木质素氧化降解制备酚类化合物研究进展

木质素作为可再生资源被认为是最具有潜力的苯酚替代物用于制备酚醛树脂,作为制浆造纸工业副产品,木质素来源丰富且低毒,但是木质素具有三维空间网状结构,分子量大,反应活性低。到目前为止,很多方法(如热化学转化、热裂解、液化、超临界水处理、氧化、还原和水解等)用于将大分子木质素降解为小分子物质,得到的小分子物质中含有重要的化工中间体可以用来制备多种产品。本论文综述了木质素氧化降解得到酚类物质的研究现状,并展望了木质素工业化的应用前景。     

光催化降解碱木质素研究

通过纳米TiO₂光催化氧化降解碱木质素,发现在木质素5g,催化剂用量为0.75 g/L、光照时间为2.5 h和pH值为10时,降解率可达70%以上。利用GC-MS对降解产物进行分析,结果表明,木质素本身具有复杂的结构形式,降解过程主要是进攻木质素侧链上的羰基和双键,使其发生氧化反应,改变结构或将侧链碎解。经过降解后可以得到紫丁香基衍生物、香草醛、愈创木基衍生物等小分子物质。     

纳米TiO2光催化降解碱木质素研究

通过纳米TiO2光催化氧化降解碱木质素,发现在木质素5g,催化剂用量为0．75g／L、光照时间为2．5h和pH值为10时,降解率可达70％以上。利用GC—MS对降解产物进行分析,结果表明,木质素本身具有复杂的结构形式,降解过程主要是进攻木质素侧链上的羰基和双键,使其发生氧化反应,改变结构或将侧链碎解。经过降解后可以得到紫丁香基衍生物、香草醛、愈创木基衍生物等小分子物质。     

TiO_2光催化氧化降解高沸醇木质素的研究

高沸醇木质素是利用高沸醇溶剂(HBS)法制备纸浆过程中获得的木质素,具有较高的化学活性。在TiO2光催化条件下,研究紫外光降解高沸醇木质素的结构变化,通过紫外分光光度法测定溶液吸光度来判断不同因素条件下高沸醇木质素降解的程度,包括TiO2加入量、光照强度、光照时间、氧化剂用量等。对降解产物进行红外谱图和GC-MS分析,结果表明木质素本身具有复杂的结构形式,经过降解后可以得到香草醛、愈创木基衍生物等小分子物质。     

木质素酚醛泡沫保温材料的制备与性能研究(摘要)

采用一种新的方法将木质素应用到甲阶酚醛树脂中.通过低温下氧化降解木质素,使降解产物中含有多种低分子量的酚类小分子化合物,提高了木质素的反应活性;采用木质素磺酸钙的氧化降解产物替代苯酚50％制备甲阶酚醛树脂,进一步制备性能良好的酚醛泡沫;研究木质素的引入对甲阶酚醛树脂和酚醛泡沫保温材料性能的影响.主要研究内容和结果如下:     

固体超强酸催化降解木质素的研究

在固体超强酸催化下用过氧化氢氧化降解高沸醇木质素,并利用红外光谱和气相色谱―质谱联用(GC-MS)分析降解产物。结果表明,SO42-/ZrO2固体超强酸催化降解高沸醇木质素可以得到小分子产物。随着固体酸用量增加,羰基和醚键数量明显减少,降解效果较好。GC-MS分析结果显示,FeSO4促催化更有利于木质素的降解。     

木质素氧化解聚制备芳香醛研究进展

木质素作为自然界最丰富的芳香族化合物资源，通过可控的氧化解聚方式得到小分子芳香醛类化合物是实现木质素高附加值利用的重要途径。芳香醛作为重要的食用及日化香料、医药中间体、大宗化学品，目前主要通过石油化工产业链生产，以木质素生产芳香醛是具有重要研究意义和应用潜力的可再生资源利用途径。本文综述了国内外有关木质素制备芳香醛的最新研究进展，包括化学氧化解聚、电化学解聚、光催化解聚和生物催化解聚；对不同方法制备芳香醛的转化率和产率进行了对比，基于不同的解聚工艺与催化体系的特点进行评述与分析，展望未来木质素生产芳香醛的研究方向，以实现木质素的高值化利用。得出多方法耦合催化是可能进一步提高木质素生产芳香醛转化率与选择性的有效策略。     

漆酶的应用技术

漆酶是一种广泛分布的多酚氧化酶,催化底物具有广谱性,被应用于造纸、环保、食品、医药、纺织等各个领域。漆酶既能催化木质素聚合,又能促进木质素降解;既被用于生漆固化成膜,木质素聚合改性、提高纤维素间的自粘合性、纸张漂白、纺织废水处理和染料合成,又被用于果汁和酒类澄清,改善饮料的色泽和口感。漆酶催化反应形成的自由基对癌细胞有杀伤作用,可制备抗癌药物。在免疫检测中,利用漆酶催化的氧化反应特性能去除胆红素和抗坏血酸等干扰物质,还可替代过氧化物酶作为新的标记酶。在生物修复中漆酶可有效降解酚类等污染物。随着分子生物学进展,漆酶的新用途将会被不断挖掘,给人类带来福音。     

木质纤维素微生物转化机理研究进展

木质纤维素是自然界中储量最大的可再生资源物质,由于木质素难以降解,阻碍了木质纤维素物质的生物转化利用,并且是相关工业生产中毒性污染物质的主要来源。自然界中存在的白腐真菌对芳香族化合物具有很强的降解能力,具有完整的木质纤维素降解体系,对这一体系的研究成为实现木质纤维素资源转化利用的关键,木腐微生物的存在,使人类通过廉价手段降解和利用木质纤维素成为可能。研究木腐微生物降解木质纤维素的机制,研究木质素降解酶类不同组分以及和小分子活性物质之间协同作用机理,筛选培育高效降解木质纤维素的菌种和木质素降解酶,为实现工业化转化利用木质纤维素奠定基础。     

木质素光催化氧化的产物分析及机理浅析

使用GC(气相色谱)-MS(质谱)联用仪对木质素光催化氧化的产物进行分析,从中检出了香兰素、愈创木基丙酮、愈创木基乙酸、1-羟基-3-愈创木基丙酮等具有较高价值的化合物。在木质素的光催化氧化降解反应中,氧化降解和交联并存,两者是一对竞争反应。木质素的氧化可以经愈创木基丙酮和1-羟基-3-愈创木基丙酮、愈创木基乙醇、愈创木基乙酸而获得香兰素,然后继续氧化成分子量更小的化合物,直至变成水和CO2。愈创木基乙醇的氧化是氧化过程的控制反应。氧化与交联的并存,使得反应过程中木质素的平均分子量呈现出先增大后减小的趋势,相应地分子量分布是先变窄后变宽,而峰值分子量则持续增加。同时交联反应的存在也降低了木质素氧化生成小分子产物的效率,而且反应时间越长,小分子化合物产率越低。     

The methanogenic toxicity of wastewater lignins and lignin related compounds

Lignin derivatives are major components of wastewater streams generated in the chemical processing of wood. The objective of this study was to evaluate the inhibitory effect of various lignins isolated from forest industry wastewaters, and selected lignin model compounds, on methanogenic bacteria. The methanogenic inhibition was determined at 30°C in standard toxicity assays, utilizing anaerobic granular sludge as inoculum. The wastewater lignins differed considerably in their inhibitory activity. Some lignin samples were nontoxic, whereas others caused 50% inhibition at concentrations ranging from 3320 to 5950 mg COD dm^?3. Experiments with ultrafiltered lignins revealed that the toxicity of the inhibitory lignin samples originated from the low molecular weight fraction. In additional studies with low molecular weight lignin model compounds, it was observed that the inhibitory activity of these compounds was related to the functional groups on the aromatic ring. Compounds with aldehyde groups or apolar substituents were highly toxic, whereas those with carboxylic groups only caused significant inhibition at high concentrations. These results indicate that low molecular weight lignin derivatives in forest industry wastewaters are potential inhibitors of anaerobic treatment systems.     

An NMR Comparison of the Whole Lignin from Milled Wood,MWL, and REL Dissolved by the DMSO/NMI Procedure

Abstract

Lignins isolated from pine milled wood, milled wood lignin (MWL), and residual enzyme lignin (REL) were compared using modified thioacidolysis, modified DFRC, gel permeation chromatography (GPC), two‐dimensional Heteronuclear Multiple Quantum Coherence (HMQC) NMR, and quantitative ¹³C NMR. Dissolution of the lignin for solution‐state NMR was accomplished by utilizing the recently reported DMSO/N‐methylimidazole/acetic anhydride solvent system. Contrary to previous reports, comparison of the lignin preparations by thioacidolysis indicated that REL was more structurally similar to the lignin in the milled wood and Wiley wood meal than MWL. Total monomer yields indicated that the MWL was lower in β‐aryl ether content than the other preparations, and this was verified by quantitative ¹³C NMR. NMR analysis indicated that the inter‐unit linkages present in all the lignin preparations are consistent with the present knowledge about lignin biosynthesis. The contribution of minor end group structures in the MWL are further decreased in the milled wood, indicating that they are preferentially isolated as low molecular weight material, possibly generated during the milling process. All other structural moieties were similar in all preparations. GPC data indicated that the milled wood and REL both contain a portion of lignin with a molecular weight of 55,000 g/mol. Data indicate that the inefficiency of the DFRC method may be related to molecular mobility or accessibility in higher molecular weight portions of the lignin polymer.     

The Present Status and Potential of Kraft Lignin-Phenol-Formaldehyde Wood Adhesives

Kraft lignin (KL), a phenolic polymer formed during the kraft pulping process, is presently burned as a low value fuel. For decades, researchers have attempted to use KL as an inexpensive substitute for phenol in phenol-formaldehyde (PF) resins, but no one has produced a commercially satisfactory KL-PF resin. This paper reviews the literature on the present status of KL-PF adhesives and makes recommendations on needed research.

Kraft lignin solutions are complex mixtures which have broad molecular weight distributions, high viscosities, relatively low reactivities, and low solubilities. Attempts to overcome these inherent problems include methylolation of lignin to improve reactivity, the use of co-solvents to improve solubility, and ultrafiltration to yield more homogeneous molecular weight fractions. Future research efforts need to focus on understanding the fundamental chemical and physical properties of kraft lignin and its resins. The search for an economic lignin-based wood adhesive should continue.     

Synthesis and characterisation of polyurethanes derived from waste black liquor lignin

Waste black liquor lignin, obtained from bagasse from the small-scale paper industry, can be utilized for the synthesis of polyurethanes (PUs). Several polyurethane samples were prepared from laboratory black liquor (LBL) by reacting varying amounts of lignin ranging from 5 to 70% (w/v) in poly(ethylene glycol) (PEG) (having molecular weights of 200, 600, 1000, 1500 and 4000) with tolylene 2,4-diisocyanate (TDI). The effects of lignin concentration and molecular weight of PEG on mechanical and thermal properties of PUs obtained were investigated. The polyurethanes synthesised were characterized for different properties such as shear strength, adhesion and thermal stability. The shear strength of PU joints with aluminum was found to decrease with increase in both lignin concentration and molecular weight of PEG. Maximum shear strength, i.e. 3.6 N/mm², was shown by 50% (w/v) lignin in PEG of molecular weight 200.     

碱木质素的微波氧化降解(英文)

The effects of oxidant dosage,oxidation temperature and time on the degradation of soda lignin by hydrogen peroxide with and without the presence of microwave irradiation were investigated.It is found that the oxidative degradation of lignin includes the cleavage of ether bond inβ-O-4 structure,the partial destruction of aromatic ring,and the re-condensation of the degraded lignin.Compared to the conventionally heated oxidation of lignin,the microwave irradiation efficiently facilitates the degradation of the lignin with high molecular weight and the re-condensation of that with low molecular weight at a low oxidant dosage,low oxidation temperature,or a short oxidation time,which leads to the formation of the degraded lignin with narrower molecular weight distribution and lower molecular weight.Additionally,the lignin degraded in the presence of microwave irradiation has the characteristics of higher content of phenolic hydroxyl group,lower content of methoxyl group,and lower degree of condensation,which enhances the reactivity of lignin.Therefore,the oxidative degradation of lignin assisted by microwave irradiation may be a new pretreatment approach for efficiently utilizing the soda lignin.     

Tailoring the molecular and thermo–mechanical properties of kraft lignin by ultrafiltration

This study has shown that ultrafiltration allows the selective extraction from industrial black liquors of lignin fraction with specific thermo‐mechanical properties, which can be matched to the intended end uses. Ultrafiltration resulted in the efficient fractionation of kraft lignin according to its molecular weight, with an accumulation of sulfur‐containing compounds in the low‐molecular weight fractions. The obtained lignin samples had a varying quantities of functional groups, which correlated with their molecular weight with decreased molecular size, the lignin fractions had a higher amount of phenolic hydroxyl groups and fewer aliphatic hydroxyl groups. Depending on the molecular weight, glass‐transition temperatures (T_g) between 70 and 170°C were obtained for lignin samples isolated from the same batch of black liquor, a tendency confirmed by two independent methods, DSC, and dynamic rheology (DMA). The Fox–Flory equation adequately described the relationship between the number average molecular masses (M_n) and T_g's‐irrespective of the method applied. DMA showed that low‐molecular‐weight lignin exhibits a good flow behavior as well as high‐temperature crosslinking capability. Unfractionated and high molecular weight lignin (M_w >5 kDa), on the other hand, do not soften sufficiently and may require additional modifications for use in thermal processings where melt‐flow is required as the first step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40799.     

Studies on ultrafiltration of spent sulfite liquor using various membranes for the recovery of lignosulphonates

Concentration and purification of lignosulphonates (LS) present in spent sulfite liquor (SSL) obtained from the paper industry were carried out through ultrafiltration (UF). The salts of lignosulphonic acid, a product of acid hydrolysis of lignin, are a major component of technical LS. In respect of molecular weight composition, LS represent a polydispersed system with a wide range of molecular weight distributions, from 200 to 150,000 Da. They have good adhesive properties and are used as plasticizers, peptizers, and stabilizers in the industry. The usefulness of LS is dependent on the molecular weight composition. Higher molecular weight LS fractions show properties of amorphous polymeric substances, which may have much industrial use. Diafiltration operation was used for purification of LS. The LS present in SSL were estimated using different membranes (polysulphone, cellulose acetate, fluoropolymer) of varied cut-off sizes (1 K, 5 K, 10 K, 20 K, 25 K, 50 K and 100 K). Sharp cut-off membranes in between 20 K and 100 K Da show close rejections (80-84%). The effect of different operating conditions such as different transmembrane pressures, dilution of SSL, membrane materials and different cut-off sizes was studied on flux and rejection. The effect of sharp and diffused cut-off membranes on flux and rejection was also studied. Continuous diafiltration (CD) was conducted over a high MWCO membrane (GR100K). It was observed that CD with a sharp cut-off membrane gave steady flux and a very good rejection of LS.     

Study on Lignin–Glyoxal Reaction by MALDI-TOF and CP-MAS 13C-NMR

Abstract

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight (MALDI-TOF) mass spectrometry was used to elucidate lignin–glyoxal reactions. The reaction of glyoxal with a low molecular weight lignin involves a number of different reactions; in particular lignin depolymerization and recombination through condensation reactions with glyoxal to form glyoxalene bridges linking both lignin units and mainly fractions of lignin units derived from degradation during depolymerization. The reactive hydroxyglyoxalated lignin is the one species still available for co-reaction for use in wood adhesives. The reactions described increase the viscosity of the lignin as the reaction proceeds towards higher molecular mass species and the condensed species grow in relative proportions. NMR analysis confirmed the existence of functional groups pertaining to structures that are formed from glyoxalation of the lignin observed by some results obtained by MALDI-TOF. MALDI-TOF mass spectrometry appears to be a suitable method for examining lignin–glyoxal reactions.     

Simulated autohydrolysis of aspen milled wood lignin in the presence of aromatic additives. Changes in molecular weight distribution

The reactions between aspen milled wood lignin (MWL) and 2-naphthol, resorcinol, and p-hydroxybenzoic acid were studied under simulated autohydrolysis conditions. The material after the reaction was separated into a dioxane-insoluble fraction (DI), a dioxane-soluble but ether-insoluble fraction (DSEI), and an ether-soluble fraction (ES). In the absence of additive, the lignin first depolymerized and remained solvent soluble, then repolymerized to become insoluble. With 2-naphthol as additive, the amount of DI lignin decreased proportionally to the amount of additive present. When more than 0.1 mole of 2-naphthol/C-9 unit was present, no DI lignin was formed, that is, all the lignin was soluble. Gel permeation chromatography studies indicated that the additive was acting effectively as a blocking agent, preventing lignin repolymerization. Small amounts of resorcinol acted as a repolymerizing agent since two or more fragments of lignin could readily condense with a molecule of the very active additive. As a result of this bridging effect, the amount of DI lignin increased. As the amount of resorcinol was increased, it behaved more like a blocking agent and a reduction in the amount of DI lignin was observed. The presence of a large excess of resorcinol resulted in the formation of soluble lignin only. The molecular weight distributions supported the proposed dual role of resorcinol as a bridging or blocking agent. The use of an excess of p-hydroxybenzoic acid prevented the formation of DI material and resulted in low molecular weight soluble lignin.