A proposed reaction mechanism for the selective oxidation of methane with nitrous oxide over Co-ZSM-5 catalyst forming synthesis gas (CO + H2)

Naseer A. Khan, Eric M. Kennedy, Bogdan Z. Dlugogorski, Adesoji A. Adesina, Michael Stockenhuber

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Probable reaction intermediates and mechanistic steps involved for the selective oxidation of methane (CH4) with nitrous oxide (N2O) forming synthesis gas (CO + H2) over Co-ZSM-5 was examined. To assess the reaction kinetics reactions were conducted within a temperature range of 300 °C–550 °C and at atmospheric pressure, and the composition of reactant feed (N2O/CH4) was varied between three fixed ratios (5, 3, and 1). TPD, XRD, TEM and FT-IR techniques were used for catalyst characterization and mechanistic studies. It was found, that H2 selectivity is higher for feeds with lower N2O concentration. Furthermore, CO formation commences at lower temperatures in comparison to H2 gas which is a result of the formation of methanol (CH3OH) and carbon oxides (CO and CO2) at low CH4 conversions. Based on the reaction conditions, the literature proposes direct and an indirect mechanistic route for synthesis gas formation. Our catalytic study suggests a direct route for the synthesis gas formation; i.e. H2 gas is formed by the decomposition of intermediate species (methoxy and CH2O). This is supported by spectroscopic investigation. Under favourable reaction conditions and over the Co-ZSM-5 catalyst, N2O first oxidizes CH4 to CH3OH, an active reaction intermediate, which then subsequently is converted into (formaldehyde) CH2O and H2. CH2O is highly reactive and decomposes into CO and H2.

Original languageEnglish
Pages (from-to)13133-13144
Number of pages12
JournalInternational Journal of Hydrogen Energy
Volume43
Issue number29
DOIs
Publication statusPublished - 19 Jun 2018
Externally publishedYes

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synthesis gas
nitrous oxides
Synthesis gas
Reaction intermediates
Methane
methane
catalysts
Oxidation
oxidation
Catalysts
Oxides
reaction intermediates
routes
Temperature programmed desorption
Gases
Formaldehyde
Reaction kinetics
Atmospheric pressure
Methanol
formaldehyde

Cite this

Khan, Naseer A. ; Kennedy, Eric M. ; Dlugogorski, Bogdan Z. ; Adesina, Adesoji A. ; Stockenhuber, Michael. / A proposed reaction mechanism for the selective oxidation of methane with nitrous oxide over Co-ZSM-5 catalyst forming synthesis gas (CO + H2). In: International Journal of Hydrogen Energy. 2018 ; Vol. 43, No. 29. pp. 13133-13144.
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abstract = "Probable reaction intermediates and mechanistic steps involved for the selective oxidation of methane (CH4) with nitrous oxide (N2O) forming synthesis gas (CO + H2) over Co-ZSM-5 was examined. To assess the reaction kinetics reactions were conducted within a temperature range of 300 °C–550 °C and at atmospheric pressure, and the composition of reactant feed (N2O/CH4) was varied between three fixed ratios (5, 3, and 1). TPD, XRD, TEM and FT-IR techniques were used for catalyst characterization and mechanistic studies. It was found, that H2 selectivity is higher for feeds with lower N2O concentration. Furthermore, CO formation commences at lower temperatures in comparison to H2 gas which is a result of the formation of methanol (CH3OH) and carbon oxides (CO and CO2) at low CH4 conversions. Based on the reaction conditions, the literature proposes direct and an indirect mechanistic route for synthesis gas formation. Our catalytic study suggests a direct route for the synthesis gas formation; i.e. H2 gas is formed by the decomposition of intermediate species (methoxy and CH2O). This is supported by spectroscopic investigation. Under favourable reaction conditions and over the Co-ZSM-5 catalyst, N2O first oxidizes CH4 to CH3OH, an active reaction intermediate, which then subsequently is converted into (formaldehyde) CH2O and H2. CH2O is highly reactive and decomposes into CO and H2.",
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A proposed reaction mechanism for the selective oxidation of methane with nitrous oxide over Co-ZSM-5 catalyst forming synthesis gas (CO + H2). / Khan, Naseer A.; Kennedy, Eric M.; Dlugogorski, Bogdan Z.; Adesina, Adesoji A.; Stockenhuber, Michael.

In: International Journal of Hydrogen Energy, Vol. 43, No. 29, 19.06.2018, p. 13133-13144.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - A proposed reaction mechanism for the selective oxidation of methane with nitrous oxide over Co-ZSM-5 catalyst forming synthesis gas (CO + H2)

AU - Khan, Naseer A.

AU - Kennedy, Eric M.

AU - Dlugogorski, Bogdan Z.

AU - Adesina, Adesoji A.

AU - Stockenhuber, Michael

PY - 2018/6/19

Y1 - 2018/6/19

N2 - Probable reaction intermediates and mechanistic steps involved for the selective oxidation of methane (CH4) with nitrous oxide (N2O) forming synthesis gas (CO + H2) over Co-ZSM-5 was examined. To assess the reaction kinetics reactions were conducted within a temperature range of 300 °C–550 °C and at atmospheric pressure, and the composition of reactant feed (N2O/CH4) was varied between three fixed ratios (5, 3, and 1). TPD, XRD, TEM and FT-IR techniques were used for catalyst characterization and mechanistic studies. It was found, that H2 selectivity is higher for feeds with lower N2O concentration. Furthermore, CO formation commences at lower temperatures in comparison to H2 gas which is a result of the formation of methanol (CH3OH) and carbon oxides (CO and CO2) at low CH4 conversions. Based on the reaction conditions, the literature proposes direct and an indirect mechanistic route for synthesis gas formation. Our catalytic study suggests a direct route for the synthesis gas formation; i.e. H2 gas is formed by the decomposition of intermediate species (methoxy and CH2O). This is supported by spectroscopic investigation. Under favourable reaction conditions and over the Co-ZSM-5 catalyst, N2O first oxidizes CH4 to CH3OH, an active reaction intermediate, which then subsequently is converted into (formaldehyde) CH2O and H2. CH2O is highly reactive and decomposes into CO and H2.

AB - Probable reaction intermediates and mechanistic steps involved for the selective oxidation of methane (CH4) with nitrous oxide (N2O) forming synthesis gas (CO + H2) over Co-ZSM-5 was examined. To assess the reaction kinetics reactions were conducted within a temperature range of 300 °C–550 °C and at atmospheric pressure, and the composition of reactant feed (N2O/CH4) was varied between three fixed ratios (5, 3, and 1). TPD, XRD, TEM and FT-IR techniques were used for catalyst characterization and mechanistic studies. It was found, that H2 selectivity is higher for feeds with lower N2O concentration. Furthermore, CO formation commences at lower temperatures in comparison to H2 gas which is a result of the formation of methanol (CH3OH) and carbon oxides (CO and CO2) at low CH4 conversions. Based on the reaction conditions, the literature proposes direct and an indirect mechanistic route for synthesis gas formation. Our catalytic study suggests a direct route for the synthesis gas formation; i.e. H2 gas is formed by the decomposition of intermediate species (methoxy and CH2O). This is supported by spectroscopic investigation. Under favourable reaction conditions and over the Co-ZSM-5 catalyst, N2O first oxidizes CH4 to CH3OH, an active reaction intermediate, which then subsequently is converted into (formaldehyde) CH2O and H2. CH2O is highly reactive and decomposes into CO and H2.

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KW - Co-ZSM-5

KW - NO

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DO - 10.1016/j.ijhydene.2018.05.026

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JF - International Journal of Hydrogen Energy

SN - 0360-3199

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