Olivine as tar removal catalyst in biomass gasification : catalyst dynamics under model conditions

Olivine ((Mg,Fe)2SiO4) has been extensively explored as an active bed material for catalytic cracking of tars during gasification of biomass in dual fluidized bed reactors. It is known that both the elemental composition, addition of Fe and high temperature calcinations influence the catalytic properties of this mineral. However, it is not clear how olivine responds to the fairly hostile environments present during gasification or what chemical state Fe takes during operation. We have investigated the stability of Austrian olivine under model conditions, resembling those in a gasifier. Powder samples were heated to 750 °C in a quartz-tube flow-reactor and sequentially exposed to oxidizing (O2, H2O, CO2) or reducing gases (CO, H2) or mixtures thereof, for various durations of time. Significant changes in phase composition of the material, depending on the gas composition and the duration of the treatments, were found using X-ray photo-electron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM). A large fraction of the Fe in the investigated material is present as free Fe-phases, which are sensitive to changes in the gas environment. After exposure to oxidizing gases, the free Fe phases are: Fe2O3 and Fe3O4 or MgFe2O4. Upon exposure to reducing gases, the iron oxides are converted into Fe0 and Fe3C and formation of graphitic carbon is observed. In addition, the elemental composition of the surface changes dramatically depending on the gas composition. After exposure to oxidizing environments, the amount of Fe at the surface is twice as high as after reduction. Both the change in chemical state of the Fe-phases, the amount of surface Fe and the build-up of surface carbon are fast processes under the applied conditions and significant changes are observed on the time scale of one minute. These observations have important implications for olivine as a tar cracking catalyst, especially when used in dual fluidized bed gasifiers. The fast reduction of the iron oxides upon switching from oxidizing to reducing conditions shows that olivine transports oxygen from the combustor into the gasifier. Furthermore, the catalytic properties of Fe depend strongly on its chemical state. Therefore, the catalytic function of olivine depends strongly on the gas environment and on the catalysts residence time in the gasifier. Finally, both the decreasing amount of surface-Fe and the carbon deposition observed after exposing olivine to reducing conditions can result in significant catalyst deactivation