A theoretical investigation on the thermal decomposition of pyridine and the effect of H2O on the formation of NOx precursors

doi:10.1007/s11705-020-2024-8

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (5) : 1217-1228 https://doi.org/10.1007/s11705-020-2024-8

RESEARCH ARTICLE

A theoretical investigation on the thermal decomposition of pyridine and the effect of H₂O on the formation of NO_x precursors

Ji Liu, Xinrui Fan, Wei Zhao, Shi-guan Yang, Wenluan Xie, 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

Pyridine is one of the main nitrogen-containing compounds in coal, and its pyrolytic mechanism to generate NO_x precursors (mainly NH₃ and HCN) remains unclear. In this work, the possible pathways for the pyrolysis of pyridine to form HCN and/or NH₃ were investigated by the density functional theory method, and the effects of H₂O on pyridine pyrolysis were also investigated. The results show that there are two possible reactions for the initial pyridine pyrolysis, i.e., internal hydrogen transfer and C–H bond homolysis, and that internal hydrogen transfer is more favorable. Nine possible reaction pathways following internal hydrogen transfer are obtained and analyzed. Among these pathways, pyridine prefers to produce HCN instead of NH₃. The existence of H₂O has significant effects on the decomposition of pyridine, as it participates in pyridine pyrolysis to form NH₃ rather than HCN as the major product.

Keywords coal pyridine pyrolysis mechanism NO_x precursors DFT

Corresponding Author(s): Qiang Lu

Just Accepted Date: 20 January 2021 Online First Date: 10 March 2021 Issue Date: 30 August 2021

Cite this article:

Ji Liu,Xinrui Fan,Wei Zhao, et al. A theoretical investigation on the thermal decomposition of pyridine and the effect of H₂O on the formation of NO_x precursors[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1217-1228.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-2024-8
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I5/1217

Fig.1 Possible initial reactions of pyridine pyrolysis.

Fig.2 Energy profiles for pyridine pyrolysis following Reaction-a.

Fig.3 Energy profiles for pyridine pyrolysis following Reaction-b and Reaction-c.

Fig.4 Energy profiles for pyridine pyrolysis following Reaction-d and Reaction-e.

Fig.5 Initial reaction mechanism based on the interaction of pyridine and H₂O.

Fig.6 Energy profiles for pyridine pyrolysis interacting with H₂O following reaction N-OH-H-C₁.

Fig.7 Energy profiles for pyridine pyrolysis interacting with H₂O following reaction ortho-OH-H-N.

Fig.8 Energy profiles for pyridine pyrolysis interacting with H₂O following reaction ortho-OH-H-C₂.

Fig.9 Energy profiles for pyridine pyrolysis interacting with H₂O following reactions meta-OH-H-C₁ and meta-OH-H-C₃.

Tab.1 Comparison of the calculated pyridine pyrolysis pathways and products

Tab.2 Comparison of calculated pyridine pyrolysis pathways and products in the presence of H₂O

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