苯为前驱物形成二噁英的反应机理

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Abstract Benzene was one of the important precursors for the formation of polychlorinated dibenzo-p-dioxins (PCDD/Fs) which widespreadly present in waste. The two stage gas-phase formation mechanisms of PCDD/Fs by benzene were studied by density functional theory (DFT) at the B3LYP/6-311+G (d, p) level, the corresponding potential barriers and reaction heats were calculated. The variational transition state theory (VTST) was used to calculate the rate constants of the elementary reactions in the 300~1300K temperature range. The chlorination process of benzene was the determining step of the whole synthesis process of PCDD/Fs with the highest barrier; Chlorophenol was more likely formed via the intramolecular dehydrogenation of chlorobenzene which attacked by HO· radicals; Ortho Cl can raise the extraction barrier of aromatic hydrocarbon H and reduce the molecular reactivity; competition mechanism existed in the formation of PCDD/Fs which was formed by phnoxy radicals via coupling of carbon-carbon or carbon-oxygen. The calculation results could be applied to evaluate the contribution of PCDD/Fs formed by benzene on the basis of total dioxin production.

Key words： density functional theory benzene polychlorinated dibenzo-p-dioxins reaction mechanism rate constants

Received: 11 June 2017

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	Articles by authors
	GAO Zheng-yang
	HAN Wen-tao
	DING Yi
	SUN Yao
	LI Ming-hui

Cite this article:

GAO Zheng-yang,HAN Wen-tao,DING Yi等. Reaction mechanism of dioxin formation with benzene as precursor[J]. CHINA ENVIRONMENTAL SCIENCECE, 2018, 38(1): 59-66.

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http://manu36.magtech.com.cn/Jweb_zghjkx/EN/ OR http://manu36.magtech.com.cn/Jweb_zghjkx/EN/Y2018/V38/I1/59

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