A Single-Event MicroKinetic model for the cobalt catalyzed Fischer-Tropsch Synthesis

[Display omitted] •Validation of Single-Event MicroKinetic methodology for the Co catalyzed Fischer-Tropsch Synthesis.•The adjustable parameters are all statistically significant and physicochemical meaningful.•Deviations from Anderson-Schulz-Flory distribution are explained by symmetry and adsorpti...

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Published in:Applied catalysis. A, General Vol. 524; pp. 149 - 162
Main Authors: Van Belleghem, Jonas, Ledesma, Cristian, Yang, Jia, Toch, Kenneth, Chen, De, Thybaut, Joris W., Marin, Guy B.
Format: Journal Article
Language:English
Published: Elsevier B.V 25.08.2016
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ISSN:0926-860X, 1873-3875
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Abstract [Display omitted] •Validation of Single-Event MicroKinetic methodology for the Co catalyzed Fischer-Tropsch Synthesis.•The adjustable parameters are all statistically significant and physicochemical meaningful.•Deviations from Anderson-Schulz-Flory distribution are explained by symmetry and adsorption effects.•Activity difference between Fe and Co catalysts is interpreted in terms of the oxygen atomic chemisorption enthalpy. The Single-Event MicroKinetic methodology has been successfully extended from Fe to Co catalyzed Fischer-Tropsch Synthesis. A total of 82 experiments were performed in a plug flow reactor with a H2 to CO molar inlet ratio between 3 and 10, a temperature range from 483 to 503K, CO inlet partial pressures from 3.7 to 16.7kPa and space time varying between 7.2 and 36.3(kgcats)mol−1. Via regression, statistically significant and physicochemically meaningful estimates were obtained for the activation energies in the model and the H, C and O atomic chemisorption enthalpies as required for the UBI-QEP method. A reaction path analysis allowed relating the observed deviations from the Anderson-Schulz-Flory distribution, i.e., a high methane and low ethene selectivity, to the symmetry numbers and a higher chemisorption enthalpy of the metal methyl species compared to the other metal alkyl species. Simulations at industrially relevant conditions show that, as a catalyst descriptor, the H atomic chemisorption enthalpy crucially determines both the CO conversion and the C5+ selectivity. The higher FTS activity of Co compared to Fe is explained via the higher oxygen atomic chemisorption enthalpy on the latter compared to the former.
AbstractList [Display omitted] •Validation of Single-Event MicroKinetic methodology for the Co catalyzed Fischer-Tropsch Synthesis.•The adjustable parameters are all statistically significant and physicochemical meaningful.•Deviations from Anderson-Schulz-Flory distribution are explained by symmetry and adsorption effects.•Activity difference between Fe and Co catalysts is interpreted in terms of the oxygen atomic chemisorption enthalpy. The Single-Event MicroKinetic methodology has been successfully extended from Fe to Co catalyzed Fischer-Tropsch Synthesis. A total of 82 experiments were performed in a plug flow reactor with a H2 to CO molar inlet ratio between 3 and 10, a temperature range from 483 to 503K, CO inlet partial pressures from 3.7 to 16.7kPa and space time varying between 7.2 and 36.3(kgcats)mol−1. Via regression, statistically significant and physicochemically meaningful estimates were obtained for the activation energies in the model and the H, C and O atomic chemisorption enthalpies as required for the UBI-QEP method. A reaction path analysis allowed relating the observed deviations from the Anderson-Schulz-Flory distribution, i.e., a high methane and low ethene selectivity, to the symmetry numbers and a higher chemisorption enthalpy of the metal methyl species compared to the other metal alkyl species. Simulations at industrially relevant conditions show that, as a catalyst descriptor, the H atomic chemisorption enthalpy crucially determines both the CO conversion and the C5+ selectivity. The higher FTS activity of Co compared to Fe is explained via the higher oxygen atomic chemisorption enthalpy on the latter compared to the former.
Author Chen, De
Yang, Jia
Toch, Kenneth
Thybaut, Joris W.
Van Belleghem, Jonas
Marin, Guy B.
Ledesma, Cristian
Author_xml – sequence: 1
  givenname: Jonas
  surname: Van Belleghem
  fullname: Van Belleghem, Jonas
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  organization: Ghent University, Laboratory for Chemical Technology, Ghent B-9052, Belgium
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  givenname: Cristian
  surname: Ledesma
  fullname: Ledesma, Cristian
  email: cristian.l.rodriguez@ntnu.no
  organization: Norwegian University of Science and Technology (NTNU), Department of Chemical Engineering, N-7491 Trondheim, Norway
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  givenname: Jia
  surname: Yang
  fullname: Yang, Jia
  email: Jia.Yang@sintef.no
  organization: SINTEF Materials and Chemistry, Oil and Gas Process Technology, Sem Sælands vei 2A, N-7491 Trondheim, Norway
– sequence: 4
  givenname: Kenneth
  surname: Toch
  fullname: Toch, Kenneth
  email: Kenneth.Toch@Ugent.Be
  organization: Ghent University, Laboratory for Chemical Technology, Ghent B-9052, Belgium
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  givenname: De
  surname: Chen
  fullname: Chen, De
  email: chen@ntnu.no
  organization: Norwegian University of Science and Technology (NTNU), Department of Chemical Engineering, N-7491 Trondheim, Norway
– sequence: 6
  givenname: Joris W.
  orcidid: 0000-0002-4187-7904
  surname: Thybaut
  fullname: Thybaut, Joris W.
  email: Joris.Thybaut@Ugent.be
  organization: Ghent University, Laboratory for Chemical Technology, Ghent B-9052, Belgium
– sequence: 7
  givenname: Guy B.
  surname: Marin
  fullname: Marin, Guy B.
  email: Guy.Marin@Ugent.Be
  organization: Ghent University, Laboratory for Chemical Technology, Ghent B-9052, Belgium
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Keywords Fischer-Tropsch Synthesis
UBI-QEP
Single-Event MicroKinetic modeling
Cobalt catalyst
CO hydrogenation
Language English
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Cobalt catalyst
Fischer-Tropsch Synthesis
Single-Event MicroKinetic modeling
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Title A Single-Event MicroKinetic model for the cobalt catalyzed Fischer-Tropsch Synthesis
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