Experimental and kinetic study on the low-temperature oxidation of pyridine as a representative of fuel-N compounds

Ling Nan Wu; Zhen Yu Tian; Jun Jie Weng; Dan Yu; Yue Xi Liu; Dong Xu Tian; Chuang Chuang Cao; Jia Biao Zou; Yan Zhang; Jiu Zhong Yang

doi:10.1016/j.combustflame.2019.01.028

Experimental and kinetic study on the low-temperature oxidation of pyridine as a representative of fuel-N compounds

Ling Nan Wu, Zhen Yu Tian^*, Jun Jie Weng, Dan Yu, Yue Xi Liu, Dong Xu Tian, Chuang Chuang Cao, Jia Biao Zou, Yan Zhang, Jiu Zhong Yang

^*Corresponding author for this work

Clean Combustion Research Center

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

Abstract

The low-temperature oxidation (LTO) of pyridine was studied in a jet-stirred reactor over the temperature range of 700–1000 K at atmospheric pressure and equivalence ratio of 2.0. Mole fraction profiles of the reaction products were obtained based on molecular beam mass spectrometry and tunable vacuum ultraviolet synchrotron photoionization techniques. Hydrogen peroxide, methanamine, acetylenamine, ethenamine, acetaldimine, ethylamine, allyamine, and methylformamide were newly identified compared with previous studies of pyridine flame and pyrolysis. HCN was found to be the dominant N-containing species of pyridine LTO. Pyrrole, acrylonitrile, acetonitrile, and ammonia were also found at the same level of N₂O and NO. Based on the new measurements and updated rate constants of several reactions including the H-abstractions of pyridine as well as the oxidation of ortho-pyridyl using density functional theory calculations, a new pyridine LTO kinetic model consisting of 588 species and 3516 reactions was developed with a reasonable agreement with the experimental results. In general, the predictions of the predominant species have been improved compared with the existing model. Rate-of-production analysis indicates that pyridine mainly consumes via C₅H₅N→C₅H₄N→C₅H₄NO₂→HCN+CO+CH₂CHC˙O, and C₅H₅N→C₅H₅NO→C₂H₂+HCN+CH₂CO. Sensitivity analysis shows that C₅H₄N+O₂=>C₅H₄NO₂, and C₅H₅N+OH[dbnd]C₅H₄N+H₂O have significant promoting effect on pyridine consumption, while the reverse of C₅H₄N+HO₂[dbnd]C₅H₄NO+OH has strong inhibiting effect. The results will enrich the understanding of pyridine low-temperature oxidation mechanism, which can be applied to the fields of coal pre-treatment, staged combustion and mild combustion.

Original language	English (US)
Pages (from-to)	394-404
Number of pages	11
Journal	Combustion and Flame
Volume	202
DOIs	https://doi.org/10.1016/j.combustflame.2019.01.028
State	Published - Apr 2019

Bibliographical note

Funding Information:
The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168), the Ministry of Science and Technology of China (2017YFA0402800) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work.

Funding Information:
The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168 ), the Ministry of Science and Technology of China ( 2017YFA0402800 ) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work.

Publisher Copyright:
© 2019 The Combustion Institute

Keywords

Intermediates
Kinetic modeling
Low-temperature oxidation
Nitrogen chemistry
Pyridine

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Fuel Technology
Energy Engineering and Power Technology
General Physics and Astronomy

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10.1016/j.combustflame.2019.01.028

Cite this

@article{1222dca66e34482d99567c6b97894f4f,

title = "Experimental and kinetic study on the low-temperature oxidation of pyridine as a representative of fuel-N compounds",

abstract = "The low-temperature oxidation (LTO) of pyridine was studied in a jet-stirred reactor over the temperature range of 700–1000 K at atmospheric pressure and equivalence ratio of 2.0. Mole fraction profiles of the reaction products were obtained based on molecular beam mass spectrometry and tunable vacuum ultraviolet synchrotron photoionization techniques. Hydrogen peroxide, methanamine, acetylenamine, ethenamine, acetaldimine, ethylamine, allyamine, and methylformamide were newly identified compared with previous studies of pyridine flame and pyrolysis. HCN was found to be the dominant N-containing species of pyridine LTO. Pyrrole, acrylonitrile, acetonitrile, and ammonia were also found at the same level of N2O and NO. Based on the new measurements and updated rate constants of several reactions including the H-abstractions of pyridine as well as the oxidation of ortho-pyridyl using density functional theory calculations, a new pyridine LTO kinetic model consisting of 588 species and 3516 reactions was developed with a reasonable agreement with the experimental results. In general, the predictions of the predominant species have been improved compared with the existing model. Rate-of-production analysis indicates that pyridine mainly consumes via C5H5N→C5H4N→C5H4NO2→HCN+CO+CH2CHC˙O, and C5H5N→C5H5NO→C2H2+HCN+CH2CO. Sensitivity analysis shows that C5H4N+O2=>C5H4NO2, and C5H5N+OH[dbnd]C5H4N+H2O have significant promoting effect on pyridine consumption, while the reverse of C5H4N+HO2[dbnd]C5H4NO+OH has strong inhibiting effect. The results will enrich the understanding of pyridine low-temperature oxidation mechanism, which can be applied to the fields of coal pre-treatment, staged combustion and mild combustion.",

keywords = "Intermediates, Kinetic modeling, Low-temperature oxidation, Nitrogen chemistry, Pyridine",

author = "Wu, {Ling Nan} and Tian, {Zhen Yu} and Weng, {Jun Jie} and Dan Yu and Liu, {Yue Xi} and Tian, {Dong Xu} and Cao, {Chuang Chuang} and Zou, {Jia Biao} and Yan Zhang and Yang, {Jiu Zhong}",

note = "Funding Information: The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168), the Ministry of Science and Technology of China (2017YFA0402800) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work. Funding Information: The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168 ), the Ministry of Science and Technology of China ( 2017YFA0402800 ) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work. Publisher Copyright: {\textcopyright} 2019 The Combustion Institute",

year = "2019",

month = apr,

doi = "10.1016/j.combustflame.2019.01.028",

language = "English (US)",

volume = "202",

pages = "394--404",

journal = "Combustion and Flame",

issn = "0010-2180",

publisher = "Elsevier",

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TY - JOUR

T1 - Experimental and kinetic study on the low-temperature oxidation of pyridine as a representative of fuel-N compounds

AU - Wu, Ling Nan

AU - Tian, Zhen Yu

AU - Weng, Jun Jie

AU - Yu, Dan

AU - Liu, Yue Xi

AU - Tian, Dong Xu

AU - Cao, Chuang Chuang

AU - Zou, Jia Biao

AU - Zhang, Yan

AU - Yang, Jiu Zhong

N1 - Funding Information: The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168), the Ministry of Science and Technology of China (2017YFA0402800) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work. Funding Information: The authors are grateful for the financial support from National Natural Science Foundation of China (No. 91541102/51476168 ), the Ministry of Science and Technology of China ( 2017YFA0402800 ) and Recruitment Program of Global Youth Experts. The authors thank the mechanism checker tool provided by Lawrence Livermore National Laboratory. The authors are very grateful for the kind help from Profs. Maria U. Alzueta and Peter Glarborg for their help in the modeling part of this work. Publisher Copyright: © 2019 The Combustion Institute

PY - 2019/4

Y1 - 2019/4

N2 - The low-temperature oxidation (LTO) of pyridine was studied in a jet-stirred reactor over the temperature range of 700–1000 K at atmospheric pressure and equivalence ratio of 2.0. Mole fraction profiles of the reaction products were obtained based on molecular beam mass spectrometry and tunable vacuum ultraviolet synchrotron photoionization techniques. Hydrogen peroxide, methanamine, acetylenamine, ethenamine, acetaldimine, ethylamine, allyamine, and methylformamide were newly identified compared with previous studies of pyridine flame and pyrolysis. HCN was found to be the dominant N-containing species of pyridine LTO. Pyrrole, acrylonitrile, acetonitrile, and ammonia were also found at the same level of N2O and NO. Based on the new measurements and updated rate constants of several reactions including the H-abstractions of pyridine as well as the oxidation of ortho-pyridyl using density functional theory calculations, a new pyridine LTO kinetic model consisting of 588 species and 3516 reactions was developed with a reasonable agreement with the experimental results. In general, the predictions of the predominant species have been improved compared with the existing model. Rate-of-production analysis indicates that pyridine mainly consumes via C5H5N→C5H4N→C5H4NO2→HCN+CO+CH2CHC˙O, and C5H5N→C5H5NO→C2H2+HCN+CH2CO. Sensitivity analysis shows that C5H4N+O2=>C5H4NO2, and C5H5N+OH[dbnd]C5H4N+H2O have significant promoting effect on pyridine consumption, while the reverse of C5H4N+HO2[dbnd]C5H4NO+OH has strong inhibiting effect. The results will enrich the understanding of pyridine low-temperature oxidation mechanism, which can be applied to the fields of coal pre-treatment, staged combustion and mild combustion.

AB - The low-temperature oxidation (LTO) of pyridine was studied in a jet-stirred reactor over the temperature range of 700–1000 K at atmospheric pressure and equivalence ratio of 2.0. Mole fraction profiles of the reaction products were obtained based on molecular beam mass spectrometry and tunable vacuum ultraviolet synchrotron photoionization techniques. Hydrogen peroxide, methanamine, acetylenamine, ethenamine, acetaldimine, ethylamine, allyamine, and methylformamide were newly identified compared with previous studies of pyridine flame and pyrolysis. HCN was found to be the dominant N-containing species of pyridine LTO. Pyrrole, acrylonitrile, acetonitrile, and ammonia were also found at the same level of N2O and NO. Based on the new measurements and updated rate constants of several reactions including the H-abstractions of pyridine as well as the oxidation of ortho-pyridyl using density functional theory calculations, a new pyridine LTO kinetic model consisting of 588 species and 3516 reactions was developed with a reasonable agreement with the experimental results. In general, the predictions of the predominant species have been improved compared with the existing model. Rate-of-production analysis indicates that pyridine mainly consumes via C5H5N→C5H4N→C5H4NO2→HCN+CO+CH2CHC˙O, and C5H5N→C5H5NO→C2H2+HCN+CH2CO. Sensitivity analysis shows that C5H4N+O2=>C5H4NO2, and C5H5N+OH[dbnd]C5H4N+H2O have significant promoting effect on pyridine consumption, while the reverse of C5H4N+HO2[dbnd]C5H4NO+OH has strong inhibiting effect. The results will enrich the understanding of pyridine low-temperature oxidation mechanism, which can be applied to the fields of coal pre-treatment, staged combustion and mild combustion.

KW - Intermediates

KW - Kinetic modeling

KW - Low-temperature oxidation

KW - Nitrogen chemistry

KW - Pyridine

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U2 - 10.1016/j.combustflame.2019.01.028

DO - 10.1016/j.combustflame.2019.01.028

M3 - Article

AN - SCOPUS:85061038970

SN - 0010-2180

VL - 202

SP - 394

EP - 404

JO - Combustion and Flame

JF - Combustion and Flame

ER -

Experimental and kinetic study on the low-temperature oxidation of pyridine as a representative of fuel-N compounds

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

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