Acid-promoted lignin reductive depolymerization under mild conditions via a condensation minimizing approach: From organosolv lignin to woody biomass

Lignin reductive depolymerization into phenolic monomers is a critical step for the scale-conversion of lignin into liquid fuels but its scale-up is still compromised by harsh reaction conditions (e.g. high temperature and high external H2 pressure) and inevitable condensations. Herein, we present an efficient acid-promoted reductive depolymerization of lignin over Ni/C without external H2 via a condensation minimizing approach using lignin monomer analogue (p-hydroxybenzyl alcohol, HBA) as the capping agent. With addition of 0.4 % H2SO4 and 0.4 mmol/g HBA, 20.42 % of phenolic monomer yield along with 31.70 % oligomer yield was achieved at 160 degrees C while the condensated/undepolymerized lignin yield was less than 10 %. HBA inhibited the acid-induced condensation by competitive reaction with the nucleophilic C6 in guaiacyl unit. When the approach was applied in lignin-first reductive fractionation of poplar, 32.72 % of phenolic monomer yield and 76.59 % of delignification were achieved at 160 degrees C in the presence of acid and HBA. Additionally, xylan was dissociated concurrently owing to the acid-catalyzed hydrolysis, resulting in a cellulose-rich solid residue. Consequently, this work proposes an efficient approach for lignin reductive depolymerization and lignin-first biomass fractionation under mild conditions through the synergism of acid and capping agent.

Automated summary

This study presents an efficient acid-promoted reductive depolymerization of lignin using lignin monomer analogues as a capping agent, achieving high yields of phenolic monomers and oligomers under mild conditions without external H2. The approach was also successful in lignin-first biomass fractionation, resulting in high yields of phenolic monomers and delignification, as well as concurrent dissociation of xylan.