Steady-state isotopic transient kinetic analysis of the Fischer-Tropsch synthesis reaction over cobalt-based catalysts

The paper presents a transient kinetic analysis of the Fischer-Tropsch synt hesis reaction using the SSITKA technique in combination with a gas-chromat ograph-mass-spectrometer (GCMS) analysis of the C-13-labeled and O-18-label ed hydrocarbon and alcohol reaction products. Experiments are performed on a Go/Ru/TiO2 catalyst and a fully metallic Go-sponge model catalyst at 498 K and 1.2 bar. The experimental results are discussed in a qualitative way to obtain mechanistic information. The Co-sponge catalyst is used to study alcohol formation, since the TiO2 support disturbs the measurements on the Co/Ru/TiO2 catalyst. The formation of hydrocarbons proceeds via a two-pool mechanism, where two carbon pools contribute to methane formation and C-C c oupling. Paraffins and olefins are both primary products, but the GCMS anal ysis demonstrates that readsorption of 1-olefins is an important step. The readsorption of iso- and 2-olefins is shown to be of less importance. The s teady-state performance of the catalyst indicates the presence of a physiso rbed hydrocarbon layer, even under process conditions where no wax build-up in the catalyst pores occurs. Although the Anderson-Schulz-Flory distribut ion gives rise to assume chain-length independence of the surface reactions starting at C-3, this does not hold when discrimination between the paraff ins and the olefins is made. Alcohol formation can be considered as a termi nation reaction that occurs via a CO insertion or a CHxO insertion mechanis m. (C) 2001 Elsevier Science Ltd. All rights reserved.