| The rapid development of human society relies on fossil fuels,which leads to a series of social problems such as environmental pollution,man-made climate change and resource and energy crisis.Therefore,under the promotion of green and sustainable development,the catalytic upgrading of compounds from biomass derivatives platform into fuels and chemicals has become a research hotspot.Biomass is a cheap,eco-friendly,renewable natural carbon source with abundant reserves.Therefore,it has a broad application prospect in solving energy and environmental problems.Furfural is a potential multi-purpose biomass platform compound,which can be obtained from pentose rich in other agricultural wastes such as wood chips,corn stalks through acid catalyzed hydrolysis and dehydration.In terms of structure and composition,furfural is a kind of unsaturated aldehyde compounds.By hydrogenation of furfural and its derivatives,furfural alcohol,dimethylfuran,tetrahydrofurfural alcohol,levulinic acid(levulinate)and y-valerolactone and other chemicals and biofuels can be obtained.In this study,three kinds of metal-supported functionalized ordered mesoporous carbon materials were prepared as catalysts,and high value-added chemicals such as furfuryl alcohol,ethyl levulinate and y-valerolactone were obtained by hydrogenation of furfural and its derivatives with biomass derivatives as substrates.The best experimental results were obtained by selecting the catalysts and optimizing the experimental conditions.Nickel-crosslinked ordered mesoporous carbon(Ni@OMC)was prepared by solvent evaporation-induced self-assembly method.The influence of synthesis conditions on the formation of ordered mesoporous structure was investigated.The morphology,pore structure and metal morphology of the synthesized catalyst were characterized by TEM,XRD and N2 adsorption-desorption tests.In the catalytic test,furfural was used as the substrate to investigate the catalytic effect of Ni@OMC prepared at different calcination temperatures,and the Ni0.5@OMC-600 with the best catalytic activity were screened out.It was used to optimize the reaction conditions(reaction solvent,temperature,hydrogen pressure and catalyst dosage,etc.),the Furfural was completely converted and the FFA yield reached 98%in the n-propanol solvent at 180℃,hydrogen partial pressure of 3 MPa,and the reaction time of 4 h.The niobium/nickel bifunctional functional catalyst(Nb/Ni@OMC)was prepared by a two-step method.First,the catalyst Ni@OMC was prepared by solvent evaporation induced self-assembly,and then the catalyst was used as a carrier,and Nb/Ni@OMC was prepared by an incipient-wetness impregnation method with different niobium loadings.Similarly,using furfural as the substrate,the catalytic effect of the conversion of furfural to ethyl levulinate with different niobium loadings of Nb/Ni@OMC in ethanol solvent was investigated,and the catalytic effect of Nb/Ni@OMC with 10%niobium loads was the best.10%Nb/Ni@OMC was selected to explore the effects of temperature,hydrogen pressure,and catalyst dosage on the yield of ethyl levulinate,the conversion of furfural,and the catalytic reaction path.Under the optimal experimental conditions,the yield of ethyl levulinate was 82%.The nickel-zinc bimetallic catalyst(Ni-Zn@OMC)was prepared in one step using the solvent evaporation-induced self-assembly method.Using levulinic acid as the substrate,the catalytic effect of Ni-Zn@OMC with different ratios of nickel to zinc on levulinic acid to catalyze the production of y-valerolactone was explored,and the Ni-Zn@OMC had the best catalytic activity when the ratio of Ni:Zn was 1:1.Ni-Zn(1:1)@OMC was used to optimized for reaction conditions,and the effects of reaction temperature,hydrogen pressure and catalyst dosage on the yield of y-valerolactone and the conversion of levulinic acid were explored.Under the conditions of 180℃,2 MPa hydrogen partial pressure and 90 min,93%y-valerolactone yield was obtainedIn this study,a green and simple solvent evaporation induced self-assembly method was developed to prepare metal loaded ordered mesoporous carbon.The catalyst prepared based on this strategy realized the efficient catalytic conversion of furfural based biomass,and expanded the application of ordered mesoporous carbon in biomass value-added conversion. |
