Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study...Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.展开更多
基金financial support from the National Natural Science Foundation of China (51576064, 51676193)Beijing Nova Program (Z171100001117064)+2 种基金Beijing Natural Science Foundation (3172030)the Foundation of Stake Key Laboratory of Coal Combustion (FSKLCCA1706)the Fundamental Research Funds for the Central Universities (2017MS071, 2016YQ05)
文摘Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.
