Characterization of lignin-derived products from Japanese beech wood as treated by two-step semi-flow hot-compressed water

Japanese beech (Fagus crenata) wood was treated by two-step semi-flow hot-compressed water (the first stage: 230 °C/10 MPa/15 min, the second stage: 270 °C/10 MPa/15 min), and produced lignin-derived products in the hot-compressed water-soluble portions at the first and second stages, and the final residue of the second stage was characterized with alkaline nitrobenzene oxidation method and gel permeation chromatographic analysis. As a result, the lignin-derived products at the first stage, where hemicellulose was also decomposed, consisted of lignin-based monomers and dimers and oligomers/polymers in the water-soluble portion. A large part of the oligomers/polymers was, however, recovered as the precipitate during 12 h setting after hot-compressed water treatment. By the analysis of nitrobenzene oxidation products, there were relatively higher contents of ether-type lignin in the precipitate at the first stage than in original beech wood. Since the ether linkages of lignin are more preferentially cleaved by this hot-compressed water, lignin-based polymeric fractions were flowed out from the porous cell walls from which hemicellulose was removed. On the other hand, at the second stage condensed-type lignin remained in the precipitate and residue. Based on these results, decomposition behavior of lignin in Japanese beech wood as treated by the two-step semi-flow hot-compressed water was discussed regarding the topochemistry of lignin structure.     

Chemical structural elucidation of total lignins in woods I: fractionation of the lignin in residual wood meal after extraction of milled wood lignin

Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

Changes of major chemical components in larch wood through combined treatment of drying and heat treatment using superheated steam

The effects of the combined treatment of drying and heat treatment using superheated steam (SHS) were studied relative to the changes of the major chemical components in larch wood. The green lumber was dried and heat-treated in SHS conditions of 250 °C and 0.5 MPa for 18 h, and the relative percentage contents of sugars, lignin, and extractives were investigated and compared with the relative percentage contents in the lumber heat-treated in hot air conditions of 250 °C and atmospheric pressure for 18 h. After both heat treatment methods, the relative percentage contents of xylan, mannan, galactan, and arabinan were greatly decreased, whereas that of the Klason lignin was increased, additionally that of glucan and extractives remained almost unchanged. Lignin may bind with furan compounds decomposed from hemicellulose following heat treatment, thus contributing to the increase in the apparent relative percentage contents of the Klason lignin. In addition, the condensate collected in the condenser after combined drying and heat treatment using SHS was investigated qualitatively and quantitatively by high-performance liquid chromatography (HPLC). A large amount of furfural and acetic acid decomposed from hemicellulose was detected and some sugar components composed of cellulose and hemicellulose were detected in the liquid condensate.     

Recycled ionic liquid 1-ethyl-3-methylimidazolium acetate pretreatment for enhancing enzymatic saccharification of softwood without cellulose regeneration

In this work, pretreatment of wood meals using a recycled ionic liquid (IL), 1-ethyl-3-methylimidazolium acetate ([Emim]Ac), enhanced glucose liberation by enzymatic saccharification, without dissolution of cellulose and lignin. In contrast, previous studies on IL pretreatment have mostly focused on lignocellulosic dissolution to regenerate cellulose and removing lignin. Softwood (Cryptomeria japonica) was pretreated with [Emim]Ac at 60–100 °C for 2–8 h without collecting regenerated cellulose. The pretreatment did not have a strong effect on wood component dissolution (weight of residues: 91.7–98.8%). The residues contained relatively high amounts of lignin (26.6–32.6%) with low adsorption of [Emim]Ac (0.9–2.7%). Meanwhile, the crystallinity index (C _r I) of cellulose in the wood was significantly reduced by pretreatment, from 50.9% to 28.4–37.1%. In spite of the high lignin contents in the residues, their glucose liberation values by enzymatic saccharification using a cellulase mixture were 3–16 times greater than that of untreated wood. A good correlation was found between the saccharification effectiveness of pretreated samples and the C _r I. Although lignin dissolved in [Emim]Ac continued to accumulate after repeated use of [Emim]Ac, the pretreatment was found to be effective for three consecutive cycles without the need to remove the dissolved materials.     

In situ measurement of tensile elastic moduli of individual component polymers with a 3D assembly mode in wood cell walls

We attempted to measure in situ the tensile elastic moduli of individual component polymers with a three-dimensional (3D) assembly mode in the cell walls of Sugi (Cryptomeria japonica D. Don) without isolating the polymers. To prepare wood tangential slices [50 × 6 × 0.2 mm (L × T × R)] consisting of lignin with a 3D assembly mode in the cell walls, cellulose and hemicellulose were removed using the method of Terashima and Yoshida (2006) to obtain methylated periodate lignin slices. To prepare wood slices consisting of polysaccharide with a 3D assembly mode in the cell walls, lignin was removed using the method of Maekawa and Koshijima (1983) to obtain holocellulose slices. Static tensile test was applied to determine the elastic moduli of 3D lignin and 3D polysaccharide slices. The followings were revealed. The elastic modulus of the 3D lignin slices was 2.8 GPa, regardless of the microfibril angle (MFA) in the slices. The elastic moduli of the 3D polysaccharide slices with MFAs of 14°, 23°, 34°, and 42° were 18, 12, 9, and 4 GPa, respectively. The former shows that the lignin with a 3D assembly mode behaves as an isotropic substance in the cell walls, while the latter suggests that the 3D polysaccharide slice shows marked anisotropic structure in the cell wall. Despite the fact that cellulose content increased after lignin removal, values of substantial elastic modulus of the cell wall slightly decreased regardless of MFA. Following two possible reasons were pointed out for explaining this phenomenon. First, lignin removal caused an artifactual deterioration in the polysaccharide slices at the level of macromolecular aggregate. Second, rigid and fusiform-shaped cellulose crystallites are dispersed in the soft matrix of amorphous polysaccharide, and those are loosely connected to each other by the intermediary of matrix polysaccharide. Those suggest that the rigid cellulose crystallite can optimize its strong mechanical performance in the polysaccharide framework of the wood cell wall in combination with the ligninification.     

Impact of thermal modification on color and chemical changes of spruce and oak wood

Thermal modification of wood is an environment-friendly alternative method for improving several properties of wood without the use of chemicals. This paper deals with the examination of color and chemical changes in spruce (Picea abies L.) and oak wood (Quercus robur F.) that occur due to thermal treatment. The thermal modification was performed at 160, 180, and 210 °C according to thermowood process. The color changes were measured by the spectrophotometer and described in the L*a*b* color system. Chemical changes were examined by wet chemistry methods, infrared spectroscopy and liquid chromatography. During the experiment, oak samples showed smaller color changes than spruce samples at all temperature values. During thermal modification, the content of cellulose, lignin, and extractives increases; however, the hemicellulose content drops by 58.85% (oak) and by 37.40% (spruce). In addition to deacetylation, new carbonyl and carboxyl groups are formed as a result of oxidation. Bonds in lignin (mainly β-O-4) and methoxyl groups are cleaved, and lignin is condensed at higher temperatures.     

Superheated steam treatment of rubberwood to enhance its mechanical,physiochemical, and biological properties

ABSTRACT

This research was aimed to investigate mechanical properties, color and cell-wall components changes, and durability of pre-dried rubberwood (Hevea brasiliensis) after superheated steam (SS) treatment. Wood samples were treated at different SS temperatures (140–180°C) for 1–3?h. The highest compression strength parallel-to-grain, hardness and impact strength were found for samples treated at 160°C for 3?h (30.7% higher than untreated), at 150°C for 1?h (26.6% higher than untreated) and at 150°C for 2?h (52.6% higher than untreated), respectively. The surface color became darker after each treatment in comparison with the untreated wood. The number of accessible hydroxyl groups decreased and the relative cellulose crystallinity increased with SS temperature, indicating decreased hygroscopicity of the treated wood. Also, SEM micrographs of wood surface showed consistent decrease in starch particles with treatment temperature. Both decay and termite resistances of treated rubberwood improved with treatment temperature. All the analyzes showed that dried rubberwood treated with SS had some improvements in the mechanical properties, decreased hygroscopicity, and increase resistance to decay.     

Fractional isolation and structural characterization of mild ball-milled lignin in high yield and purity from <Emphasis Type="Italic">Eucommia ulmoides</Emphasis> Oliv

Sequential extractions of the mild ball-milled Eucommia ulmoides Oliv with 80% neutral dioxane, 75% dioxane containing 0.025 M HCl, 75% dioxane containing 0.1 M NaOH, 60% ethanol containing 0.5 M NaOH, 5% KOH, 5% NaOH, and 8% KOH at 75°C for 3 h released 91.3% of the original lignin. The results showed that the procedure for extracting lignin from the mild ball-milled wood with mild alkaline organic solvent was more efficient than the traditional method of neutral and mild acidic dioxane extractions. The structure of the seven lignin fractions were analysed using wet chemical analysis, such as alkaline nitrobenzene oxidation, FT-IR, and solution-state ¹H, ¹³C, and ³¹P NMR techniques. It is clear that the sequential mild acidic and alkaline organic solvent extractions of the mild ball-milled E. ulmoides Oliv offered significant yield improvements over the traditional signal acidolysis procedure for isolating lignin from wood, and the alkaline organic solvent extraction led to more lignin release than that of the mild acidolysis. This new procedure proposed in this study could be used for the lignin structural analysis, whereby wood is mild ball-milled and successively extracted with both mild acidic and alkaline organic solvents as well as aqueous alkalis to produce lignin fractions with high yield and purity and representing the total lignin in wood.     

Carbonization mechanism of bamboo（phyllostachys） by means of Fourier Transform Infrared and elemental analysis

Bamboo was carbonized at different temperatures ranging from 200℃ to 600℃.The dependence of the change of hemicellulose,cellulose,and lignin on the temperature was investigated by means of elemental analysis and Fourier Transform Infrared (FTIR) spectra of the residual solid products.The results showed:(1)Below 200℃,hemicellulose in bamboo wasdecomposed and a large amount of hydroxyl groups are dislocated from hemicellulose and cellulose,accompanied by the evolution of water to escape.(2)200℃-250℃,cellulose in bamboo was brastically decomposed whereas the net structure of lignin keep stable,with the except of the dislocation of methoxyl groups from lignin.(3)250℃-400℃,the net structure of lignin collapse,up to 400℃,followed by that the more position in aryl groups are substituted.(4)For bamboo carbonization,the aromatization of residual carbon has approximately completed at the temperature as high as 600℃.But the fusion of aromatic rings possibly does not occur.     

Reactions between Cr(VI) and wood and its model compounds

Wood, macromolecular and simple model compounds, were reacted with CrO₃ or K₂CrO₄ aqueous solutions. Extracted lignin, guaiacol, vanillin, vanillyl alcohol and homovanillyl alcohol were chosen as model compounds for lignin, whilst cellulose, gum Ghatti, xylan, extracted hemicellulose from pine, methyl-β-D-glucopyranoside and methyl-β-cellobioside were used as models for wood polysaccharides. The kinetics of the reduction reactions of Cr(VI) were monitored using UV-Vis spectroscopy and the results obtained for several temperatures are discussed. In general terms, wood, lignin and lignin model compounds reduced Cr(VI) faster and to a greater extent than polysaccharides or simple sugar molecules. Moreover, lignin model compounds were reduced even faster than lignin. Simple sugars showed a reduction pattern similar to that of cellulose. Extracted hemicellulose revealed to be a poorer reductant while gum Ghatti was the strongest among the polysaccharides. As expected, CrO₃ aq. behaved as a more powerfull oxidant than K₂CrO₄ aq. for these substances. Even at 100 °C, sugars or polysaccharides did not seem to be oxidised by K₂CrO₄ aq. 0.01 M. These results suggest that, because of the differences in reactivity, lignin reacts preferentially when wood is treated with Cr(VI)-containing formulations, like those which are applied in wood preservation treatments.     

Mechanics and pyrolysis analyses of rotation welding with pretreated wood dowels

This study examined the mechanics and pyrolysis analyses of rotation welding with treated dowels. Test results indicated that welding specimens with dowels immersed in CuCl₂ solution exhibited higher pullout resistance than untreated specimens. Scanning electron microscopy was used to observe and analyze the welding interface. Wood dowels immersed in CuCl₂ solution provided more flowing molten polymer to obtain better connection than untreated wood dowels. Based on the chemical analyses of X-ray photoelectron spectroscopy, and thermogravimetric analyses, the hydrolysis of cellulose and hemicellulose was detected after immersion of the dowels in a CuCl₂ solution. Pyrolysis of cellulose, hemicellulose and lignin occurred during the welding process. The hydrolysis of cellulose and hemicellulose may promote the pyrolysis and efficient connection of wood components during the welding process.     

Changes of chemical properties and the water vapour sorption of <Emphasis Type="Italic">Eucalyptus pellita</Emphasis> wood thermally modified in vacuum

The aim of this study was to evaluate the chemical composition and the dynamic water vapour sorption properties of Eucalyptus pellita wood thermally modified in vacuum. For this purpose, wood samples were thermally modified in a vacuum oven at 160–240 °C for 4 h. Chemical composition were investigated by wet chemical analysis, elemental analysis, as well as Fourier transform infrared (FTIR) analysis, and dynamic water vapour sorption properties were evaluated by dynamic vapour sorption apparatus. The results showed that holocellulose and alpha-cellulose contents decreased and lignin and extractives contents relatively increased during the heat process. Elemental analysis showed a reduction in hydrogen content and an increase in carbon content. FTIR analysis indicated that the degradation of hemicellulose and condensation reactions of lignin occurred. In addition, the thermo-vacuum resulted in a reduction in the equilibrium moisture content of wood during the adsorption or desorption process. And the sorption hysteresis had a decreasing trend with increasing treatment temperature. The development of the hygroscopicity was related to the increase in the relative content of lignin, the degradation of the carbonyl groups in xylan and the loss of carbonyl group linked to the aromatic skeleton in lignin after heat treatment.     

干法无胶纤维板粘合机理的研究Ⅲ．木材主要化学成分的影响

分别用氢氧化钾和亚氯酸钠处理木材原料，以移去木材原料中的一部分半纤维素和木素。用这些特制浆料压制的无胶纤维板，无论是板的强度性能还是板的耐水性能都比未处理木材原料制造的无胶纤维板的性能有明显的下降。这一结果表明，木材原料中的半纤维素和木素都对纤维间自生胶粘因素的形成具有重要的影响     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin V: effects of steam pretreatment

This study evaluated the potential of steam pre-treatment for making highly compressed phenol-formaldehyde (PF) resin-impregnated wood at a low pressing pressure. Sawn veneers of Japanese cedar (Cryptomeria japonica) were first subjected to saturated steam at different steaming temperatures (140°-200°C), followed by impregnation with a 20% low molecular weight PF resin aqueous solution resulting in a weight gain of around 50%-55%. Four oven-dried treated veneers were laminated and compressed up to a pressing pressure of 1 MPa at a pressing temperature of 150°C and pressing speed of 5 mm/min, and the pressure was held for 30 min. Steam treatment, causing partial hydrolysis of hemicellulose, accelerated the compressibility of Japanese cedar in the PF resin-swollen condition. As a consequence, a discernible increment in density was achieved at a pressing pressure of 1 MPa due to steam pretreatment between 140° and 200°C for 10 min. It was also found that even a short steaming time such as 2 min at 160°C is sufficient for obtaining appreciable compression of PF resin-impregnated wood. The density, Young’s modulus, and bending strength of steam-treated (200°C for 10 min) PF resin-impregnated wood composite reached 1.09 g/cm³, 20 GPa, and 207MPa, respectively. In contrast, the values of untreated PF resin-impregnated wood composite were 0.87 g/cm³, 13 GPa, and 170MPa, respectively.     

碱性离子液体TBAH预处理对桉木结构和酶解性能的影响

为探究碱性离子液体四丁基氢氧化铵(TBAH)在桉木预处理中作用机理,采用响应面分析法设计模型,得到离子液体TBAH预处理桉木的最佳条件为:预处理时间57.19 min,预处理温度71.98℃,TBAH质量分数11.78％,并验证了模型的科学性、准确性和有效性.通过对比未处理、NaOH、四丁基氟化铵(TBAF)和TBAH...     

Analysis of the temperature dependence of water sorption for wood on the basis of dual mode theory

Isotherm curves of water sorption for wood at various temperatures were analyzed based on the dual mode theory where the total coverage was represented by a linear combination of the Langmuir and Henry equations. The saturation concentration and affinity constant of the Langmuir equation and the parameter of Henry’s law had a transition point near 60°C. The analysis based on the dual mode theory found that the constants for whole wood were related to those of wood components and depended more on their glass transition temperatures. That is, it was theoretically demonstrated that the characteristic tem-perature dependence of water sorption for wood occurs because wood consists of three components (cellulose, hemicellulose, and lignin) with different glass transition temperatures.     

Influence of inorganic matter on wood pyrolysis at gasification temperature

The influence of inorganic matter on the pyrolysis of Japanese cedar (Cryptomeria japonica) wood was studied at a gasification temperature of 800°C with demineralization through acid washing. Some influences on the formation of char, tar, and low molecular weight products coincided with results reported at temperatures lower than the gasification temperature. However, the carbonization behavior of the volatile products and the yield of polysaccharide fraction were not able to be explained as a sum of the pyrolysis of cellulose, hemicellulose, and lignin even after demineralization. These results suggest some interactions between wood constituent polymers other than the influence of inorganic matter.     

Two-step hydrolysis of Japanese beech as treated by semi-flow hot-compressed water

A two-step hydrolysis of Japanese beech (Fagus crenata) was conducted by semi-flow treatment with hot-compressed water. The first treatment stage was conducted at 230°C/10 MPa for 15 min and the second at 270°C/10 MPa for 15 min. Hemicellulose and lignin were found to be hydrolyzed in the first stage, while crystalline cellulose was hydrolyzed in the second stage. The treatment solubilized 95.6% of the Japanese beech wood flour into water with 4.4% remaining as water-insoluble residue, which was composed mainly of lignin. Hydrolysis products from the first stage were xylose and xylo-oligosaccharides, glucuronic acid and acetic acid from O-acetyl-4-O-methylglucuronoxylan, and hydrolyzed monomeric guaiacyl and syringyl units and their dimeric condensed-type units from lignin. Products from the second hydrolysis stage were glucose and cello-oligosaccharides from cellulose. The dehydrated products levoglucosan, 5-hydroxymethylfurfural (5-HMF), and furfural, as well as fragmented products glycolaldehyde, methylglyoxal, and erythrose, were recovered in the first stage from hemicellulose, and to a greater extent in the second stage from cellulose. Furthermore, organic acids such as glycolic, formic, acetic, and lactic acids were recovered in both stages. Based on these lines of evidence, decomposition pathways of O-acetyl-4-O-methylglucuronoxylan and cellulose are independently proposed.     

Interaction of lignin and polysaccharides in beech wood (Fagus sylvatica) during drying processes

Summary ¹³C CP MAS NMR spectroscopy was used to characterize the structural changes of cell wall polymers in beech wood Fagus sylvatica during drying processes. The analysis of five wood samples, namely, untreated, untreated dried, pre-treated by steam and/or NaOH subjected to drying showed partial depolymerization of lignin component as well as the change of the ratio of the crystalline and of the amorphous parts of cellulose as the consequence of wood pre-treatment. In addition, T_1ρ(¹H) relaxation times were determined in beech wood sample pre-treated with steam at 135 °C and the lignin isolated from this sample. The magnitudes of the relaxation times were found comparable in both samples as well as in the lignin-cellulose model compound. These unique T_1ρ (¹H) values indicate that spin diffusion is complete and homogeneous due to spatial proximity of spins and confirmed the formation of lignin-cellulose complex during thermal treatment of wood. Received 30 June 1997     

A review of wood thermal pretreatments to improve wood composite properties

The objective of this paper is to review the published literature on improving properties of wood composites through thermal pretreatment of wood. Thermal pretreatment has been conducted in moist environments using hot water or steam at temperatures up to 180 and 230 °C, respectively, or in dry environments using inert gases at temperatures up to 240 °C. In these conditions, hemicelluloses are removed, crystallinity index of cellulose is increased, and cellulose degree of polymerization is reduced, while lignin is not considerably affected. Thermally modified wood has been used to manufacture wood–plastic composites, particleboard, oriented strand board, binderless panels, fiberboard, waferboard, and flakeboard. Thermal pretreatment considerably reduced water absorption and thickness swelling of wood composites, which has been attributed mainly to the removal of hemicelluloses. Mechanical properties have been increased or sometimes reduced, depending on the product and the conditions of the pretreatment. Thermal pretreatment has also shown to improve the resistance of composites to decay.