The Fractionation and Composition Properties of Wheat Straw Lignin and LCC Extracted by Alkaline Solution at Ambient Temperature

采用酸化沉淀法程序分级分离室温麦草碱抽提液中本质素、木质素-碳水化合物复合体(LCC),得到了pH值10.5、9.0和2.0三个级分.pH值10.5级分得率较高,为12.24％,该组分含有大量的碳水化合物,可能是以水不溶性LCC为主.随着pH值的降低,级分中的木质素含量逐渐增加,碳水化合物含量逐渐减少,pH值9.0和2 0组分均是以木质素为主.pH值2.0级分中碳水化合物含有较多的阿拉伯糖和半乳糖,该级分中LCC组成与pH值10.5和9.0级分LCC组成可能不同.抽提液中的SiO2大部分沉淀在pH值10.5和9.0级分中,pH值9.0级分中灰分质量分数高达13.29％.酸化沉淀程序分离法是一种分级分离麦草碱抽提液中木质素、LCC的有效方法.     

中空纤维管式超滤分离麦草碱提取液水溶性木质素-碳水化合物复合体

用溶剂抽提法分离出含钠盐及低相对分子质量(Mr)物质的麦草常温碱提取水溶性木质素-碳水化合物复合体(LCC)级分,采用中空纤维管式超滤技术定量去除LCC中钠盐及低Mr(＜1000)物质等杂质.研究结果表明,在超滤压力为0.10 MPa、超滤浓度为0.5%(以质量分数计)的条件下,水溶性LCC经10次循环超滤后,其中钠盐及低Mr物质得到了有效去除,分离得到高得率、高纯度、富含碳水化合物的水溶性LCC级分.     

蓝花楹木质素-碳水化合物复合体在硫酸盐法蒸煮过程中的变化

以蓝花楹为原料提取木质素-碳水化合物复合体(LCC),并对LCC的结构进行分析,同时模拟硫酸盐法蒸煮过程,采用蒸煮的方法对LCC进行处理,并对处理后的产物进行红外光谱和核磁共振分析,研究蓝花楹LCC的结构变化,探讨其在硫酸盐法蒸煮过程中LCC的形成和降解情况。研究发现:蓝花楹LCC中的碳水化合物在蒸煮过程中非常不稳定,大部分发生降解,而蒸煮产物中含有对碱稳定的LCC结构,也含有新形成的LCC结构,这种新形成的LCC是5-5缩合型木质素结构与木聚糖形成的以化学键连接的LCC结构,且其对碱也非常稳定。     

利用CaO/PAC选择性去除预水解液中木质素

利用CaO结合聚合氯化铝(PAC)来选择性去除预水解液中的木质素。分别探讨了酸化法、碱化法及其结合PAC选择性去除木质素的效果,并分析了PAC选择性去除木质素的机理。结果表明:酸化法pH值为1.5时,木质素去除率最大(杨木15.68%,麦草18.76%);而采用CaO调节pH值为12时,木质素去除率最大(杨木33.33%,麦草30.67%),碱化法去除效果优于酸化法。添加CaO将pH值调至10并使PAC浓度为36 mmol/L时,预水解液中木质素的去除率(杨木50.59%,麦草49.17%)及选择性(杨木86.57%,麦草82.76%)效果最佳。     

碱性H2O2法分离常春油麻藤纤维素级分的结构特性

研究碱性H2O2法分级分离常春油麻藤纤维所得4种纤维素级分的结构特性.随着分离级数增加,纤维素分子链发生断裂的程度加剧,重均分子质量逐渐减小.第1级、2级、3级和4级纤维素属于纤维素Ⅰ,除1级纤维素中含有少量的木质素和半纤维素成分外,其余3种高纯度纤维素中基本不含木质素和半纤维素.经分级分离后,从第1级到4级纤维素的物理结构发生了很大的变化,使纤维束由最初的长粗变得更短更细.从第1级到4级纤维素的结晶度依次升高,但1级纤维素的结晶度相对要低得多.     

绿液预处理对麦草化学成分及酶水解糖化的影响

主要探讨在不同温度、用碱量和硫化度条件下绿液预处理对麦草化学成分及酶水解效率的影响。随着预处理用碱量和硫化度的提高木质素的脱除率增加,但同时也加剧了碳水化合物的降解,导致麦草浆得率下降。绿液预处理废液的pH值小于9.5,弱碱介质可以减少碳水化合物的降解,同时避免禾草原料含量较高的硅溶解在黑液中,有利于废液的碱回收利用。预处理后浆料经过由纤维素酶、木聚糖酶和β-葡萄糖苷酶组合而成的混合酶液水解,纤维素酶用量从5 FPU/g增加到10 FPU/g时,总糖得率及转化率显著增加。在酶用量为10 FPU/g条件下经过48 h的酶水解后,温度130℃、用碱量8%、硫化度40%条件下的预处理浆料总糖得率达到最大值43%,总糖转化率为73.1%。     

麦草碱性亚硫酸盐制浆生物炼制的研究(I) ——深度脱木质素及木质素磺化特性

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响。结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱木质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0%,亚硫酸化度85.0%,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8%,黏度为33.3 mPa.s的优良纸浆,此时黑液中磺化木质素磺酸基含量达2.16 mmol/g(以固形物计)。从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景。     

Study on Wheat Straw Alkaline Sulfite Pulping Biorefinery(Ⅰ)——Characteristics of Extended Delignification and Lignin Sulfonation

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响.结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱本质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0％,亚硫酸化度85.0％,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8％,黏度为33.3 mPa·s的优良纸浆,此时黑液中磺化本质素磺酸基含量达2.16 mmol/g(以固形物计).从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景.     

磨木木质素在硫酸盐法蒸煮过程中的降解及与木糖的缩合

在木糖存在的条件下,采用硫酸盐法蒸煮对蓝花楹磨木木质素(MWL)进行处理,然后对处理后的产物进行红外光谱和13 CNMR分析,研究蓝花楹MWL的结构变化,探讨在硫酸盐法蒸煮过程中木质素-碳水化合物复合体(LCC)的形成情况.研究发现:蓝花楹MWL结构单元之间的α-烷基芳基醚键、β-O-4型连接键很容易发生断裂,而在这些连接键发生断裂的同时,形成的木质素中间体与木糖通过化学键的结合,形成新的LCC结构.这种新形成的LCC结构主要是由β-O-4型木质素结构和5-5′缩合型木质素结构与木糖形成的以苯甲醚键连接的LCC,这种新形成的LCC结构对碱非常稳定.     

棉秆与麦草蒸煮反应的动力学比较

比较了棉秆和麦草蒸煮反应的脱木质素速率常数,提出一种研究蒸煮反应动力学的实验和计算新方法。通过对不同恒温条件下的反应速率常数计算,采用与实际蒸煮反应相同的液比,用较短时间周期的有效碱浓度变化值和木质素含量变化值计算得出了两种原料烧碱-蒽醌法蒸煮反应的活化能。棉秆烧碱-蒽醌法蒸煮反应的活化能和麦草烧碱-蒽醌法蒸煮反应的活化能在整个脱木质素阶段基本是不变的。麦草烧碱-蒽醌蒸煮反应的活化能为51.0 kJ/mol。棉秆烧碱-蒽醌法蒸煮反应的活化能是138.1 kJ/mol,高于麦草蒸煮反应活化能,说明麦草蒸煮脱木质素反应比棉秆更容易。     

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     

Ester linkages between lignin and glucuronoxylan in a lignin-carbohydrate complex from beech (Fagus crenata) wood

Summary A water-soluble lignin-carbohydrate complex (LCC) isolated from beech (Fagus crenata) MWL was investigated. Results from gelfiltration chromatography and the infrared spectrum of the LCC treated with alkali under mild conditions indicated that the LCC contained alkali-labile bonds. Decrease of uronic acid content and the detection of 4-O-methylglucose in the sodium borohydride-reduced LCC suggested the presence of an ester linkage between lignin and glucuronic acid in the glucuronoxylan. Conductometric titration also indicated the existence of glucuronic acid ester linked to lignin. From these results, it is concluded that the LCC contained an ester linkage between lignin and glucuronoxylan and that about one-third of the glucuronic acid present in the LCC was involved in this ester linkage.     

Lignin fragments rich in detached side-chain structures found in water-soluble LCC

The content of the glyceraldehyde-2-aryl ether-type structure in water-soluble lignin–carbohydrate complex (LCC) fractions, which were obtained from Japanese cedar and birch residual wood meal after milled wood lignin isolation, was determined by ozonation. Quite high amounts of the glyceraldehyde-2-aryl ether-type structure were found in water-soluble LCC fractions of both species; about 3–5 times higher than those of other fractions. This result, as well as the high content of the β-1 structure in these fractions shown in our previous reports, suggest that lignin in these fractions has the characteristics of endwise-type lignin, because the glyceraldehyde-2-aryl ether-type structure and β-1 structure are typical characteristics of this type of lignin fraction. These results are in good agreement with the generally accepted hypothesis that the glyceraldehyde-2-aryl ether-type structure and β-1 structure are generated at the same time by a radical coupling reaction. The results also indicated that these two structures are present in close proximity in the lignin.     

Structure of small lignin fragment retained in water-soluble polysaccharide extracted from sugi MWL isolation residue

In order to analyze the structural features of small lignin fragments that are closely associated to polysaccharides, lignin carbohydrate complex (LCC) with low lignin content was extracted with water from the residual wood meal (sugi, Cryptomeria japonica) of milled wood lignin (MWL) isolation. This LCC exhibited almost the same neutral sugar composition as those extracted by other LCC solvents (dimethylformamide, dimethylsulfoxide, and others) but the lignin content was only 5.3%, which was much lower than others. Gel filtration chromatography demonstrated that lignin in this LCC was found together with carbohydrates at the higher molecular weight region, but after the treatment with carbohydrate-degrading enzymes the apparent molecular weight of both lignin and carbo-hydrates decreased significantly. Using a mild alkaline treatment, the apparent molecular weight of lignin also decreased while that of polysaccharide was not affected. These data indicated that lignin in this LCC is present as small fragments attached to high molecular weight polysaccharide at least partly by alkali-unstable linkages. Structural analysis by ozonation method revealed that the lignin in this LCC was lower in erythro/threo ratio of -O-4 structure and relatively richer in the threo type structure carrying C-aryl linkages at -position (-5 and/or -1) than other lignin fractions present in MWL, LCCs extracted by other solvents, and their extraction residues. It was suggested that the chemical structure of lignin closely associated to carbohydrates was different from that of the main part of lignin.This paper was presented in part at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002, at the 47th Lignin Symposium, Gifu, Japan, October 2002, and at the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

Effect of the presence of lignin on the structure and reactivity to hydrolysis of lignincarbohydrate complexes of poplar wood obtained by sulfate pulping

Summary Lignincarbohydrate complexes (LCC) of poplar wood obtained by sulfate pulping and containing lignin in amounts of 0.9–8.3% have been studied by X-ray diffractometry. Heterogeneous hydrolysis methods have been used to determine their reactivity. The content of the crystalline fraction in LCC depends on the lignin removal and increases with the decrease of the lignin content. The degree of crystallinity of cellulose in sawdust and in LCC is fairly high and changes slightly with the lignin removal. The presence of lignin plays a blocking role in the heterogeneous hydrolysis and decreases the rate constant. It is suggested that lignin is bonded to cellulose on the outer surfaces of the crystalline part of the cellulose fibril. Some possible variants of these bonds are discussed.     

A mathematical model of kraft pulping related to the alkali concentration in the cooking liquor

Summary A new mathematical model for checking and controlling the kraft pulping process has been derived. The model is based on the modified relationship between the lignin content and the alkali concentration of a cooking liquor expressed as the ratio of lignin/active alkali vs. concentration of the active alkali in a cooking liquor. The derived model characterizes the variation of the lignin content of the partially delignified wood or pulp with the concentration of the residual alkali in a cooking liquor during an entire pulping cycle, i.e. during the initial, transition, bulk and residual phases of the kraft delignification. The relationship between the lignin content of the partially delignified wood ships or pulp and the concentration of the residual alkali in a cooking liquor is expressed by the logarithmic straight line equation or its power form. The slope and intercept constants of the derived equation for the individual phase of delignification have different values. Received 5 June 1996     

Molecular properties of lignin-carbohydrate complexes from beech (Fagus crenata) and pine (Pinus densiflora) woods

Summary Lignin-carbohydrate complexes (LCC) were isolated from pine (Pinus densiflora) and beech (Fagus crenata) milled-wood lignins. The LCCs were treated with enzyme to obtain precipitates (A-P, B-P) and water soluble fractions. The water soluble fraction from beech LCC was subjected to gel filtration to give LCC fragments (B-E-I). In order to protect the phenolic hydroxyl group, B-E-I and B-P were methylated with diazomethane, resulting in nonphenolic LCC fractions B-E-Ip and B-Pp, respectively. On treatment of B-E-I and B-P with sodium hydroxide, a remarkable amount of xylose and a trace of arabinose were detected as monomeric sugars. However, the same alkaline treatment of B-E-Ip and B-Pp gave only a faint trace of xylose. With DDQ treatment of acetylated B-E-I and B-P, monomeric sugars were released in the same amount as those obtained on alkaline treatment. Methylation of the monomeric sugars gave monomethylated xylose. From these results, it was concluded that xylose residues participate in lignin-carbohydrate linkages, and that lignin is linked to xylose at the 0–2 or 0–3 positions through an alkali-labile benzyl ether bond. The molecular-weight distributions of the lignin moieties, measured by HPLC, indicate that the lignin moieties of beech LCC are 100 times larger but less frequent than those of pine LCC. This nonuniformity of distribution of lignin and carbohydrate moieties in hardwood LCC molecules would result in less hydrophobic interaction in aqueous solutions.     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

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