Thermodynamic Equilibrium Analysis of Product Distribution in the Fischer–Tropsch Process Under Different Operating Conditions

Thermodynamic equilibrium analysis is necessary to provide a fundamental understanding of the distribution of the products formed in the Fischer-Tropsch process. The thermodynamic equilibrium distribution of the products formed at constant temperature and pressure was studied based on the minimization of the total Gibbs free energy of the system. The effects of temperature, pressure, and feed ratio on the product distribution were investigated under typical operating conditions. The distribution of the total products obtained from the reactions of added ethylene or ethanol was also studied. The results indicated that the products formed in a state of thermodynamic equilibrium follow Anderson-Schulz-Flory's general polymerization distribution at carbon numbers greater than about three. Both olefins and paraffins are primary products and there are essentially no alcohol and water at high degrees of conversion when the conditions for thermodynamic equilibrium are satisfied. The olefins formed in the Fischer-Tropsch process consist essentially of propylene. The product distribution is very sensitive to feed composition, and to temperature and pressure to a lesser extent. The product spectrum can be described broadly by the probability of chain growth relative to chain termination. This parameter decreases with increasing temperature, the feed ratio of hydrogen to carbon monoxide, and after the addition of ethanol to the feed, but increases with increasing pressure and after the addition of ethylene to the feed. An increase in reaction temperature results in a shift in selectivity towards low carbon number hydrocarbons and more hydrogenated products.