In situ Mössbauer Spectroscopy Study of the Activation and Reducibility of Chromium- and Aluminium-doped Iron Oxide based Water-Gas Shift Catalysts under Industrially Relevant Conditions

The influence of chromium and aluminium doping on the over-reduction during activation of iron-oxide-based water-gas shift catalysts was investigated using Mössbauer spectroscopy for the first time. In situ Mössbauer spectra of catalysts exposed to industrially relevant gas compositions were recorded with increasingly reducing R factors R = [CO]*[H2]/[CO2]*[H2O]. Whereas α-Fe and cementite formed during exposure of a non-doped iron-oxide catalyst to process conditions with an R factor of 2.09, such phases were only observed at R = 4.60 for a chromium-doped catalyst, showing that chromium stabilizes the catalyst. Over-reduction was enhanced to R = 2.88 in a chromium-copper co-doped catalyst. α-Fe was already observed at R = 1.64 in an aluminium-doped catalyst, while cementite formation occurred at R = 2.09, showing that over-reduction was enhanced, the presence of aluminium delaying carburization. Co-doping copper in the aluminium-doped catalyst showed cementite formation at R = 2.09, the same as a non-doped catalyst.