Upgrading AquaSolv Omni (AqSO) biorefinery: access to highly ethoxylated lignins in high yields through reactive extraction (REx)

Chemical modification of lignin (i.e., ethoxylation) improves its properties for specific applications. Reactive extraction (REx)-the simultaneous functionalization and extraction of lignin from biomass-is a green, simple, and powerful solution to minimize subsequent steps in biorefinery operations, while upgrading the isolated products (i.e., lignin or lignin-carbohydrate hybrids). In this work, we successfully introduced REx into our recently reported AquaSolv Omni (AqSO) integrated biorefinery. Here, hydrothermally treated wood solids were refluxed with various EtOH : H2O mixtures (70-99 v/v%) in the presence of catalytic amounts of H2SO4 (c = 0.15-1.2 M). The effects of the process variables on the structures and properties of the obtained lignins and residual solids were elucidated by comprehensive NMR analyses (HSQC, quantitative 13C and 31P), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). In addition, we discuss different analytical approaches-NMR vs. chromatographic methods for the quantification of ethoxy groups in lignin. Implementing REx allowed the isolation of ethoxylated lignins in 27-52% yields (based on the initial lignin content) and to tune the degree of substitution (DS) up to 40.8 EtO-groups/100 Ar (based on quantitative 13C NMR)-which is approximately five times higher compared to other established organosolv processes (i.e., Alcell). Moreover, solution state NMR analysis of residual solids after REx showed that ethoxylation also occurs in the cellulose-rich fraction. REx highly ethoxylated lignins produced through a simple and green process enhanced the performance of polyurethane (PU) adhesive formulations compared to formulations using non-ethoxylated lignins. Ethanol-mediated reactive extraction is a green and simple process to simultaneously extract and functionalize lignin from wood. Ethoxy groups were incorporated in up to 40.8/100 Ar and the lignins were found suitable for adhesive formulations.