysis process of BDE-209 and ZnO was studied by differential thermal gravimetric analysis(DTA-TG), X-ray diffraction(XRD), GC and GC/MS. The results showed that the addition of zinc oxide reduced the activation energy of BDE-209 thermal degradation reaction, thus reducing the thermal degradation temperature of BDE-209; after the addition of zinc oxide, BDE-209 pyrolysis produced more brominated dioxins at 400 ℃ When BDE-209 and ZnO were degraded at 400 ℃ at 2.4∶1(m/m), the degradation rate reached 100% at 2 h.- DOI:10.3969/j.issn.1000-1565.2022.01.005氧化锌对十溴联苯醚热解的污染控制机理分析高兰1,2,雷源3,李占圣1,刘芃岩1(1.河北大学 化学与环境科学学院,河北 保定 071002;2. 保定学院 生物化工与环境工程学院, 河北 保定 071001;3. 河北大学 生态环境学院,河北 保定 071002)摘 要:十溴联苯醚(BDE-209)热解过程中容易产生毒性较高的低溴代联苯醚和溴代二噁英,氧化锌对BDE-209的热解过程及热解产物有较大地影响.利用差热-热重(DTA-TG)分析,X线衍射(XRD)分析和GC、GC/MS对热解产物种类以及相对含量进行分析,结果表明:氧化锌的加入降低了BDE-209热降解反应的活化能,从而降低了BDE-209的热降解温度;氧化锌加入后,BDE-209在400 ℃时热解产生的溴代二噁英较多; BDE-209和氧化锌以2.4∶1(质量比)在400 ℃进行热降解,其降解率2 h达到100%,此时,六溴代和七溴代二噁英类产物相对含量较低,六溴苯和五溴苯类产物的相对含量最高.结合Arrhenius公式计算以及软硬酸碱理论,并根据热解残余物的XRD产物分析,对BDE-209和氧化锌的混合热解机理进行了深入探讨,为热处理废旧印刷电路板的污染防控提供了理论依据. 关键词:氧化锌;十溴联苯醚(BDE-209);热降解;溴代二噁英 中图分类号:S852.61 文献标志码:A 文章编号:1000-1565(2022)01-0029-09Pollution control mechanism analysis of thermal degradation of decabromodiphenyl ether by zinc oxideGAO Lan1,2, LEI Yuan3, LI Zhansheng1, LIU Pengyan1(1. College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China;2. College of Biochemical and Environmental Engineering,Baoding University, Baoding 071001, China;3.School of Eco-Environment,Hebei University,Baoding 071002,China)Abstract: Low brominated diphenyl ethers and brominated dioxins with high toxicity were easily produced in the pyrolysis process of decabromodiphenyl ethers, Based on this, the pyrolysis process of BDE-209 and ZnO was studied by differential thermal gravimetric analysis(DTA-TG), X-ray diffraction(XRD), GC and GC/MS. The results showed that the addition of zinc oxide reduced the activation energy of BDE-209 thermal degradation reaction, thus reducing the thermal degradation temperature of BDE-209; after the addition of zinc oxide, BDE-209 pyrolysis produced more brominated dioxins at 400 ℃ When BDE-209 and ZnO were degraded at 400 ℃ at 2.4∶1(m/m), the degradation rate reached 100% at 2 h.- 收稿日期:2021-11-10 基金项目:国家自然科学基金资助项目(21377033);河北省自然科学基金资助项目(B2018201224);河北省高等学校科技研究指导项目(ZC2016148);保定学院转型发展研究基金资助项目(2015Z06) 第一作者:高兰(1982—),女,河北唐县人,保定学院副教授,河北大学在读博士,主要从事环境与食品分析方向研究.E-mail:bdxygl@163.com 通信作者:刘芃岩(1964—),女,河北蠡县人,河北大学教授,博士生导师,主要从事环境中典型污染物的降解与迁移转化以及食品污染检测方法研究.E-mail:hbupyliu@163.com第1期高兰等:氧化锌对十溴联苯醚热解的污染控制机理分析At this time, the relative content of hexabromo to heptabromo- dioxins was lower, and the relative content of hexabromobenzene to pentabromobenzene was the highest. Combined with Arrhenius formula calculation, soft and hard acid-base theory and XRD product analysis of pyrolysis residue, the mixed pyrolysis mechanism of BDE-209 and zinc oxide was deeply discussed, which provided a theoretical basis for pollution prevention and control of waste printed circuit boards in heat treatment.
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