One of the most effective and renewable utilization methods for lignocellulosic feedstocks is the transformation from solid materials to liquid products. In this work, corn stalk (CS) was liquified with polyethylene glycol 400 (PEG400) and glycerol as the liquefaction solvents, and sulfuric acid as the catalyst. The liquefaction conditions were optimized with the liquefaction yield of 95.39% at the reaction conditions of 150 °C and 120 min. The properties of CS and liquefaction residues (LRs) were characterized using ATR–FTIR, TG, elemental analysis and SEM. The chemical components of liquefied product (LP) were also characterized by GC–MS. The results indicated that the depolymerization and repolymerization reaction took place simultaneously in the liquefaction process. The depolymerization of CS mainly occurred at the temperature of <150 °C, and the repolymerization of biomass derivatives dominated at a higher temperature of 170 °C by the lignin derivatives repolymerization with cellulose derivatives, hemicellulose derivatives and PEG400 and self-condensation of lignin derivatives. The solvolysis liquefaction of CS could be classified into the mechanism of electrophilic substitution reaction attacked by the hydrogen cation.
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