ABSTRACT
Natural kaolin-based Ni catalysts have been developed for low-temperature CO2 methanation. The catalysts were prepared via a one-step co-impregnation of Ni and Ce onto a natural kaolin-derived metakaolin using a microwave-assisted hydrothermal method as an acid-/base-free synthesis method. The influences of microwave irradiation and Ce promotion on the catalytic enhancement including the CO2 conversion, CH4 selectivity, and CH4 yield were experimentally investigated by a catalytic test of as-prepared catalysts in a fixed-bed tubular reactor. The relationship between the catalyst properties and its methanation activities was revealed by various characterization techniques including X-ray fluorescence, X-ray diffraction, Brunauer-Emmett-Teller, scanning electron microscopy, selected area electron diffraction, transmission electron microscopy, elemental mapping, H2 temperature-programmed reduction, and X-ray absorption near-edge structure analyses. Among the two enhancement methods, microwave and Ce promotion, the microwave-assisted synthesis could produce a catalyst containing highly dispersed Ni particles with a smaller Ni crystallite size and higher catalyst reducibility, resulting in a higher CO2 conversion from 1.6 to 7.5% and a better CH4 selectivity from 76.3 to 79.9% at 300 °C. Meanwhile, the enhancement by Ce addition exhibited a great improvement on the catalyst activities. It was experimentally found that the CO2 conversion increased approximately 7-fold from 7.5 to 52.9%, while the CH4 selectivity significantly improved from 79.9 to 98.0% at 300 °C. Though the microwave-assisted synthesis could further improve the catalyst activities of Ce-promoted catalysts, the Ce addition exhibited a more prominent impact than the microwave enhancement. Cerium oxide (CeO2) improved the catalyst activities through mechanisms of higher CO2 adsorption capacity with its basic sites and the unique structure of CeO2 with a reversible valence change of Ce4+ and Ce3+ and high oxygen vacancies. However, it was found that the catalyst prepared by microwave-assisted synthesis and Ce promotion proved to be the optimum catalyst in this study. Therefore, the present work demonstrated the potential to synthesize a nickel-based catalyst with improved catalytic activities by adding a small amount of Ce as a catalytic promoter and employing microwave irradiation for improving the Ni dispersion.
ABSTRACT
In this paper, a facile synthesis method for CaFe2O4 is introduced that produces a catalyst capable of significant photocatalytic degradation of POME under visible light irradiation. The co-precipitation method was used to produce two catalysts at calcination temperatures of 550⯰C and 700⯰C dubbed CP550 and CP700. CP550 demonstrated the maximum COD removal of 69.0% at 0.75â¯g/L catalyst loading after 8â¯h of visible light irradiation which dropped to 61.0% after three consecutive cycles. SEM images indicated that the higher calcination temperature of CP700 led to annealing which reduced the pore volume (0.025â¯cm3/g) and pore diameter (10.3â¯nm) while simultaneously creating a smoother and more spherical surface with lower SBET (9.73â¯m2/g). In comparison, CP550 had a rough hair-like surface with higher SBET (27.28â¯m2/g) and pore volume (0.077â¯cm3/g) as evidenced by BET analysis. XRD data indicated the presence of CaFe5O7 in the CP550 composition which was not present in CP700. The presence of Wustite-like FeO structures in CaFe5O7 are likely the cause for lower photoluminescence intensity profile and hence better charge separation of CP550 as these structures in CaFe2O4 have been known to increase resistivity and electron localization. The COD removal of CP550 dropped from 69.0% to just 7.0% upon adding a small quantity of isopropanol into the reaction mixture indicating hydroxyl radicals as the primary reactive oxidative species.
