In Situ Regeneration of Alumina-Supported Cobalt–Iron Catalysts for Hydrogen Production by Catalytic Methane Decomposition

Abstract

A novel approach to the in situ regeneration of a spent alumina-supported cobalt–iron catalyst for catalytic methane decomposition is reported in this work. The spent catalyst was obtained after testing fresh catalyst in catalytic methane decomposition reaction during 90 min. The regeneration evaluated the effect of forced periodic cycling; the cycles of regeneration were performed in situ at 700 °C under diluted O2 gasifying agent (10% O2/N2), followed by inert treatment under N2. The obtained regenerated catalysts at different cycles were tested again in catalytic methane decomposition reaction. Fresh, spent, and spent/regenerated materials were characterized using X-ray powder diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), N2-physisorption, H2-temperature programmed reduction (H2-TPR), thermogravimetric analysis (TGA), and atomic absorption spectroscopy (AAS). The comparison of transmission electron microscope and X-ray powder diffraction characterizations of spent and spent/regenerated catalysts showed the formation of a significant amount of carbon on the surface with a densification of catalyst particles after each catalytic methane decomposition reaction preceded by regeneration. The activity results confirm that the methane decomposition after regeneration cycles leads to a permanent deactivation of catalysts certainly provoked by the coke deposition. Indeed, it is likely that some active iron sites cannot be regenerated totally despite the forced periodic cycling.