A feasibility study on green biorefinery of high lignin content agro-food industry waste through supercritical water treatment

This work discusses hydrolysis of defatted grape in supercritical water (SCW) at 380 °C and 260 bar from 0.18 s to 1 s focusing attention to sugars recovery in the liquid phase of the product and detailed characterization of remaining solid phase enriched in polyaromatics (e.g. lignin, flavonoids, etc.). After the longest reaction time of 1 s, 56% of carbohydrates could be recovered in the liquid phase, as a result of carbohydrate hydrolysis. The high content of insoluble lignin in biomass (36%), acts as a mass transfer limitation and presents an important feature in the hydrolysis process, slowing down the conversion of carbohydrate fraction, as after the maximum time of 1s, 10% of carbohydrates still remained in the solid phase. Milled wood lignin, extracted from biomass and dioxane extract from the solid phase were characterized in order to understand the main structural changes during the SCW hydrolysis process. Dioxane (80%) extraction of solids produces a very complex mixture of lipophilic extractives, flavonoids and lignin with a certain amount of chemically linked carbohydrates. 2D NMR analysis of dioxane extract shows remarkably subtle changes in the amounts of main lignin moieties (β-O-4′, β-β’ (resinol) and β-5 (phenylcoumaran)). This subtle change of the main lignin structures is an important feature in the further valorisation of this sulfur-free lignin residue.