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Mechanism and kinetic analysis of PCDD/Fs formation from aliphatic hydrocarbons (C2H2, C2H4, C3H6, C4H8) precursors

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Abstract

Density functional theory calculations were performed to gain insight into the mechanism and kinetic studies of homogeneous gas-phase formation of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) via aliphatic hydrocarbons (C2H2, C2H4, C3H6 and C4H8). The calculated results demonstrated that the intra-annular elimination of H is the rate-determining step throughout the reaction chain; the presence of ortho-Cl increases the abstraction barrier of arene H and decreases the reactivity of the molecule. The phenoxy radicals undergoes dimerization via carbon–carbon or carbon–oxygen coupling to form PCDD/Fs and the two coupling pathways are competitive. Our work indicates that aliphatic hydrocarbons are less reactive precursors in PCDD/F formation compared with chlorophenoxy radicals and phenoxy radicals among primary precursors of PCDD/Fs. The results presented here could be used to evaluate the contribution of aliphatic hydrocarbons acting as precursors to PCDD/Fs formation.

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Acknowledgments

This work was supported by Beijing Natural Science Foundation (2182066), Natural Science Foundation of Hebei Province of China (B2018502067).

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Authors and Affiliations

  1. School of Energy and Power Engineering, North China Electric Power University, Baoding, 071003, China

    Zhengyang Gao, Yao Sun, Minghui Li & Wentao Han

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  1. Zhengyang Gao
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  2. Yao Sun
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  3. Minghui Li
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  4. Wentao Han
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Correspondence to Yao Sun.

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Gao, Z., Sun, Y., Li, M. et al. Mechanism and kinetic analysis of PCDD/Fs formation from aliphatic hydrocarbons (C2H2, C2H4, C3H6, C4H8) precursors. J Mol Model 24, 267 (2018). https://doi.org/10.1007/s00894-018-3807-4

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