Biorefineries, which process biomass feedstocks into valuable (bio)products, aim to replace fossil fuel-based refineries to produce energy and chemicals, reducing environmental and health hazards, including climate change, and supporting a sustainable economy. In particular, lignocellulose-based biorefineries, utilizing the most abundant renewable feedstock on Earth, have significant potential to supply sustainable energy, chemicals and materials. Ionic liquids (ILs, organic salts with low melting temperatures) and deep eutectic solvents (DESs, mixtures with eutectic points lower than the ideal mixture) are capable of dissolving some of the key lignocellulose polymers, and even the whole biomass. Furthermore, they have intrinsic advantages over molecular solvents, including safer usage profiles and high tunability, which allow tailored physicochemical properties. Such properties provide unique opportunities for the development of new processes that could unlock the full potential of future biorefineries. Here, we review the current state of lignocellulosic biomass processing with ILs and DESs, with a specific focus on the pretreatment chemistry, process flow and products from each component; followed by discussions on sustainability assessments and technological challenges. We aim to inform the research community about the opportunities, challenges and perspectives in developing truly sustainable lignocellulose-based biorefineries.

The impact of pretreatment severity in the acidic protic ionic liquid (IL) N,N-dimethylbutylammonium hydrogen sulfate, [DMBA][HSO₄] using pine softwood was investigated using a modified severity factor that considers the IL solution acidity based on Hammett acidity. A Box-Behnken experimental design was employed to evaluate pretreatment severity with temperature, pretreatment time, and IL concentration as factors and degree of delignification as the response variable. The optimal pretreatment conditions were found to be at 170 °C, 30 min, and 80 wt % IL, which yielded nearly 90% of delignification and 95% of glucose yield in enzymatic saccharification. The modified severity factor showed an improved correlation with the fractionation indicators relative to the classical pretreatment severity factor, indicating that it can better predict the pretreatment outcomes, particularly for delignification and hemicellulose removal. The fate of hemicellulose, its conversion to humins, and its impact on the precipitated lignin properties were also investigated and correlated to the modified pretreatment severity factor. It was found that such parameters alone cannot be used to predict the fate of dissolved hemicellulose sugars in the IL medium. Furthermore, IL acidity greatly impacts the degradation of the dissolved hemicellulose sugars and the formation of humins.