TY - JOUR
T1 - Co-oxidation of methane (CH 4 ) and carbon disulfide (CS 2
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
Y1 - 2019
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.
KW - Co-oxidation of CS and CH
KW - Enhanced ignition of CH by CS
KW - Jet-stirred reactor
KW - Kinetic model
KW - Sulfur-bearing radicals
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U2 - 10.1016/j.proci.2018.08.011
DO - 10.1016/j.proci.2018.08.011
M3 - Article
AN - SCOPUS:85052486317
SN - 1540-7489
VL - 37
SP - 677
EP - 685
JO - Proceedings of the Combustion Institute
JF - Proceedings of the Combustion Institute
IS - 1
ER -