An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst

Suwardiyanto, Russell F Howe, Emma K Gibson, C Richard A Catlow, Ali Hameed, James McGregor, Paul Collier, Stewart F Parker, David Lennon

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Abstract

A ZSM-5 catalyst is examined in relation to the methanol-to-hydrocarbon (MTH) reaction as a function of reaction temperature and time-on-stream. The reaction profile is characterised using in-line mass spectrometry. Furthermore, the material contained within a catch-pot downstream from the reactor is analysed using gas chromatography-mass spectrometry. For a fixed methanol feed, reaction conditions are selected to define various stages of the reaction coordinate: (i) initial methanol adsorption at a sub-optimum reaction temperature (1 h at 200 °C); (ii) initial stages of reaction at an optimised reaction temperature (1 h at 350 °C); (iii) steady-state operation at an optimised reaction temperature (3 days at 350 °C); and (iv) accelerated ageing (3 days at 400 °C). Post-reaction, the catalyst samples are analysed ex situ by a combination of temperature-programmed oxidation (TPO) and spectroscopically by electron paramagnetic resonance (EPR), diffuse-reflectance infrared and inelastic neutron scattering (INS) spectroscopies. The TPO measurements provide an indication of the degree of 'coking' experienced by each sample. The EPR measurements detect aromatic radical cations. The IR and INS measurements reveal the presence of retained hydrocarbonaceous species, the nature of which are discussed in terms of the well-developed 'hydrocarbon pool' mechanism. This combination of experimental evidence, uniquely applied to this reaction system, establishes the importance of retained hydrocarbonaceous species in effecting the product distribution of this economically relevant reaction system.

Original languageEnglish
Pages (from-to)447-471
Number of pages25
JournalFaraday Discussions
Volume197
Early online date14 Feb 2017
DOIs
Publication statusPublished - 2017

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Hydrocarbons
Methanol
methyl alcohol
hydrocarbons
catalysts
Catalysts
Inelastic neutron scattering
Temperature
Mass spectrometry
Paramagnetic resonance
Oxidation
Coking
Gas chromatography
temperature
Cations
electron paramagnetic resonance
inelastic scattering
neutron scattering
mass spectroscopy
Aging of materials

Keywords

  • Journal Article

Cite this

Suwardiyanto, Howe, R. F., Gibson, E. K., Catlow, C. R. A., Hameed, A., McGregor, J., ... Lennon, D. (2017). An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst. Faraday Discussions, 197, 447-471. https://doi.org/10.1039/c6fd00195e

An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst. / Suwardiyanto, ; Howe, Russell F; Gibson, Emma K; Catlow, C Richard A; Hameed, Ali; McGregor, James; Collier, Paul; Parker, Stewart F; Lennon, David.

In: Faraday Discussions, Vol. 197, 2017, p. 447-471.

Research output: Contribution to journalArticle

Suwardiyanto, , Howe, RF, Gibson, EK, Catlow, CRA, Hameed, A, McGregor, J, Collier, P, Parker, SF & Lennon, D 2017, 'An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst', Faraday Discussions, vol. 197, pp. 447-471. https://doi.org/10.1039/c6fd00195e
Suwardiyanto, ; Howe, Russell F ; Gibson, Emma K ; Catlow, C Richard A ; Hameed, Ali ; McGregor, James ; Collier, Paul ; Parker, Stewart F ; Lennon, David. / An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst. In: Faraday Discussions. 2017 ; Vol. 197. pp. 447-471.
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N1 - Acknowledgements The UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (grants EP/I038748/1, EP/I019693/1, EP/K014706/1, EP/K014668/1, EP/K014854/1,EP/K014714/1 and EP/M013219/1). Project support from the EPSRC via grant EP/K503903/1 (University of Glasgow) is also acknowledged. The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. Johnson Matthey plc is thanked for the provision of the ZSM-5 catalyst and its characterisation. A. Hameed acknowledges the support of the Iraqi Ministry of Higher Education and Scientific Research and the Chemical Engineering Department, University of Technology, Baghdad, Iraq

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N2 - A ZSM-5 catalyst is examined in relation to the methanol-to-hydrocarbon (MTH) reaction as a function of reaction temperature and time-on-stream. The reaction profile is characterised using in-line mass spectrometry. Furthermore, the material contained within a catch-pot downstream from the reactor is analysed using gas chromatography-mass spectrometry. For a fixed methanol feed, reaction conditions are selected to define various stages of the reaction coordinate: (i) initial methanol adsorption at a sub-optimum reaction temperature (1 h at 200 °C); (ii) initial stages of reaction at an optimised reaction temperature (1 h at 350 °C); (iii) steady-state operation at an optimised reaction temperature (3 days at 350 °C); and (iv) accelerated ageing (3 days at 400 °C). Post-reaction, the catalyst samples are analysed ex situ by a combination of temperature-programmed oxidation (TPO) and spectroscopically by electron paramagnetic resonance (EPR), diffuse-reflectance infrared and inelastic neutron scattering (INS) spectroscopies. The TPO measurements provide an indication of the degree of 'coking' experienced by each sample. The EPR measurements detect aromatic radical cations. The IR and INS measurements reveal the presence of retained hydrocarbonaceous species, the nature of which are discussed in terms of the well-developed 'hydrocarbon pool' mechanism. This combination of experimental evidence, uniquely applied to this reaction system, establishes the importance of retained hydrocarbonaceous species in effecting the product distribution of this economically relevant reaction system.

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