Supercritical phase Fischer-Tropsch synthesis inhibition of carbon dioxide selectivity for enhanced hydrocarbon production.

摘要

This thesis presents the results from research conducted on Fischer-Tropsch synthesis (FTS) in supercritical CO2 from syngas (H2:CO =1:1) typically produced from coal gasification and using a Fe-Zn-K catalyst. Experiments were conducted with syngas alone at different pressures (200 psi--1050 psi) and temperatures (275, 350 and 375°C). Experiments were also conducted with a syngas pressure of 200 psi and at different partial pressures of an inert diluent (N2) such that the total pressure varied from 200 psi to 1050 psi. Finally, experiments were conducted with CO2 as a diluent and at a syngas pressure of 200 psi. The CO2 partial pressure was increased from 0 psi to 1400 psi (non critical to supercritical conditions). The data show an enhancement in the hydrocarbon selectivity and reduction in the parasitic loss of carbon efficiency due to CO2 formation along with significant improvement in the conversion rates.;The experiments were conducted in a unique reactor setup that can conduct gas phase or supercritical phase FT synthesis in both batch or flow modes. The use of the supercritical CO2 (ScCO2) inhibited both CH 4 and CO2 selectivities while enhancing the rates of synthesis. In addition, the use of supercritical CO2 is expected to prolong the life of the catalyst presumably by removing the heat of reaction from the catalyst's surface and solubilizing the waxes that tend to deposit on the surface.;Although not within the scope of this thesis, the products from such a reactor system can be easily separated without the need of an additional unit process simply by tuning the pressure and temperature. The product spectrum and the selectivities for the different products are presented for each set of experiments. The effects of process parameters such as temperature, pressure, N2 partial pressure, and CO2 partial pressure on the product spectrum are also discussed. The clear increase in CO conversion at H2:CO ratio of 1:1 in supercritical phase as compared to gas phase reaction, the decrease in CO2 and CH4 selectivity, and an overall shift in the product distribution towards higher hydrocarbons have been demonstrated. Thus the use of supercritical CO2 has the potential through the FT process to convert coal to liquid fuels using Fe based catalysts, especially since the reactions can be conducted in a two phase regime without losing the benefits of the 3-phase slurry reactor systems.