One-pot preparation and characterization of lignin-based cation exchange resin and its utilization in Pb (II) removal.

Lignin is a renewable source of aromatics, and the conversion of lignin to chemicals, fuels and materials is very attractive. Herein, a novel lignin-based cation exchange resin (LBR) was easily synthesized through an economical one-pot method. Results demonstrated that the sulfonic acid groups were successfully introduced into the skeleton of the resins, and the S contents and swelling capacity of the prepared LBRs gradually increased with the increment of the sulfonation reagents dosage. A maximum ion-exchange capacity of 2.26 mmol/g was achieved for the LBR obtained at 120 °C for 4 h with a molar ratio of phenol to formaldehyde (P:F) of 1:5 (SSPL-0.50), which was comparable to the commercial phenol type cation exchange resin. Furthermore, the SSPL-0.50 exhibited a high adsorption capacity (167.2 mg/g) for Pb (II) removal. The LBR can be considered as a promising substitute for the petroleum-based ion exchange resin in the purification of wastewater.

Effect of various pretreatments on improving cellulose enzymatic digestibility of tobacco stalk and the structural features of co-produced hemicelluloses.

Hereon, tobacco stalk was deconstructed by lyophilization, ball-milling, ultrasound-assisted alkali extraction, hydrothermal pretreatment (HTP), and alkali presoaking, respectively, followed by dilute alkali cooking to both improve its enzymatic digestibility and isolate the hemicellulosic streams. It was found that a maximum cellulose saccharification rate of 93.5% was achieved from the integrated substrate by ball-milling and dilute alkali cooking, which was 4.4-fold higher than that from the raw material. Interestingly, in this case, 76.9% of hemicelluloses were simultaneously recovered during the integrated treatment. Structural determination indicated that the hemicelluloses released from tobacco stalk by dilute alkali cooking were mixed polysaccharides, and the (1 â†’ 4)-linked ß-D-Xylp backbone branched with L-Araf units at O-2/O-3 and 4-O-Me-α-D-GlcpA units at O-2 of the xylose residues was the main structure. In comparison, ultrasound-assisted alkali extraction, ball-milling, and HTP favored the extraction of hemicelluloses with less branched structure and lower molecular weights in the following alkali cooking.

Structural elucidation of lignin macromolecule from abaca during alkaline hydrogen peroxide delignification.

To maximize the utilization of Abaca lignin in the current biorefinery, structural characteristics of native lignin from Abaca were firstly comprehensively investigated. Parallelly, effective delignification of Abaca was achieved by alkaline hydrogen peroxide (AHP) process, which facilitated the production of specialty paper in industry. The structural changes of lignin macromolecules during the AHP delignification were illustrated by comparing the structural differences of the released lignin fraction and corresponding native lignin, which were analyzed via the advanced analytical methods, such as 2D-HSQC NMR, 31P NMR, pyrolysis-GC/MS, and GPC techniques. It was found that Abaca lignin is a HGS-type lignin, which is overwhelmingly composed of ß-O-4 linkages and abundant hydroxycinnamic acids (mainly p-coumaric acid). In addition, partial cleavage of ß-O-4 linkages and p-coumarate in lignin occurred during the AHP delignification process. Meanwhile, AHP process also led to the elevation of H-type lignin units in AHPL. Considering that ß-O-4 bond is vulnerable in the catalytic degradation process of lignin, the lignin with abundant ß-O-4 linkages is beneficial to the downstream conversion of lignin into aromatic chemicals.

Carbon microspheres prepared from the hemicelluloses-rich pre-hydrolysis liquor for contaminant removal.

Pre-hydrolysis liquor (PHL) from the kraft-based dissolving pulp process contains large amounts of hemicelluloses, which is usually treated as an effluent and further efforts have to be involved to eliminate the pollution disposal. However, the hemicelluloses-rich PHL is a promising candidate for the production of carbon microspheres via hydrothermal carbonization. The yield of the carbon microspheres directly derived from the hydrothermal carbonization of the hemicelluloses-rich PHL (22.1%) was almost twice than that from xylose (13.1%). Furthermore, sulfuric acid and the lignin in the PHL could significantly improve the yield and change the size of the carbon microspheres obtained from the PHL. Additionally, the activated carbon microspheres functionalized with acrylic acid showed improved adsorption capacities for Pb(II) ion (273.4 mg/g) and methylene blue (701.3 mg/g). The hydrothermal carbonization of the PHL not only utilizes the hemicelluloses in the PHL, but also reduces the pollution load of the PHL significantly.

Unraveling the Fate of Lignin from Eucalyptus and Poplar during Integrated Delignification and Bleaching.

Efficient deconstruction of lignocellulose is vitally important for the biorefinery industry because lignin structures play a crucial role in the high value-added conversion of lignin. In this study, an integrated process based on hydrothermal pretreatment (HTP) and Kraft delignification was proposed to deconstruct lignocellulosic biomass. It was found that the HTP not only facilitated the production of xylo-oligosaccharides but also reduced the chemicals dosage of the following delignification. The structural characteristics of lignin obtained from the integrated process were investigated by NMR spectroscopy and gel-permeation chromatography. Additionally, double enzymatic lignins (DELs) isolated from different feedstocks were used as "model lignin" to delineate the structural transformations of lignin during H2 O2 , ClO2 , and O3 bleaching. Significant changes of the lignin structure were observed during the ClO2 bleaching process, including degradation of aromatic rings, enrichment in p-hydroxyphenyl units, and increase of carboxylic groups. A comparison of the structural characteristics of the bleached lignins indicated that HTP benefited the subsequent bleaching process. Enhanced knowledge of lignin chemistry during deconstruction and delignification could provide valuable insight into the current lignocellulose biorefinery.

Structural Features of Alkaline Dioxane Lignin and Residual Lignin from Eucalyptus grandis × E. urophylla.

In the present study, lignin from eucalyptus was extracted with 80% alkaline dioxane (0.05 M NaOH) from ball-milled wood and subsequently fractionated by gradient acid precipitation from the filtrate. Meanwhile, the residual lignin was prepared by a double enzymatic hydrolysis process. The yield of the lignin extracted by alkaline dioxane (LA-2) was 29.5%. The carbohydrate contents and molecular weights of the gradient acid precipitated lignin fractions gradually decreased from 4.90 to 1.36% and from 7770 to 5510 g/mol, respectively, with the decline of the pH value from 6 to 2. Results from two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (NMR) and 31P NMR spectroscopy showed an evident reduction of ß- O-4 ' linkages with the pH value decrease, while the contents of aliphatic -OH, phenolic -OH, and carboxylic groups displayed an increasing trend. Moreover, the residual lignin exhibited the highest molecular weight (11690 g/mol), the most abundant ß- O-4 ' linkages (71.1%), and the highest S/G ratio (4.68).

Evaluation of xylooligosaccharide production from residual hemicelluloses of dissolving pulp by acid and enzymatic hydrolysis.

Xylooligosaccharides (XOS) are useful food and pharmaceutical additives, which can be produced from various xylans. However, the XOS prepared from lignocellulosic materials are difficult to purify due to the complexity of the degradation products. Thus, hemicelluloses with a high-purity will be the preferred feedstock for XOS production. In this work, acid hydrolysis and enzymatic hydrolysis were applied to prepare XOS from the residual hemicelluloses of the dissolving pulp. The results showed that the highest XOS yield (45.18%) obtained from the acid hydrolysis was achieved with 1% sulfuric acid at 120 °C for 60 min, and xylohexaose accounted for 47% of the XOS. For enzymatic hydrolysis, under optimal conditions, the highest XOS yield of 42.96% was observed, and xylobiose and xylotriose comprised 90.5% of the XOS. It is suggested that the distribution of the XOS could be controlled significantly according to the enzymatic or acid hydrolysis conditions used.