Structural basis for lignin recalcitrance during sulfite pulping for production of dissolving pulp from pine heartwood

Dissolving pulps are technically produced by prehydrolysis kraft, one-stage or two-stage acid sulfite pulping . Like other pulping methods, the delignification process is incomplete and bleaching is required for complete lignin removal. Here, we explored the molecular aspects of lignin recalcitrance during the pulping, in order to gain insights that could inform future pulping efforts. For this purpose, we adopted a protocol for the controlled fractionation of pulp into soluble fractions that could be analyzed by spectroscopic methods including size exclusion chromatography (SEC) and 2D NMR methods. In addition, lignosulfonates (i.e. technical lignin) was analysed as a reference to gain insights on the structural basis for dissolution. Overall, the results identify a sequence of reactions responsible for the dissolution of lignin. In the first stage, the sulfonation of lignin begins and occurs at the α-carbon of β-O-4 and β-5 sub-structures. In the second stage the cleavage of lignin carbohydrate bonds (LCC) of benzyl ether, gamma ester and phenylglycosides types, all of which were detected in the residual lignin of the earlier phases, occurs and enhances lignin dissolution. Finally, condensation reactions of benzylic cations with activated positions on aromatic ring were detected in lignosulfonates. This suggest that a competing reaction mode to the sulfonation at C-α position in lignin was occurring at prolonged pulping conditions, here considered to be unproductive. • 100% Pine heartwood was subjected to acidic sulfite pulping to produce dissolving grade pulp. • In pulp samples sulfonated lignin structures like α-sulfonated β-O-4 and β-5 units were identified. • Phenyl glycosides, gamma esters and benzyl ethers type LCC bonds were detected in pulp sample with NMR studies. • Condensation reactions between activated aromatic rings and benzylic cation on lignin during acid conditions were observed. • Cleavage of LCC bonds is probably required to dissolve sulfonated lignin as substantiated by NMR studies.