Han-Yin Li

Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw

Due to the enormous abundance of lignin and its unique aromatic nature, lignin has great potential for the production of industrially useful fuels, chemicals, and materials. However, the rigid and compact structure of the plant cell walls significantly blocks the separation of lignin. In this study, wheat straw was hydrothermally pretreated at different temperatures (120–200 °C) followed by post-treatment with 70% ethanol containing 1% NaOH to improve the isolation of lignin. Results demonstrated that the content of associated carbohydrates of the lignin fractions was gradually reduced with the increment of the hydrothermal severity. The structure of the lignins changed regularly with the increase of the pretreatment temperature from 120 to 200 °C. In particular, the contents of β-O-4′, β-β′, β-5′ linkages and aliphatic OH in the lignins showed a tendency of decrease, while the content of phenolic OH and thermal stability of the lignin fractions increased steadily as the increment of the pretreatment temperature.

Structural variation of eucalyptus lignin in a combination of hydrothermal and alkali treatments

In this work, the structural features of the lignin isolated with 2% NaOH at 90°C for 2.5h from the hydrothermally pretreated eucalyptus fibers at different temperatures (100-200°C) for different times (15-60min) were thoroughly investigated. Results showed that the hydrothermal pretreatment facilitated the separation of alkali lignin from the pretreated fibers. It was found that the linkages of β-O-4, β-β, and β-5 decreased gradually with the increase of hydrothermal severity. Furthermore, decreased molecular weights (1630-510g/mol), associated carbohydrates contents (1.99-0.05%) and aliphatic OH contents (3.37-0.65mmol/g), and increased phenolic OH contents (0.71-2.98mmol/g) and thermal stability of the alkali lignins were observed with the increase of the hydrothermal severity.

Structural characterization of hemicelluloses and topochemical changes in Eucalyptus cell wall during alkali ethanol treatment

Eucalyptus was sequentially extracted with 70% ethanol containing 0.4, 1.0, 2.0, 3.0, and 5.0% NaOH for 2h at 80°C. The chemical composition and structural features of the hemicellulosic fractions obtained were comparatively characterized by the combination of high-performance anion-exchange chromatography, gel permeation chromatography, Fourier transform infrared, and nuclear magnetic resonance spectroscopies. Furthermore, the main component distribution and their changes in cell wall were investigated by confocal Raman microscopy. Based on the Fourier transform infrared and nuclear magnetic resonance analyses, the hemicelluloses extracted from Eucalyptus mainly have a linear backbone of (1→4)-linked-β-d-xylopyranosyl residues decorated with branch at O-2 of 4-O-methyl-α-glucuronic acid unit. Raman analysis revealed that the dissolution of hemicelluloses was different in the morphological regions, and the hemicelluloses released mainly originated from the secondary wall. The information obtained from the study conducted by combining chemical characterization with ultrastructure provides important basis for studying the mechanism of the alkali treatment.

Revealing the structure and distribution changes of Eucalyptus lignin during the hydrothermal and alkaline pretreatments

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. 31P 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.

Effect of compression combined with steam treatment on the porosity, chemical compositon and cellulose crystalline structure of wood cell walls.

The changes of porosity, chemical composition and cellulose crystalline structure of Spruce (Picea abies Karst.) wood cell walls due to compression combined with steam treatment (CS-treatment) were investigated by nitrogen adsorption, confocal Raman microscopy (CRM) and X-ray diffraction (XRD), respectively. A number of slit-shaped mesopores with a diameter of 3.7nm was formed for the CS-treated wood, and more mesopores were found in the steam-treated wood. CRM results revealed cellulose structure was affected by treatment and β-aryl-ether links associated to guaiacyl units of lignin was depolymerized followed by re-condensation reactions. The crystallinity index (CrI) and crystallite thickness (D200) of cellulose for CS-treated wood were largely increased due to crystallization in the semicrystalline region. Higher degree of increase in both CrI and D200 was observed in both the earlywood and latewood of steam-treated wood, ascribing to the greater amount of mesopores in steam-treated wood than CS-treated wood.

Amination of biorefinery technical lignins using Mannich reaction synergy with subcritical ethanol depolymerization

The alcoholic depolymerization and Mannich reaction were conducted to improve the chemical activity of biorefinery technical lignins and introduce amino groups into lignins, respectively. To understand the chemical structural transformations and examine the reaction mechanism, GPC and solution-state NMR techniques were performed. Element analysis was also used to quantify the amount of amine groups. The NMR characterization the depolymerized lignins indicated of the depolymerization, demethoxylation, and bond cleavage of linkages occurred during the depolymerization process. Results showed that the depolymerization temperature instead of the addition of capping reagents was the main factor for improving the reactivity of lignin under the given conditions. The Mannich reaction was very selective, primarily occurred at H3,5 and G5 positions, and the H units present a higher chemical reactivity. It is believed that the understanding of the fundamental chemistry of lignin during depolymerization and Mannich reaction process will contribute to the extension of high value-added applications of biorefinery lignin.