RESEARCH ARTICLE

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

  • Ji Liu 1,2 ,
  • Shuang-Wei Yang 1 ,
  • Wei Zhao 1 ,
  • Yu-Long Wu 3,4 ,
  • Bin Hu 1 ,
  • Si-Han Hu 1 ,
  • Shan-Wei Ma 1 ,
  • Qiang Lu , 1
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  • 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
qianglu@mail.ustc.edu.cn, qlu@ncepu.edu.cn

Received date: 21 Apr 2022

Accepted date: 08 Jun 2022

Published date: 15 Mar 2023

Copyright

2022 Higher Education Press

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.

Cite this article

Ji Liu , Shuang-Wei Yang , Wei Zhao , Yu-Long Wu , Bin Hu , Si-Han Hu , Shan-Wei Ma , Qiang Lu . Theoretical study on the mechanism of sulfur migration to gas in the pyrolysis of benzothiophene[J]. Frontiers of Chemical Science and Engineering, 2023 , 17(3) : 334 -346 . DOI: 10.1007/s11705-022-2209-4

Acknowledgments

The authors thank the National Natural Science Foundation of China (Grant Nos. 52006069, 51922040, 51821004), Fundamental Research Funds for the Central Universities (Grant No. 2020MS020), and Hunan Science and Technology Planning Project (Grant No. 2020RC5008) for financial support.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2209-4 and is accessible for authorized users.
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