Harnessing the potential of biphasic solvent systems in lignocellulosic biomass fractionation through computational insights†

Biphasic solvent systems have emerged as a transformative approach for the efficient fractionation of lignocellulosic biomass (LCB), driving substantial progress in biofuel and biochemical production. By precisely partitioning lignin into the organic phase and hemicellulose into the aqueous phase while maintaining cellulose within the solid fraction, biphasic systems present a sophisticated and integrative strategy for LCB processing. This dual-phase approach achieves superior product separation and significantly enhances economic viability through the recyclability of solvents and catalysts. Several biphasic systems, including those employing 2-methyltetrahydrofuran, immiscible alcohol-based systems (butanol, pentanol, and phenoxyethanol), and ketones (Methyl isobutyl ketone), have been developed for LCB fractionation. Among these, immiscible alcohol-based systems have emerged as the most effective, demonstrating the ability to minimize cellulose degradation (1.0–30.0%) while optimizing the removal of hemicellulose (80.0–98.0%) and lignin (65.0–92.0%). The efficiency of these systems is largely due to strong hydrogen bonding interactions between the solvents–catalysts and xylan and lignin, which enhance effective extraction, as confirmed by mechanistic computational analyses. Other factors such as selective lignin dissolution, phase separation, low polarity, and energy-efficient recovery are also emphasized. This review indicates that immiscible alcohol-based methods achieve superior glucose yields following enzymatic hydrolysis (85.0–95.0%) at high solid loadings (10.0–13.0%). Sustainability assessments further emphasize the advantages of biphasic systems, predicting a reduced environmental footprint and improved economic feasibility relative to conventional methods. Integrating artificial intelligence techniques with these findings holds the potential to accelerate the industrial adoption of biphasic systems, optimizing process efficiency and reducing costs.