Mechanism insight into the formation of H<sub>2</sub>S from thiophene pyrolysis: A theoretical study

doi:10.1007/s11783-021-1404-8

Front. Environ. Sci. Eng.

2021, Vol. 15

Issue (6) : 120 https://doi.org/10.1007/s11783-021-1404-8

RESEARCH ARTICLE

Mechanism insight into the formation of H₂S from thiophene pyrolysis: A theoretical study

Shiguan Yang, Xinrui Fan, Ji Liu, Wei Zhao, Bin Hu, Qiang Lu(

)

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

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Abstract

• Possible formation pathways of H₂S were revealed in thiophene pyrolysis.

• The influence of hydrogen radicals on thiophene pyrolysis was examined.

• Thiophene decomposition starts with hydrogen transfer between adjacent C atoms.

• The presence of hydrogen radicals significantly promotes the formation of H₂S.

Pyrolysis is an efficient and economical method for the utilization of waste rubber, but the high sulfur content limits its industrial application. Currently, the migration and transformation of the element S during pyrolysis of waste rubber is far from well known. In this work, a density functional theory (DFT) method was employed to explore the possible formation pathways of H₂S and its precursors (radicals HS· and S·) during the pyrolysis of thiophene, which is an important primary pyrolytic product of rubber. In particular, the influence of reactive hydrogen radicals was carefully investigated in the thiophene pyrolysis process. The calculation results indicate that the decomposition of thiophene tends to be initiated by hydrogen transfer between adjacent carbon atoms, which needs to overcome an energy barrier of 312.4 kJ/mol. The optimal pathway to generate H₂S in thiophene pyrolysis involves initial H migration and S-C bond cleavage, with an overall energy barrier of 525.8 kJ/mol. In addition, a thiol intermediate that bears unsaturated C-C bonds is essential for thiophene pyrolysis to generate H₂S, which exists in multiple critical reaction pathways. Moreover, the presence of hydrogen radicals significantly changes the decomposition patterns and reduces the energy barriers for thiophene decomposition, thus promoting the formation of H₂S. The current work on H₂S formation from thiophene can provide some theoretical support to explore clean utilization technologies for waste rubber.

Keywords Density functional theory Waste rubber Thiophene H₂S Pyrolysis

Corresponding Author(s): Qiang Lu

Issue Date: 02 March 2021

Cite this article:

Shiguan Yang,Xinrui Fan,Ji Liu, et al. Mechanism insight into the formation of H₂S from thiophene pyrolysis: A theoretical study[J]. Front. Environ. Sci. Eng., 2021, 15(6): 120.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1404-8
https://academic.hep.com.cn/fese/EN/Y2021/V15/I6/120

Fig.1 Space structure diagram of thiophene.

Fig.2 Three initial reaction modes and their energy barriers.

Fig.3 Paths a-1, a-2, a-3 and a-4 with their primary intermediates and transition state structures.

Fig.4 Paths a-5, a-6 and a-7 with their primary intermediates and transition state structures.

Fig.5 Paths b-1 and b-2 with their primary intermediates and transition state structures.

Fig.6 Paths b-3, b-4 and b-5 with their primary intermediates and transition state structures

Fig.7 Paths b-6 and b-7 with their primary intermediates and transition state structures.

Fig.8 Paths c-1, c-2, c-3 and c-4 with their primary intermediates and transition state structures.

Fig.9 Two models of the electrophilic attraction of the H· radical for thiophene.

Fig.10 Paths d-1, d-2 and d-3 with their primary intermediates and transition state structures.

Fig.11 Paths e-1, e-2 and e-3 with their primary intermediates and transition state structures.

Fig.12 Paths e-4, e-5 and e-6 with their primary intermediates and transition state structures.

Tab.1 Comparison of the optimal pathways for thiophene pyrolysis

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