The Fischer-Tropsch Reaction Over Ti-Modified Cobalt Catalysts: From Catalyst Preparation Via Oxalate Precursors to Reaction Kinetics Under Transient and Steady State Conditions

Andrew Ronald Raub

doi:10.7273/000005272

This dissertation presents research done to investigate the promoter effects of small amounts of titanium oxides (TiOx) on unsupported cobalt metal catalysts for the atmospheric pressure Fischer-Tropsch (CO+H2) reaction. It is known that cobalt catalysts with TiO2 supports can have their performance for the Fischer-Tropsch reaction enhanced due to interactions between cobalt metal and the support. Small TiOx species can migrate onto the surface of metal particles during reductive treatment, termed the “strong metal-support interaction” (SMSI). Interactions between TiOx species and the cobalt metal are expected to influence its catalytic behavior. Techniques were developed to create unsupported cobalt metal catalysts dosed with controlled amounts of TiOx via oxalate precursors. By eliminating the presence of a supporting material, interactions between cobalt metal and TiOx could be focused on. This is the first time that TiOx alone has been studied as a promoter species in controlled amounts over an unsupported cobalt catalyst for the atmospheric pressure CO+H2 reaction. Steady state and chemical transient kinetic (CTK) reaction studies revealed that very small amounts of Ti (~1-2 atom%, relative to cobalt) induce changes in the catalyst structure and product selectivity. The addition of TiOx to the cobalt resulted in increased selectivity toward alkenes and suppression of CH4 and C2H6 that persisted over long reaction times. When TiOx is present, CTK measurements revealed the presence of surface intermediates that are absent over pure cobalt and react with different kinetics to form chain lengthened hydrocarbons. Estimated carbon amounts on the catalyst surfaces showed ~3 carbon atoms/cobalt metal site for pure cobalt catalysts, and ~5-6 carbon atoms/cobalt metal site for Ti-modified cobalt catalysts. General observations made about formation and decay behavior for hydrocarbon products during CTK studies were in good agreement with those obtained for similar work done on CoMgO and CoMnOx catalysts. Suggestions for the direction of future work on Ti-modified cobalt catalysts are made at the end of this dissertation. Some effort has also been spent on using methyl formate, which can be considered a liquid form of syngas, to produce chain lengthened hydrocarbons using CoMnTi catalysts. This ternary catalyst composition was selected due to its industrial relevance. Some transient kinetic studies were performed but turned out challenging to interpret due to the complexity of parallel decomposition pathways for methyl formate. In view of the complexity of the CoMnTi catalyst composition, it was deemed important to first focus on the CoTi case as a prerequisite for studying more complicated catalyst formulations.

The Fischer-Tropsch Reaction Over Ti-Modified Cobalt Catalysts: From Catalyst Preparation Via Oxalate Precursors to Reaction Kinetics Under Transient and Steady State Conditions

Files and links (1)

Abstract

Metrics

Details