醋酸水溶液处理对杉树材影响

为了研究醋酸水溶液处理给杉树材重量带来的变化,使用醋酸水溶液对杉树材进行了处理。结果发现处理后杉树材重量的减小量大约等于抽出物的重量,而且随着醋酸水溶液浓度的增加而增加。利用傅立叶变换红外光谱法对处理后的杉树材及抽出物进行了光谱分析。从处理后杉树材的光谱图可以观察到3400cm-1附近的OH伸缩振动及1510cm-1附近的木质素中苯环C=C伸缩振动的吸收强度有增加倾向。从醋酸水溶液抽出物光谱图可以发现用浓度30%醋酸水溶液处理时木质素被溶出。图2表2参6。     

Treatment of sugi （Cryptomeria japonica D.） sapwood with aqueous solution of acetic acid

Sugi sapwood samples were processed with aqueous solution of acetic acid in order to find the response of the weight of sugi sapwood and the treatment of aqueous solution of acetic acid. The result showed that loss of weight for the treated sugisapwood was about equal to yield of extracts from sugi sapwood, and increased with the increment of the concentration of aqueous solution of acetic acid. Fourier transform infrared spectroscopy spectra changes of the treated sugi wood and extracts from sugi sapwood were analyzed by FT-IR spectroscopic technique. Increasing tendency of absorption intensities of the stretching vibration at 3 400 cm^-1 of hydroxyl group (OH) and C=C in lignin stretching vibration at 1510 cm^-1 of benzene ring inlignin were observed from FT-IR of the treated sugi sapwood. From FT-IR spectra of extracts from sugi sapwood by aqueoussolution of acetic acid, the dissolution of lignin was observed during the treatment with 30% acetic acid solution aqueous.     

Reduction of aluminum toxicity to radish by alkaline oxygen treated kraft lignin

To obtain a soil-conditioning agent for acid soil containing excess aluminum ions (AL), kraft lignin was modified by alkaline oxygen treatment. The growth of radish root in solution and in soil containing AL with or without addition of these lignins under controlled pH was examined. We concluded the following. Growth inhibition of radish roots by AL can be removed by adding alkaline oxygentreated lignins in the range of pH 4.5–4.8 in soil. A similar result was obtained at pH 4.5 in a culture solution. The reduction of AL toxicity to plant may be due to the aggregation between AL and the modified lignin at low concentrations of modified lignin because soluble AL could not be detected. On other hand, elongation of radish root was not obviously inhibited, although the soluble AL in the solution culture was at an extremely high level when the dosage of a modified lignin was high. This suggests that the reduction in AL toxicity to plants was due to formation of a complex between AL and acidic groups of the modified lignin.Part of this report was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999 and the 44th Lignin Symposium, Gifu, October 1999     

A method for isolation of milled-wood lignin involving solvent swelling prior to enzyme treatment

Summary A new lignin isolation method has been developed. Wood and pulp were subjected to ball milling, swelled in an organic solvent, and then treated with a cellulase. The enzyme digestion time could be shortened to 1 day with this method. The lignin obtained has been named Swelled Enzyme Lignin (SEL). Swelling and enzyme digestion conditions and their effects on lignins were investigated. The SEL's from wood could be directly washed with water, while those from pulp had to be washed with aqueous acetic acid because they were water soluble. The purification of crude SEL's was accomplished by extracting them with dioxane-water, and then precipitating and washing with ethyl ether. Lignin yields were 24–67% based on the total amount of lignin present. The characteristics of the SEL's were further investigated by gel-permeation chromatography (GPC), infrared and ¹³C nuclear magnetic resonance (NMR) spectroscopy.Symbols SUKP Softwood Unbleached Kraft Pulp - BUKP Birch Unbleached Kraft Pulp - TD Todomatsu (Abies sachalinensis) wood - MWL Milled Wood Lignin - MWLS (BK, TD) Milled Wood Lignin of SUKP (BUKP, TD) - SEL-C Swelled Enzyme Lignin (crude) - SELS-C SEL-C of SUKP, other materials named in the same way - SELS-90 SEL-C of SUKP and extracted with 90% dioxane-water - SELS-96 SEL-C of SUKP and extracted with 96% dioxane-water, other materials named in the same way     

乙酸木质素基聚氨酯硬泡的制备与性能

将乙酸制浆法废液中的木质素进行提取和精制,采用红外光谱(FTIR)、31P-NMR谱和凝胶渗透色谱(GPC)对其结构进行表征,并利用乙酸木质素、聚醚多元醇和甲苯二异氰酸酯在发泡剂和催化剂的条件下合成聚氨酯硬泡。采用TG、DSC和压缩测试对聚氨酯硬泡的热学和力学性能进行研究,并用扫描电子显微镜观察聚氨酯硬泡的泡孔结构。结果表明:乙酸木质素作为多羟基聚合物,可以部分代替聚醚多元醇和异氰酸酯发生反应制备聚氨酯材料;当乙酸木质素添加量为5%时,聚氨酯硬泡的压缩强度达到1.325MPa,比未添加木质素的泡沫高出约63%,此时的压缩模量也达到0.181MPa;随着乙酸木质素添加量增加,乙酸木质素基聚氨酯硬泡的最快分解温度下降,而玻璃化转变温度没有明显升高;乙酸木质素基聚氨酯硬泡泡孔平整均匀。     

木质纤维成分的乙酸分离方法及表征

研究了一种用含有少量硫酸的乙酸溶液分离杨木成分的方法。考察了反应时间、乙酸浓度、液比和催化剂浓度对木材成分分离的影响。对分离出的木材三种成分进行了表征。结果表明,分离杨木成分的较佳条件为:硫酸浓度0.3%,液比6,反应时间3h和乙酸浓度90%。残渣的主要成分是α-纤维素和半纤维素。水不溶沉淀物(乙酰化木质素)的重均分子量分布在341到253之间,分散性系数分布在1.1到1.2这一窄范围内。糖分析结果表明,可溶性成分主要来源于半纤维素,以单糖形式存在。     

二乙醇胺基木质素非离子表面活性剂的制备及表征

依据酸沉淀法对碱木质素进行了分级,分级后pH值4 ～ 6的木质素与环氧氯丙烷、二乙醇胺反应,制备了木质素基非离子表面活性剂.通过红外光谱、含氮量的测定对产物的结构进行了表征,通过表面张力测定对产品的表面活性进行了分析.结果表明:木质素基非离子表面活性剂固含量为32.6%,含氮量为1.99%,红外光谱分析可确定在木质素上引入了环氧氯丙烷和二乙醇胺,水溶液表面张力降低到53.27mN/m,表明二乙醇胺基木质素非离子表面活性剂(DLNS)具有良好的表面活性.另外通过与十二烷基磺酸钠(SDS)复配后浊度的测定,表明产品在SDS与DLNS的体积比为20: 3 ～ 20: 20范围与SDS复配,浊度较低,复配效果较好.     

Effect of oxalic,acetic acid,and ammonia on leaching of Cr and Cu from preserved wood

Wood treated with CCB (chromated copper borate) has an expected service life of 20–50 years, depending on conditions of service and method of treatment. After this period, treated wood is discarded as special waste. Due to toxic elements (Cu, Cr, and B) in such treated wood, burning and landfill disposal are not considered as environmentally sound solutions. Chemical extraction seems more promising. The principle of the method is to convert fixed biocides in wood into soluble form and leach them out of the wood. In order to elucidate this process, copper(II) sulfate, potassium dichromate, and CCB-treated samples were leached using five different agents, namely, water, an aqueous solution of oxalic or acetic acid, and an aqueous solution of oxalic or acetic acid with ammonia. Afterwards, the amounts of leached copper and chromium were determined. In a parallel experiment, electron paramagnetic resonance measurements of wet- and dry-leached and unleached samples were performed in order to determine the paramagnetic complexes that were formed. The highest chromium leaching was achieved with the aqueous solution of oxalic acid, as chromium was converted into water-soluble chromium oxalate. While the mixture of oxalic acid and ammonia resulted in the highest copper leaching, EPR observation revealed that in this case water-soluble complexes of copper, oxalic acid, and ammonia were formed. We found out that oxalates formation is not the only mechanism responsible for copper or chromium leaching. High acidity may play an important role too.     

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     

Activated carbon sheet prepared from softwood acetic acid lignin

As an example of activated carbon (AC) moldings, AC sheets were prepared from thermoplastic acetic acid lignin by lamination. The resulting AC sheets are a new type of product that can be applied as water and air cleaners. Powdered softwood acetic acid lignin (SAL) was molded into sheets by a thermal pressing method. When the sheet was carbonized under a stream of nitrogen at 1000°C, it was deformed with expansion and contained much foam. The deformation during carbonization was suppressed by the addition of pulp to the lignin. A sheet prepared by mixing lignin with pulp was directly carbonized without thermostabilization. The carbonized sheet was activated with steam for 2h. The resulting AC sheet had adsorption properties, such as specific surface and iodine adsorption capacity, comparable to those of commercial AC powders or granules. Furthermore, the AC sheet had a larger capacity to adsorb methane than did the commercial AC powder. Therefore, SAL seems to be a promising source for the AC moldings.     

醋酸水溶液预处理对柳杉木材炭化的影响

杉木(日本柳杉)经醋酸水溶液处理后，重量减少。将处理前后柳杉木材在4℃下进行炭化，得到了木醋液、木焦油和木炭。与未处理材相比，处理材木醋液的收率增加，而木焦油和木炭的收率减少。处理液的醋酸浓度增加后，木醋液和木焦油的收率几乎不变，但木炭的收率稍微减少了。用毛细管气相色谱法对木醋液的成分进行了定量分析。与未处理材相比，处理材木醋液中糠醛(呋喃甲醛)及5-羟甲基糠醛的收量增加，而羧酸类、苯酚类、邻苯二酚、愈创木酚类及麦芽酚的收量几乎不变。当醋酸浓度从0增至3％时，糠醛的收量随着增加，但是当醋酸浓度从3％增至30％时，其收量却几乎不变。     

离子液体[Hmim][CF_3SO_3]在木质素及其模型化合物生物降解中的应用

研究了在室温下,离子液体[Hmim][CF_3SO_3]溶解木质素及其模型化合物后,与酶液在小分子有机酸作用下形成的三元液相平衡体系,及在此体系中进行酶促反应的过程。结果表明:小分子有机酸使水-离子液体形成的两相转化为均相的主要贡献是由羧基提供的,[Hmim][CF_3SO_3]在溶解木质素后依旧保留与有机酸和水形成三元相平衡体系的能力;以酶液作为水相,以溶解了木质素的离子液体作为疏水相,甲酸的掺入在起到平衡水相和疏水相的同时也作为木质素降解酶反应过程中的自由基稳定剂;在三元液相体系的反应中,离子液体引起酶的部分失活;随着反应的进行,碱木质素和木质素脱氢聚合物(DHPs)的降解率分别为56.5%和66.5%,甲氧基分别降低了46.7%和45.3%,生成的酚类化合物分别为204.7和207.0 mg/L,甲酸分别消耗了0.57和0.76 g。DHPs在降解过程中,由于甲酸的过度消耗导致了平衡体系的解体。     

Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC1₃. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC1₃. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin.     

Formation of a complex with aluminum by ozone-treated kraft lignins and their low molecular weight fragments

The formation of a complex with aluminum by low molecular weight compounds and saponified ozone-treated kraft lignins was evaluated based on the decrease in pH of their solutions on the addition of 0.1 M AlCl₃. Decreases in pH were observed with the solutions containing compounds having adjacent carboxyl groups (oxalic acid), carboxyl/alcoholic hydroxyl groups (glycolic acid), carboxyl/formyl groups (glyoxylic acid), and phenolic hydroxyl groups (protocatechuic acid) on the addition of 0.1 M AlCl₃. The malonic and phthalic acids, having two carboxyl groups, were also effective. These results show that the compounds were effective in forming complexes with aluminum. This finding corresponds to the fact that aluminum toxicity is reduced by formation of a complex with aluminum, except in phthalic acid. The chemical structures stated above in ozone-treated kraft lignins contribute, at least partly, to the complex with aluminum. The pH of solutions containing saponified ozone-treated kraft lignins and alkaline-treated kraft lignin decreased more than that without modified kraft lignins on the addition of 0.1 M AlCl₃, showing that they were effective in forming a complex with aluminum. The high molecular weight part of saponified ozone-treated kraft lignin was effective in forming a complex with aluminum and in reducing its toxicity.     

Chemical characterization of Pinus halepensis sapwood and heartwood

ABSTRACT

This paper describes the chemical composition of sapwood (SW) and heartwood (HW) of Pinus halepensis Mill stem. Extractives were first isolated by accelerated solvent extraction and then analysed by gas chromatography-mass spectrometry (GC-MS). The cellulosic polysaccharide content present in the pre-extracted wood samples was determined with acid hydrolysis and GC. The hemicelluloses content was determined with acid methanolysis and GC. Free monomers were additionally analysed by GC. The amount of lignin was determined gravimetrically by the Klason lignin method and the acid-soluble lignin was determined by a UV method. Formic and acetic acids in wood were determined after alkaline hydrolysis and analysed by HP-SEC. It was found that lipophilic and hydrophilic extractives were more abundant in heartwood (1.6% and 2.5%) than in sapwood (1.1% and 1.8%). Celluloses content was higher in sapwood (42.5%) than in heartwood (39.7%), whereas lignin, hemicelluloses and sugar monomer contents were more abundant in heartwood (28.9%, 26.8% and 0.3%) than in sapwood (28.0%, 24.5% and 0.2%). The variation in acetic and formic acids and ash contents between sapwood (0.7%, 0.2% and 0.5%) and heartwood (0.6%, 0.1% and 0.4%) was small. The acetylation degrees were found to be slightly similar in sapwood (0.4) and heartwood (0.3).     

Kinetics of acid-catalysed delignification of Eucalyptus globulus wood by acetic acid

Summary The kinetics of HCl-catalysed delignification of Eucalyptus globulus wood by 70% (w/w) acetic acid solution were satisfactorily explained by a model in which 5% of the lignin fraction could not be eliminated and the remaining 95% was eliminated by a single process which, in view of the activation energy calculated from the data was attributed to the hydrolysis of -aryl ether bonds. The selectivity of the process was effectively independent of HCl concentration and operating temperature for pulp yields >50%. At high temperature (160 °C) and catalyst concentration (0.027 MHCl), lignin condensation and precipitation became significant and the data were better fitted by a model comprising two consecutive processes: lignin solubilization followed by lignin condensation.The authors are grateful to the CICYT for financial support of this work (Project AGF93-0605) and also to the DGICYT for a research grant awarded to J. González     

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     

生物基极性非质子溶剂/对甲苯磺酸耦合体系中竹粉定向解聚研究

以两种生物基极性非质子溶剂γ-戊内酯（GVL）和二氢左旋葡萄糖酮（Cyrene）,分别与对甲苯磺酸水溶液（TsOH aq）构成耦合体系，对竹粉定向解聚及其酶解过程开展了研究。实验结果表明：质量浓度为75 g/L的TsOH,溶剂体积比为4∶1的GVL/TsOH aq体系在130℃预处理毛竹60 min后，半纤维素和木质素分离效率更高，半纤维素分离率（S_H）和木质素分离率（S_L）分别达到98.5%和98.4%,同时纤维素保留率（R_C）为91.5%;而质量浓度为30 g/L的TsOH,溶剂体积比为0.8∶1的Cyrene/TsOH aq体系在120℃预处理毛竹60 min后，R_C达到87.3%,S_H和S_L仅为85.5%和79.4%。预处理后固体样品的表征结果表明：竹粉经GVL/TsOH aq预处理后的样品木质纤维致密结构被有效破坏，无定形的半纤维素和木质素绝大部分被分离，结晶度达68.27%,结构更接近于微晶纤维素，同时暴露出更多的游离羟基，有利于后续酶解。而酶...     

GA_3和IAA对慈竹木质素动态积累和S/G的调控效应

以慈竹为材料,通过喷洒不同浓度和比例的赤霉素(GA3)和吲哚乙酸(IAA),研究慈竹茎部木质素动态积累规律以及GA3和IAA对慈竹茎部木质素S/G比例的调控效应。结果表明,GA3和IAA组合处理对慈竹茎杆木质素含量动态积累的调控效应不同:50 mg.L-1GA3+200 mg.L-1IAA(GA350IAA200)组合处理和对照(清水处理)的慈竹的木质素含量动态积累趋势基本一致,二者都在处理10 d和30 d时出现2个高峰;GA350IAA200处理具有降低木质素含量的作用;而200 mg.L-1GA3+50 mg.L-1IAA(GA3200IAA50)组合处理改变了慈竹木质素含量动态积累趋势,具有增加慈竹木质素含量的作用。GA3和IAA组合处理改变了慈竹茎部S/G比值的变化趋势,具有降低S/G比值的作用;GA3和IAA组合处理对慈竹茎部木质素和S/G比值的调控作用因GA3和IAA浓度和配比不同而不同。     

麦草碱木质素三甲基季铵盐对酸性染料溶液的絮凝性能影响

以从造纸黑液中提取的麦草碱木质素为原料,通过曼尼希反应合成麦草碱木质素三甲基季铵盐,以脱色率为指标检测其对酸性黑ATT、酸性橙GG和酸性红B的絮凝性能。实验结果表明:对于0.1 g/l酸性黑ATT溶液,pH为2,麦草碱木质素三甲基季铵盐使用浓度在0～3 500 mg/l范围内时,脱色率随浓度增大而升高;麦草碱木质素三甲基季铵盐使用浓度为2 884 mg/l时,在pH为1～4范围内,脱色率随pH降低而增加。酸性橙GG和酸性红B也有类似的规律。由上述结论结合麦草碱木质素三甲基季铵盐和酸性染料的结构特点,认为絮凝过程先是麦草碱木质素三甲基季铵盐中的铵离子与酸性染料中的磺酸根之间氢键吸引,然后染料间产生"架桥"现象,具有三维网状结构的碱木质素分子继续网捕和卷扫脱除染料。