Fischer–Tropsch Synthesis: Preconditioning Effects Upon Co-Containing Promoted and Unpromoted Catalysts

Abstract

In the preparation and evaluation of Fischer–Tropsch (FT) catalysts, active catalysts formed by both incipient wetness impregnation (IWI) and atomic layer deposition (ALD) of major components were demonstrated. ALD-deposited Co on a silica support was more effective than a similar catalyst deposited upon a support of ALD-deposited Al2O3 on silica. The addition of Co reduction promoters including Pt, Ir and Ru using either ALD or IWI has been shown to strongly affect the catalyst pre-conditioning step. CO conversion results were consistent with previously reported Temperature Programmed Reduction X-ray Absorption Near-edge Structure/Extended X-ray Absorption Fine Structure Spectroscopy (TPR-XANES/EXAFS) experiments observing the nature of chemical transformations occurring during the activation of cobalt-based FT catalysts in hydrogen. Specifically, there exists a 2-step reduction process involving Co3O4 to CoO and CoO to Co0 transformations. The extent of catalyst preconditioning was strongly affected by the reduction temperature (with 400 °C preferred) and the loading of the promoter. This was demonstrated using a continuous-flow catalytic-bed unit with a 2:1 molar blend of H2:CO, at temperatures ranging from about 260 to 300 °C, pressures averaging 1.3 MPa (190 psia), and gas space velocities about 24 NL/h-g.