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

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 differences in physisorption, solubility, or diffusivity. Preferential physisorption of longer hydrocarbons and increase of the solubility with chain length influences the product distribution and results in a decreasing olefin-to-paraffin ratio with increasing chain length. Process development and reactor design should be based on reliable kinetic expressions and detailed selectivity models.