Toward a Consolidated Lignin Biorefinery: Preserving the Lignin Structure through Additive‐Free Protection Strategies

As part of the continuing efforts in lignin‐first biorefinery concepts, this study concerns a consolidated green processing approach to obtain high yields of hemicelluloses and lignin with a close to native molecular structure, leaving a fiber fraction enriched in crystalline cellulose. This is done by subcritical water extraction of hemicelluloses followed by organosolv lignin extraction. This initial report focuses on a detailed characterization of the lignin component, with the aim of unravelling processing strategies for the preservation of the native linkages while still obtaining good yields and high purity. To this effect, a static cycle process is developed as a physical protection strategy for lignin, and advanced NMR analysis is applied to study structural changes in lignin. Chemical protection mechanisms in the cyclic method are also reported and contrasted with the mechanisms in a reference batch extraction process where the role of homolytic cleavage in subsequent repolymerization reactions is elucidated.