Theoretical study on the mechanism of sulfur migration to gas in the pyrolysis of benzothiophene

doi:10.1007/s11705-022-2209-4

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (3) : 334-346 https://doi.org/10.1007/s11705-022-2209-4

RESEARCH ARTICLE

Theoretical study on the mechanism of sulfur migration to gas in the pyrolysis of benzothiophene

Ji Liu^1,², Shuang-Wei Yang¹, Wei Zhao¹, Yu-Long Wu^3,⁴, Bin Hu¹, Si-Han Hu¹, Shan-Wei Ma¹, Qiang Lu¹(

)

¹. National Engineering Research Center of New Energy Power Generation, North China Electric Power University, Beijing 102206, China
². Suzhou Institute of North China Electric Power University, Suzhou 215000, China
³. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China
⁴. School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi City 830046, China

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Abstract

The release and control of sulfur species in the pyrolysis of fossil fuels and solid wastes have attracted attention worldwide. Particularly, thiophene derivatives are important intermediates for the sulfur gas release from organic sulfur, but the underlying migration mechanisms remain unclear. Herein, the mechanism of sulfur migration during the release of sulfur-containing radicals in benzothiophene pyrolysis was explored through quantum chemistry modeling. The C₁-to-C₂ H-transfer has the lowest energy barrier of 269.9 kJ·mol^–1 and the highest rate constant at low temperatures, while the elevated temperature is beneficial for C−S bond homolysis. 2-Ethynylbenzenethiol is the key intermediate for the formation of S and SH radicals with the overall energy barriers of 408.0 and 498.7 kJ·mol^–1 in favorable pathways. The generation of CS radicals is relatively difficult because of the high energy barrier (551.8 kJ·mol^–1). However, it can be significantly promoted by high temperatures, where the rate constant exceeds that for S radical generation above 930 °C. Consequently, the strong competitiveness of S and SH radicals results in abundant H₂S during benzothiophene pyrolysis, and the high temperature is more beneficial for CS₂ generation from CS radicals. This study lays a foundation for elucidating sulfur migration mechanisms and furthering the development of pyrolysis techniques.

Keywords benzothiophene sulfur migration pyrolysis density functional theory

Corresponding Author(s): Qiang Lu

Online First Date: 12 December 2022 Issue Date: 17 March 2023

Cite this article:

Ji Liu,Shuang-Wei Yang,Wei Zhao, et al. Theoretical study on the mechanism of sulfur migration to gas in the pyrolysis of benzothiophene[J]. Front. Chem. Sci. Eng., 2023, 17(3): 334-346.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2209-4
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I3/334

Fig.1 (a) Optimized geometry, (b) LOL-π isosurface map and (c) LOL-π plane color map of benzothiophene.

Fig.2 (a) Energy barriers and (b) rate constants of the initial reaction steps in benzothiophene pyrolysis.

Fig.3 (a) The S radical formation pathways and (b) corresponding energy diagrams following the initial decomposition of Mode A.

Fig.4 (a) The S radical formation pathways and (b) corresponding energy diagrams following the initial decomposition of Modes B, C, D, and E.

Fig.5 (a) The SH radical formation pathways and (b) corresponding energy diagrams following the initial decomposition of Modes A and B.

Fig.6 (a) The SH radical formation pathways and (b) corresponding energy diagrams following the initial decomposition of Mode C.

Fig.7 (a) The SH radical formation pathways and (b) corresponding energy diagrams following the initial decomposition of Modes D and E.

Fig.8 (a) The CS radical formation pathways and (b) corresponding energy diagrams.

Fig.9 Dominant pathways and key intermediates for the formation of the sulfur-containing radicals.

Fig.10 (a) Rate constants of the rate-determining steps for intermediate a3-3i generation and (b) for the formation of sulfur-containing radicals in the range of 400?1100 °C.

Tab.1 Dominant pathways and rate-determining steps for the formation of the sulfur-containing radicals

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