Canadian Journal of Chemical Engineering, Vol.86, No.6, 1062-1069, 2008
NOTES ON THE ISSUES OF EQUILIBRIUM IN THE FISCHER-TROPSCH SYNTHESIS
The product distribution for the Fischer-Tropsch synthesis is normally described using the kinetically derived (Anderson-Schultz-Flory) ASF model. Variations of the kinetic model have been proposed to explain deviations from the ASF distribution. The Fischer-Tropsch system can be equally well described using a pseudo-element (CH2, H-2, O) equilibrium approach. A one-parameter equilibrium model is derived for the product distributions for alkenes, alkanes and alcohols. The Fischer-Tropsch system should be considered as three separate partial equilibria systems: the product homologous series; the water gas shift system, and the redox behaviour of the catalyst with the H-2/O ratio of the gas. This approach correctly predicts the impacts of changes in a variety of parameters (temperature pressure, feed composition) on the ASF product distribution. In addition, the catalyst phase changes with gas composition and pressure, indicative of an equilibrium response. Equilibrium is of much greater importance to the Fischer-Tropsch system than previously thought, and the decision to use a complex kinetics-based model rather than a simpler equilibrium based model should be taken with care.
Keywords:Fischer-Tropsch reaction;product distribution model;partial equilibrium;chain growth equilibrium