Fractionation of oil palm fronds using ethanol-assisted deep eutectic solvent: Influence of ethanol concentration on enhancing enzymatic saccharification and lignin ß-O-4 content.

Numerous fractionation methods have been developed in recent years for separating components such as cellulose, hemicellulose, and lignin from lignocellulosic biomass wastes. Deep eutectic solvents (DES) have recently been widely investigated as captivating green solvents for biomass fractionation. However, most acidic-based deep eutectic solvent fractionation produces condensed lignin with low ß-O-4 content. Besides, most DESs exhibit high viscosity, which results in poor mass transfer properties. This study aimed to address the challenges above by incorporating ethanol into the deep eutectic solvent at various concentrations (10-50 wt%) to fractionate oil palm fronds at a mild condition, i.e., 80 °C, 1 atm. Cellulose residues fractionated with ethanol-assisted deep eutectic solvent showed a maximum glucose yield of 85.8% when 20 wt% of ethanol was incorporated in the deep eutectic solvent, significantly higher than that achieved by pure DES (44.8%). Lignin extracted with ethanol-assisted deep eutectic solvent is lighter in color and higher in ß-O-4 contents (up to 44 ß-O-4 per 100 aromatic units) than pure DES-extracted lignin. Overall, this study has demonstrated that incorporating ethanol into deep eutectic solvents could enhance the applicability of deep eutectic solvents in the complete valorization of lignocellulosic biomass. Highly enzymatic digestible cellulose-rich solid and ß-O-4-rich lignin attained from the fractionation could serve as sustainable precursors for the production of biofuels.

Recent advances in the application of alcohols in extracting lignin with preserved ß-O-4 content from lignocellulosic biomass.

Utilizing lignocellulosic biomass wastes to produce bioproducts is essential to address the reliance on depleting fossil fuels. However, lignin is often treated as a low-value-added component in lignocellulosic wastes. Valorization of lignin into value-added products is crucial to improve the economic competitiveness of lignocellulosic biorefinery. Monomers obtained from lignin depolymerization could be upgraded into fuel-related products. However, lignins obtained from conventional methods are low in ß-O-4 content and, therefore, unsuitable for monomer production. Recent literature has demonstrated that lignins extracted with alcohol-based solvents exhibit preserved structures with high ß-O-4 content. This review discusses the recent advances in utilizing alcohols to extract ß-O-4-rich lignin, where discussion based on different alcohol groups is considered. Emerging strategies in employing alcohols for ß-O-4-rich lignin extraction, including alcohol-based deep eutectic solvent, flow-through fractionation, and microwave-assisted fractionation, are reviewed. Finally, strategies for recycling or utilizing the spent alcohol solvents are also discussed.

The application of green solvent in a biorefinery using lignocellulosic biomass as a feedstock.

The high dependence on crude oil for energy utilization leads to a necessity of finding alternative sustainable resources. Solvents are often employed in valorizing the biomass into bioproducts and other value-added chemicals during treatment stages. Unfortunately, despite the effectiveness of conventional solvents, hindrances such as expensive solvents, unfavourable environmental ramifications, and complicated downstream separation systems often occur. Therefore, the scientific community has been actively investigating more cost-effective, environmentally friendly alternatives and possess the excellent dissolving capability for biomass processing. Generally, 'green' solvents are attractive due to their low toxicity, economic value, and biodegradability. Nonetheless, green solvents are not without disadvantages due to their complicated product recovery, recyclability, and high operational cost. This review summarizes and evaluates the recent contributions, including potential advantages, challenges, and drawbacks of green solvents, namely ionic liquids, deep eutectic solvents, water, biomass-derived solvents and carbon dioxide in transforming the lignocellulosic biomass into high-value products. Moreover, research opportunities for future developments and potential upscale implementation of green solvents are also critically discussed.

Investigation into Lewis and Brønsted acid interactions between metal chloride and aqueous choline chloride-oxalic acid for enhanced furfural production from lignocellulosic biomass.

Furfural has been identified as a valuable biobased platform chemical that can be further converted into bioenergy and biochemicals. Furfural is derived from lignocellulosic biomass and can also be regarded as a sustainable alternative to petrochemical products. Herein, the performance of trivalent metal chlorides (FeCl3, AlCl3) and tetravalent metal chlorides (SnCl4, TeCl4) as Lewis acidic cocatalysts was investigated in an aqueous choline chloride-oxalic acid (16.4 wt% H2O) deep eutectic solvent (DES) system for producing furfural from oil palm fronds (OPFs). The metal chlorides with greater electrical field gradients were stronger Lewis acids that enhanced both furfural production and degradation reactions. The main degradation product in this reaction system was humin, and this result was confirmed by FTIR analysis. By subjecting OPFs to an aqueous DES reaction (120 °C, 45 min) with SnCl4 (2.50 wt%), a furfural yield of 59.4% was obtained; without incorporated metal chlorides, the furfural yield was 46.1%. Characterization studies showed synergistic Lewis and Brønsted acid interactions between metal chlorides and DES components. Overall, the residual OPFs showed high glucan content, which led to the production of glucose (71.4%) as a byproduct via enzymatic hydrolysis. Additionally, the aqueous DES system was recycled and reused for several additional runs. The proposed aqueous DES system presents a promising biorefinery approach for the conversion of OPFs to biochemicals.