Depolymerization of Technical Lignins in Supercritical Ethanol: Effects of Lignin Structure and Catalyst

Three complementary Kraft lignins and a Soda lignin were characterized by NMR (P-31, C-13, and HSQC) and GPC. Their theoretical yield in monomers (TMY) assuming a complete cleavage of all beta-O-4 linkages was calculated based on these analyses. The most recalcitrant Kraft lignin according to the TMY criteria was depolymerized in supercritical ethanol (250 degrees C, H-2, 110 bar) with Pt/C, Ni/C, and Ru/C catalysts. All catalysts present an important effect on monomers (analyzed by GC/MS), oligomers (by UV fluorescence), and char yields. They promote cracking reactions and the stabilization of the broken bonds by H-transfers. The hydrogenation of the side chains of the monomers is also promoted to notably produce propyl-guaiacol. We show that an oligomeric pool prevails for all catalysts. Then, the effect of lignin structure on the depolymerization mechanism was studied by comparing the 4 lignins with the least precious catalyst (Ni/C). The S/G ratio of monomers is well related to the S/G ratio of lignins. Under our conditions, the beta-O-4 content and the TMY do not control the yields in monomers. They are not relevant indicators for the depolymerization of these recalcitrant technical lignins. Future work should focus on novel catalysts and processes to improve the selective conversion of C-C bonds if monomers remain the targeted product.

Automated summary

Three complementary Kraft lignins and a Soda lignin were characterized by NMR and GPC, with their theoretical yield in monomers calculated based on the analyses. The most recalcitrant Kraft lignin was depolymerized in supercritical ethanol with Pt/C, Ni/C, and Ru/C catalysts, demonstrating the important effect of catalysts on monomers, oligomers, and char yields. The study also showed that lignin structure plays a role in the depolymerization mechanism.