Characterisation of alumina-supported vanadium oxide catalysts by kinetic analysis of H2-TPR data

Alumina-supported vanadium oxide catalysts with vanadium contents of 2, 5 and 11 wt.% were prepared by incipient wetness impregnation and characterised by XRD, Raman spectroscopy and H₂-TPR. The catalysts with the low vanadium contents contained vanadium mainly in the well-dispersed phase, but the catalyst with the highest vanadium content contained also some crystalline AlVO₄ according to XRD and Raman spectroscopic results. The reduction kinetics of the vanadium catalysts was modelled based on the hydrogen consumption during the TPR. The reduction kinetics could be described with a single-reducible-site random nucleation model for the catalyst containing the lowest amount of vanadium. The reduction kinetic models for the other catalysts required a combination of multiple processes to describe the experiments properly. In the catalyst with 5 wt.% V, a part of vanadium species possibly reduces as a homogeneous random nucleation process, but topochemical reduction by nuclei growth also takes place. In the catalyst with 11 wt.% V, reduction by nuclei growth seems to be the predominant reduction mechanism. The characterisation of the reduced catalysts by XRD and during reduction by Raman spectroscopy enabled the identification of the features of the TPR profiles.