Fischer–Tropsch synthesis: supercritical conversion using a Co/Al2O3 catalyst in a fixed bed reactor☆

Modeling of the supercritical fluid mixture indicated that an important increase in density occurs above a threshold of approximately 4 MPa for the reaction temperature of 220 °C studied. While transport parameters of the fluid are largely retained, the observed improvement in wax solubility was noteable. lt catalyst (25%Co/γ-Al2O3) was used in a fixed bed reactor under a pressure/density tuned supercritical fluid mixture of n-pentane/n-hexane. By using inert gas as a balancing gas to maintain a constant pressure, the density of the supercritical fluid could be tuned near the supercritical point while maintaining constant space velocity within the reactor. The benefits of the mixture allowed for optimization of transport and solubility properties at an optimum reaction temperature for Fischer–Tropsch synthesis with a cobalt catalyst. Indeed, above 4 MPa, increases in wax yields from sampling and carefully controlled gas measurements using an internal standard demonstrated an important increase in conversion due to greater accessibility to active sites after extraction of heavy wax from the catalyst. Additional benefits included decreased methane and carbon dioxide selectivities. Decreased paraffin/(olefin+paraffin) selectivities with increasing carbon number were also observed, in line with extraction of the hydrocarbon from the pore. Faster diffusion rates of wax products resulted in lower residence times in the catalyst pores, and therefore, decreased probability for readsorption and reaction to the hydrogenated product. Even so, there was not an observable increase in the alpha value for higher carbon number products over that obtained with just the inert gas.