lignin structure
木质素的高值化利用研究进展
木质素的高值化利用研究进展————————————————————————————————作者：————————————————————————————————日期：1木质素的高值化利用研究进展XXX化工学院13级化学工程学号：40130100x摘要：目前国内外所开发的木质素产品已经有数百种，但是，由于木质素本身结构非常复杂且木质素的种类繁多，使得开发木质素产品存在一定的盲目性，我国仅约6％的木质素得到利用。
如何有效地利用木质素的结构特性来控制已有木质素产品的性能稳定性、开发更多性能优良的木质素产品以及实现木质素高附加值产品生产的规模化、产业化等，将成为木质素研究的一个重要方面。
文章结合近年来木质素产品的研究及开发，介绍了木质素结构与功能之间的联系，以期能够充分利用木质素的结构特点来改进和生产木质素产品，以得到具有工业应用价值的产品，不仅具有环保意义，更具有经济意义。
关键词：木质素；高值化利用；木质素改性Research Progress of Lignin in High Value UseXXXnChemical Engineering of Chemical Engineering InstituteNO. 401301xxAbstract:Now the development of domestic and foreign products have hundreds of lignin.But be cause the type of lignin structure is very complicated and lignin is various, which makes the deve lopment of lignin products exist blindness,China is only about 6% of the lignin obtained by.How to effectively use the structure characteristics of lignin to control the performance stability of lig nin products,develop of more excellent performance of wood products and the realization of lign in products with high added value production scale, industrialization,will become an important a spect of the study of lignin.This paper based on the research and development of lignin products in recent years,Introduces the relationship of lignin structure and function,In order to make full u se of the characteristics of the structure of lignin to improvement and production of lignin produc ts and get the Industrial application value products.It not only has the significance of environmen tal protection, but also has a greater economic significance.Key words:Lignin; high value use; lignin modification1 前言木质素是一种复杂的、非结晶性的、三维网状多羟基芳香族化合物，它广泛存在于高等植物细胞中，是针叶树类、阔叶树类和草类植物的基本化学组成之一[1-3]，也是木材水解工业和制浆造纸工业的主要副产物[4-5]。
26488403_木质素羟基化改性及其在聚氨酯合成中的应用
·木质素的羟基化改性·木质素羟基化改性及其在聚氨酯合成中的应用靳汇奇贾文超盛雪茹牛梅红石海强*（大连工业大学轻工与化学工程学院/辽宁省生物质与化学重点实验室，辽宁大连，116034）摘要：工业木质素主要来源于制浆和纤维素乙醇生物精炼的副产物，产量巨大；且木质素具有替代多元醇合成聚氨酯材料的应用潜力。
对木质素进行羟基化改性，可以控制木质素分子质量和增加羟基含量，从而提高木质素的反应活性和在合成体系中的相容性，减少木质素在聚氨酯中的聚集，增加聚氨酯材料的微观均匀性，从而增强聚氨酯材料的机械性能；同时还可能赋予聚氨酯抗紫外、吸油、可降解等性能。
本文对木质素基本理化性质进行简要介绍，重点介绍了目前国内外木质素羟基化改性方法的研究进展；最后探讨了木质素基聚氨酯合成领域的研究和应用前景。
关键词：木质素；羟基化；聚氨酯；改性；机械性能中图分类号：TS721；O636.2文献标识码：ADOI ：10.11980/j.issn.0254-508X.2021.10.016Hydroxylation of Lignin and Its Application in Synthesis of PolyurethaneJIN Huiqi JIA Wenchao SHENG Xueru NIU Meihong SHI Haiqiang *（School of Light Industry and Chemical Engineering/Key Lab of Biomass and Chemistry of Liaoning Province ，Dalian Polytechnic University ，Dalian ，Liaoning Province ，116034）（*E -mail ：Shihq@ ）Abstract ：Industrial lignin with huge output was mainly derived from the by -products of pulping and cellulosic ethanol biorefinery ，and it had the potential to replace polyol to synthetic polyurethane materials.The hydroxylation of lignin could control the molecular weight and in⁃crease the hydroxyl content of lignin ，improving the reactivity of lignin and its compatibility in the synthesis system.It also could reduce the aggregation of lignin in the polyurethane ，increase the micro -uniformity of the polyurethane materials to enhance the mechanical properties of the polyurethane materials.At the same time ，it could also give polyurethane materials anti -ultraviolet ，oil absorption ，degradable and otherproperties.The basic physicochemical properties of lignin were briefly introduced ，and the current research progress of lignin hydroxylationmethods at home and abroad were also introduced.The research and application prospects in the field of synthesis of lignin -based polyure⁃thane materials were discussed.Key words ：lignin ；hydroxylation ；polyurethane ；modification ；mechanical properties木质素是自然界储量第二大的天然高分子化合物，在植物细胞壁中，木质素与纤维素和半纤维素结合在一起为细胞提供支撑[1]。
ENVI中常见植被指数介绍
作业9 植被指数植被指数概念：利用卫星不同波段探测数据组合而成的，能反映植物生长状况的指数。
植物叶面在可见光红光波段有很强的吸收特性，在近红外波段有很强的反射特性，这是植被遥感监测的物理基础，通过这两个波段测值的不同组合可得到不同的植被指数。
不同的植被覆盖类型可以通过其特有的光谱特征进行区分，这是由于叶绿素在红波段内对太阳辐射的吸收以及叶片细胞结构对红外波段内太阳辐射的强反射。
Broadband Greenness(5 indices)（宽带绿色指标(5)）宽带绿度指数可以简单度量绿色植被的数量和生长状况，它对植物的叶绿素含量、叶子表面冠层、冠层结构比较敏感，这些都是植被光合作用的主要物质，与光合有效辐射（fAPAR）也有关系。
宽带绿度指数常用于植被物候发育的研究，土地利用和气候影响评估，植被生产力建模等。
宽带绿度指数选择的波段范围在可见光和近红外，一般的多光谱都包含这些波段。
下面的公式中规定波段的中心波长：ρNIR=800nm，ρRED=680nm，ρBLUE=450nm。
1. Normalized Difference Vegetation Index归一化植被指数增强在近红外波段范围绿叶的散射与红波段范围叶绿素的吸收差异。
简称NDVI： NDVI=(NIR-R)/(NIR+R)（1）应用：检测植被生长状态、植被覆盖度和消除部分辐射误差等；（2）-1<=NDVI<=1，负值表示地面覆盖为云、水、雪等，对可见光高反射；0表示有岩石或裸土等，NIR和R近似相等；正值，表示有植被覆盖，且随覆盖度增大而增大；（3）NDVI的局限性表现在，用非线性拉伸的方式增强了NIR和R的反射率的对比度。
对于同一幅图象，分别求RVI和NDVI时会发现，RVI值增加的速度高于NDVI增加速度，即NDVI 对高植被区具有较低的灵敏度；（4）NDVI能反映出植物冠层的背景影响，如土壤、潮湿地面、学、枯叶、粗超度等，且与植被覆盖有关；2.Simple Ratio Index比值植被指数在近红外波段范围绿叶的散射与红波段范围叶绿素吸收的比值。
木质素分离及主要物理和力学性能的研究进展
第 2 期第 122-134 页材料工程Vol.52Feb. 2024Journal of Materials EngineeringNo.2pp.122-134第 52 卷2024 年 2 月木质素分离及主要物理和力学性能的研究进展Research progress in isolation ，main physical and mechanical properties of wood lignin周博鑫1，沈姿伶1，江京辉2，漆楚生1*，戴璐1*（1 北京林业大学 木质材料科学与应用教育部重点实验室，北京 100083；2 中国林业科学研究院 木材工业研究所，北京 100091）ZHOU Boxin 1，SHEN Ziling 1，JIANG Jinghui 2，QI Chusheng 1*，DAI Lu 1*（1 Key Laboratory of Wood Material Science and Application （Ministry of Education ），Beijing Forestry University ，Beijing 100083，China ；2 Wood Industry Research Institute ，ChineseAcademy of Forestry Science ，Beijing 100091，China ）摘要：木质素是木材细胞壁的重要组成成分，其吸湿特性、热特性、力学特性等在木材的微宏观尺度相互影响，并对其高值化应用起决定性作用。
本文从分子结构、分离方法、吸湿特性、热特性、力学特性五个方面综述了木材木质素的研究进展。
木材木质素是高异质、不规则的三维网状高分子结构，相比原位木质素，不同分离方法的分离木质素有不同程度的解聚缩合，导致分离木质素分子结构、吸湿性、热特性、力学特性存在差异性。
木材木质素具有近似 S 型等温吸附曲线且存在吸湿滞后现象，平衡含水率在20%（质量分数）以下，可用 BET ，GAB 理论定性描述和定量分析单层水分子吸附量。
碳纤维增强木质素基酚醛树脂复合材料的制备及其性能
木质素溶液冷却至70 ℃，逐滴加入甲醛溶液，搅 拌1 h后，升至90 ℃继续搅拌反应1 h，得到甲阶 LPF水溶液，在鼓风烘箱中升至150 ℃固化1 h，得 到LPF。固定酚醛摩尔比为1.0∶1.5，分别制备了木 质素替代率（即EHL质量与EHL和苯酚总质量之 比）为10%，20%，30%，40%的LPF，同时制备PF为 对照样。 1.3.3 LPFCF复合材料的制备
1 实验部分 1.1 主要原料
酶解木质素（EHL），龙力生物科技股份有限 公司。苯酚，分析纯，西陇科学股份有限公司。氢 氧化钠，分析纯；甲醛水溶液，纯度38%（w）；浓硫 酸，纯度98%（w）：广试试剂科技有限公司。N,N二甲基甲酰胺，分析纯，天津百世化工有限公司。 3k碳纤维布（平纹），杰创碳纤维制品有限公司。 去离子水，实验室自制。 1.2 主要设备与仪器
分子质量高，同时复杂的三维结构导致反应活性
收稿日期： 2023-08-26；修回日期： 2023-10-26。 作者简介： 周彭，男，1997年生，硕士，2023年毕业于五邑 大学纺织科学与工程专业，主要从事生物质高分子材料的 资源化与回收利用工作。E-mail：1912874805@。 基金项目： 江门市基础与理论科学研究类科技计划项目 （2020JC01025）。 * 通信联系人。E-mail：wangchg007@。
表1 EHL酚化处理的工艺条件
木质素结构及其催化转化方法的研究进展
木质素结构及其催化转化方法的研究进展耿莉莉;张宏喜;周婷婷;魏婷;李楠【期刊名称】《广州化工》【年(卷),期】2016(044)020【摘要】木质素是自然界目前唯一由芳香结构组成的最丰富的可再生能源，其化学结构使得木质素非常适合生产芳香类化合物。
目前，对木质素的研究主要集中于利用催化转化方法生产高附加值的化学品和生物油方面。
本文介绍了木质素的基本结构及其催化转化制备化学品的方法及研究现状。
最后，指出目前催化转化过程中存在的一些问题，并对未来发展进行了展望。
%Lignin is the most abundant renewable energy source with aromatic structure in nature at present. Its chemical structure makes it very suitable for the production of aromatic chemicals. Currently, the research is mainly focused on the conversion of lignin into high added-value products and bio-oil using catalytic transformation methods. A brief overview about the basic structure and catalytic transformation methods of lignin into chemicals and their research status was described, some problems existing in the catalytic transformation were pointed out, and its future development was prospected.【总页数】4页(P4-6,26)【作者】耿莉莉;张宏喜;周婷婷;魏婷;李楠【作者单位】昌吉学院化学与应用化学系，新疆昌吉 831100;昌吉学院化学与应用化学系，新疆昌吉 831100;昌吉学院化学与应用化学系，新疆昌吉 831100;昌吉学院化学与应用化学系，新疆昌吉 831100;昌吉学院化学与应用化学系，新疆昌吉 831100【正文语种】中文【中图分类】TQ351【相关文献】1.玉米秸秆酶解木质素及麦草甲酸木质素在钙钛矿催化体系下催化活性比较 [J], 邓海波;王方;龙柱;吕勇2.木质素催化液化用催化剂的研究进展 [J], 罗显峰;金庆辉;孙雄康3.木材白腐菌分解木质素的酶系统-锰过氧化物酶、漆酶和木质素过氧化物酶催化分解木质素的机制 [J], 池玉杰;伊洪伟4.木质素制备燃料电池阴极电催化炭材料研究(Ⅲ)——改性酶解木质素炭的微观结构演变 [J], 左宋林;金凯楠;桂有才;申保收;王珊珊;杨梦梅5.木质素制备燃料电池阴极电催化炭材料研究(Ⅱ)——改性酶解木质素炭的化学结构演变 [J], 金凯楠;左宋林;桂有才;申保收;王珊珊;胡欣因版权原因，仅展示原文概要，查看原文内容请购买。
桉木木素含量与结构
Lignin Composition and Structure in Young versus Adult Eucalyptus globulus Plants1Jorge Rencoret,Ana Gutie´rrez,Lidia Nieto,J.Jime´nez-Barbero,Craig B.Faulds,Hoon Kim,John Ralph,A´ngel T.Martı´nez,and Jose´C.del Rı´o*Instituto de Recursos Naturales y Agrobiologı´a de Sevilla,Consejo Superior de Investigaciones Cientı´ficas, E–41080Seville,Spain(J.Rencoret,A.G.,J.C.d.R.);Centro de Investigaciones Biolo´gicas,Consejo Superior de Investigaciones Cientı´ficas,E–28040Madrid,Spain(L.N.,J.J.-B.,C.B.F.,A.T.M.);and Departments of Biochemistry and Biological Systems Engineering and Department of Energy Great Lakes Bioenergy Research Center,University of Wisconsin,Madison,Wisconsin53706(J.Rencoret,H.K.,J.Ralph)Lignin changes during plant growth were investigated in a selected Eucalyptus globulus clone.The lignin composition and structure were studied in situ by a new procedure enabling the acquisition of two-dimensional nuclear magnetic resonance (2D-NMR)spectra on wood gels formed in the NMR tube as well as by analytical pyrolysis-gas chromatography-mass spectrometry.In addition,milled-wood lignins were isolated and analyzed by2D-NMR,pyrolysis-gas chromatography-mass spectrometry,and thioacidolysis.The data indicated that p-hydroxyphenyl and guaiacyl units are deposited at the earlier stages,whereas the woods are enriched in syringyl(S)lignin during late lignification.Wood2D-NMR showed that b-O-4#and resinol linkages were predominant in the eucalypt lignin,whereas other substructures were present in much lower amounts. Interestingly,open b-1#structures could be detected in the isolated lignins.Phenylcoumarans and cinnamyl end groups were depleted with age,spirodienone abundance increased,and the main substructures(b-O-4#and resinols)were scarcely modified.Thioacidolysis revealed a higher predominance of S units in the ether-linked lignin than in the total lignin and,in agreement with NMR,also indicated that resinols are the most important nonether linkages.Dimer analysis showed that most of the resinol-type structures comprised two S units(syringaresinol),the crossed guaiacyl-S resinol appearing as a minor substructure and pinoresinol being totally absent.Changes in hemicelluloses were also shown by the2D-NMR spectra of the wood gels without polysaccharide isolation.These include decreases of methyl galacturonosyl,arabinosyl,and galactosyl (anomeric)signals,assigned to pectin and related neutral polysaccharides,and increases of xylosyl(which are approximately 50%acetylated)and4-O-methylglucuronosyl signals.Plant cell walls are composed mainly of three struc-tural polymers,the carbohydrates cellulose and the hemi-celluloses and the aromatic polymer lignin.The lignin polymer provides mechanical support to the plant.In addition,it waterproofs the cell wall,enabling trans-port of water and solutes through the vascular system, and plays a role in protecting plants against patho-gens.Lignin is a complex polymer synthesized mainly from three hydroxycinnamyl alcohols differing in their degree of methoxylation:p-coumaryl,coniferyl,and sinapyl alcohols(Higuchi,1997;Boerjan et al.,2003;Ralph et al.,2004a).Each of these monolignols gives rise to a different type of lignin unit called p-hydroxy-phenyl(H),guaiacyl(G),and syringyl(S)units,re-spectively,when incorporated into the polymer.The amount and composition of lignins vary among taxa, cell types,and individual cell wall layers and also with environmental conditions.Softwood lignin con-sists almost exclusively of G-type lignin,while hard-wood lignin also consists of S units(H units being minor components).After their synthesis,the lignin monomers are transported to the cell wall,where they are polymerized in a combinatorial fashion by free radical coupling mechanisms in a reaction mediated by peroxidases and/or laccases,generating a variety of structures and linkages within the polymer(Boerjan et al.,2003;Ralph et al.,2004a).Wood(secondary xylem)is produced seasonally at the periphery of the trunk by the vascular cambium(De´jardin et al.,2010). Lignin deposition is one of thefinal stages of xylem cell differentiation and mainly takes place during secondary thickening of the cell wall.Lignification starts in the middle lamella and cell corners and proceeds toward the lumen,filling up pores in the al-ready deposited polysaccharide network(Donaldson, 2001;Boerjan et al.,2003).The relative abundance of the different linkages formed depends on the relative1This study was supported by the Spanish project AGL2005–01748,the Consejo Superior de Investigaciones Cientı´ficas(project nos.200640I039and201040E075),the European Union projects BIORENEW(grant no.NMP2–CT–2006–026456),WALLESTER (grant no.PIEF–GA–2009–235938),and LIGNODECO(grant no. KBBE–244362),the Department of Energy Great Lakes Bioenergy Research Center(grant no.BER DE–FC02–07ER64494),and the Spanish Ministry of Education(postdoctoral fellowship to J. Rencoret).*Corresponding author;e-mail delrio@irnase.csic.es.The author responsible for distribution of materials integral to the findings presented in this article in accordance with the policy described in the Instructions for Authors()is: Jose´C.del Rı´o(delrio@irnase.csic.es)./cgi/doi/10.1104/pp.110.167254contribution of the particular monomers to the po-lymerization process as well as on steric hindrances and chemical interactions in the growing wall.There-fore,the differences in the timing of monolignol de-position and the changes in cell wall ultrastructure during growth would regulate lignin composition and structure during lignification.A main challenge in elucidating the structure of lignins is in obtaining high-yield isolation from wood in a chemically unaltered form(the same applies to hemicellulose polysaccharides).Several lignin isola-tion procedures have been developed,but it is well recognized that the different procedures,including the reference milled-wood lignin(MWL),yield only a part of the native lignin in wood and may not be represen-tative of the whole lignin.Indeed,it has also been demonstrated that MWL can undergo some structural modifications during isolation,especially during the milling process,and often contains some amount of “contaminating”compounds(such as lignin-linked carbohydrates;Fujimoto et al.,2005;Guerra et al.,2006; Hu et al.,2006;Balakshin et al.,2008).Because lignin is intimately interpenetrating the other major compo-nents(cellulose and hemicelluloses),it is obvious that its truly native form can only be studied by analytical methods applicable directly on the whole plant mate-rial.For this purpose,in this paper,the wood samples were analyzed in situ by two-dimensional(2D)-NMR spectroscopy and pyrolysis-gas chromatography-mass spectrometry(Py-GC-MS).The use of these techniques avoids isolation procedures that may lead to partial or modified polymer extraction.For in situ NMR analy-ses,a recent approach has been developed that con-sists of swellingfinely ground plant material in deuterated dimethyl sulfoxide(DMSO-d6;Kim et al., 2008;Rencoret et al.,2009)or DMSO-d6:pyridine-d5 (4:1;Kim and Ralph,2010)and forming a gel directly in the NMR tube,which is readily amenable to NMR analysis.Heteronuclear single quantum correlation (HSQC)NMR of these gels has been shown to be an efficient method for the rapid in situ analysis of lignin in plants without the need of prior isolation.The method requires only low amounts of sample and can be used for rapid characterization of the major struc-tural features of plant lignins(i.e.interunit linkages and H-G-S composition),also providing information on the hemicellulose polysaccharides.Py-GC-MS is another powerful tool for the in situ characterization of plant constituents,especially lignin(Ralph and Hatfield,1991;Rodrigues et al.,1999;del Rı´o et al., 2005;Rencoret et al.,2007).Wood lignin is pyrolyzed to produce a mixture of relatively simple phenols,which result from cleavage of ether and certain carbon-carbon linkages.These phenols retain their substitu-tion patterns from the lignin polymer,and it is thus possible to identify compounds from the H,G,and S lignin units.The aim of this paper is to elucidate the changes produced in the composition and structure of the lignin in eucalypt wood with maturation and includes analyses of young plants and adult trees.This knowl-edge is important not only for providing additional insight into the mechanisms of lignin deposition but also for the industrial processing of wood for pulp, chemical,or biofuel production,as the lignin compo-sition and structure greatly influence the delignifica-tion reactions(Gonza´lez-Vila et al.,1999;del Rı´o et al., 2005).For this purpose,samples of Eucalyptus globulus wood from the same clone(to avoid genetic variations within species)were collected at different stages of growth(1month,18months,and9years)and the composition and structure of their lignins were thor-oughly investigated.A combination of the above-mentioned2D-NMR and Py-GC-MS of whole wood samples was used for the in situ study of lignin changes.In order to obtain further insights into their structures and compare with the results from the in situ analyses,MWL was also isolated from the differ-ent woods and analyzed by NMR,pyrolysis,and thioacidolysis.As far as we know,this is thefirst report describing in situ structural analyses of wood lignin during tree growth using a combination of2D-NMR and other techniques.RESULTS AND DISCUSSIONAfter a general analysis of wood composition in E. globulus plants of different ages(young and adult trees from a clonal plantation),the changes in lignin(and hemicellulose)during growth were analyzed in situ by a combination of Py-GC-MS and2D-NMR of whole wood,and the results were compared(and comple-mented)with those obtained from lignins(MWL) isolated from the same samples.Wood Composition during Eucalypt GrowthThe contents of the main wood constituents(i.e.ace-tone extractives,water-soluble material,Klason lignin, acid-soluble lignin,crystalline cellulose,amorphous glucan,xylan,arabinan,galactan,mannan,rhamnan, fucan,total uronic acids,and ash)in the selected E. globulus clone at different stages of growth are sum-marized in Table I.The total lignin content(Klason lignin plus acid-soluble lignin)increased during growth(from16%in the1-month-old sample to25% in the9-year-old wood),whereas the content of other constituents(namely acetone extractives,water-soluble material,and ash)decreased with maturity.Interest-ingly,there is also a great variation in the composition of polysaccharides(from neutral sugar analysis)dur-ing maturation,with a depletion of Ara,Gal,and Man and a progressive enrichment of Xyl.The amount of crystalline cellulose has the highest content(37%)after 18months,while that of amorphous glucan was lower and showed a progressive increase during growth. Finally,the uronic acid content was the highest after 1month(7%)and showed only a moderate decrease during growth.Variations in the uronic acid natureRencoret et al.during growth are discussed after the NMR analyses below.Py-GC-MS of Whole Woods and Their Isolated Lignins Py-GC-MS,although not a fully quantitative tech-nique,has been successfully used to analyze the relative H-G-S composition of lignin in different hard-woods,including eucalypt wood(Rodrigues et al., 1999;Yokoi et al.,1999,2001;del Rı´o et al.,2005; Rencoret et al.,2007,2008).Pyrograms from the euca-lypt wood samples after different growth periods and their corresponding MWLs are shown in Figures1and 2,and the identities and relative molar abundances of the released lignin-derived compounds are listed in Table II.The pyrolysis of the different eucalypt woods re-leased both carbohydrate-and lignin-derived com-pounds.Among the latter,guaiacol-and syringol-type phenols,derived from the G and S lignin units,were identified,including guaiacol(compound2),4-vinyl-guaiacol(8),syringol(11),4-methylsyringol(14),4-vinyl-syringol(22),4-allylsyringol(25),trans-4-propenylsyringol (32),syringaldehyde(34),and trans-sinapaldehyde (49).In addition,significant amounts of compounds derived from H lignin units,such as phenol(1), methylphenols(3and4),and dimethylphenol(6), could be detected after pyrolysis of the youngest wood,although some of them can also derive from polysaccharides(Ralph and Hatfield,1991).The H-G-S composition of the lignin in the different woods, obtained from the molar areas of all the lignin-derived compounds,is shown in Table II.In all samples,the S-type phenols were released in higher abundances than the respective G-type phenols,with a S-G ratio ranging from1.4in the youngest wood to3.8in the oldest wood.The amount of H-type compounds from the youngest wood(9%)decreases during maturation(to only2%in the oldest wood).This indicates that H units are depositedfirst,followed by G and then S units,in agreement with previous microautoradiogra-phy and microspectroscopy studies in other plants (Terashima et al.,1986).An increase of lignin S-G ratio with plant maturity has also been reported after Py-GC-MS of nonwoodyfibers(Mazumder et al.,2005). This difference in timing of monolignol deposition would also be responsible for the within-tree variation of the S-G ratio observed in Eucalyptus camaldulensis wood(Ona et al.,1997;Yokoi et al.,1999).Pyrolysis of the MWLs isolated from the different E. globulus woods(Fig.2)released a similar distribution of lignin-derived compounds as from their respective woods,although the content of H units was lower (Table II).This is especially evident in the case of the MWL isolated from the1-month-old wood.However, we must note that MWL may reflect only the most accessible part of the native lignin in the plant,which may be depleted in highly condensed H lignin units. In any case,the same trend observed in the pyrolysis of woods,which indicates an increase of S lignin units and a decrease of H and G lignin units with maturity, was also observed in the pyrolysis products of MWL, supporting the in situ analysis and confirming a monolignol deposition order of H,G,and then S during E.globulus lignification.2D-NMR of Wood Gels and Their Isolated LigninsThe eucalypt wood samples from different growing periods were analyzed by2D-NMR(in the gel state)to overcome the drawbacks associated to polymer isola-tion,namely low yield and artifact formation,and the spectra were compared with those from the lignins (MWL)isolated from the same woods.The HSQC spectra of the different woods,and their MWLs,are shown in Figures3and4.Carbohydrate signals were predominant in the spectra of the whole wood.They included correlations in the range d C/d H 60to85/2.5to5.5,which partially overlapped with lignin signals,and the well-resolved anomeric corre-lations in the range d C/d H90to110/3.5to6.0.How-ever,lignin signals were also clearly observed in the HSQC spectra,including that of the youngest wood with the lowest lignin content.On the other hand,the spectra of the MWL presented mostly lignin signals that,in general terms,matched those observed in the HSQC spectra of the woods.Lignin and carbohydrate contours in the HSQC spectra were assigned by comparison with the litera-ture(A¨mma¨lahti et al.,1998;Ralph et al.,1999,2004b; Capanema et al.,2001,2004,2005;Balakshin et al.,2003, 2005;Liitia¨et al.,2003;Ha et al.,2005;Golovchenko et al.,2007;Ibarra et al.,2007a,2007b;del Rı´o et al., 2008,2009;Kim et al.,2008;Rencoret et al.,2008,2009; C¸etinkol et al.,2010;Kim and Ralph,2010;Ralph and Landucci,2010).The main lignin correlation assign-ments are listed in Table III,and the main lignin substructures found in the different eucalypt woods are depicted in Figure5.The assignments of the main carbohydrate signals are listed in Table IV.Table I.Abundances(%)of the main constituents of E.globuluswood at different growth stagesConstituents1Month18Months9YearsAcetone extractives8.60.50.6Water-soluble extracts 6.6 1.4 2.2Klason lignin13.017.519.8Acid-soluble lignin 2.7 5.2 4.7Cellulose(crystalline)25.036.729.9Glucan(amorphous)11.415.016.2Xylan12.214.017.1Arabinan 3.80.90.8Galactan 2.7 1.2 1.5Mannan0.90.40.4Rhamnan0.70.40.5Fucan0.30.10.1Uronic acids7.4 5.9 5.8Ash 4.60.70.4Lignin in Young and Adult Eucalypt PlantsSide Chain Region of the HSQC Spectra:Analysis of Interunit Linkages in LigninThe side chain region of the spectra gave useful information about the interunit linkages present in lignin.All the spectra showed prominent signals corresponding to b-O-4#ether units(substructure A). The C a-H a correlations in b-O-4#substructures were observed at d C/d H71to72/4.7to4.9ppm,while the C b-H b correlations were observed at d C/d H84/4.3and 86/4.1ppm for substructures linked to G and S units, respectively.The C g-H g correlations in b-O-4#sub-structures were observed at d C/d H59/3.4and3.7ppm, partially overlapped with other signals.In addition, strong signals for resinol(b-b#)substructures(B)were observed in all spectra,with their C a-H a,C b-H b,and the double C g-H g correlations at d C/d H85/4.7,54/3.1, and71/3.8and4.2,respectively.Phenylcoumaran (b-5#)substructures(C)were also found,although in lower amounts,the signals for their C a-H a and C b-H b correlations being observed at d C/d H87/5.5and54/ 3.5,respectively,and that of the C g-H g correlation overlapping with other signals around d C/d H63/3.7. Finally,small signals corresponding to spirodienone (b-1#/a-O-a’)substructures(D)could also be ob-served in the spectra,their C a-H a,C a#-H a#,C b-H b, and C b#-H b#correlations being at d C/d H82/5.1,87/4.4, 60/2.8,and79/4.1,respectively.Other small signals observed in the side chain region of the HSQC spectra corresponded to C b-H b correlations(at d C/d H84/5.2) of b-O-4#substructures bearing a C a carbonyl group (F)and the C g-H g correlation(at d C/d H62/4.1)as-signed to p-hydroxycinnamyl alcohol end groups(I). The HSQC spectra of the isolated MWL also reflected the same side chain signals observed in the spectra of the whole woods,although they were better resolved and some new signals were observed.These included small signals corresponding to C b-H b correlations(atdC/d H55/2.8)of conventional open b-1#substructures (E;Lundquist,1987)that were observed only in the MWL spectra.Some aliphatic(nonoxygenated)cross-signals appeared in the d C/d H10to40/0.5to2ppm region(not included in Fig.4),which were especially abundant in the1-month sample and couldincludecutin-like material(Deshmukh et al.,2005)or other polymethylenic structures.Aromatic Region of the HSQC Spectra:Analysis ofLignin UnitsThe main cross-signals in the aromatic region of the HSQC spectra corresponded to the aromatic rings of the different lignin units.Correlations from S,G,and H lignin units could be observed in the spectra of whole wood and their MWLs.The S lignin units showed a prominent signal for the C2,6-H2,6correlation at d C/d H 104/6.7,while the G units showed different correlations for C2-H2(d C/d H111/7.0),C5-H5(d C/d H115/6.7and 7.0),and C6-H6(d C/d H119/6.8).Signals corresponding to C2,6-H2,6correlations in C a-oxidized S lignin units(S#) were observed at d C/d H107/7.3and107/7.2.Signals of H lignin units at d C/d H115/6.7and128/7.2for C3,5-H3,5 and C2,6-H2,6respectively,were only detected in the HSQC spectra of the youngest wood sample(1month), in agreement with the higher presence of H units shown by Py-GC-MS.An extra and well-resolved sig-nal was also detected at d C/d H109/7.1in this sample (in both wood and MWL)that was tentatively assigned to a G-type structure.Olefinic cross-signals of fatty acid structures with one/two double bonds,similar to those from oleic acid(d C/d H130/5.3)and linoleic acid(d C/d H 128/5.3and130/5.3),were also identified(Fig.4).They probably originate from the cutin-like structures men-tioned in the previous section.The cross-signal of pyridine used to form the wood gels was also observed (d C/d H around124/7.3).Summary of Changes in Lignin Structure as Revealedby2D-NMRThe relative abundances of the H,G,and S lignin units,and those of the main interunit linkages(re-ferred to as per100aromatic units and as a percentage of the total side chains),calculated from the HSQC spectra of the whole woods and of their respective MWLs,are shown in Table V.The H-G-S composition and the S-G ratio(ranging from1.2in the youngest wood to3.3in the oldest one)are in closeagreementwith the data obtained by Py-GC-MS,indicating a decrease of H and G units and an increase of S lignin units during lignification.The content of H lignin in the isolated MWL was lower than in the respective wood samples,as already observed by Py-GC-MS.With respect to the different linkage types,all the lignins showed a predominance of b-O-4#units(A and F;69%–72%of total side chains)followed by b-b# resinol-type units(B;16%–19%)and lower amounts of b-5#phenylcoumaran-type(C;1%–5%)and b-1#spiro-Table II.Identification and relative molar abundance(%)of the lignin-derived compounds identified in the Py-GC-MS of E.globulus wood at the different growth stages and from their isolated MWLspounds1Month18Months9Years Wood MWL Wood MWL Wood MWL1Phenol 5.5 1.00.80.20.70.32Guaiacol8.78.4 4.0 3.6 3.5 3.83Methylphenol0.90.50.30.10.30.24Methylphenol 2.70.50.40.10.40.254-Methylguaiacol 2.97.3 1.7 3.5 2.2 3.06Dimethylphenol0.30.60.40.20.50.174-Ethylguaiacol 1.9 2.60.60.80.50.884-Vinylguaiacol9.710.0 4.5 3.9 4.9 3.39Eugenol0.90.50.60.60.60.610Propylguaiacol0.50.20.10.10.10.111Syringol11.813.414.110.711.413.112cis-Isoeugenol0.70.60.50.70.40.613trans-Isoeugenol 5.4 2.3 3.1 2.5 2.7 2.5144-Methylsyringol 3.99.07.99.09.68.515Vanillin0.9 2.60.7 2.40.8 1.916Propynylguaiacol0.40.40.5 1.00.40.417Propynylguaiacol0.40.50.6 1.10.40.518Homovanillin0.00.20.30.90.50.9194-Ethylsyringol 2.9 3.2 2.3 1.90.2 2.120Vanillic acid methyl ester0.00.30.00.30.00.321Acetoguaiacone0.6 1.60.8 1.30.6 1.3224-Vinylsyringol12.68.714.6 6.612.3 6.923Guaiacylacetone0.8 1.20.30.50.40.424Propylsyringol0.00.60.00.70.00.825Allylsyringol 2.40.4 3.4 1.6 3.5 1.726Propiovanillone0.10.40.10.30.10.327Guaiacylvinylketone0.00.40.0 1.10.0 1.028cis-Propenylsyringol 1.9 1.0 2.1 1.9 1.9 2.029Propynylsyringol0.50.6 1.8 1.7 2.4 1.130Propynylsyringol0.30.40.9 1.2 1.10.731Vanillic acid0.00.50.00.20.00.132trans-Propenylsyringol 6.4 3.011.2 6.511.47.133Dihydroconiferyl alcohol0.70.50.90.30.70.334Syringaldehyde 1.8 5.5 4.610.4 5.29.135Homosyringaldehyde0.00.00.7 2.3 3.2 3.136Syringic acid methyl ester0.10.30.20.60.20.537Acetosyringone 1.4 2.6 2.6 4.2 3.5 4.338trans-Coniferyl alcohol 3.00.00.80.50.30.839Coniferaldehyde0.5 1.30.8 1.6 1.1 1.440Syringylacetone 2.2 2.3 2.3 1.4 3.0 1.541Propiosyringone0.70.90.7 1.10.9 1.042Syringyl-3-oxo-propanal0.00.60.00.60.00.743Syringylvinylketone0.10.10.2 1.20.3 1.144Syringic acid0.00.70.00.70.00.545Dihydrosinapyl alcohol0.60.2 1.10.4 1.20.546cis-Sinapyl alcohol0.50.00.60.50.40.747cis-Sinapaldehyde0.00.10.10.10.10.148trans-Sinapyl alcohol 1.30.00.60.70.3 1.849trans-Sinapaldehyde0.7 2.0 4.8 6.0 5.7 5.7Total H9.4 2.6 1.90.7 1.90.8Total G38.542.021.227.520.424.3Total S52.155.476.971.877.674.9 Rencoret et al.dienone-type (D;1%–5%)units.The conventional open b -1#structures (E;Lundquist,1987),which were ob-served only in the MWL samples,ranged from 1%to 2%.Some interesting information could be obtained from the wood NMR data.First,it is clear that the changes in monolignol availability during growth influence not only the unit composition but also af-fect the abundances of some interunit linkages.For example,despite the relative percentage of the b -O -4#linkages remaining relatively constant with growth,their abundances per aromatic unit slightly increases (from 46to 50linkages per 100aromatic units),and the same happens with the b -b #resinol-type structures (which increase from 10to 12linkages per 100aro-matic units),probably as a consequence of the increase of S units.Interestingly,the ratio between theabun-Figure 3.HSQC NMR spectra (d C /d H 45–135/2.5-8.0ppm)of the E.globulus wood samples at different growth stages after forming a gel in DMSO-d 6:pyridine-d 5(4:1).See Table III for lignin signal assignment and Figure 5for the main lignin structures identified.The assignments of the carbohydrate signals are listed in Table IV.Figure 4.HSQC NMR spectra (d C /d H 45–135/2.5-8.0ppm)of the MWLs isolated from the E.globulus wood samples at different growth stages.See Table III for lignin signal assignment and Figure 5for the main lignin structures identified.Olefinic cross-signals of unsaturated fatty acid structures (U F )were also identified.Lignin in Young and Adult Eucalypt Plantsdances of b-O-4#and b-b#resinol-type structures seems to remain more or less constant along lignifica-tion.The spirodienone-b-1#ratio also increased during growth(from0.8to3.2).In contrast,the abundance of phenylcoumaran structures decreases with lignifica-tion,which is most probably related to the decrease in G lignin observed.On the other hand,a small but continuous oxidation of the C a of the lignin side chain (from one to four C a oxidized b-O-4#linkages per100 aromatic units)occurs during lignification,probably as a result of wood aging.Finally,the abundance of cinnamyl alcohol end groups decreases with lignifica-tion,as also observed by Py-GC-MS.Hemicellulose PolysaccharidesThe HSQC spectra also reveal differences in the carbohydrates present in eucalypt wood after the different growth periods,which are observed in two differentiated regions of the spectra:the aliphatic-oxygenated region and the region corresponding to the anomeric correlations(Fig.3).The aliphatic-oxy-genated region shows strong signals from carbohy-drates,including naturally acetylated hemicelluloses. Among them,signals from O-acetylated xylans(3-O-acetyl-b-D-xylopyranoside[X#3]and2-O-acetyl-b-D-xylopyranoside[X#2])and,at the earlier stages of growth,O-acetylated mannans(2-O-acetyl-b-D-man-nopyranoside[M#2])were observed.Other signals in this region correspond to C2-H2,C3-H3,C4-H4,and C5-H5correlations of xylans(b-D-xylopyranoside[X2,X3, X4,and X5]),which overlap with unassigned cross-signals of other pentose and hexose polysaccharide units(note that crystalline cellulose is practically“in-visible”in the HSQC spectra of the wood gels due to its reduced mobility),and the C4-H4correlation for 4-O-methyl-a-D-GlcUA(U4).However,the main differences are observed in the carbohydrate anomeric region of the spectra,which have been depicted in detail in Figure6.The main C1-H1correlation signals in this region,which are listed in Table IV,were assigned according to Kim and Ralph (2010),together with some additional references for pectin(Ha et al.,2005;Golovchenko et al.,2007, Hedenstro¨m et al.,2008).Cross-signals from arabinans (Ar1and Ar1(T)),mannans(M1),galactans(Ga1),xylans (X1,a X1(R),and b X1(R)),and glucans including non-crystalline cellulose(Gl1),as well as signals from O-acetylated mannans and xylans(M#1and X#1)and from the4-O-methyl-a-D-glucuronic(U1)and galact-uronic(UGA1)acids(the latter forming part of pectin as the methyl ester)are readily apparent and well resolved in this region of the spectra.A small signal ofa-Rha(R1)units was also observed,especially in the 18-month-old wood.Interestingly,the signals of arab-inans,mannans,and galactans,which are observed inTable III.Assignments of the lignin13C-1H correlation signals in the HSQC spectra of E.globuluswood at the different growth stages and their isolated MWLsLabels d C/d H AssignmentppmC b53.5/3.46C b-H b in phenylcoumaran substructures(C)B b53.5/3.06C b-H b in resinol substructures(B)E b55.0/2.75C b-H b in b-1#substructures(E)-OMe55.6/3.73C-H in methoxylsA g59.4/3.40and3.72C g H g in b-O-4#substructures(A)D b59.6/2.75C b-H b in spirodienone substructures(D)I g61.3/4.09C g-H g in cinnamyl(sinapyl/coniferyl)alcohol endgroups(I)C g62.5/3.72C g-H g in phenylcoumaran substructures(C)B g71.0/3.83and4.19C g-H g in resinol substructures(B)A a71.7/4.86C a-H a in b-O-4#substructures(A)D b#79.3/4.11C b#-H b#in spirodienone substructures(D)D a81.2/5.09C a H a in spirodienone substructures(D)A b(G)83.5/4.28C b-H b in b-O-4#linked to a G unit(A)F b83.8/5.23C b-H b in oxidized(C a=O)b-O-4#substructures(F)B a84.8/4.67C a-H a in resinol substructures(B)D a#84.8/4.75C a#H a#in spirodienone substructures(D)A b(S)85.8/4.11C b-H b in b-O-4#linked to a S unit(A)C a86.8/5.46C a-H a in phenylcoumaran substructures(C)S2,6103.8/6.69C2,6-H2,6in etherified syringyl units(S)S#2,6106.6/7.32and7.19C2,6-H2,6in oxidized(C a=O)phenolic syringyl units(S#)G2110.9/6.99C2-H2in guaiacyl units(G)D2#113.2/6.27C2#H2#in spirodienone substructures(D)H3,5114.9/6.74C3,5-H3,5in p-hydroxyphenyl units(H)G5/G6114.9/6.72and6.94;118.7/6.77C5-H5and C6-H6in guaiacyl units(G)D6#118.9/6.09C6#H6#in spirodienone substructures(D)H2,6128.0/7.23C2,6-H2,6in p-hydroxyphenyl units(H)Rencoret et al.。
木质素的高值化利用研究进展
木质素的高值化利用研究进展————————————————————————————————作者：————————————————————————————————日期：1木质素的高值化利用研究进展XXX化工学院13级化学工程学号：40130100x摘要：目前国内外所开发的木质素产品已经有数百种，但是，由于木质素本身结构非常复杂且木质素的种类繁多，使得开发木质素产品存在一定的盲目性，我国仅约6％的木质素得到利用。
如何有效地利用木质素的结构特性来控制已有木质素产品的性能稳定性、开发更多性能优良的木质素产品以及实现木质素高附加值产品生产的规模化、产业化等，将成为木质素研究的一个重要方面。
文章结合近年来木质素产品的研究及开发，介绍了木质素结构与功能之间的联系，以期能够充分利用木质素的结构特点来改进和生产木质素产品，以得到具有工业应用价值的产品，不仅具有环保意义，更具有经济意义。
关键词：木质素；高值化利用；木质素改性Research Progress of Lignin in High Value UseXXXnChemical Engineering of Chemical Engineering InstituteNO. 401301xxAbstract:Now the development of domestic and foreign products have hundreds of lignin.But be cause the type of lignin structure is very complicated and lignin is various, which makes the deve lopment of lignin products exist blindness,China is only about 6% of the lignin obtained by.How to effectively use the structure characteristics of lignin to control the performance stability of lig nin products,develop of more excellent performance of wood products and the realization of lign in products with high added value production scale, industrialization,will become an important a spect of the study of lignin.This paper based on the research and development of lignin products in recent years,Introduces the relationship of lignin structure and function,In order to make full u se of the characteristics of the structure of lignin to improvement and production of lignin produc ts and get the Industrial application value products.It not only has the significance of environmen tal protection, but also has a greater economic significance.Key words:Lignin; high value use; lignin modification1 前言木质素是一种复杂的、非结晶性的、三维网状多羟基芳香族化合物，它广泛存在于高等植物细胞中，是针叶树类、阔叶树类和草类植物的基本化学组成之一[1-3]，也是木材水解工业和制浆造纸工业的主要副产物[4-5]。
植物细胞壁组成物质
植物细胞壁组成物质The composition of the plant cell wall is a complex and fascinating topic that plays a crucial role in thestructure and function of plants. Composed primarily of cellulose, hemicellulose, and lignin, the plant cell wall provides strength, support, and protection to plant cells. This intricate network of molecules also contributes to various physiological processes, such as cell expansion, cell-to-cell communication, and defense against pathogens. Understanding the composition of the plant cell wall is essential for comprehending the biology of plants and their interactions with the environment.Cellulose, the main component of the plant cell wall,is a long-chain polymer made up of glucose units. It forms microfibrils that are embedded in a matrix of hemicellulose and pectin. Cellulose provides structural integrity to the cell wall and gives plants their rigidity. It is a remarkable molecule that can withstand tremendous mechanical stress, allowing plants to grow upright andresist external forces. The arrangement and orientation of cellulose microfibrils determine the mechanical properties of the cell wall, making it adaptable to different tissues and plant species.Hemicellulose, another major component of the plant cell wall, is a heterogeneous group of polysaccharides. It surrounds and interacts with cellulose microfibrils, providing cross-linking and stability to the cell wall structure. Hemicellulose also plays a role in regulating cell expansion and plant growth. Different types of hemicellulose can be found in various plant tissues, reflecting their specific functions and requirements. For example, xyloglucans are prevalent in primary cell walls and are involved in cell expansion, while xylans are abundant in secondary cell walls and contribute to their strength and rigidity.Lignin, a complex phenolic polymer, is a crucial component of the secondary cell wall. It provides additional strength and water impermeability to the cell wall, allowing plants to withstand mechanical stresses andresist microbial attack. Lignin also contributes to the woody nature of plant tissues, enabling the formation of sturdy structures like tree trunks. However, lignin poses challenges in the utilization of plant biomass for various industrial applications, such as biofuel production, due to its recalcitrant nature and resistance to degradation.Besides cellulose, hemicellulose, and lignin, the plant cell wall also contains other components such as pectin, proteins, and various minor polysaccharides. Pectin is a complex polysaccharide that acts as a glue, binding cells together and providing flexibility to the cell wall. Proteins are crucial for cell wall synthesis, remodeling, and signaling. They contribute to the structural integrity of the cell wall and participate in various physiological processes. Minor polysaccharides, such as arabinogalactans and arabinans, are involved in cell wall assembly and modification.The composition of the plant cell wall is not static but can change in response to developmental and environmental cues. For example, during cell expansion, thecomposition and arrangement of cellulose, hemicellulose, and pectin may be modified to accommodate the growth of the cell. Similarly, in response to pathogen attack, the cell wall can undergo structural changes to strengthen its defense mechanisms. Understanding these dynamic changes in the composition of the plant cell wall is crucial for developing strategies to enhance plant growth, improve crop yield, and protect plants against diseases and pests.In conclusion, the plant cell wall is a complex and dynamic structure composed of cellulose, hemicellulose, lignin, pectin, proteins, and minor polysaccharides. This intricate network of molecules provides strength, support, and protection to plant cells, allowing them to grow upright and resist external forces. The composition of the cell wall can change in response to developmental and environmental cues, reflecting the adaptability and resilience of plants. By unraveling the composition and functions of the plant cell wall, scientists can gain valuable insights into plant biology and develop innovative strategies to enhance plant growth and protect crops.。
第三章 木质素chapter 3 lignin
可合成500万亿ｔ木质素。
按热焓 enthalpy 容量计算，生物学上产生能量 40% 储存 在木质素中store in lignin，来源丰富、价格低廉的可再生植 物资源regenerated plant resource。 工业木质素industrial lignin：主要来源于造纸制浆蒸煮废水
2000～3000，木质素磺酸盐lignosulfonate一般为
20000～50000）
3.1 植物细胞壁的木质素化作用 lignification of plant cell wall
（3）碱木质素alkali lignin因分子上缺乏 be short of the hydrophilic and hydrophobic groups 亲油亲水性均较理 想的官能团，在有机相和水相中的溶解度 solubility均不高，溶于碱性介质； （4） 组成不稳定unstable，使产品性能波 动大。；
ห้องสมุดไป่ตู้
3.1 植物细胞壁的木质素化作用 lignification of plant cell wall
3.1.1 木质素（ lignin）资源
一、木质素资源lignin resource
地球上资源丰富的天然聚合物nature polymer，在植物中的 存在量仅次于纤维素second to cellulose。全球陆生植物每年
Formation of resonance-stabilized phenoxy radicals by the enzymic dehydrogenation of coniferyl alcohol. 松柏醇被过氧化酶和H2O2hydrogen peroxide 的脱氢dehydrogenation作用 p80
木质素化学分离的研究进展
木质素化学分离的研究进展朱建良;王倩倩;杨晓瑞;姚律;梁金花【摘要】As the most abundant natural renewable aromatic polymers,the structure of lignin is complex and can be affected by the plant sources and extraction methods.The structure of lignin was briefly introduced,and the work principles and research progress of several typical chemical methods to separate lignin,and the advantages and disadvantages,available materials,process efficiency and lignin structure of those methods were compared and discussed.The further development of lignin separation methods were prospected.%木质素是自然界中含量最丰富的可再生芳香族聚合物,其结构复杂,植物来源及分离提取方法对木质素的结构都有一定的影响.简要地介绍了木质素的结构,阐述了几种典型的化学法分离木质素的原理及研究进展,并对不同方法的优劣、适用范围、分离效果及所得木质素结构等方面进行了对比,对木质素分离方法的发展趋势进行了展望.【期刊名称】《南京工业大学学报（自然科学版）》【年(卷),期】2018(040)003【总页数】9页(P122-130)【关键词】木质素;结构;化学分离;分离原理【作者】朱建良;王倩倩;杨晓瑞;姚律;梁金花【作者单位】南京工业大学生物与制药工程学院,江苏南京211800;南京工业大学生物与制药工程学院,江苏南京211800;南京工业大学生物与制药工程学院,江苏南京211800;南京工业大学生物与制药工程学院,江苏南京211800;南京工业大学生物与制药工程学院,江苏南京211800【正文语种】中文【中图分类】O636.2;TK6随着煤和石油等化石燃料的快速消耗和人们环保意识的逐渐增强,生物质资源以其原料来源丰富、再生速度快、温室气体排放量少等优势已成为研究的热点。
木质素的生物降解及其应用
第20卷第6期2010年12月皮革科学与工程LEATHER SCIENCE AND ENGINEERINGVol.20，No.6Dec.2010文章编号：1004-7964（2010）06-0027-05木质素的生物降解及其应用李海涛，姚开*，何强，贾冬英（四川大学轻纺与食品学院，四川成都610065）收稿日期：2010-04-18基金项目：国家公益性农业科研专项基金（200803033-A004C ）第一作者简介：李海涛（1985-），男，河南永城人，硕士研究生，研究方向为食物资源化学，E-mail ：lihaitaoyong@ 。
通讯联系人：姚开，教授，E-mail ：yaokai555@ 。
摘要：综述了具有降解木质素能力的微生物和酶的种类及其降解特性，阐述了木质素生物降解在生物化学制浆、纸浆生物漂白、造纸废水生物处理、饲料工业、生物肥料等领域的应用现状，展望了木质素生物降解技术研究的发展趋势。
关键词：木质素；生物降解；微生物；酶；应用中图分类号：Q 948.12文献标识码：ABiodegradation and Applications of LigninLI Hai-tao ，YAO Kai *，HE Qiang ，JIA Dong-ying（College of Light Industry and Food Engineering ，Sichuan University ，Chengdu 610065，China ）Abstract ：In this paper ，the types and the degradation characteristics of ligninolytic microorganisms and lignin-degrading enzymes are introduced．In addition ，the practical applications of lignin biodegradation in biochemical pulping ，biological bleaching of pulp ，biological treatment of papermaking wastewater ，feed industry and bio-fertilizer are summarized．And tech-nology trends in lignin biodegradation are outlook．Key words ：lignin ；biodegradation ；microbes ；enzymes ；applications木质素资源十分丰富，是植物光合作用制造的总量仅次于纤维素的有机化合物，估计全球的木质素年产量可达1500亿t 。
以木质素为原料合成聚氨酯的研究进展
以木质素为原料合成聚氨酯的研究进展刘育红1席丹2(1.西安交通大学环境与化学工程学院710049)(2.西安交通大学生命科学院710049)摘要:综述了国内外以木质素、改性木质素代替多元醇为原料合成聚氨酯的研究方法,并对木质素在聚氨酯领域中的应用前景作了展望。
关键词:木质素;改性;聚氨酯1木质素的结构与特点木质素(Lignin)简称木素,是数量上仅次于纤维素的第二类天然芳香族高分子材料[1]。
木质素主要含有碳、氢、氧3种元素,禾草类分离木质素中还含有少量的氮。
木质素的分子结构中存在着芳香基、酚羟基、醇羟基、羰基、甲氧基、羧基、共轭双键等活性基团,可以进行氧化、还原、水解、醇解、酸解、光解、酰化、烷基化、卤化、硝化、缩聚或接枝共聚等许多化学反应[2]。
木质素的主体结构是苯丙烷,它共有3种基本结构,分别为:愈创木基结构、紫丁香基结构和对羟苯基结构。
其结构式如下图所示。
总体说来,木质素是由以上3种结构单元通过醚键(约占2/3)和碳-碳单键连接在一起的具有三维体型结构的天然酚类无规共聚物。
制浆造纸工业的蒸煮废液中产生大量含有木质素等物质的废液,若不进行回收利用,不仅会对环境带来严重的污染,而且造成了物质资源的极大浪费,因而人们在不断开发木质素资源的用途。
现在木质素已经广泛应用于工农业生产和人们的生活中,比如:木质素可以作水泥缓凝剂、分散剂和表面活性剂,可以制备皮革鞣剂、螯合铁微肥,还可以用于制造离子交换树脂、橡胶添加剂,它还用于防晒护肤品生产、有机饲料生产、苗木促长、土壤改良、公路除尘、陶瓷加工、黑色金属冶炼等领域[2]。
木质素分子中含有醇羟基、酚羟基等含活性氢的基团,并且还可以进行改性,引入更多的基团和链段。
木质素作为一种可再生资源,可以作为合成聚氨酯的原料,变废为宝。
2用木质素合成聚氨酯的研究聚氨酯由多元醇和二异氰酸酯缩聚而成。
木质素分子中有多个羟基,所以可代替多元醇与二异氰酸酯进行缩聚。
近年来这项研究已成为木质素在高分子领域应用中的研究热点之一,内容涉及到材料的力学性能、微观形态、热稳定性以及交联结构等各方面。
木质素在离子液体中溶解及改性的研究进展
木质素在离子液体中溶解及改性的研究进展李文婷【摘要】木质素是自然界中含量仅次于纤维素、唯一含有苯环结构的可再生生物质资源，对其进行有效的开发利用具有较高的经济价值和社会价值。
离子液体作为一种新型绿色溶剂，在木质纤维素溶解方面展现了良好性能，本文粗略地概述了木质素的基本结构和性质，对木质素在离子液体中的溶解及改性等方面的研究进行了总结和综述，并在离子液体在木质素溶解降解方面应用研究的发展前景进行了分析讨论。
%As the material only secondly abundant to cellulose in the nature, lignin is the only renewable biomass resources containing benzene ring structure. It has not only high economic value but also the social value to carry on the effective exploitation. Ionic liquids, as a new type of green solvents, show a good performance in the dissolution of lignocellulose. The basic structure and properties of lignin were shortly outlined, the performance of structure change of lignin after dissolved in ionic liquids were reviewed, and the development research prospects of application of ionic liquids in the dissolution and depolymerization lignin were discussed.【期刊名称】《广州化工》【年(卷),期】2015(000)010【总页数】4页(P50-52,97)【关键词】木质素;生物质;离子液体;溶解;改性【作者】李文婷【作者单位】安徽理工大学化学工程学院，安徽淮南 232001【正文语种】中文【中图分类】TQ03-39木质素作为地球上第二大可再生生物质资源，广泛存在于植物体中，与纤维素、半纤维素一起构成了植物体的基本骨架。
木质素木质素碳水化合物结构解析与高值化利用
木质素木质素碳水化合物结构解析与高值化利用Wood is composed mainly of cellulose, hemicellulose, and lignin, which are collectively referred to as lignocellulosic biomass. These components are interconnected in a complex structure, making it challenging to effectively break down and utilize wood for various purposes. Among the three main components, lignin is particularly difficult to degrade due to its complex and irregular structure, which limits the efficient utilization of wood in various industries.木材主要由纤维素、半纤维素和木质素组成，这些成分共同被称为木质纤维素生物质。
这些组分在复杂的结构中相互连接，使得有效地分解和利用木材变得具有挑战性。
在这三种主要组分中，木质素特别难以降解，因为它复杂而不规则的结构，限制了木材在各个行业的有效利用。
Efforts have been made to understand the structure of lignin at a molecular level to devise more efficient ways to break it down and convert it into value-added products. Analytical techniques like nuclear magnetic resonance (NMR) spectroscopy and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) have been employed to elucidate the chemical structure of lignin. Thesetechniques provide insights into the composition and bonding patterns of lignin molecules, which are crucial for designing effective methods for lignin depolymerization.为了制定更有效的方法来分解木质素并将其转化为有附加值的产品，人们已经做出了努力从分子水平理解木质素的结构。
木质素的研究进展
⽊质素的研究进展Botanical Research 植物学研究, 2016, 5(1), 17-25Published Online January 2016 in Hans. /doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html /journal/br/doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html /10.12677/br.2016.51004Progress in Research on LigninYongbin Meng1*, Lei Xu1, Zidong Zhang1, Ying Liu2, Ying Zhang2, Qinghuan Meng2,Siming Nie2, Qi Lu1,21National Engineering Laboratory for Ecological Use of Biological Resources, Harbin Heilongjiang2Key Laboratory of Forest Plant Ecology, Ministry of Education, Northeast Forestry University, Harbin Heilongjiang Email:347576614@/doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html , luqi42700473@/doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.htmlReceived: Dec. 10th, 2015; accepted: Dec. 24th, 2015; published: Dec. 30th, 2015Copyright ? 2016 by authors and Hans Publishers Inc.This work is licensed under the Creative Commons Attribution International License (CC BY)./doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html /licenses/by/4.0/AbstractLignin is a renewable aromatic polymer in nature, and it can be used in the process of high added value. In addition, the oil and natural gas are facing the serious situation of increasingly exhausted.Lignin as a part of alternative fossil raw materials shows a good application prospect. In order to realize the use of lignin, firstly, we must understand the composition and structure of lignin. Stat-ing from the chemical composition of lignin, this paper analyzed and compared some methods and techniques for separation as well as extraction, and application of lignin extraction, focused on the latest progress in the structure of lignin, and forecasted the development direction of lignin ap-plication.KeywordsLignin, Structure, Separation, Application⽊质素的研究进展孟永斌1*，徐蕾1，张⼦东1，刘英2，张莹2，孟庆焕2，聂思铭2，路祺1,21⽣物资源⽣态利⽤国家地⽅联合⼯程实验室，⿊龙江哈尔滨2东北林业⼤学森林植物⽣态学教育部重点实验室，⿊龙江哈尔滨Email: 347576614@/doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html , luqi42700473@/doc/45ea9dfbf71fb7360b4c2e3f5727a5e9856a276d.html收稿⽇期：2015年12⽉10⽇；录⽤⽇期：2015年12⽉24⽇；发布⽇期：2015年12⽉30⽇*第⼀作者。
木质素基本结构、热解机理及特性研究进展
第8卷 第1期 新 能 源 进 展Vol. 8 No. 12020年2月ADVANCES IN NEW AND RENEWABLE ENERGYFeb. 2020* 收稿日期：2019-12-10 修订日期：2019-12-22基金项目：国家自然科学基金项目（51922040，51906060）；霍英东教育基金会项目（161051） † 通信作者：陆 强，E-mail ：qlu@文章编号：2095-560X （2020）01-0006-09木质素基本结构、热解机理及特性研究进展*王则祥，李 航，谢文銮，胡 斌，李 凯，陆 强†（华北电力大学，生物质发电成套设备国家工程实验室，北京 100206）摘 要：木质素是由三种苯基丙烷单元通过醚键和C —C 键相互偶联形成的复杂高分子聚合物，并且与碳水化合物交联形成复杂的结构，其在自然界中的储量仅次于纤维素，传统木质素利用方式效率低，资源浪费严重。
热解是一种重要的木质素高效转化利用技术，木质素复杂的结构特性会显著影响其热解过程和产物分布。
本文综述了木质素结构和热解机理，概述了不同原料和不同提取方式木质素的热解特性，最后对木质素热解转化进行了展望，为木质素的资源化利用提供理论基础。
关键词：木质素；生物质；提取；快速热解；结构中图分类号：TK6 文献标志码：A doi ：10.3969/j.issn.2095-560X.2020.01.002Progress in Basic Structure, Pyrolysis Mechanism andCharacteristics of LigninWANG Ze-xiang, LI Hang, XIE Wen-luan, HU Bin, LI Kai, LU Qiang(National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China)Abstract: Lignin is a complex polymer formed by coupling three phenyl propane units through ether and C —C bonds, and cross-linked with carbohydrates. It is the second abundant biomass component only to cellulose. Traditional utilization methods are inefficient that cause a considerable waste of resources. Pyrolysis is an important technology for efficient conversion and utilization of lignin. The complex structures of lignin will affect the pyrolysis process and product distribution significantly. In this paper, the structure and pyrolysis mechanism of lignin were reviewed, the pyrolysis characteristics of lignin from different raw materials and different extraction methods were summarized, and the related research and application trend were prospected, hence to provide a theoretical basis for the utilization of lignin. Key words: lignin; biomass; extraction; fast pyrolysis; structure0 引 言木质纤维素类生物质有着巨大的可利用量，是唯一可再生的碳源，其清洁高效利用能够缓解化石能源短缺的严峻形势，也与目前的可持续发展政策相符。
liggghts的微观本构关系
liggghts的微观本构关系
LIGGGHTS是一种基于离散元方法 (DEM) 的颗粒动力学模拟
软件，可以模拟颗粒间的相互作用和动力学行为。
在LIGGGHTS中，微观本构关系是描述颗粒间相互作用的关键
部分。
LIGGGHTS中常用的微观本构关系包括：
1. 硬球模型（Hard Sphere Model）：这是LIGGGHTS中最简
单的微观本构关系，假设颗粒之间的相互作用为完全弹性碰撞，颗粒之间互不产生附加的相互作用。
2. 弹簧-阻尼模型（Spring-Dashpot Model）：此模型在硬球模
型的基础上进一步引入了阻尼和弹簧作用。
阻尼可以模拟颗粒间的摩擦和阻尼效应，而弹簧用于模拟颗粒之间的弹性行为。
3. 粘弹性模型（Viscoelastic Model）：粘弹性模型是一种复杂
的微观本构关系，考虑了颗粒间的粘性和弹性特性。
该模型适用于颗粒间存在粘性力的情况，例如粉尘颗粒、液滴等。
除了以上常见的微观本构关系，LIGGGHTS还提供了一些其
他的颗粒间相互作用模型，如静电力、磁力等，以模拟更为复杂的物理现象。
需要注意的是，微观本构关系是根据具体问题的性质和要求来选择和调整的，不同的问题可能需要不同的微观本构关系来准
确地描述颗粒的行为。
在使用LIGGGHTS进行模拟时，用户可以根据实际需求选择合适的微观本构关系。
23第三节木素的化学构造
Fig. 4.27
12
How to analyze the phenolic hydroxyl groups (continued)?
The aminolysis is based on the finding that phenolic acetates are cleaved with pyrrolidine(吡咯烷）much faster than aliphatic acetates. The pyrrolidine acetates formed in the reaction of an acetylated lignin is determined by GC (gas chromatography) (Fig.4.28)
云杉和山毛榉MWL的元素分析值与甲氧基含量
木素 云杉MWL 山毛榉MWL
元素分析值/%
C
H
O
OCH3
64.77 6.39 28.58 16.13
60.58 6.23 33.19 21.46
示性式
C9H8.83O2.37(OCH3)0.96 C9H8.49O2.86(OCH3)1.43
C/H比例比较高，显示芳香族特性。
19
How to analyze the units containing double bonds?
Two methods have been used with some success . One is based on the catalytic hydrogenation of the double bonds in cinnamaldehyde and cinnamyl alcohol structures and measurement of the UV difference spectrum. The other uses the difference in UV adsorption in neutral and alkaline solution to measure the amount of phenolic stilbene structures.
木质素解聚 催化反应动力学
木质素解聚催化反应动力学英文回答：Lignin depolymerization catalytic reaction kinetics refers to the study of the rate at which lignin is broken down into its constituent components under the influence of a catalyst. Lignin is a complex polymer found in the cell walls of plants and is composed of phenylpropanoid units.It is one of the most abundant natural polymers on Earth and is a major component of lignocellulosic biomass.The depolymerization of lignin is a complex processthat involves the cleavage of various chemical bonds within the polymer structure. This process can be catalyzed by a variety of catalysts, including transition metal ions, enzymes, and acid/base catalysts. The choice of catalyst can significantly impact the reaction kinetics and the selectivity of the depolymerization process.The reaction kinetics of lignin depolymerization can bestudied using various techniques, including spectroscopy, chromatography, and mass spectrometry. These techniquesallow researchers to monitor the changes in the molecular structure of lignin over time and determine the rate at which the depolymerization reaction occurs.The kinetics of lignin depolymerization are influenced by several factors, including the nature of the catalyst, reaction temperature, reaction time, and concentration of reactants. The choice of catalyst is particularly important, as different catalysts can selectively break down specific bonds within the lignin polymer. This selectivity can be used to control the composition of the depolymerization products and tailor them for specific applications.Understanding the kinetics of lignin depolymerizationis crucial for the development of efficient and sustainable lignin valorization processes. By optimizing the reaction conditions and catalyst choice, it is possible to enhance the rate of lignin depolymerization and improve the yieldof valuable depolymerization products. This knowledge can contribute to the development of new lignin-based materials,biofuels, and chemicals, thereby reducing our reliance on fossil resources and promoting a more sustainable bioeconomy.中文回答：木质素解聚的催化反应动力学研究是指在催化剂的作用下，木质素被分解为其组成部分的速率研究。