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The selectivity of alkali treatment (AT) for hemicellulose separation is reduced due to the alkali solubility of lignin. It was improved using freeze-thaw-assisted alkaline treatment (FT/AT). In this study, bamboo hemicellulose was separated via a one-step freeze-thaw-assisted alkali treatment (OFT/AT). The effects of freezing temperature, freezing time, alkali concentration, and treatment time on bamboo components were studied. The separation yield of hemicellulose was 73.26%, compared to 64.00% using conventional FT/AT. The separation of lignin and cellulose was inhibited as alkali concentration decreased from 7.0% to 5.0%. The extraction yield of hemicellulose increased from 46.35% to 56.12%. Structural analysis of extracted hemicellulose revealed the effective inhibition of the breakage of the xylose backbone and arabinose side chain of hemicellulose. This indicated that the molecular structure of extracted hemicellulose was relatively complete. It provides theoretical support for the efficient separation of hemicellulose by AT., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The molecular weight is one of the most important factors influencing the utilization of industrial lignin obtained from chemical pulping process. In this paper, a facile operative green solvent system was successfully developed for molecular weight-controllable fractionation of industrial alkali lignin (IAL) at room temperature. The results showed that through adjusting the ratio of water, ethanol and γ-Valerolactone (GVL), the industrial lignin was fractionated into six levels with molecular weight stepwise controllable from low to high. The fractionation is a physical process according to FTIR and 2D-HSQC NMR analysis, and the chemical structure of lignin has not changed. Additionally, the polydispersity of fractionated lignin with higher molecular weight tends to be narrower. The content of hydroxyl and carboxyl group is higher for the fractionated lignin with lower molecular weight, which would be beneficial for the chemical reactivity in the down-stream application., (Copyright © 2022. Published by Elsevier B.V.)

In recent years, the biological activity of polysaccharides and their derivatives has been widely studied. However, in addition to the natural polysaccharides directly extracted from plants and animals, there are rich polysaccharides in the pulping waste liquor that have not been fully utilized. The extracted polysaccharide from eucalyptus Alkaline Peroxide Mechanical Pulping (APMP) waste liquor was used as a raw material. For the production of carboxymethyl polysaccharide, the effects of temperature (T), the amount of alkali (NaOH) and the amount of etherifying agent (ClCH 2 COOH) on the degree of substitution (DS) were investigated, the optimal preparation conditions are: reaction time 2 h, temperature 75 °C, and the molar ratio of polysaccharide, NaOH and ClCH2COOH is 1:1:2, the highest DS is 1.47; FT-IR, NMR and GPC were used to characterize the structure and Molecular weight, the results show that the polysaccharide of APMP waste liquor is rich in xylan, and it was proved that the carboxymethyl substitution was successful and the positions of the substituent group were determined. The characterization and biological activity research of xylan polysaccharide (XP) and carboxymethyl xylan polysaccharide (CMXP), such as antioxidation, moisture absorption/retention, bacteriostatic action and cytotoxicity were discussed. CMXP shows better effects compared with XP., (Copyright © 2021. Published by Elsevier B.V.)

In this study, five acid or alkali catalyzed ethylene glycol (EG) organosolv pretreatments were proposed and compared for sugar production from bagasse. The results showed that compared with single EG/H 2 O pretreatment, the EG/H 2 O-HCl pretreatment was more efficient for both hemicellulose (~99.3%) and lignin (~67.1%) remove due to the synergistic effect of HCl and EG. The EG/H 2 O-NaOH pretreatment was also beneficial for lignin remove (~90.9%), but it was weak for hemicellulose degradation (~28.8%). Both EG/H 2 O-HCl and EG/H 2 O-NaOH pretreatments have good capacity to reserve the cellulose in pretreated solids. Following enzymatic saccharification, the largest glucose recovery yield from EG/H 2 O-HCl pretreatment was 94.3%, a slightly higher than this from EG/H 2 O-NaOH pretreatment (92.5%). However, its xylose recovery yield was only 77.3%, significantly lower than that of EG/H 2 O-NaOH pretreatment (93.5%). Besides, a certain amount of lignin also can be recovered from above acid or alkali catalyzed organosolv pretreatments through diluting or acidizing the pretreated liquids., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This work investigated the changes in the physical structure of autohydrolyzed poplar sapwood chips and the effect on the subsequent alkali liquor diffusion properties for chemi-mechanical pulping (CMP). An alkali impregnation process was conducted by using the autohydrolyzed poplar sapwood with different levels of autohydrolysis intensity. The results showed that the volume porosity, water constraint capacity, and saturated water absorption of the autohydrolyzed poplar sapwood chips increased. Also, the effective capillary cross-sectional area (ECCSA) in the radial direction and the diffusion coefficients of NaOH solution in both the radial and axial directions all increased. Autohydrolysis pretreatment enhanced the alkali liquor diffusion properties in poplar sapwood chips, and the diffusion coefficient was increased more greatly in the radial direction than that in the axial direction., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

An integrated pretreatment process based on hydrothermal pretreatment (HTP) followed by alkaline pretreatment has been applied to treat Eucalyptus. The chemical composition and structure changes of lignin during the pretreatment were comprehensively characterized. The surface morphology of the cell walls and lignin distribution of the pretreated Eucalyptus were detected by scanning electron and confocal Raman microscopies. It was found that the chemical bonds between lignin and hemicelluloses were cleaved during the pretreatment. The results also indicated that the contents of β-O-4', β-β', and β-5' linkages were decreased with the increase of hydrothermal pretreatment temperature and the cleavage of β-O-4' linkages in lignin was accompanied with repolymerization reactions. 31 P NMR analysis showed that the content of aliphatic OH was reduced as the temperature increased and the total phenolic OH was elevated and then declined with the increase of temperature. Raman spectra analysis revealed that the dissolution rate of lignin in the secondary wall regions was faster than that in cell corner middle lamella regions during the pretreatment. These results will enhance the understanding of the cell wall deconstruction during the pretreatment and the mechanism of the integrated pretreatment process acting on Eucalyptus.

In this study, cellulose-rich fractions from bamboo were prepared with steam explosion pretreatment (SEP) followed by a successive alkaline delignification to improve the enzymatic digestibility for an efficient bioethanol production. The cellulose-rich fractions obtained were characterized by FT-IR, XRD, CP/MAS (13)C NMR, SEM, and BET surface area. It was found that the SEP alone significantly removed partial hemicelluloses, while the synergistic treatment by SEP and alkaline delignification removed most hemicelluloses and lignin. Results from enzymatic hydrolysis showed that SEP alone improved the enzymatic hydrolysis rate by 7.9-33.1%, while the synergistic treatment by SEP and alkaline delignification enhanced the rate by 45.7-63.9%. The synergistic treatment by SEP at 2.0 MPa for 5 min with water impregnation followed by a successive alkaline delignification with 0.5% NaOH and 70% ethanol containing 1.5% NaOH resulted in a maximum enzymatic hydrolysis rate of 70.6%., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The enzymatic hydrolysis of the bagasse pulp prepared from the treatment process with active oxygen and MgO-based solid alkali was studied. The hydrolysates were tested by IC (ionic chromatography) for the analysis of monosaccharide. Additionally, the changes of pulp before and after hydrolysis were characterized with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), Kajaani cellulose automatic analyzer and atomic force microscopy (AFM) techniques. The results showed that an optimized sugar yield of 82.38% was obtained at the substrate concentration of 5% for 72h with the enzyme dosage of 15IU/g. Furthermore, as the length of the cellulose fiber decreased, the crystallinity of cellulose increased, and more depressions appeared on the surface of pulp after enzymatic hydrolysis., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The cooking with solid alkali and active oxygen has a high selectivity for delignification. In the present work, the O(2) and H(2)O(2) were separately combined with MgO used in cornstalk cooking for investigating their effects on delignification. After cooking, the lignins in raw material, pulp, and yellow liquor were all characterized by HSQC NMR. The results showed that the syringyl (S/S'/S″) units and β-O-4' (A/A'/A″) structures had different reactivity in the cooking with MgO and H(2)O(2) due to their different structures on side-chains. Whereas the syringyl (S/S'/S″) units could be completely decomposed when the MgO and O(2) were used, and the β-O-4' (A/A'/A″) structures could be partly degraded. A novel structure G' unit with a carbonyl group was only generated in the cooking with MgO and O(2). In addition, the H unit, non-phenolic β-β' (B) and β-5' (C) structures were all stable in both of the two cooking processes., (Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.)

A novel, efficient, and environmentally friendly technology is used in cornstalk cooking, active oxygen (O₂ and H₂O₂) cooking with solid alkali (MgO). After the cooking, the milled wood lignin in the raw material and pulp and the water-soluble and insoluble lignin in the yellow liquor were all characterized by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional heteronuclear single-quantum coherence NMR. The results showed that the cooking procedure with solid alkali and active oxygen had a high selectivity for delignification, which could remove 85.5% of the lignin from the raw material. The syringyl (S/S'/S') units could be dissolved preferentially because of their high reactivity, and a novel guaiacyl unit with a carbonyl group (G') was generated in the cooking process. Moreover, during the cooking, the β-O-4' (A/A'/A″) structures as the main side-chain linkages in all the lignins could be partly broken and the β-O-4' (A') with a ring-conjugated structure was readily attacked by oxygen, whereas the H unit and β-5' and β-β' structures were found to stay stable without characteristic reaction.

This study presents a novel, efficient and environmentally friendly process for the cooking of corn stalk that uses active oxygen (O2 and H2O2) and a recoverable solid alkali (MgO). The structural changes on the surface of corn stalk before and after cooking were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The results showed that lignin and extractives were effectively removed, especially those on the surface of corn stalk. Additionally, the changes included becoming fibrillar, the exposure of cellulose and hemi-cellulose and the pitting corrosion on the surface, etc. The results also showed that the removal reaction is from outside to inside, but the main reaction is possibly on the surface. Furthermore, the results of active oxygen cooking with a solid alkali are compared with those of alkaline cooking in the paper., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Although the moderate load (COD of 5000-10,000 mg/L) and biodegradability of the APMP pulping effluent should allow biological treatment, toxic compounds in the effluent can interfere with this type of treatment. Studies were conducted to determine if treatment of the effluent with Aspergillus niger S13 was feasible. Under the optimized conditions (3% inoculum, pH 6, shaking at 160 rpm, 60-72 h, and 30°C), this fungus was able to remove about 97% of the methyl tertiary butyl ether (MTBE) extractives, and 60%, 77% and 43% of the chemical oxygen demand, turbidity and color even without a pre-flocculation step. These results are of practical interest in China because the APMP process has become popular, and efficient and cost-effective effluent treatment technologies are in high demand., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Molecular iodine has been introduced into the alkali lignin (AL) solutions to adjust the π-π aggregation, and the effect of lignin-iodine complexes on the aggregation and assembly characteristics of AL have been investigated by using fluorescence, UV-vis spectroscopy, light scattering, and viscometric techniques. Results show that AL form π-π aggregates (i.e., J-aggregates) in THF driven by the π-π interaction of the aromatic groups in AL, and the π-π aggregates undergo disaggregation in THF-I(2) media because of the formation of lignin-iodine charge-transfer complexes. By using iodine as a probe to investigate the aggregation behaviors and assembly characteristics, it is estimated that about 18 mol % aromatic groups of AL form π-π aggregates in AL molecular aggregates. When molecular iodine is introduced into the AL solutions, lignin-iodine complexes occur with charge-transfer transition from HOMO of the aromatic groups of AL to the LUMO of iodine. The formation of lignin-iodine complexes reduces the affinity of the aromatic groups approaching each other due to the electrostatic repulsion and then eliminates the π-π interaction of the aromatic groups. The disaggregation of the π-π aggregates brings a dissociation behavior of AL chains and a pronounced molecular expansion. This dissociation behavior and molecular expansion of AL in the dipping solutions induce a decrease in the adsorbed amount and an increase in the adsorption rate, when AL is transferred from the dipping solution to the self-assembled adsorbed films. Consequently, the adsorption behavior of AL can be controlled by adjusting the π-π aggregation. Above observations give insight into the occurrence of J-aggregation of the aromatic groups in the AL molecular aggregates and the disaggregation mechanism of AL aggregates induced by the lignin-iodine complexes for the first time. The understanding can provide an academic instruction in the efficient utilization of the alkali lignin from the waste liquor and also leads to further development in expanding functionalities of the aromatic compounds through manipulation of the π-π aggregation.

The effect of hot-water extraction on alkaline pulping was investigated. The properties of black liquor and pulp strength of bagasse were analyzed. The extraction was conducted at 160 degrees C for 30min where 13.2% of the mass was dissolved in the extraction liquor. Untreated bagasse and extracted bagasse were digested by soda and soda-AQ processes at 17% and 15.5% (with 0.1% AQ) alkali charge (NaOH). Cooking temperatures were 160 degrees C and 155 degrees C respectively. The pulp from extracted bagasse had a lower Kappa number and a higher viscosity compared to the pulp from the untreated bagasse. The black liquor from pulping extracted bagasse had a lower solid content, a lower viscosity and a lower silica content, but a higher heating value than that from pulping of untreated bagasse. Hot-water extraction resulted in a significant decrease in bleaching chemical consumption and the formation of chlorinated organics. Pulp strength properties such as the tensile index and the burst index were found to be lower, but the tear index, bulk, opacity and pulp freeness were found to be higher when hot-water extraction was applied., (Copyright 2010 Elsevier Inc. All rights reserved.)

The dewaxed cell walls of Populus gansuensis were delignified with NaClO(2) and then sequentially extracted with 0.25, 0.5, and 1.0 M KOH under a solid to liquid ratio of 1: 25 (g mL(-1)) at 25 degrees C for 10 h. The successive treatments together resulted in the dissolution of 83.7% of original hemicelluloses. The solubilized hemicellulosic fractions were further fractionated into six hemicellulosic subfractions by an iodine-complex precipitation technique. Their chemical and physical characteristics were determined by HPAEC, GPC, FT-IR, and (1)H and (13)C NMR spectroscopy. Neutral sugar composition and molecular weight analysis showed that, for each extract, the hemicellulosic subfractions that precipitated with aqueous potassium iodide-iodine had lower overall uronic acid/xylose (Uro/Xyl) ratios and higher molecular weights (M(w)) than those remaining in the solution. FT-IR, (1)H, and (13)C NMR spectroscopy analysis indicated that the alkali-soluble hemicelluloses of Populus gansuensis had a structure composed of the (1 --> 4)-linked beta-D-xylopyranosyl backbone with 4-O-methyl-alpha-D-glucuronic acid attached to O-2 of the xylose residues.