The Effect of Acidic Ternary Deep Eutectic Solvent Treatment on Native Lignin

Ternary deep eutectic solvents (DESs) are gaining increased attention to serve as a cheap green alternative medium for the processing of lignocellulosic biomass. For example, mixtures of choline chloride (ChCl), ethylene glycol (EG), and oxalic acid (OA) were recently explored for the fractionation of lignocellulosic biomass into its main components. Interestingly, during this processing, the recovered lignin was structurally modified by incorporation of EG, which altered its solubility properties and led to the need for different lignin recovery strategies. This offers an excellent starting point for a deeper investigation of the effect of acidic DES systems on the structure of lignin. In particular, native-like residual enzyme lignins (RELs) that are hard to completely dissolve in organic solvents are specifically suitable for this task. Here, a ternary DES is used consisting of ChCl/EG with OA or trifluoromethanesulfonic acid (HOTf) as a third component. The results showed that both solvent systems led to high EG incorporation into REL. The HOTf system showed a lesser extent of lignin depolymerization at similar modification levels as it already induced modification at lower temperature (25-30 °C). Low recovery yields from typical acidic precipitation were observed for treatment with both acidic DES systems. Analysis of THF and DCM extracts showed that the products in the water phase included small EG modified lignin fragments and aromatic monomers released from lignin aryl ether linkage cleavage. This analysis details the types of other products that can be expected and where these will end up during fractionation. These results show that the treatment of lignin with acidic DES in the presence of alcohols leads to low- and high-molecular-weight products that are not effectively recovered by typical precipitation procedures.