The first half of this dissertation reports the development of supported Fe FT catalysts including the effects of various, carefully chosen preparation methods on the performance of alumina-supported iron/copper/potassium (FeCuK/Al2O3); it was determined that non-aqueous slurry impregnation and co-impregnation yielded catalysts with activities as high as any reported in the literature. Furthermore, the effects of support properties including pore size, hydroxyl group concentration, and support stabilizer were investigated for FeCuK/Al2O3 catalysts containing 20 or 40% Fe. For the first time, we report the performance of a supported Fe FT catalyst that is not only more active and stable than any supported Fe catalyst previously reported, but also has activity equivalent to that of the most active, unsupported catalysts. More importantly, the catalyst is extremely stable as evidenced by the fact that after 700 h on stream, its activity and productivity are still increasing. These catalyst properties result from the use of a novel γ-alumina support material doped with silica and pretreated at 1100°C. This unique support has a high pore volume, large pore diameter, and unusually high thermal stability. The ability to pretreat this support at 1100°C enables preparation of a material having a low number of acid sites and weak metal oxide-support interactions, all desirable properties for an FT catalyst. The second half of this dissertation investigates the effects of operating conditions including the partial pressures of CO and H2 and temperature on the deactivation by carbon of 25 wt% Co/ 0.25 wt% Pt/Al2O3 catalyst. It also reports the kinetics of the main FT reaction on this catalyst. As temperature increases, the H2 and CO orders for the main reaction (in the absence of deactivation) become more positive and more negative, respectively. A new mechanism was proposed to account for the inhibition effect of CO at high reaction temperatures, which includes H-assisted dissociation of CO to C* and OH*. Further, twelve samples of the CoPt/Al2O3 catalyst were tested over a period of 800 hours and XCO < 24%, each at a different set of CO and H2 partial pressures and temperature (220-250°C). At reaction temperature of 230°C, increasing PCO or PH2 increases the deactivation rate; possibly due to formation of polymeric carbons. The H2 and CO partial pressure orders for the deactivation rate at 230°C were found to be 1.12 and 1.43, respectively using a generalized-power-law-expression (GPLE) with limiting activity of 0.7 and 1st order deactivation. For a H2/CO of 2 (PH2 = 10 bar and PCO = 5 bar) the deactivation rate increases as process temperature increases from 220 to 250°C with an activation energy of 81 kJ/mol. However, at higher CO partial pressure (PCO = 10 bar) the deactivation rate for the Co catalyst of this study decreases with increasing temperature; this can possibly be attributed to the formation of more active cobalt sites at higher temperatures due to surface reconstruction.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

Fischer-Tropsch Synthesis (FTS) is a promising technology for the production of ultra-clean fuels and chemical feedstocks from biomass, coal, or natural gas. Iron catalysts are ideal for conversion of coal and biomass. However, precipitated iron catalysts used in slurry-bubble column reactors suffer from high attrition resulting in difficulty separating catalysts from product and increased slurry viscosity. Thus, development of an active and selective-supported iron catalyst to manage attrition is needed. This thesis focuses on the development of a supported iron catalyst and kinetic models of FTS on the catalyst using advanced statistical methods for experimental design and analysis. A high surface area alumina, modified by the addition of approximately 2 wt% lanthanum, was impregnated with approximately 20 wt% Fe and 1% Pt in a two step procedure. Approximately 10 wt% Fe and 0.5 wt% Pt was added in each step. The catalyst had a CO uptake of 702 μmol/g, extent of reduction of 69%, and was reduced at 450°C. The catalyst was stable over H2 partial pressures of 4-10 atm, CO partial pressures of 1-4 atm, and temperatures of 220-260°C. Weisz modulus values were less than 0.15. A Langmuir-Hinshelwood type rate expression, derived from a proposed FTS mechanism, was used with D-optimal criterion to develop experiments sequentially at 220°C and 239°C. Joint likelihood confidence regions for the rate expression parameters with respect to run number indicate rapid convergence to precise-parameter estimates. Difficulty controlling the process at the designed conditions and steep gradients around the D-optimal criterion resulted in consecutive runs having the same optimal condition. In these situations another process condition was chosen to avoid consecutive replication of the same process condition. A kinetic model which incorporated temperature effects was also regressed. Likelihood and bootstrap confidence intervals suggested that the model parameters were precise. Histograms and skewness statistics calculated from Bootstrap resampling show parameter-effect nonlinearities were small.