The depolymerization of lignin in water/acetone/formic acid synergistic solvents to produce high-value added phenolic monomers without external hydrogen and catalyst

The limited solubility of lignin in commonly used solvents poses a challenge for its depolymerization into high-value monomers. This paper investigates the solubility of alkali lignin in water, methanol, ethanol, acetone, 1,4-dioxane, and their binary solution, and examines their impact on lignin depolymerization. The distribution of depolymerization products was correlated with the chemical structure changes in various solvent. Among the solvents tested, water-acetone mixtures demonstrated exceptional solubility for alkali lignin (95.24%) and provide the highest yield of bio-oil and phenolic monomers. The enhanced solubility of guaiacol units in acetone, combined with the addition of water in the co-solvent system dramatically improved the solubility of alkali lignin. Moreover, formic acid donated hydrogen protons to facilitate lignin depolymerization and prevented the repolymerization of unstable intermediates. Optimal reaction conditions were achieved at 300 °C for 120 mins using a mixed solvent composed of water, acetone, and formic acid in a ratio of 5:5:1 (v/v/v), corresponding to the highest yield of bio-oil with 81.45 wt%, the lowest yield of residue with 6.20 wt%, and a phenolic monomer content of 57.48%. Furthermore, this co-solvent system revealed satisfactory adaptability for converting various lignin into phenolic monomers.