速生杨硫酸盐浆中木素的存在对纤维素水解反应性能及其产物结构的影响(英文)

对木素含量为0.9％～8.3％的速生杨硫酸盐浆进行了X-射线分析研究。利用多相水解方法测定了其反应性能。研究确定,浆中结晶纤维素含量取决于木素脱出程度并随着木素含量的降低而增加。木屑和浆中的纤维素结晶度相当高,而在脱木素过程中只呈微小变化。木素存在于多相水解反应过程中起着阻碍纤维素水解的作用,降低其反应速度常数。基于研究结果还提出了木素与纤维素结晶部分外表面联结的结论,并探讨了这种联结键的可能方式.     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

Eucalyptus wood decay: effects on productivity and quality of cellulose

We evaluated the effect of wood decay, caused by fungi Hypoxylon spp., on pulp productivity and quality. Wood samples with different proportions of contamination (0, 25, 50, 75, and 100%) were used to produce Kraft pulp under the same pulping conditions. In the second step, cookings were performed to achieve the same Kappa number (Kn = 17 ± 1), varying only the alkali charge. Wood and pulp were also analysed by scanning electron microscope (SEM). The risk of occurrence of wood decay reached its maximum between September and October, under inappropriate storage conditions and juvenile wood without bark. It was observed that the increase in the decayed content (DC) of wood chips affected the Kappa number (Kn), according to the model Kn = 1/(0.0595?0.00324*DC^0.34102). An increase of 38.7% of alkali charge was necessary to reach the same Kappa number with decayed wood. The yield for the contaminated wood was lower (48%) when compared to non‐contaminated wood (53%). Once contaminated, the wood chips demand more severe cooking conditions because of the difficulty of impregnation. This condition affected the pulp quality, reducing its viscosity by 30% and hemicelluloses content by 5%. In addition, losses of resistance were also observed in the final pulp, where the zero span and tensile indexes were reduced by 5 and 16%, respectively. The SEM observations showed that the ascostroma fungi tissue was not totally degraded during the Kraft process, resulting in the deposition of pitch on fibres. Considering the results achieved, it was possible to conclude that the eucalyptus wood decay, caused by the fungi Hypoxylon spp., significantly affects the pulp process and quality.     

Impact of Ceratocystis wilt on eucalyptus tree growth and cellulose pulp yield

In this study, we determined the effects of Ceratocystis fimbriata wilt on volumetric growth and cellulose pulp yield of eucalyptus. Seven‐year‐old healthy and infected trees were separated into different classes of severity, and the individual volume of each whole tree with bark was determined. Volumetric losses were found regardless of the class of disease severity, resulting in reduction in volumetric growth of the trees from 65% to 87%, depending on the infection level. Two approaches were used for evaluating the effects of the disease on cellulose pulp yield: (i) evaluation of wood basic density and chemical composition, contents of ethanol/toluene extractives and Klason lignin, and the alkaline load and screen yield across Kraft pulping to kappa number 18 ± 0.5 for both healthy and discoloured materials; (ii) determination of the alkaline load and yield across Kraft pulping to kappa number 18 ± 0.5 of woods with different levels of discoloration (0, 25, 50, 75 and 100% of discoloured wood). Discoloured wood presented lower basic density, higher ethanol/toluene extractives and Klason lignin, higher alkaline load and lower pulp screened yield at kappa number 18 ± 0.5 compared with the healthy ones. Increasing the fraction of infected wood in chip furnishes resulted in proportionally increased alkaline load demand and decreased screen yields. Adding 50% of infected wood in the chip furnish resulted in 23.8% increase in the alkali load and 13.7% reduction in the pulp screen yield at kappa number 18 ± 0.5. The results obtained have proved that the disease reduces volumetric growth, increases wood consumption and reduces yield in eucalyptus pulp production.     

Effect of the amount of lignin on tensile properties of single wood fibers

Chemical components are the main factors affecting the mechanical properties of wood fibers. Lignin is one of the main components of wood cell walls and has a critical effect on the mechanical properties of paper pulp and wood fiber based composites. In this study, we carried out tensile tests on single mature latewood tracheids of Chinese fir (Cunninghamia lanciolata (Lamb.) Hook.), using three different delignified treatment methods to obtain different amounts of lignin. We applied single fiber tests to study the effect of the amount of lignin on mechanical tensile properties of single wood fibers at the cellular level. The results show that in their dry state, the modulus of elasticity of single fibers decreased with the reduction in the amount of lignin; even their absolute values were not high. The amount of lignin affects the tensile strength and elongation of single fibers considerably. Tensile strength and elongation of single fibers increase with a reduction in the amount of lignin.     

氧漂过程中脱木质素与木质素氧化之间定量关系的研究

对氧碱漂白过程中木质素氧化进行定量分析,分析方法是基于氧化前后高锰酸钾消耗量的变化。该方法对溶出残余木质素的氧化结果分析发现其呈明显3个阶段：第一段木质素氧化的当量电荷数约4～5／木质素单元;木质素总氧化电荷数大约为9／木质素单元。这些数据以及甲氧基的脱除（75％）均表明：木质素的氧化不仅发生在酚型木质素单元,同时也发生在非酚型结构单元上。只有第一阶段氧化反应是木质素与氧气直接反应,而在第二、三阶段主要是协同氧化作用,氧化反应过程中产生的活性氧基团扮演了一定角色。通过对低浓度针叶材硫酸盐浆的氧漂研究发现：当卡伯值下降一半（25．4至13．4）时平均每个木质素单元氧化3当量电子,氧漂后的纸浆中仍然有大量未被氧化的残余木质素。定量地证明了在氧漂过程中木质素氧化是脱木质素反应的实质。     

Structure of small lignin fragments retained in water-soluble polysaccharides extracted from birch MWL isolation residue

To analyze the structural features of lignin in the vicinity of lignin–carbohydrate linkages, water-soluble lignin–carbohydrate complex (LCC) with low lignin content was prepared from residual birch wood meal after the extraction of milled wood lignin (MWL). The molecular weight distribution of lignin in this LCC appeared together with carbohydrate in the relatively high molecular weight region of the gel permeation chromatogram. This result was consistent with our previous results obtained for the same fraction of Japanese cedar (sugi); however, after treatment with polysaccharide-degrading enzyme, the molecular weight distribution of carbohydrate and that of lignin shifted significantly to the lower region. These results demonstrated that molecular size of this LCC is determined by carbohydrates while lignin is present as a minor fragment in this fraction. The syringyl/guaiacyl (S/V) ratio of this LCC was higher than other lignin fractions. Ozonation analysis implied that this LCC has a relatively high number of β-1 structures. It is likely that lignin that exists near lignin–carbohydrate linkages has more endwise-type features than other lignin fractions.This paper was presented in part at the 48th Lignin Symposium, Fukui, Japan, October 2003 and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

Biobleaching of unbleached and oxygen-bleached hardwood kraft pulp by culture filtrate containing manganese peroxidase and lignin peroxidase fromPhanerochaete chrysosporium

Unbleached and oxygen-bleached hardwood kraft pulp (UKP and OKP), respectively, were bleached with a culture filtrate containing manganese peroxidase (MnP) and lignin peroxidase (LiP) fromPhanerochaete chrysosporium Burds. The brightness increases of UKP upon biobleaching with the culture filtrate with and without MnSO₄ were the same. The brightness increase of OKP with MnSO₄ decreased to about half that seen without MnSO₄. Changes in the brightness of UKP and OKP by treatment with the culture filtrate were determined. The brightness increased sharply by about eight points during the first 3h. The 3-h treatment was repeated seven times. The brightness increased linearly with the bleaching of UKP. On bleaching of OKP, the brightness increased slowly and stopped at about 78%.Part of this report was presented at the 62nd Pulp and Paper Research Conference of the Japan Tappi, Tokyo, June 1995     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Characterization of mean stem density,fibre length and lignin from two Acacia species and their hybrid

The objective of this study was to compare the wood properties related to wood pulp quality of two widely planted Acacia species viz.Acacia mangium Willd.and Acacia auriculiformis A.Cunn.Ex Benth.and their hybrid.Acid insoluble lignin content(Klason),mean stem density and fibre length differed considerably among the species and hybrids.A.mangium possessed a high percent of lignin content compared to A.auriculiformis and the Acacia hybrid.However,mean stem density of A.auriculiformis was higher than A.mangium and the hybrid.Fibre length of heartwood tissues was generally shorter than that of sapwood tissues.The hybrid had longer fibres than the parent species.Lignin was negatively correlated with mean stem density.Generally,the wood properties of the hybrid were superior to its parent species.The significant intraspecific variation observed for wood properties of Acacia species could be used in breeding superior hybrids combining desirable traits of the two species.Considering thedifficulty involved in accurately measuring the lignin content compared to mean stem density,selection for plants with low lignin content can be achieved by indirect selection of high mean stem density.     

Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp

Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.Part of this paper was presented at the 46th Annual Meeting of the Japan Wood Research Society, Kumamoto, April 1996; the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June 1999; and the 67th Pulp and Paper Research Conference, Tokyo, June 2000     

Relation between growth stress and lignin concentration in the cell wall: Ultraviolet microscopic spectral analysis

Lignin content in the cell wall was investigated to examine its relation with growth stress, using an ultraviolet microscopic spectrum analyzer. Although a weak correlation existed between the growth stress and lignin concentration in the compound middle lamella, it was believed that the compound middle lamella did not contribute to compressive growth stress generation as there was no correlation between growth stress and lignin concentration in the cell corner part of the intercellular layer. In the secondary wall, larger compressive growth stress was associated with higher lignin concentration especially in the outer part. This finding confirms that lignin contributes positively to the generation of compressive longitudinal growth stresses in the compression wood and more substantially in the outer part of the secondary wall. This experimental result strongly supports our hypothesis of growth stress generation given by the model.This paper was presented at the International Academy of Wood Science Meeting at Vancouver, Canada, July 1997     

Genetic parameters of growth and wood quality traits in Picea abies

Genetic parameters were estimated for wood and growth traits in two 19-yr-old clonal trials and a 40-yr-old full-sib progeny trial of Norway spruce [Picea abies (L.) Karst.]. In the clonal trials high (>0.4) broad-sense heritabilities were found for wood density traits, lignin content, number of internal cracks, growth traits, spiral grain and number of resin canals. Moderate (0.2–0.4) heritabilities were found for tracheid lumen diameter and cell wall thickness, microfibril angle and tracheid length, while low heritabilities (<0.2) were found for pulp yield, fibre strength, wood stiffness and wood colour. Lignin content and pulp yield showed low genetic variation, whereas the genotypic coefficient of variation for most other traits ranged between 5 and 15%. Most traits showed low levels of genotype by environment interaction. Among the wood properties, latewood proportion, earlywood density and ring density showed significant, adverse correlations with volume in both clonal trials.     

An improved acetyl bromide procedure for determining lignin in woods and wood pulps

Summary The acetyl bromide procedure for spectrophotometrically determining lignin in wood and wood pulp samples has been modified by adding perchloric acid to the digestion medium. This enables faster dissolution of the materials and the use of coarser samples. Subsequent treatment of the digestion mixtures with larger amounts of sodium hydroxide than those used in the conventional procedure has obviated the need for treatment with hydroxylamine. The modified method has been successfully applied to woodmeals and pulps from Pinus radiata and Eucalyptus species.     

Condensation of lignin during heating of wood

Summary The structural change of lignin during heating of wood was investigated quantitatively by a method combining nucleus exchange and nitrobenzene oxidation. Lignin modification during heating was mainly a diphenylmethane type condensation. About 40 and 75% of noncondensed units in protolignins were converted to diphenylmethane type units by heating of dry and wet wood meals up to 220 °C, respectively. On the other hand, during heating of modified lignin (dioxane lignin) various types of modifications in addition to diphenylmethane type condensation occurred. Lignin modification via the diphenylmethane type condensation was proposed as a new route for its utilization.     

Lignin Characteristics of Steam Exploded Bamboo Residue during Hot Pressing

bamboo(Phyllostachys edulis) residue was subjected to steam explosion treatment to produce superior fibers for binderless boards.Then,lignin was isolated from extract-free bamboo meal,steam exploded pulp,and binderless boards with characteristics being determined by thermo-gravimetry (TG),differential scanning calorimetry (DSC),and fourier transform infrared spectroscopy (FTIR).Results showed that:1) the yield of lignin directly extracted with dioxane-water from steam exploded bamboo pulp(SEBPL) and binderless board (SEBBL) was higher than that of milled bamboo lignin (MBL).Also,the yield of SEBBL was lower than that of SEBPL.2) FTIR results showed cleavage of ester and ether bonds between lignin and p-coumaric acid during steam explosion treatment.3) SEBBL showed two glass transitions at 115℃and 200℃, while MBL gave one glass transitions at 155℃.And 4) the modulus of rupture(MOR) and modulus of elasticity(MOE) decreased with an increase in steaming time;whereas internal bonding(IB) increased.In all cases the dimensional stability of boards did not exceed the maximum requirements for type GB/T 11718- 1999.     

Studies on the lignin of the bamboo species Phyllostachys makinoi Hay.

Summary Milled wood lignin (MWL) isolated from Phyllostachys makinoi was investigated by chemical and physical methods. The bamboo lignin is rich in syringyl units which is indicated by a high methoxyl content and respective bands in the IR spectrum. The distinct absorption bands for aromatic ring vibrations are attributed to final p-coumaryl ester groups. In the UV spectrum the extinction maximum in the range of 280 nm is shifted to longer wavelengths compared to wood lignin. With NaOH and TFA mainly an arabinoxylan with a Xyl: Ara ratio of 14:1 was extracted from bamboo saw dust. The lignin proportion in the NaOH extract, which derives mainly from the secondary walls has a lower methoxyl content, the lignin proportion in the TFA extract, which derives from the compound middle lamellae has a higher methoxyl content compared to MWL.     

Delignification of cell walls of <Emphasis Type="Italic">Chamaecyparis obtusa</Emphasis> during alkaline nitrobenzene oxidation

To clarify the behavior of whole lignins in wood cell walls during alkaline nitrobenzene oxidation, the delignification process from cell walls in normal and compression woods of Chamaecyparis obtusa Endl. (Cupressaceae) was observed using ultraviolet and transmission electron microscopies. The lignin content conspicuously decreased to around 10% after 35min in normal wood. The lignin content in compression wood finally leveled off at aroumd 10% after 50min. In gel filtration of oxidation products in ethyl acetate, a high molecular weight fraction was prominent in extracts from the early stage of the reaction. As the oxidation progressed, the high molecular weight fraction became less prominent in both normal and compression wood. Changes in the weights of cell wall residues during reaction indicated that approximately half of the components other than lignin were also removed from the cell walls. This shows that the majority of lignin with relatively high molecular weight is removed from the cell walls together with polysaccharides in the early stage of the reaction and that further oxidative degradation occurs in solution in later stages. Only a small amount of the lignin with low molecular weight could be analyzed by gas chromatography.Parts of this report were presented at the 47th (Kochi, April 1997) and 48th (Shizuoka, April 1998) Annual Meetings of the Japan Wood Research Society, and at the Lignin Symposium, Sapporo, October 1997     

Lignin biochemistry: Biosynthesis and biodegradation

Summary Lignin biosynthesis via shikimate-cinnamate pathways in plants, and the biosynthetic differences of guaiacyl-and syringyl lignins between gymnosperms and angiosperms have been elucidated by tracer experiments using ¹⁴C labeled precursors and the following enzyme reactions. The formation of guaiacyl lignin but not syringyl lignin in gymnosperms was attributed to the following factors; absence of ferulate-5-hydroxylase, poor affinity of O-methyltransferase toward 5-hydroxyferulate, and lack of activation and/or reduction of sinapatc. A mechanism of lignin-carbohydrate complexes formation in wood cell walls was elucidated based on the reaction of the quinone methide of guaiacylglycerol--guaiacyl ether with sugars, and the analysis of DHP-polysaccharide complexes.The main cleavage mechanisms of side chains and aromatic rings of lignin model compounds and synthetic lignin (DHP) by white-rot fungi and their enzymes, lignin peroxidase and laccase have been elucidated using ²H, ¹³C and ¹⁸O-labeled lignin substructure dimcrs with ¹⁸O₂ and H₂ ¹⁸O. Side chains and aromatic rings of these substrates were cleaved via aryl cation radical and phenoxy radical intermediates, in reaction mediated only by lignin peroxidase/H₂O₂ and laccase/O₂.Academy Lecture presented at the Cellucon 88 in Japan, International Symposium on New Functionalisation Developments in Cellulosics and Wood, held in Kyoto, Japan, November 28 to December 1, 1988This paper is a conclusion of our investigations on the biosynthesis and microbial degradation of lignin for 30 years in the Research Section of Lignin Chemistry, Wood Research Institute, Kyoto University. The author is greatly indebted to Drs. M. Shimada, F. Nakatsubo, T. Yamasaki, H. Ohashi, M. Tanahashi, Y. Nakamura, H. Kuroda, H. Kutsuki, T. Katayama, Y. Kamaya, T. Umezawa and Messrs. H. Fushiki, M. Ohta, A. Noguchi, H. Namba, T. Habe, S. Kawai, S. Yokota, and T. Hattori for their kind cooperation in these investigations. These invstigations were supported in part by Grant-in-Aid Nos. 548047, 57480058, 59760124, 60760130, 60440015, 61760142, 61560193, 62790250 for Scientific Research, and 1980 Grant-in-Aid for Environmental Science (R-33-8), No. 403064 from the Ministry of Education, Science and Culture of Japan, and a 1980 Weyerhaeuser grant