Synthesis of biomass-derived ethyl levulinate from steam-exploded corn straw

Abstract

Ethyl levulinate (EL) production from steam-exploded corn straw (SCS) in a cascade of reaction using a Brønsted (B) acid and a Lewis (L) acid in ethanol was studied. The entangled structure of corn straw could be obviously damaged through steam explosion when the pressure was 1.5 MPa holding 10 min. The content of cellulose can be increased from 35.9% to 46.8%, and the contents of hemicellulose and lignin were changed from 16.7% to 8.8% and 22.6% to 27.5%, respectively. EL yield was significantly increased from 10.7 to 24.6 wt% under optimal reaction conditions (L/B = 1/20 [mol/mol], 205°C, 90 min, 1.8 g of SCS, 60 mL of ethanol). According to kinetic models, the activation energies for the main and side reactions were 56.8 and 110.5 kJ mol⁻¹, respectively. It suggested that SCS was more easily to be converted to EL rather than other by-products. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gaps (HOMO-LUMO gaps) of cellobiose over the mixed acids in ethanol were significantly reduced with frontier molecular orbital (FMO) theory. This work provides an effective strategy for EL production from agricultural waste straws.