Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

A critical review of the kinetics and selectivity of the Fischer–Tropsch synthesis (FTS) is given. The focus is on reaction mechanisms and kinetics of the water–gas shift and Fischer–Tropsch (FT) reactions. New developments in the product selectivity as well as the overall kinetics are reviewed. It is concluded that the development of rate equations for the FTS should be based on realistic mechanistic schemes. Qualitatively, there is agreement that the product distribution is affected by the occurrence of secondary reactions (hydrogenation, isomerization, reinsertion, and hydrogenolysis). At high CO and H2O pressures, the most important secondary reaction is readsorption of olefins, resulting in initiation of chain growth processes. Secondary hydrogenation of α-olefins may occur and depends on the catalytic system and the process conditions. The rates of the secondary reactions increase exponentially with chain length. Much controversy exists about whether these chain-length dependencies stem from differe...

Kinetics and Selectivity of the Fischer–Tropsch Synthesis: A Literature Review

https://dspace.library.uu.nl/bitstream/handle/1874/26040/Catal.Today-Weckhuysen-2003.pdf?sequence=1

Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis

The effects of metal particle size in catalysis are of prime scientific and industrial importance and call for a better understanding. In this paper the origin of the cobalt particle size effects in Fischer−Tropsch (FT) catalysis was studied. Steady-State Isotopic Transient Kinetic Analysis (SSITKA) was applied to provide surface residence times and coverages of reaction intermediates as a function of Co particle size (2.6−16 nm). For carbon nanofiber supported cobalt catalysts at 210 °C and H2/CO = 10 v/v, it appeared that the surface residence times of reversibly bonded CHx and OHx intermediates increased, whereas that of CO decreased for small (<6 nm) Co particles. A higher coverage of irreversibly bonded CO was found for small Co particles that was ascribed to a larger fraction of low-coordinated surface sites. The coverages and residence times obtained from SSITKA were used to describe the surface-specific activity (TOF) quantitatively and the CH4 selectivity qualitatively as a function of Co particl...

On the origin of the cobalt particle size effects in Fischer-Tropsch catalysis.

National Natural Science Foundation of China [20625310, 20923004]; National Basic Research Program of China [2005CB221408, 2010CB732303]; Research Fund for the Doctoral Program of Higher Education [20090121110007]; Key Scientific Project of Fujian Province [2009HZ0002-1]

J.G. Goodwin

Papers

Characterization of silica- and alumina-supported vanadia catalysts using temperature programmed reduction

In-Situ XAFS Investigation of K-Promoted Co Catalysts

Zr Promotion of Co/SiO2 for Fischer-Tropsch Synthesis

The effect of alkali promotion on CO hydrogenation over Rh/TiO2

Effect of Pretreatment on the Activity of a Ru-Promoted Co/Al2O3Fischer–Tropsch Catalyst☆