Journal article
Hydrodesulfurization of Thiophene over γ-Mo2N catalyst
Molecular Catalysis, Vol.459, pp.21-30
2018
Abstract
Catalytic removal of the S-content from thiophene is a central step in efforts aiming to reduce the environmental burdens of transportation fuels. In this contribution, we investigate the hydrodesulfurization (HDS) mechanisms of thiophene (C4H4S) over γ-Mo2N catalyst by means of density functional theory (DFT) calculations. The thiophene molecule preferentially adsorbs in a flat mode over 3-fold fcc nitrogen hollow sites. The HDS mechanism may potentially proceed either unimolecularly (direct desulfurization) or via H-assisted reactions (hydrogenation). Due to a sizable activation barrier required for the first CS bond scission of 54.6 kcal/mol, we predict that the direct desulfurization to contribute rather very insignificantly in the HDS mechanism. Transfer of adsorbed hydrogen atoms on the γ-Mo2N surface to the thiophene ring substantially reduces activation barrier required in the CS bond scission to only 24.1 kcal/mol in a process that affords an adsorbed C4H6* species and an S atom. Further hydrogenation of the unsaturated C4H6* produces 2-butene. Kinetics and thermodynamics attributes dictate the occurrence of partial rather than full hydrogenation of C4H6*. Calculated rate constants for all individual steps could be utilized to construct a robust kinetic model for the overall HDS process. Estimated conversion values of thiophene predict 50–70% consumption of thiophene at 700 K and low values of gas hourly space velocities. Reaction routes and kinetic parameters provided herein are useful to design stand-alone γ-Mo2N-based catalysts for applications entailing partial hydrogenation and hydrodesulfurization of severely contaminated S-fuels.
Details
- Title
- Hydrodesulfurization of Thiophene over γ-Mo2N catalyst
- Authors/Creators
- Z.N. Jaf (Author/Creator)M. Altarawneh (Author/Creator)H.A. Miran (Author/Creator)Z-T Jiang (Author/Creator)B.Z. Dlugogorski (Author/Creator)
- Publication Details
- Molecular Catalysis, Vol.459, pp.21-30
- Publisher
- Elsevier
- Identifiers
- 991005543915207891
- Copyright
- © 2018 Elsevier B.V.
- Murdoch Affiliation
- School of Engineering and Information Technology
- Language
- English
- Resource Type
- Journal article
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- Collaboration types
- Domestic collaboration
- International collaboration
- Citation topics
- 2 Chemistry
- 2.41 Catalysts
- 2.41.1267 Desulfurization Catalysts
- Web Of Science research areas
- Chemistry, Physical
- ESI research areas
- Chemistry