Collaborative Conversion of Biomass Carbohydrates into Valuable Chemicals: Catalytic Strategy and Mechanism Research.

Levulinate is one of the high added-value biomass-derived chemicals that is primarily produced from hexoses in cellulose and hemicellulose. Producing levulinate from pentoses in hemicellulose that is extensively distributed in biomass is still highly challenging. In this study, biomass materials and carbohydrates (including cellulose, xylan, glucose, fructose, and xylose) were collaboratively converted into levulinates efficiently over various zeolites with ethanol/dimethoxymethane as cosolvents. The key process for converting pentoses into levulinates is the synthesis of intermediates (furfural) into alkoxy methyl furfural via electrophilic substitution or their conversion into furfuryl alcohol via in situ hydrogenation. The substitution was achieved by the synergic effect between bifunctional catalysts and cosolvents, which promotes conversion of furfural into alkoxy methyl furfural via the electrophilic addition of alkoxy methyl radicals. Hydrogenation of furfural into furfuryl alcohol was impelled by the cooperative process between in situ generated H-donor from alcohol solvents and zeolite catalysts. Moreover, a favorable yield of 21.05 mol % of levulinates was achieved by simultaneous and collaborative conversion of cellulose and hemicellulose with the one-pot process using ethanol/dimethoxymethane as a cosolvent and the zeolite with B and L acid sites as a catalyst.