A series of metal-modified phosphotungstates were prepared and performed for direct synthesis of ethyl levulinate from fructose in ethanol. Considering the cost of catalysts, catalytic activity of catalysts, and easy separation of catalysts together, K-HPW-1 was chosen as the most suitable catalyst for synthesis of ethyl levulinate from fructose. A high ethyl levulinate yield of 64.6 mol% was obtained at 150 °C within 2 h in ethanol. The introduction of low polar toluene as a co-solvent improved the yield of ethyl levulinate to 68.7 mol%. The recovered catalyst remained high activity with the yield of ethyl levulinate converted from fructose above 50 mol% after being used five times. Moreover, the generality of the catalyst was further demonstrated by glucose, sucrose, inulin, and cellulose with ethyl levulinate yielding 14.5, 35.4, 52.3, and 14.8 mol%, respectively.

The fundamental understanding of glucose conversion to 5-ethoxymethylfurfural (EMF) and ethyl levulinate (EL) (value-added chemicals from biomass) in ethanol solution catalyzed by a Brønsted acid is limited at present. Consequently, here, the reaction pathways and mechanism of glucose conversion to EMF and EL catalyzed by a Brønsted acid were studied, using an experimental method and quantum chemical calculations at the B3LYP/6-31G(D) and B2PLYPD3/Def2TZVP level under a polarized continuum model (PCM-SMD). By further verification through GC/MS tests, the mechanism and reaction pathways of glucose conversion in ethanol solution catalyzed by a Brønsted acid were revealed, showing that glucose is catalyzed by proton and ethanol, and ethanol plays a bridging role in the process of proton transfer. There are three main reaction pathways: through glucose and ethyl glucoside (G/EG), through fructose, 5-hydroxymethylfurfural (HMF), levulinic acid (LA), and EL (G/F/H/L/EL), and through fructose, HMF, EMF, and EL (G/F/H/E/EL). The G/F/H/E/EL pathway with an energy barrier of 20.8 kcal mol⁻¹ is considered as the thermodynamic and kinetics primary way, in which the reaction rate of this is highly related to the proton transfer in the isomerization of glucose to fructose. The intermediate HMF was formed from O5 via a ring-opening reaction and by the dehydration of fructose, and was further converted to the main product of EMF by etherification or by LA through hydrolysis. EMF and LA are both unstable, and can partially be transformed to EL. This study is beneficial for the insights aiding the understanding of the process and products controlling biomass conversion in ethanol solution.

5-Ethoxymethylfurfural (EMF) is a new type of biofuel with a high energy density and excellent fuel properties. One-pot production of EMF from renewable carbohydrate catalyzed by heterogeneous catalysts has the potential to be an attractive reaction pathway. In this study, fructose was directly converted to EMF in ethanol medium catalyzed by ultra stable Y zeolite (USY). The effects of different reaction conditions on EMF yields were investigated, and an optimum reaction condition was obtained by utilizing response surface methodology. Under the optimum reaction conditions, which were a temperature of 132 °C, substrate density of 60 g/L, and catalyst dosage of 2.1 wt%, a maximum EMF yield of 73.8 mol% with the prediction error of 1.6% was achieved in 25 min. Moreover, the reusability of USY and characterization were evaluated. This study demonstrated a promising strategy for EMF production from fructose.