The oscillating Fischer-Tropsch reaction

Zhang, Rui; Wang, Yong; Gaspard, Pierre; Kruse, Norbert

doi:10.1126/science.adh8463

The oscillating Fischer-Tropsch reaction

Journal Article · Thu Oct 05 00:00:00 EDT 2023 · Science

DOI:https://doi.org/10.1126/science.adh8463· OSTI ID:2263294

^[1]; ^[2]; Gaspard, Pierre ^[3]; ^[4]

Washington State Univ., Pullman, WA (United States)
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
Université Libre de Bruxelles, Brussels (Belgium)
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis; Université Libre de Bruxelles, Brussels (Belgium)

The mechanistic steps that underlie the formation of higher hydrocarbons in catalytic carbon monoxide (CO) hydrogenation at atmospheric pressure over cobalt-based catalysts (Fischer-Tropsch synthesis) have remained poorly understood. Here, we reveal nonisothermal rate-and-selectivity oscillations that are self-sustained over extended periods of time (>24 hours) for a cobalt/cerium oxide catalyst with an atomic ratio of cobalt to cerium of 2:1 (Co₂Ce₁) at 220°C and equal partial pressures of the reactants. A microkinetic mechanism was used to generate rate-and-selectivity oscillations through forced temperature oscillations. Experimental and theoretical oscillations were in good agreement over an extended range of reactant pressure ratios. Additionally, phase portraits for hydrocarbon production were constructed that support the thermokinetic origin of our rate-and-selectivity oscillations.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830; FG02-05ER15712

OSTI ID:: 2263294

Report Number(s):: PNNL-SA--193537

Journal Information:: Science, Journal Name: Science Journal Issue: 6666 Vol. 382; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Reaction rate oscillations during Fischer-Tropsch synthesis on Fe-precipitated Nu-1 zeolite-type catalysts Tsotsis, T. T.; Rao, V. U. S.; Polinski, L. M. AIChE Journal, Vol. 28, Issue 5 https://doi.org/10.1002/aic.690280527	journal	September 1982
Mixing Copper Nanoparticles and ZnO Nanocrystals: A Route towards Understanding the Hydrogenation of CO2 to Methanol? Meunier, Frederic C. Angewandte Chemie International Edition, Vol. 50, Issue 18 https://doi.org/10.1002/anie.201100011	journal	March 2011
Stabilität und Zeitverhalten von Durchfluß‐Kreislauf‐Reaktoren Hugo, P. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 74, Issue 2 https://doi.org/10.1002/bbpc.19700740210	journal	February 1970
Chain Growth by CO Insertion in the Fischer–Tropsch Reaction van Santen, Rutger A.; Markvoort, Albert J. ChemCatChem, Vol. 5, Issue 11 https://doi.org/10.1002/cctc.201300173	journal	June 2013
Manipulation of Fischer-Tropsch Synthesis for Production of Higher Alcohols Using Manganese Promoters Paterson, James; Peacock, Mark; Purves, Russell ChemCatChem, Vol. 10, Issue 22 https://doi.org/10.1002/cctc.201800883	journal	October 2018
Thermisch und kinetisch verursachte Instabilitäten im Reaktionsverhalten einzelner Katalysatorkörner Beusch, H.; Fieguth, P.; Wicke, E. Chemie Ingenieur Technik, Vol. 44, Issue 7 https://doi.org/10.1002/cite.330440702	journal	April 1972
Dynamic Hydrogen–Deuterium Exchange to Determine Metallic Surface Areas of Catalysts Schweicher, Julien; Bundhoo, Adam; Frennet, Alfred Catalysis Letters, Vol. 144, Issue 2 https://doi.org/10.1007/s10562-013-1161-9	journal	December 2013
Chemical Transient Kinetics in Studies of the Fischer–Tropsch Reaction and Beyond Raub, Andrew; Karroum, Hafsa; Athariboroujeny, Motahare Catalysis Letters, Vol. 151, Issue 3 https://doi.org/10.1007/s10562-020-03294-w	journal	August 2020
Simultaneous MS-IR Studies of Surface Formate Reactivity Under Methanol Synthesis Conditions on Cu/SiO2 Yang, Y.; Mims, C. A.; Disselkamp, R. S. Topics in Catalysis, Vol. 52, Issue 10 https://doi.org/10.1007/s11244-009-9320-3	journal	June 2009
Characterization of CoCu- and CoMn-Based Catalysts for the Fischer–Tropsch Reaction Toward Chain-Lengthened Oxygenates Voss, Jenny M.; Xiang, Yizhi; Collinge, Greg Topics in Catalysis, Vol. 61, Issue 9-11 https://doi.org/10.1007/s11244-018-0938-x	journal	April 2018
Fischer-Tropsch synthesis on cobalt and ruthenium. Metal dispersion and support effects on reaction rate and selectivity Iglesia, E. Journal of Catalysis, Vol. 137, Issue 1 https://doi.org/10.1016/0021-9517(92)90150-G	journal	September 1992
Methanol Synthesis Waugh, K. C. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80122-4	journal	May 1992
Origin of organic matter in early solar system—I. Hydrocarbons Studier, Martin H.; Hayatsu, Ryoichi; Anders, Edward Geochimica et Cosmochimica Acta, Vol. 32, Issue 2 https://doi.org/10.1016/S0016-7037(68)80002-X	journal	January 1968
Fischer–Tropsch synthesis: Metal–support interfacial contact governs oxygenates selectivity over CeO2 supported Pt–Co catalysts Gnanamani, Muthu Kumaran; Ribeiro, Mauro C.; Ma, Wenping Applied Catalysis A: General, Vol. 393, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.11.019	journal	February 2011
CO-insertion mechanism based kinetic model of the Fischer–Tropsch synthesis reaction over Re-promoted Co catalyst Todic, Branislav; Ma, Wenping; Jacobs, Gary Catalysis Today, Vol. 228 https://doi.org/10.1016/j.cattod.2013.08.008	journal	June 2014
Determination of formate decomposition rates and relation to product formation during CO hydrogenation over supported cobalt Lorito, D.; Paredes-Nunez, A.; Mirodatos, C. Catalysis Today, Vol. 259 https://doi.org/10.1016/j.cattod.2015.06.027	journal	January 2016
Reflections on the Fischer-Tropsch synthesis: Mechanistic issues from a surface science perspective Weststrate, C. J.; van Helden, P.; Niemantsverdriet, J. W. Catalysis Today, Vol. 275 https://doi.org/10.1016/j.cattod.2016.04.004	journal	October 2016
Crystal plane effects of CeO2 on supported cobalt and its catalytic performance for Fischer-Tropsch synthesis Liu, Yan; Hou, Bo; Jia, Litao Fuel, Vol. 324 https://doi.org/10.1016/j.fuel.2022.124518	journal	September 2022
Temperature oscillation in a catalytic particle of Fischer–Tropsch synthesis Derevich, I. V. International Journal of Heat and Mass Transfer, Vol. 53, Issue 1-3 https://doi.org/10.1016/j.ijheatmasstransfer.2009.09.045	journal	January 2010
Metal–support interactions and reactivity of Co/CeO2 catalysts in the Fischer–Tropsch synthesis reaction Spadaro, L.; Arena, F.; Granados, M. Journal of Catalysis, Vol. 234, Issue 2 https://doi.org/10.1016/j.jcat.2005.07.006	journal	September 2005
CO activation pathways and the mechanism of Fischer–Tropsch synthesis Ojeda, Manuel; Nabar, Rahul; Nilekar, Anand U. Journal of Catalysis, Vol. 272, Issue 2 https://doi.org/10.1016/j.jcat.2010.04.012	journal	June 2010
In situ magnetometer study on the formation and stability of cobalt carbide in Fischer–Tropsch synthesis Claeys, M.; Dry, M. E.; van Steen, E. Journal of Catalysis, Vol. 318 https://doi.org/10.1016/j.jcat.2014.08.002	journal	October 2014
Morphology control of Co2C nanostructures via the reduction process for direct production of lower olefins from syngas An, Yunlei; Zhao, Yonghui; Yu, Fei Journal of Catalysis, Vol. 366 https://doi.org/10.1016/j.jcat.2018.03.024	journal	October 2018
Microkinetic modelling of the formation of C1 and C2 products in the Fischer–Tropsch synthesis over cobalt catalysts Storsæter, Sølvi; Chen, De; Holmen, Anders Surface Science, Vol. 600, Issue 10 https://doi.org/10.1016/j.susc.2006.02.048	journal	May 2006
Study on the Synergistic Catalysis of CeO₂ Regulated Co⁰–Co^δ+ Dual Sites for Direct Synthesis of Higher Alcohols from Syngas Wang, Peng; Wei, Shuai; Sun, Kai Industrial & Engineering Chemistry Research, Vol. 61, Issue 11 https://doi.org/10.1021/acs.iecr.1c04663	journal	March 2022
Understanding the Strong Metal–Support Interaction (SMSI) Effect in Cu_xNi_1–x/CeO₂ (0 < x < 1) Nanoparticles for Enhanced Catalysis Figueiredo, Wallace T.; Della Mea, Guilherme B.; Segala, Maximiliano ACS Applied Nano Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsanm.9b00569	journal	April 2019
The Catalytic Mechanics of Dynamic Surfaces: Stimulating Methods for Promoting Catalytic Resonance Shetty, Manish; Walton, Amber; Gathmann, Sallye R. ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c03336	journal	September 2020
An Investigation into the Effects of Mn Promotion on the Activity and Selectivity of Co/SiO ₂ for Fischer–Tropsch Synthesis: Evidence for Enhanced CO Adsorption and Dissociation Johnson, Gregory R.; Werner, Sebastian; Bell, Alexis T. ACS Catalysis, Vol. 5, Issue 10 https://doi.org/10.1021/acscatal.5b01578	journal	September 2015
Effects of Sodium on the Catalytic Performance of CoMn Catalysts for Fischer–Tropsch to Olefin Reactions Li, Zhengjia; Zhong, Liangshu; Yu, Fei ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.6b03478	journal	April 2017
Insight into the Formation of Co@Co ₂ C Catalysts for Direct Synthesis of Higher Alcohols and Olefins from Syngas Zhao, Ziang; Lu, Wei; Yang, Ruoou ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b02403	journal	December 2017
Competing Mechanisms in CO Hydrogenation over Co-MnO _x Catalysts Athariboroujeny, Motahare; Raub, Andrew; Iablokov, Viacheslav ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b00967	journal	May 2019
Oscillatory Kinetics in Heterogeneous Catalysis Imbihl, Ronald.; Ertl, Gerhard. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a012	journal	May 1995
Behavior of metallic iron catalysts during Fischer-Tropsch synthesis studied with Mössbauer spectroscopy, x-ray diffraction, carbon content determination, and reaction kinetic measurements Niemantsverdriet, J. W.; Van der Kraan, A. M.; Van Dijk, W. L. The Journal of Physical Chemistry, Vol. 84, Issue 25 https://doi.org/10.1021/j100462a011	journal	December 1980
Carburization of supported iron synthesis catalysts Amelse, J. A.; Butt, J. B.; Schwartz, L. H. The Journal of Physical Chemistry, Vol. 82, Issue 5 https://doi.org/10.1021/j100494a012	journal	March 1978
Studies of the Fischer--Tropsch Synthesis. V. Activities and Surface Areas of Reduced and Carburized Cobalt Catalysts Anderson, Robert B.; Hall, W. Keith.; Krieg, Abraham. Journal of the American Chemical Society, Vol. 71, Issue 1 https://doi.org/10.1021/ja01169a047	journal	January 1949
The Role of Bulk Cobalt Carbide in the Fischer—Tropsch Synthesis ¹ Weller, Sol; Hofer, L. J. E.; Anderson, R. B. Journal of the American Chemical Society, Vol. 70, Issue 2 https://doi.org/10.1021/ja01182a108	journal	February 1948
Hydrocarbon Chain Lengthening in Catalytic CO Hydrogenation: Evidence for a CO-Insertion Mechanism Schweicher, Julien; Bundhoo, Adam; Kruse, Norbert Journal of the American Chemical Society, Vol. 134, Issue 39 https://doi.org/10.1021/ja3068484	journal	September 2012
Long-Chain Terminal Alcohols through Catalytic CO Hydrogenation Xiang, Yizhi; Chitry, Véronique; Liddicoat, Peter Journal of the American Chemical Society, Vol. 135, Issue 19 https://doi.org/10.1021/ja402512r	journal	May 2013
Density Functional Theory Study of the CO Insertion Mechanism for Fischer−Tropsch Synthesis over Co Catalysts Zhuo, Mingkun; Tan, Kong Fei; Borgna, Armando The Journal of Physical Chemistry C, Vol. 113, Issue 19 https://doi.org/10.1021/jp900281h	journal	April 2009
Chemical Transient Kinetics Applied to CO Hydrogenation over a Pure Nickel Catalyst Bundhoo, Adam; Schweicher, Julien; Frennet, Alfred The Journal of Physical Chemistry C, Vol. 113, Issue 24 https://doi.org/10.1021/jp902647z	journal	May 2009
DRIFTS/MS Studies during Chemical Transients and SSITKA of the CO/H ₂ Reaction over Co-MgO Catalysts Schweicher, Julien; Bundhoo, Adam; Frennet, Alfred The Journal of Physical Chemistry C, Vol. 114, Issue 5 https://doi.org/10.1021/jp909754w	journal	January 2010
Cobalt carbide nanoprisms for direct production of lower olefins from syngas Zhong, Liangshu; Yu, Fei; An, Yunlei Nature, Vol. 538, Issue 7623 https://doi.org/10.1038/nature19786	journal	October 2016
Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins Xiang, Yizhi; Kruse, Norbert Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13058	journal	October 2016
Rate and selectivity hysteresis during the carbon monoxide hydrogenation over promoted Co/MnOx catalysts Xiang, Yizhi; Kovarik, Libor; Kruse, Norbert Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11836-z	journal	September 2019
Mechanistic Aspects of the Formation of Hydrocarbons and Alcohols from CO Hydrogenation Hindermann, J. P.; Hutchings, G. J.; Kiennemann, A. Catalysis Reviews, Vol. 35, Issue 1 https://doi.org/10.1080/01614949308013907	journal	February 1993
The role of Fischer‐Tropsch catalysis in solar nebula chemistry Kress, Monika E.; Tielens, Alexander G. G. M. Meteoritics & Planetary Science, Vol. 36, Issue 1 https://doi.org/10.1111/j.1945-5100.2001.tb01811.x	journal	January 2001
Organic Compounds in Meteorites: They may have formed in the solar nebula, by catalytic reactions of carbon monoxide, hydrogen, and ammonia Anders, E.; Hayatsu, R.; Studier, M. H. Science, Vol. 182, Issue 4114 https://doi.org/10.1126/science.182.4114.781	journal	November 1973

Similar Records

Fischer-Tropsch synthesis for clean transportation fuels

Conference · Tue Dec 30 23:00:00 EST 1997 · OSTI ID:324773

Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

Technical Report · Sat Dec 31 23:00:00 EST 1988 · OSTI ID:6923858

Fischer-Tropsch process

Patent · Wed Dec 31 23:00:00 EST 1986 · OSTI ID:866270

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

The oscillating Fischer-Tropsch reaction

Citation Formats

References (47)

Similar Records

Related Subjects