The?study?of?catalytic?preparation?amine?compounds?from?biomass-based?alcohols

With the development of green and clean renewable biomass resources catalysis technology,the comprehensive utilization of biomass resources has been continuously improved,and the production of high value-added biomass-based derivatives has become hot research topics.Among them,amine compounds were prepared using biomass-based alcohols and carbonyl compounds,which can be widely used in the field of pharmaceutical and chemical engineering.Therefore,this paper starts from biomass-based alcohols and uses a simple and effective two-step conversion method to prepare widely applied amine compounds.The main content of the thesis is:(1)Series of highly efficient,selective and reusable environment-friendly,cesium-doped manganese oxide catalysts(Cs/MnO_x)were prepared.After Cs⁺ doped to MnO_x,the basicity of MnO_x is enhanced,the oxygen vacancy defects are increased.Cs/MnO_x catalysts have larger specific surface area and richer pore structure than MnO_x.Therefore,Cs/MnO_x catalysts have higher catalytic activity than that of traditional MnO_x,VO_x/TiO₂,and OMS-2 catalysts.Under mild conditions,the molecular oxygen(O₂)is activated by Cs/MnO_x to promote 5-hydroxymethylfurfural(HMF),benzyl alcohol,n-octanol and other biomass alcohols oxidized into carbonyl compounds such as 2,5-diformylfuran(DFF),benzaldehyde,n-octaldehyde.The yield is as high as 87.6 99.1%.In addition,fructose was oxidized by using a combination of Amberlyst-15 and Cs/MnO_x composite catalysts through a "two-step,one-pot process",the target product 2,5-diformylfuran(DFF)was finally obtained with the yield of 82%.(2)A novel nitrogen-doped carbon material supported Co nanoparticles catalyst(Co@NC-800)was prepared using o-phenylenediamine as a ligand.The catalyst has high catalytic activity for the reductive amination reaction of various carbonyl compounds.Under mild conditions,it demonstrated high efficiency for the selectively produce of amine compounds from biomass-based alcohol compounds such as HMF,furfuryl alcohol,benzyl alcohol,et al.The derivatized carbonyl compounds are reductively aminated to the corresponding primary amines with high selectivity and high yields ranging from 82.1 99.6%.The kinetic study of the reductive amination reaction of carbonyl compounds showed that the imine was the intermediate of this reaction,the increase of concentration of NH₃ promoted the conversion of imine into primary amine.More importantly,the prepared Co@NC-800 catalyst has good stability,and catalytic activity in recycling experiment.It is a highly efficient,selective and reusable environment-friendly catalyst,which will be beneficial for industrial applications.