Transformation Furfural Derivatives Into Oxygenated Compounds By Catalytic Process

As renewable carbonaceous resource,biomass is abundant in nature.And it contains a large number of oxygen atoms and specific structural units.Making full use of the structure to preparation high-value chemicals has the potential advantage for development.Furfural is an important bio-based platform compound which produced from agricultural and forestry wastes such as corn cob and bagasse in the industry with the mature production process.China is a country with abundant agricultural that can provide raw materials for production of furfural.And the development of downstream products of furfural is of great significance to improving the national economy.1,2-Pentanediol and gamma-butyrolactone are important fine chemicals with high valued which had large demand.The use of furfural derivatives for the preparation of 1,2-pentanediol and?-butyrolactone is of great significance for the utilization of biomass.1,2-pentanediol and furfural alcohol have five carbon atoms.And both gamma-butyrolactone and tetrahydrofurfuryl alcohol?furfural derivatives?have similar structural units?such as oxygen-containing five-membered rings?with similar ratio of C/H and C/O.Herein,we investigated catalytic of furfural derivatives including furfuryl alcohol and tetrahydrofurfuryl alcohol to 1,2-Pentanediol and gamma-butyrolactone.In this paper,a novel method for the preparation of 1,2-pentanediol through hydrogenolysis of furfuryl alcohol catalyzed by Cu/MnCO3 was focued.By investigating the catalytic activity of different supported Cu catalysts,it was found that Cu/MnCO₃ exhibits good catalytic activity for the hydrogenolysis of furfuryl alcohol.Subsequently,the catalytic activity of Cu/MnCO₃ was also investigated under various experimental conditions.With isopropanol as solvent,furfural alcohol with 81%conversion and 1,2-pentanediol with 50%selectivity could be obtained at 413 K and 6 MPa H₂ catalyzed by Cu/MnCO₃ whose ratio of Cu and Mn is 1:2.The stability of products showed that the pivotal intermediate of furfural alcohol to 1,2-pentanediol is not tetrahydrofurfuryl alcohol.Tetrahydrofurfuryl alcohol is converted into gamma-butyrolactone with the C-C bond cleavage catalyzed by vanadium oxides.The catalytic activity of different vanadium oxides was investigated and it was found that VO?mal?2 exhibited good catalytic activity for tetrahydrofurfuryl alcohol.The effects of experimental conditions such as reaction temperature,pressure,solvent and reaction time on the catalytic activity were investigated.Without solvent,tetrahydrofurfural alcohol with 98%conversion and gamma-butyrolactone with 71%selectivity could be obtained at 373 K and 1.5 MPa O₂ catalyzed by 1 mol%VO?mal?₂.According to the change rule and stability analysis of each product with the reaction time,tetrahydrofurfuryl alcohol was obtained.Tetrahydrofurfural formate and tetrahydrofurfuric acid are two intermediates for the oxidation of tetrahydrofurfuryl alcohol to?-butyrolactone.In this study,biomass and its derivatives were used as raw materials to develop a new method for the production of 1,2-pentanediol and?-butyrolactone.This method can not only reduce the dependence on fossil resources,but also provide a new idea to make full use of biomass.