Synthesis strategies of Zr- and Y-promoted mixed oxides derived from double-layered hydroxides for syngas production via dry reforming of methane

Abstract

Ni-based Mg/Al double-layered hydroxides, also called hydrotalcites (HTs), were co-precipitated with Zr (5 wt%) and impregnated with Y (0.2, 0.4, 0.6 wt%), and compared to the catalyst co-precipitated with both Y (0.4 wt%) and Zr (5 wt%). Their performance in dry reforming of methane was determined in the temperature range of 850–600 °C and stability tests at 700 °C for 5 h. The materials were characterized by X-ray powder diffraction, X-ray fluorescence, nitrogen adsorption/desorption, H2-TPR, CO2-TPD, hydrogen chemisorption, thermogravimetric analysis, transmission electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. A decrease in reducibility and lower total number of basic sites were observed for the sample promoted only with zirconia compared to the unpromoted material. After promotion with yttrium, no formation of ZrO2–Y2O3 solid solution was evident from XRD. The Ni dispersion was decreased due to decoration of the surface with Y species, leading to blockage of available nickel sites. All Zr and Y promoted samples were, however, more active in DRM than unpromoted HTNi. The co-precipitated Zr and Y catalyst (HTNi-ZrY0.4-cop) exhibited increasing conversion over time, and a H2/CO close to 1 in the isothermal test at 700 °C. H2-TPSR on the spent catalysts revealed that the promotion with yttrium favored regeneration of the catalytic bed, consuming the majority of removable coke and decreasing the formation of unreactive coke.