Selective Cleavage of Methylene Linkage in Kraft Lignin over Commercial Zeolite in Isopropanol

Lignin is an aromatic polymer that constitutes over 30 wt% of lignocellulosic biomass and is the most important source of renewable aromatics in nature. The global paper industry generates more than 70 million tons of Kraft lignin annually. Depolymerization of Kraft lignin to value-added monomers can significantly enhance the profitability of biorefinery. However, the method is impeded by the severe condensation of Kraft lignin during the pulping process, which forms robust C-C bonds and results in low monomer yields. In this study, we present a stepwise approach for producing valuable aromatic monomers from Kraft lignin through the cleavage of both C-O and C-C bonds. The approach initiated with complete cleavage of C-O bonds between lignin units within Kraft lignin through alcoholysis in isopropanol, resulting in a monomer yield of 8.9 %. Subsequently, the selective cleavage of methylene linkages present in the residual dimers and oligomers was achieved with commercial MCM-41 zeolite in the same pot, proceeding with an additional monomer yield of 4.0 %, thereby increasing the total monomer yield by 45 %. This work provides an avenue for increasing the depolymerization efficiency of Kraft lignin. Depolymerization of Kraft lignin to value-added monomers can significantly enhance the profitability of lignocellulosic biorefinery. In this work, the efficient transformation of highly condensed Kraft lignin to valuable aromatic monomers through stepwise alcoholysis and zeolite-catalyzed methylene linkage cleavage is disclosed.image