Mechanism of cobalt-catalyzed CO hydrogenation: 2. Fischer-Tropsch synthesis

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

19 Citaties (Scopus)

Uittreksel

Fischer-Tropsch (FT) synthesis is one of the most complex catalyzed chemical reactions in which the chain-growth mechanism that leads to formation of long-chain hydrocarbons is not well understood yet. The present work provides deeper insight into the relation between the kinetics of the FT reaction on a silica-supported cobalt catalyst and the composition of the surface adsorbed layer. Cofeeding experiments of 12C3H6 with 13CO/H2 evidence that CHx surface intermediates are involved in chain growth and that chain growth is highly reversible. We present a model-based approach of steady-state isotopic transient kinetic analysis measurements at FT conditions involving hydrocarbon products containing up to five carbon atoms. Our data show that the rates of chain growth and chain decoupling are much higher than the rates of monomer formation and chain termination. An important corollary of the microkinetic model is that the fraction of free sites, which is mainly determined by CO pressure, has opposing effects on CO consumption rate and chain-growth probability. Lower CO pressure and more free sites leads to increased CO consumption rate but decreased chain-growth probability because of an increasing ratio of chain decoupling over chain growth. The preferred FT condition involves high CO pressure in which chain-growth probability is increased at the expense of the CO consumption rate.

TaalEngels
Pagina's8061-8071
Aantal pagina's11
TijdschriftACS Catalysis
Volume7
Nummer van het tijdschrift12
DOI's
StatusGepubliceerd - 1 dec 2017

Vingerafdruk

Fischer-Tropsch synthesis
Carbon Monoxide
Cobalt
Hydrogenation
Hydrocarbons
Kinetics
Silicon Dioxide
Chemical reactions
Carbon
Monomers
Silica
Atoms
Catalysts
Chemical analysis

Trefwoorden

    Citeer dit

    @article{13d8253774db49e18c6e6e51930dfa27,
    title = "Mechanism of cobalt-catalyzed CO hydrogenation: 2. Fischer-Tropsch synthesis",
    abstract = "Fischer-Tropsch (FT) synthesis is one of the most complex catalyzed chemical reactions in which the chain-growth mechanism that leads to formation of long-chain hydrocarbons is not well understood yet. The present work provides deeper insight into the relation between the kinetics of the FT reaction on a silica-supported cobalt catalyst and the composition of the surface adsorbed layer. Cofeeding experiments of 12C3H6 with 13CO/H2 evidence that CHx surface intermediates are involved in chain growth and that chain growth is highly reversible. We present a model-based approach of steady-state isotopic transient kinetic analysis measurements at FT conditions involving hydrocarbon products containing up to five carbon atoms. Our data show that the rates of chain growth and chain decoupling are much higher than the rates of monomer formation and chain termination. An important corollary of the microkinetic model is that the fraction of free sites, which is mainly determined by CO pressure, has opposing effects on CO consumption rate and chain-growth probability. Lower CO pressure and more free sites leads to increased CO consumption rate but decreased chain-growth probability because of an increasing ratio of chain decoupling over chain growth. The preferred FT condition involves high CO pressure in which chain-growth probability is increased at the expense of the CO consumption rate.",
    keywords = "chain growth, cobalt, Fischer-Tropsch, mechanism, SSITKA",
    author = "W. Chen and I.A.W. Filot and R. Pestman and E.J.M. Hensen",
    year = "2017",
    month = "12",
    day = "1",
    doi = "10.1021/acscatal.7b02758",
    language = "English",
    volume = "7",
    pages = "8061--8071",
    journal = "ACS Catalysis",
    issn = "2155-5435",
    publisher = "American Chemical Society",
    number = "12",

    }

    Mechanism of cobalt-catalyzed CO hydrogenation : 2. Fischer-Tropsch synthesis. / Chen, W.; Filot, I.A.W.; Pestman, R.; Hensen, E.J.M.

    In: ACS Catalysis, Vol. 7, Nr. 12, 01.12.2017, blz. 8061-8071.

    Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

    TY - JOUR

    T1 - Mechanism of cobalt-catalyzed CO hydrogenation

    T2 - ACS Catalysis

    AU - Chen,W.

    AU - Filot,I.A.W.

    AU - Pestman,R.

    AU - Hensen,E.J.M.

    PY - 2017/12/1

    Y1 - 2017/12/1

    N2 - Fischer-Tropsch (FT) synthesis is one of the most complex catalyzed chemical reactions in which the chain-growth mechanism that leads to formation of long-chain hydrocarbons is not well understood yet. The present work provides deeper insight into the relation between the kinetics of the FT reaction on a silica-supported cobalt catalyst and the composition of the surface adsorbed layer. Cofeeding experiments of 12C3H6 with 13CO/H2 evidence that CHx surface intermediates are involved in chain growth and that chain growth is highly reversible. We present a model-based approach of steady-state isotopic transient kinetic analysis measurements at FT conditions involving hydrocarbon products containing up to five carbon atoms. Our data show that the rates of chain growth and chain decoupling are much higher than the rates of monomer formation and chain termination. An important corollary of the microkinetic model is that the fraction of free sites, which is mainly determined by CO pressure, has opposing effects on CO consumption rate and chain-growth probability. Lower CO pressure and more free sites leads to increased CO consumption rate but decreased chain-growth probability because of an increasing ratio of chain decoupling over chain growth. The preferred FT condition involves high CO pressure in which chain-growth probability is increased at the expense of the CO consumption rate.

    AB - Fischer-Tropsch (FT) synthesis is one of the most complex catalyzed chemical reactions in which the chain-growth mechanism that leads to formation of long-chain hydrocarbons is not well understood yet. The present work provides deeper insight into the relation between the kinetics of the FT reaction on a silica-supported cobalt catalyst and the composition of the surface adsorbed layer. Cofeeding experiments of 12C3H6 with 13CO/H2 evidence that CHx surface intermediates are involved in chain growth and that chain growth is highly reversible. We present a model-based approach of steady-state isotopic transient kinetic analysis measurements at FT conditions involving hydrocarbon products containing up to five carbon atoms. Our data show that the rates of chain growth and chain decoupling are much higher than the rates of monomer formation and chain termination. An important corollary of the microkinetic model is that the fraction of free sites, which is mainly determined by CO pressure, has opposing effects on CO consumption rate and chain-growth probability. Lower CO pressure and more free sites leads to increased CO consumption rate but decreased chain-growth probability because of an increasing ratio of chain decoupling over chain growth. The preferred FT condition involves high CO pressure in which chain-growth probability is increased at the expense of the CO consumption rate.

    KW - chain growth

    KW - cobalt

    KW - Fischer-Tropsch

    KW - mechanism

    KW - SSITKA

    UR - http://www.scopus.com/inward/record.url?scp=85036476102&partnerID=8YFLogxK

    U2 - 10.1021/acscatal.7b02758

    DO - 10.1021/acscatal.7b02758

    M3 - Article

    VL - 7

    SP - 8061

    EP - 8071

    JO - ACS Catalysis

    JF - ACS Catalysis

    SN - 2155-5435

    IS - 12

    ER -