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The reductive catalytic fractionation (RCF) of lignocellulosic biomass is an attractive method for the conversion of lignin toward valuable low‐molecular weight aromatics. A limitation to the upscaling of such technology is represented by the use ofpressurized hydrogen gas. Here, the role of hydrogen gas within the RCF of wheat straw biomass is investigated. The use of H2 is shown to enhance lignin depolymerization, by virtue of an improved hydrogenolysis and hydrogenation of lignin fragments, with a yield of phenolic monomers that increased from ca. 12 wt % of acid‐insoluble lignin in the initial biomass under inert atmosphere to up to ca. 25 wt % under H2 (in methanol, at 250 °C, with Ru/C). The adoption of methanol, ethanol or isopropanol as hydrogen‐donor solvents was also investigated in the absence of H2. Ethanol was found to give the highest yield of monophenolic compounds (up to ≈20 wt %) owing to a better balance between solvolysis, hydrogenolysis, and hydrogenation of lignin. Nevertheless, a substantial loss of the carbohydrate fraction was observed. The use of a lower temperature (200 °C) in combination with H3PO4 resulted in an improved recovery of cellulose in the pulp and in the solubilization of hemicellulose and lignin, with the formation of monosaccharides (≈14 wt % of polysaccharides in the initial biomass) and phenolic monomers (up to 18 wt %, in the absence of H2). Overall, a tradeoff exists between the removal of H2 from the process and the production of low‐molecular weight phenolics during RCF. [ABSTRACT FROM AUTHOR]

Sodium dithionite is utilized as a reducing agent in the organosolv fractionation of lignocellulose to concomitantly produce cellulosic pulp and promote the reductive conversion of lignin into phenolic monomers. Reactions with model compounds highlight the role of sodium dithionite with respect to the reductive cleavage of β-O-4 bonds in lignin and the consequent formation of phenolic monomers. [ABSTRACT FROM AUTHOR]

Abstract: Switchgrass was used as a lignocellulosic feedstock for second generation ethanol production, after pretreatment using sulfuric acid-catalyzed modified clean fractionation based on NREL’s (National Renewable Energy Laboratory) original procedure. Optimization of temperature, catalyst concentration and solvent composition was performed using Response Surface Methodology, and 59.03±7.01% lignin recovery, 84.85±1.34% glucose, and 44.11±3.44% aqueous fraction xylose yields were obtained at 140.00°C, 0.46% w/w catalyst concentration, 36.71% w/w ethyl acetate concentration, and 25.00% w/w ethanol concentration. The cellulose fraction did not inhibit the fermentation performance of Saccharomyces cerevisiae and resulted in an ethanol yield of 89.60±2.1%. [Copyright &y& Elsevier]

Abstract: The main objective of this study was to fractionate prairie cordgrass (PCG) obtaining the highest cellulose digestibility. Following clean fractionation (CF) processing, the PCG lignocellulosic biomass was fractionated into three main building blocks: cellulose, hemicellulose and lignin. Effects of processing factors such as time, temperature, catalyst concentration and organic solvent mixture composition were evaluated. Organic solvent–aqueous mixture contained methyl isobutyl ketone (MIBK), ethanol and water in different proportions. Sulfuric acid was used as a catalyst. In order to evaluate the degree of pre-treatment, enzymatic saccharification was employed on the cellulose fraction obtained from the CF process. Response surface methodology was used for process optimization and statistical analysis. Optimal conditions (39min, 154°C, 0.69% catalyst and 9% MIBK) resulted in 84% glucose yield and 87% acid insoluble lignin (AIL). [Copyright &y& Elsevier]

• The process promoted by Na 2 S 2 O 4 boosts lignin depolymerization and formation of monophenolics. • Higher temperature and longer reaction time favored lignin and hemicellulose extraction. • The combination of n -butanol and water improved lignin extraction and depolymerization. • The process was effective for treating lignocellulose from various biomass sources. • A techno-economic assessment highlights potential economic viability of the upgrading process. The development of biomass pretreatment approaches that, next to (hemi)cellulose valorization, aim at the conversion of lignin to chemicals is essential for the long-term success of a biorefinery. Herein, we discuss a dithionite-assisted organosolv fractionation (DAOF) of lignocellulose in n -butanol and water to produce cellulosic pulp and mono-/oligo-aromatics. The study frames the technicalities of this biorefinery process and relates them to the features of the obtained product streams. We comprehensively identify and quantify all products of interest: solid pulp (acid hydrolysis-HPLC, ATR-FTIR, XRD, SEM, enzymatic hydrolysis-HPLC), lignin derivatives (GPC, GC–MS/FID, 1H–13C HSQC NMR, ICP-AES), and carbohydrate derivatives (HPLC). These results were used for inspecting the economic feasibility of DAOF. In the best process configuration, a high yield of monophenolics was reached (∼20 wt%, based on acid insoluble lignin in birch sawdust). Various other lignocellulosic feedstocks were also explored, showing that DAOF is particularly effective on hardwood and herbaceous biomass. Overall, this study demonstrates that DAOF is a viable fractionation method for the sustainable upgrading of lignocellulosic biomass. [ABSTRACT FROM AUTHOR]