Study On Catalytic Hydrogenation Of Furfural To Furfuryl Alcohol/methyl Furan

Biomass resources can be transformed into a variety of biomass-based platform compounds by hydrolysis,acidolysis and other technologies.Due to the extensive industrial use of furfural（FFR）,its abundant downstream product lines and its advantages as raw material for bulk industrial products,the research on the synthesis of downstream derivatives from FFR has attracted wide attention in recent years.Among the downstream products of FFR,furfuryl alcohol（FFA）is a very important monomer,industrial solvent and intermediate in the synthesis of furan resin,and methylfuran（MF）has excellent combustion performance,high oxygen content and high octane number,so it can be used as fuel additive.In addition,MF can also be used as solvent and raw material to produce antimalarial drugs（chloroquine）,chrysanthemum pesticides,spices and other important organic compounds.According to the industrial value of FFA and MF,we need to develop more green,efficient,stable and selective catalysts in the synthesis process.we developed and synthesized Co₃Al₁O_x oxide catalyst and in-situ Cu-Ni3 catalyst,and systematically studied their catalytic performance for FFR to prepare FFA and MF.A Co₃Al₁O_x catalyst was developed to catalyze furfural（FFR）to furfuryl alcohol（FFA）.Co₃Al₁O_x catalyst was screened as the best catalyst,in 1,4-dioxane solvent,98.95%FFR conversion and 96.25%FFA yield were obtained under the reaction conditions of 170℃,2 MPa H2 and 3 h.And the catalyst had good reusability.Through XRD,H2-TPR,NH3-TPD and XPS analysis,it was found that the specific surface area,pore volume,pore size and acid site strength of the catalyst were greatly affected by the Co/Al ratio,which further affected the conversion of furfural（FFR）and the yield of furfural alcohol（FFA）.By adjusting the proportion of active metal components in bimetallic oxides,Co3AIOx catalyst with better catalytic activity for conversion of FFR to FFA was obtained.The structure analysis of the catalyst showed that it existed in the form of mixed phase of CoAl2O4 and Co2O3.An in-situ Cu1Ni3 catalyst system for converting FFR into MF was established.The preparation of in-situ Cu1Ni3 catalyst was based on the decomposition of formic acid to produce hydrogen to provide reducibility.In the experiment,Cu（HCOO）2·4H2O and NiCO3·2Ni（OH）2·4H2O were used as precursors to prepare in-situ Cu1Ni3 catalyst.During the formation of in-situ Cu1Ni3 catalyst,FFR was reduced to FFA.The preparation of catalyst and one pot hydrogenation reduction of FFR were realized simultaneously.At 170℃ for 12 h,the conversion of FFR was 93.4%,the selectivity of MF was 79.1%,and the yield was 73.8%.Due to the formation of Cu/Ni alloy in the process of catalyst synthesis,the catalyst particles were significantly smaller than those of in-situ monometallic catalysts,and have larger specific surface area,pore volume,pore size and moderate surface acidity,which promoted the selectivity towards MF.Compared with the CuiNi3 catalyst prepared by coprecipitation method,the in-situ Cu1Ni3 catalyst showed better performance in reducing FFR to MF under low pressure.