Efficient non-catalytic depolymerization of lignin in hydrogen donor solvent for monomeric phenols and its pathways

Thermal degradation of lignin in hydrogen donor solvent (HDS) has been reported to be an efficient method to generate aromatics and phenols. High pressure H2 and catalyst are not required which simplifies this degradation method. This work aims to advance the knowledge of reaction pathway with depolymerization of enzymatic hydrolysis lignin (EHL) in 9,10-dihydroanthracene (DHA) as an example. For this purpose, the liquid products were characterized in detail by GC, GPC, 31P NMR and 2D-HSQC NMR. Results indicate that the yield of monomeric phenols is up to 20.2 wt% at 375–400 °C. This yield is comparable to literature results with high-pressure H2 and catalysts at 220–320 °C. The depolymerization starts with the cleavage of ether linkages and decarboxylation of acrylate linkages, which are followed by the removal of aliphatic-OH, hydrogenation of Cal = Cal, decarbonylation of Cal = O, dealkylation of alkyl substituents and demethylation of aromatic-methoxy groups. The amount of phenolic-OH is about 2.78 mmol/g in the liquid product obtained at 400 °C: 36% from the cleavage of β-O-4 and α-O-4 linkages and about 16% from the demethylation of aromatic-methoxy group. The number-average molecular weight is roughly inversely proportional to the amount of bond cleavage.