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Water-Induced Formation of Cobalt-Support Compounds under Simulated High Conversion Fischer–Tropsch Environment

  • Moritz Wolf
    Moritz Wolf
    Catalysis Institute and c*change (DST-NRF Centre of Excellence in Catalysis), Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa
    More by Moritz Wolf
  • Emma K. Gibson
    Emma K. Gibson
    UK Catalysis Hub, Research Complex at Harwell, RAL, Oxford OX11 0FA, United Kingdom
    School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, United Kingdom
  • Ezra J. Olivier
    Ezra J. Olivier
    Centre for High Resolution Transmission Electron Microscopy, Physics Department, Nelson Mandela University, PO Box 77000, Port Elizabeth 6031, South Africa
  • Jan H. Neethling
    Jan H. Neethling
    Centre for High Resolution Transmission Electron Microscopy, Physics Department, Nelson Mandela University, PO Box 77000, Port Elizabeth 6031, South Africa
  • C. Richard A. Catlow
    C. Richard A. Catlow
    UK Catalysis Hub, Research Complex at Harwell, RAL, Oxford OX11 0FA, United Kingdom
    Department of Chemistry, University College London, London WC1H 0AJ, United Kingdom
  • Nico Fischer
    Nico Fischer
    Catalysis Institute and c*change (DST-NRF Centre of Excellence in Catalysis), Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa
    More by Nico Fischer
  • , and 
  • Michael Claeys*
    Michael Claeys
    Catalysis Institute and c*change (DST-NRF Centre of Excellence in Catalysis), Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa
    *E-mail: [email protected]
Cite this: ACS Catal. 2019, 9, 6, 4902–4918
Publication Date (Web):April 18, 2019
https://doi.org/10.1021/acscatal.9b00160
Copyright © 2019 American Chemical Society
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Abstract

Herein we present a comparative study on the water-induced formation of metal–support compounds from metallic cobalt in a simulated high conversion Fischer–Tropsch environment. Literature on the deactivation of supported cobalt catalysts via oxidation to cobalt(II) oxide or cobalt-support compounds is contradictory due to a lack of use in suitable model catalysts and insufficient direct characterization of the metallic cobalt phase under reaction conditions. The particular carrier materials stabilize the active cobalt nanoparticles, but also dictate the likelihood of the formation of nonactive cobalt-support compounds. In this study, well-defined cobalt nanoparticles of 5 nm were deposited on alumina, silica, and three titania carriers. The stability of the reduced nanoparticles against water-rich H2 atmospheres during exposure to simulated high Fischer–Tropsch conversion levels was monitored in an in situ magnetometer. Co/SiO2 was shown to be the most stable model catalyst, while various Co/TiO2 model systems readily formed large amounts of cobalt-support compounds at low ratios of the Fischer–Tropsch product H2O to reactant H2 or even during the preceding reduction of the oxidic precursor. Co/Al2O3 displayed a surprisingly high stability at industrially relevant conditions, in contradiction to thermodynamic predictions. However, cobalt aluminate forms at increased concentrations of water. The existence of hard-to-reduce metal–support compounds in the spent catalysts was confirmed and characterized by means of X-ray absorption near edge structure spectroscopy and high-resolution scanning transmission electron microscopy of the exposed and passivated model catalysts.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b00160.

  • Details on Jiles-Atherton method and an exemplary application on a measured hysteresis, XRD analysis, nitrogen adsorption–desorption isotherms, pore size distributions, TEM images of the support materials, extended data of the in situ magnetic characterization, alternative LCF fitting of XANES spectra, HRSTEM, and EELS analysis of the spent single-phase titania-supported catalysts (PDF)

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This article is cited by 18 publications.

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  2. Thulani M. Nyathi, Nico Fischer, Andrew P. E. York, Michael Claeys. Environment-Dependent Catalytic Performance and Phase Stability of Co3O4 in the Preferential Oxidation of Carbon Monoxide Studied In Situ. ACS Catalysis 2020, 10 (20) , 11892-11911. https://doi.org/10.1021/acscatal.0c02653
  3. Mahmood Rahmati, Mohammad-Saeed Safdari, Thomas H. Fletcher, Morris D. Argyle, Calvin H. Bartholomew. Chemical and Thermal Sintering of Supported Metals with Emphasis on Cobalt Catalysts During Fischer–Tropsch Synthesis. Chemical Reviews 2020, 120 (10) , 4455-4533. https://doi.org/10.1021/acs.chemrev.9b00417
  4. Thulani M. Nyathi, Mohamed I. Fadlalla, Nico Fischer, Andrew P.E. York, Ezra J. Olivier, Emma K. Gibson, Peter P. Wells, Michael Claeys. Support and gas environment effects on the preferential oxidation of carbon monoxide over Co3O4 catalysts studied in situ. Applied Catalysis B: Environmental 2021, 297 , 120450. https://doi.org/10.1016/j.apcatb.2021.120450
  5. Moritz Wolf, Nico Fischer, Michael Claeys. Formation of metal-support compounds in cobalt-based Fischer-Tropsch synthesis: A review. Chem Catalysis 2021, 1 (5) , 1014-1041. https://doi.org/10.1016/j.checat.2021.08.002
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  7. Ljubiša Gavrilović, Erik A. Jørgensen, Umesh Pandey, Koteswara R. Putta, Kumar R. Rout, Erling Rytter, Magne Hillestad, Edd A. Blekkan. Fischer-Tropsch synthesis over an alumina-supported cobalt catalyst in a fixed bed reactor – Effect of process parameters. Catalysis Today 2021, 369 , 150-157. https://doi.org/10.1016/j.cattod.2020.07.055
  8. Moritz Wolf. Thermodynamic assessment of the stability of bulk and nanoparticulate cobalt and nickel during dry and steam reforming of methane. RSC Advances 2021, 11 (30) , 18187-18197. https://doi.org/10.1039/D1RA01856F
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  11. Chengwu Qiu, Yaroslav Odarchenko, Qingwei Meng, Peixi Cong, Martin A. W. Schoen, Armin Kleibert, Thomas Forrest, Andrew M. Beale. Direct observation of the evolving metal–support interaction of individual cobalt nanoparticles at the titania and silica interface. Chemical Science 2020, 11 (48) , 13060-13070. https://doi.org/10.1039/D0SC03113E
  12. Moritz Wolf, Nico Fischer, Michael Claeys. Water-induced deactivation of cobalt-based Fischer–Tropsch catalysts. Nature Catalysis 2020, 3 (12) , 962-965. https://doi.org/10.1038/s41929-020-00534-5
  13. Hannah Kirsch, Natalie Lochmahr, Christiane Staudt, Peter Pfeifer, Roland Dittmeyer. Production of CO2-neutral liquid fuels by integrating Fischer-Tropsch synthesis and hydrocracking in a single micro-structured reactor: Performance evaluation of different configurations by factorial design experiments. Chemical Engineering Journal 2020, 393 , 124553. https://doi.org/10.1016/j.cej.2020.124553
  14. N Fischer, M Claeys. In situ characterization of Fischer–Tropsch catalysts: a review. Journal of Physics D: Applied Physics 2020, 53 (29) , 293001. https://doi.org/10.1088/1361-6463/ab761c
  15. M. Peacock, J. Paterson, L. Reed, S. Davies, S. Carter, A. Coe, J. Clarkson. Innovation in Fischer–Tropsch: Developing Fundamental Understanding to Support Commercial Opportunities. Topics in Catalysis 2020, 63 (3-4) , 328-339. https://doi.org/10.1007/s11244-020-01239-6
  16. Calvin H. Bartholomew, Mahmood Rahmati, Marcus A. Reynolds. Optimizing preparations of Co Fischer-Tropsch catalysts for stability against sintering. Applied Catalysis A: General 2020, 602 , 117609. https://doi.org/10.1016/j.apcata.2020.117609
  17. Moritz Wolf, Nico Fischer, Michael Claeys. Preparation of isolated Co 3 O 4 and fcc-Co crystallites in the nanometre range employing exfoliated graphite as novel support material. Nanoscale Advances 2019, 1 (8) , 2910-2923. https://doi.org/10.1039/C9NA00291J
  18. Moritz Wolf, Nico Fischer, Michael Claeys. Capturing the interconnectivity of water-induced oxidation and sintering of cobalt nanoparticles during the Fischer-Tropsch synthesis in situ. Journal of Catalysis 2019, 374 , 199-207. https://doi.org/10.1016/j.jcat.2019.04.030