Unraveling interplay between lignocellulosic structures caused by chemical pretreatments in enhancing enzymatic hydrolysis.

To investigate the interplay between substrate structure and enzymatic hydrolysis (EH) efficiency, poplar was pretreated with acidic sodium-chlorite (ASC), 3 % sodium-hydroxide (3-SH), and 3 % sulfuric acid (3-SA), resulting in different glucose yields of 94.10 %, 74.35 %, and 24.51 %, respectively, of pretreated residues. Residues were fractionated into cellulose, lignin and unhydrolyzed residue after EH (for lignin-carbohydrate complex (LCC) analysis) and analyzed using HPLC, FTIR, XPS, CP MAS 13C NMR and 2D-NMR (Lignin and LCC analysis). After delignification, holocellulose exhibited a dramatic increase in glucose yield (74.35 % to 90.82 % for 3-SH and 24.51 % to 80.0 % for 3-SA). Structural analysis of holocellulose suggested the synergistic interplay among cellulose allomorphs to limit glucose yield. Residual lignin analysis from un/pretreated residues indicated that higher ß-ß' contents and S/G ratios were favorable to the inhibitory effect but unfavourable to the holocellulose digestibility and followed the trend in the following order: 3-SA (L3) > 3-SH (L2) > native-lignin (L1). Analysis of enzymatically unhydrolyzed pretreated residues revealed the presence of benzyl ether (BE1,2) LCC and phenyl glycoside (PG) bond linking to xylose (X) and mannose (M), which yielded a xylan-lignin-glucomannan network. The stability, steric hindrance and hydrophobicity of this network may play a central role in defining poplar recalcitrance.

Unrevealing the influence of reagent properties on disruption and digestibility of lignocellulosic biomass during alkaline pretreatment.

Beyond the conventional consideration of pretreatment severity (PS) responsible for biomass disruption, the influence of reagent properties on biomass (LCB) disruption is often overlooked. To investigate the LCB disruption as a function of reagent properties, reagents with distinct cations (NaOH and KOH) and significantly higher delignification potential were chosen. NaOH solution (3 % w/v) with a measured pH of 13.05 ± 0.01 is considered the reference, against which a KOH solution (pH = 13.05 ± 0.01) was prepared for LCB pretreatment under the same PS. Despite comparable lignin content, varying glucose yield of NaOH (68.76 %) and KOH (46.88 %) pretreated residues indicated the presence of heterogeneously disrupted substrate. Holocellulose extracted from raw poplar (ASC, control) and alkaline pretreated residues (C-NaOH and C-KOH) were analyzed using HPLC, XRD, SEM, TGA/DTG, XPS, and 13CP MAS NMR to investigate the pretreatment-induced structural modification. Results revealed that, despite the same pretreatment severity, better disruption in C-NaOH (higher accessible fibril surface and less-ordered region) leading to higher digestibility than C-KOH, likely due to the smaller ionic radius of Na+, facilitates better penetration into dense LCB matrix. This study elucidates the importance of considering the reagent properties during LCB pretreatment, eventually enhancing consciousness while selecting reagents for efficient LCB utilization.

Combination of surfactants and enzyme cocktails for enhancing woody biomass saccharification and bioethanol production from lab-scale to pilot-scale.

Converting woody biomass to bioethanol might be more affordable, environmentally friendly, and efficient for making biofuel commercially feasible, but it would still need a significant optimization process and expand pilot-scale research. A combination of commercial low enzymes loading at 10 FPU/g glucan and compound additives utilizing Tween 80, PEG8000 and sophorolipid applied from lab-scale to pilot-scale have been studied in this work at economically viable dosages for enhancing bioethanol production. In lab-scale saccharification and fermentation, pretreated poplar at a high solid loading of 20% yielded the highest ethanol titers of 30.96 g/L and theoretical ethanol yield of 92.79%. Additionally, pilot-scale operation was used to investigate the bioethanol amplification, a final volume of 33 m3 which yielded the greatest ethanol amount of 599.6 kg from poplar wood while gaining on-site value-added production of hemicellulosic and cellobiose liquor 1122 kg and lignin residues 2292 kg.

Structural characterizations of lignins extracted under same severity using different acids.

As the vital renewable feedstock originated from carbon-neutral resources, due to prominent aromaticity lignin owns the potential to produce high value-added products. Multi-functional lignin valorization demands efficient lignin extraction at milder conditions to keep its structure intact to substitute petroleum-based reactants. Lignin extraction severity (LES) is considered as the primary factor affecting the structure of extracted lignin and ultimately determines its applications. Except for the LES, the selection of suitable reagents for lignin extraction concerned with specific applications is crucially important. To explore the influence of different reagents, this study focused on lignin extraction employing the commonly used strong acids at the same LES. Four lignin preparations were extracted using 80% aqueous dioxane with the addition of H2O (L1), HCl, H2SO4 and HNO3 (pH = 1.30 ± 0.01 L2, L3 and L4, respectively). Analytical high-sensitive NMR (31P and 2D-HSQC) together with other characterizations (FTIR and GPC) were successfully employed and quantified while unveiling the structural heterogeneity among extracted lignin preparations. At the same LES, different reagents yielded lignin with varying structural characteristics and were potentially suitable for different applications.