Theoretical and experimental study of 5-ethoxymethylfurfural and ethyl levulinate production from cellulose

Theoretical simulations and experiments were taken to explore the mechanism of cellulose conversion into 5-ethoxymethylfurfural (EMF) and ethyl levulinate (EL) catalyzed by a mixed acid of Lewis acid and Brønsted acid. Up to 64.8 % total yield of EMF and EL can be obtained when the ratios of Lewis/Brønsted acid and water/ethanol (v/v) were 1:2 and 3:7 respectively. The results showed that Lewis acid and water could reduce the activation energy of EMF formation from 75.6 to 47.9 kJ mol−1, and mixed acids and water/ethanol system were beneficial to the accumulation of EMF. Moreover, the results of molecular dynamics (MD) simulation indicated that Lewis acid could promote the distribution of Bronsted acid around the β-1,4 glycosidic bond of cellobiose. The combination of DFT and frontier molecular orbital (FMO) calculation demonstrated that the breakage of the β-1,4 glycosidic bond was the main rate-limiting step of cellulose hydrolysis. Meanwhile, the mixed acid and water/ethanol system could accelerate the hydrolysis due to the reducing energy barrier and HOMO-LUMO gap. This study gave a deep insight into the mechanism of Lewis acid with Brønsted acid on cellulose conversion into EMF and EL.