Abstract

Structure and catalytic performance of niobia-supported cobalt catalysts were studied based on crystal phase, porosity and cobalt loading. Crystalline niobia as support proved to be a prerequisite to obtain highly active and selective Co/niobia Fischer–Tropsch catalysts, whereas amorphous niobia showed minimal activity. Crystallization changed the porous morphology of Nb2O5·nH2O resulting in a dense material with low specific pore volume and specific surface area. Multiple impregnations on crystalline Nb2O5 were necessary to achieve cobalt loadings higher than 6wt.%; this led to larger cobalt particles, diminished interaction of cobalt with niobia and therefore decreased activity per unit weight of cobalt and C5+ selectivity. Carbon deposition via sucrose pyrolysis was employed in order to partly maintain the porosity during crystallization. The obtained porous crystalline niobia was used as support for cobalt catalysts with higher metal loadings. STEM-EDX mapping characterization of the catalysts provided unique information for this kind of materials, e.g. cobalt distribution and particle size. The catalysts showed high cobalt-normalized catalytic activity and C5+ selectivity for the Fischer–Tropsch synthesis under industrially relevant conditions. Moreover, higher cobalt loadings led to an increased catalyst-weight normalized catalytic activity.

Highlights

  • Fischer–Tropsch synthesis involves the transformation of synthesis gas to chemicals and ultra-clean fuels

  • Niobium oxide hydrate was characterized by powder X-ray diffraction (XRD) and N2-physisorption after the different thermal treatments

  • The pore structure of amorphous niobium oxide hydrate was determined to be intricate with 2–5 nm mesopores giving rise to high specific surface and pore volume

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Summary

Introduction

Fischer–Tropsch synthesis involves the transformation of synthesis gas (a mixture of H2 and CO) to chemicals and ultra-clean fuels. Niobium oxide hydrate can be effectively used as precursor for niobia via thermal crystallization at temperatures greater than 500 °C as has been shown by Schmal and co-workers [2,3,4] This thermal treatment decreases considerably porosity and specific surface area. Polymerization and pyrolysis over the niobium oxide hydrate surface was employed in order to maintain the porosity during crystallization This facile method resulted in a crystalline niobia material which preserved a great fraction of the mesoporous structure of the niobium oxide hydrate. Material was used as support to prepare cobalt catalysts and tested for the Fischer–Tropsch synthesis These catalysts showed high cobaltspecific catalytic activity and good C5+ selectivity, due to the higher cobalt loading the catalyst weight-based activity was markedly higher

Catalyst preparation
Characterization
Catalytic testing
Niobium oxide hydrate thermal treatment
Modified niobia crystallization
Conclusions
Full Text
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