Co-oxidation of methane (CH                         4                         ) and carbon disulfide (CS                         2

Zhe Zeng; Bogdan Z. Dlugogorski; Ibukun Oluwoye; Mohammednoor Altarawneh

doi:10.1016/j.proci.2018.08.011

Co-oxidation of methane (CH ₄ ) and carbon disulfide (CS ₂

Zhe Zeng
, Bogdan Z. Dlugogorski
, Ibukun Oluwoye
, Mohammednoor Altarawneh

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

10 Citations (Scopus)

Abstract

Sulfur-containing species persist as important impurities in fossil fuels, affecting the combustion process of constituent hydrocarbons. This contribution reports the promotion effects of carbon disulfide (CS ₂ ) on oxidation of methane (CH ₄ ), with experiments conducted in a jet-stirred reactor (JSR), and explains the experimental findings from comprehensive kinetic modelling of CH ₄ /CS ₂ /O ₂ systems. This includes neat oxidation of CH ₄ /O ₂ and CS ₂ /O ₂ under stoichiometric conditions, as compared with co-oxidation of CH ₄ /CS ₂ /O ₂ , containing different measures of CS ₂ . Addition of small amounts of CS ₂ (50?ppm and 100?ppm) enhances the oxidation of CH ₄ (500?ppm) as characterised by a lower onset temperature (1300?K versus 1200?K and 1060?K). In contrast, the presence of CH ₄ delays the process of CS ₂ oxidation. Considering the similarity in the core charge of O and S, we propose the reactivity of S ₂ , SO and in particular S towards CH ₄ to be responsible for the observed behaviours, in addition to an important effect of O radicals generated in oxidation of CS ₂ on engendering the oxidation of CH ₄ . As reported in the literature, in analogy to O ₂ and O which oxidise CH ₄ into CO ₂ , the S/S ₂ /SO could also 'sulfurdise' CH ₄ into CS ₂ or COS under oxygen-lean conditions. Quantum chemistry calculations of the CH ₄ ?+?O, CH ₄ ?+?S, CH ₄ ?+?S ₂ , CH ₄ ?+?SO and CH ₄ ?+?O ₂ reactions further reveal the reactivity of O, O ₂ , S, S ₂ and SO towards H abstraction from CH ₄ . The sensitivity analysis of the kinetic modelling of the proposed co-oxidation reactions indicates that, the radicals formed during the CS ₂ conversion process promote the oxidation of CH ₄ at lower temperatures. However, the consumption of radicals in the CH ₄ oxidation also inhibits the decomposition of CS ₂ as observed in the experiments.

Original language	English
Pages (from-to)	677-685
Number of pages	9
Journal	Proceedings of the Combustion Institute
Volume	37
Issue number	1
DOIs	https://doi.org/10.1016/j.proci.2018.08.011
Publication status	Published - 2019
Externally published	Yes

Keywords

Co-oxidation of CS and CH
Enhanced ignition of CH by CS
Jet-stirred reactor
Kinetic model
Sulfur-bearing radicals

ASJC Scopus subject areas

General Chemical Engineering
Mechanical Engineering
Physical and Theoretical Chemistry

Access to Document

10.1016/j.proci.2018.08.011

Cite this

Co-oxidation of methane (CH ₄ ) and carbon disulfide (CS ₂ . / Zeng, Zhe; Dlugogorski, Bogdan Z.; Oluwoye, Ibukun et al.
In: Proceedings of the Combustion Institute, Vol. 37, No. 1, 2019, p. 677-685.

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

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title = " Co-oxidation of methane (CH 4 ) and carbon disulfide (CS 2 ",

abstract = " Sulfur-containing species persist as important impurities in fossil fuels, affecting the combustion process of constituent hydrocarbons. This contribution reports the promotion effects of carbon disulfide (CS 2 ) on oxidation of methane (CH 4 ), with experiments conducted in a jet-stirred reactor (JSR), and explains the experimental findings from comprehensive kinetic modelling of CH 4 /CS 2 /O 2 systems. This includes neat oxidation of CH 4 /O 2 and CS 2 /O 2 under stoichiometric conditions, as compared with co-oxidation of CH 4 /CS 2 /O 2 , containing different measures of CS 2 . Addition of small amounts of CS 2 (50?ppm and 100?ppm) enhances the oxidation of CH 4 (500?ppm) as characterised by a lower onset temperature (1300?K versus 1200?K and 1060?K). In contrast, the presence of CH 4 delays the process of CS 2 oxidation. Considering the similarity in the core charge of O and S, we propose the reactivity of S 2 , SO and in particular S towards CH 4 to be responsible for the observed behaviours, in addition to an important effect of O radicals generated in oxidation of CS 2 on engendering the oxidation of CH 4 . As reported in the literature, in analogy to O 2 and O which oxidise CH 4 into CO 2 , the S/S 2 /SO could also 'sulfurdise' CH 4 into CS 2 or COS under oxygen-lean conditions. Quantum chemistry calculations of the CH 4 ?+?O, CH 4 ?+?S, CH 4 ?+?S 2 , CH 4 ?+?SO and CH 4 ?+?O 2 reactions further reveal the reactivity of O, O 2 , S, S 2 and SO towards H abstraction from CH 4 . The sensitivity analysis of the kinetic modelling of the proposed co-oxidation reactions indicates that, the radicals formed during the CS 2 conversion process promote the oxidation of CH 4 at lower temperatures. However, the consumption of radicals in the CH 4 oxidation also inhibits the decomposition of CS 2 as observed in the experiments. ",

keywords = "Co-oxidation of CS and CH, Enhanced ignition of CH by CS, Jet-stirred reactor, Kinetic model, Sulfur-bearing radicals",

author = "Zhe Zeng and Dlugogorski, \{Bogdan Z.\} and Ibukun Oluwoye and Mohammednoor Altarawneh",

note = "Funding Information: This study has been supported by funds from the Australian Research Council (ARC) and National Computational Infrastructure (NCI) Australia. We express our appreciation to Dr Olivier Herbinet and Professor Fr{\'e}d{\'e}rique Battin-Leclerc for sharing the design of their JSR. We also thank Andrzej Pekalski of Shell Global Solutions (UK) for suggesting this topic to us. ",

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AU - Zeng, Zhe

AU - Dlugogorski, Bogdan Z.

AU - Oluwoye, Ibukun

AU - Altarawneh, Mohammednoor

N1 - Funding Information: This study has been supported by funds from the Australian Research Council (ARC) and National Computational Infrastructure (NCI) Australia. We express our appreciation to Dr Olivier Herbinet and Professor Frédérique Battin-Leclerc for sharing the design of their JSR. We also thank Andrzej Pekalski of Shell Global Solutions (UK) for suggesting this topic to us.

PY - 2019

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N2 - Sulfur-containing species persist as important impurities in fossil fuels, affecting the combustion process of constituent hydrocarbons. This contribution reports the promotion effects of carbon disulfide (CS 2 ) on oxidation of methane (CH 4 ), with experiments conducted in a jet-stirred reactor (JSR), and explains the experimental findings from comprehensive kinetic modelling of CH 4 /CS 2 /O 2 systems. This includes neat oxidation of CH 4 /O 2 and CS 2 /O 2 under stoichiometric conditions, as compared with co-oxidation of CH 4 /CS 2 /O 2 , containing different measures of CS 2 . Addition of small amounts of CS 2 (50?ppm and 100?ppm) enhances the oxidation of CH 4 (500?ppm) as characterised by a lower onset temperature (1300?K versus 1200?K and 1060?K). In contrast, the presence of CH 4 delays the process of CS 2 oxidation. Considering the similarity in the core charge of O and S, we propose the reactivity of S 2 , SO and in particular S towards CH 4 to be responsible for the observed behaviours, in addition to an important effect of O radicals generated in oxidation of CS 2 on engendering the oxidation of CH 4 . As reported in the literature, in analogy to O 2 and O which oxidise CH 4 into CO 2 , the S/S 2 /SO could also 'sulfurdise' CH 4 into CS 2 or COS under oxygen-lean conditions. Quantum chemistry calculations of the CH 4 ?+?O, CH 4 ?+?S, CH 4 ?+?S 2 , CH 4 ?+?SO and CH 4 ?+?O 2 reactions further reveal the reactivity of O, O 2 , S, S 2 and SO towards H abstraction from CH 4 . The sensitivity analysis of the kinetic modelling of the proposed co-oxidation reactions indicates that, the radicals formed during the CS 2 conversion process promote the oxidation of CH 4 at lower temperatures. However, the consumption of radicals in the CH 4 oxidation also inhibits the decomposition of CS 2 as observed in the experiments.

AB - Sulfur-containing species persist as important impurities in fossil fuels, affecting the combustion process of constituent hydrocarbons. This contribution reports the promotion effects of carbon disulfide (CS 2 ) on oxidation of methane (CH 4 ), with experiments conducted in a jet-stirred reactor (JSR), and explains the experimental findings from comprehensive kinetic modelling of CH 4 /CS 2 /O 2 systems. This includes neat oxidation of CH 4 /O 2 and CS 2 /O 2 under stoichiometric conditions, as compared with co-oxidation of CH 4 /CS 2 /O 2 , containing different measures of CS 2 . Addition of small amounts of CS 2 (50?ppm and 100?ppm) enhances the oxidation of CH 4 (500?ppm) as characterised by a lower onset temperature (1300?K versus 1200?K and 1060?K). In contrast, the presence of CH 4 delays the process of CS 2 oxidation. Considering the similarity in the core charge of O and S, we propose the reactivity of S 2 , SO and in particular S towards CH 4 to be responsible for the observed behaviours, in addition to an important effect of O radicals generated in oxidation of CS 2 on engendering the oxidation of CH 4 . As reported in the literature, in analogy to O 2 and O which oxidise CH 4 into CO 2 , the S/S 2 /SO could also 'sulfurdise' CH 4 into CS 2 or COS under oxygen-lean conditions. Quantum chemistry calculations of the CH 4 ?+?O, CH 4 ?+?S, CH 4 ?+?S 2 , CH 4 ?+?SO and CH 4 ?+?O 2 reactions further reveal the reactivity of O, O 2 , S, S 2 and SO towards H abstraction from CH 4 . The sensitivity analysis of the kinetic modelling of the proposed co-oxidation reactions indicates that, the radicals formed during the CS 2 conversion process promote the oxidation of CH 4 at lower temperatures. However, the consumption of radicals in the CH 4 oxidation also inhibits the decomposition of CS 2 as observed in the experiments.

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KW - Enhanced ignition of CH by CS

KW - Jet-stirred reactor

KW - Kinetic model

KW - Sulfur-bearing radicals

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