Characterization of the products resulting from ethylene glycol liquefaction of cellulose

The composition of liquefied cellulose in the presence of ethylene glycol (EG) was studied. The liquefied products were fractionated and analyzed with highperformance liquid chromatography and nuclear magnetic resonance. EG-glucosides were detected as the only saccharides and 2-hydroxyethyl levulinate as the highly decomposed compound derived from cellulose. Quantitative analysis of the EG-glucosides and levulinic acid that comes from the levulinate shows the presence of the following mechanism in the EG-liquefaction of cellulose. First, cellulose is degraded and produces considerable amounts of EG-glucosides during the early stage of liquefaction. Then, when liquefaction is prolonged, the glucosides are decomposed, leading to a large quantity of levulinates.     

木粉及其组分的多元醇酸催化热化学液化

分别将木粉、纤维素和木质素在乙二醇中进行热化学液化。研究结果表明木粉中纤维素的非结晶区、木质素和半纤维素首先被液化,而纤维素的结晶区较慢被液化,到液化反应中期基本降解完全,液化产率高于97%。利用在线红外光谱仪跟踪检测了整个液化反应过程,结合GC-MS结果发现:乙二醇在反应过程中脱水生成了二甘醇和三甘醇。在液化反应中,纤维素的糖苷键断裂后生成葡萄糖苷结构,随后葡萄糖苷中的吡喃环也被打开,生成的活性中间体相互反应或与乙二醇反应生成了如3-(2-甲基-[1,3]-二氧戊环-2-基)-丙酸乙酯、乙酰丙酸丁酯等酯类;木质素的苯丙烷结构主要降解为苯酚、2,6-甲氧基苯酚等芳香族衍生物,因此木粉液化产物是聚醚/酯混合多元醇。     

小麦秸秆加压液化制备乙酰丙酸乙酯

以小麦秸秆为原料,浓硫酸为催化剂,乙醇为溶剂进行液化实验,分析了液化产物的组成,考察了不同条件对目标产物乙酰丙酸乙酯(EL)得率及液化率的影响。结果表明:在浓硫酸用量10%、反应温度190℃、反应时间60 min,液固比为18∶1(g∶g)条件下,小麦秸秆的液化效果较好,液化率为75%,此时EL的得率为18.11%;经红外光谱分析可知秸秆在反应过程中发生降解;液体产物中包含醛、酮、酯、酚、酸类等多种含氧化合物,纤维素降解生成葡萄糖、葡萄糖苷、乙氧基甲基糠醛等中间产物,并最终转化为乙酰丙酸乙酯。     

Liquefaction and product identification of main chemical compositions of wood in phenol

To clarify liquefaction ratios and their construction variations of the main chemical compositions of wood in phenol using phosphoric acid as a catalyst, the chemical ingredients of wood such as holocellulose, cellulose and lignin, were measured and extracted according to GB methods. With Fourier transform infrared （FTIR）, the product identification of reactant before and after liquefaction in phenol was investigated. The molecular weights and their distributions of the liquefaction results （acetone soluble parts） were studied by gel permeation chromatography （GPC）. Results show that the molecular weights and their distributions of poplar and Chinese fir are almost the same. In poplar, the distribution of cellulose is the largest, and that ofholocellulose the smallest after liquefaction. For Chinese fir, the distribution of holocellulose is the largest, and that of cellulose the smallest. After liquefaction of poplar cellulose, the change bands of FTIR spectrum observed below 1 600 cm^-1, can be attributed to new substitute groups. The same is true for poplar lignin. For Chinese fir, the spectra of liquefaction results of all chemical compositions differ from that of wood meal. This reveals the more activity groups were produced because of the reactions between Chinese fir and phenol. The research shows that the liquefaction ratios of poplar decrease in the following order： holocellulose 〉 lignin 〉 cellulose, and those of Chinese fir in the order： lignin 〉 cellulose 〉 holocellulose.     

Liquefaction of wood (Metasequoia glyptostroboides) in allyl alkyl imidazolium ionic liquids

The results of wood liquefaction by allyl alkyl imidazolium ionic liquids indicated that wood (Metasequoia glyptostroboides) without any pretreatment is liquefied in ionic liquids at temperatures below 100°C within 40 min. Acidic ionic liquids show low residue even at 70°C and 30 min. The liquid/wood ratio of the reactants affects the reaction course. After the reaction is over, ionic liquids can be separated from the products and recycled at least five times maintaining good liquefaction activity. The suitability of the ionic liquids for wood liquefaction is ascribed to the functional groups of the ionic liquids. Influencing factors of wood liquefaction are discussed in relation to the ionic composition of the ionic liquids.     

Characterisation of the curing of liquefied wood by rheometry, DEA and DSC

Liquefied wood is a naturally based product which has the potential to be used as an adhesive. The bonding of wood with liquefied wood requires a high enough temperature to cure the liquid polymers and achieve bond strength. Dielectric analysis, rheometry and differential scanning calorimetry were used to analyse the curing process of low solvent liquefied wood. For the liquefaction, ethylene glycol was used as a solvent and sulphuric acid was used as a catalyst. The dielectric analysis was used for in situ measurements of the curing of liquefied wood during the bonding of wood. It was found that curing started after a temperature of 100 °C had been reached in the bond. This is correlated with the water evaporation and the diffusion of water and ethylene glycol from the liquefied wood into the wood substrate. Rheological measurements proved the influence of the substrate on the curing of the liquefied wood during bonding. Differential scanning calorimetry showed that the curing of liquefied wood occurs in two parts: first, the initial elimination of water and ethylene glycol from the liquefied wood, and then the chemical reaction of the liquefied wood at higher temperatures.     

基于微波液化的木质纤维素组分分离和转化——纤维素组分的理化和酶解性质

【目的】将微波加热与甘油利用相结合的综合炼制工艺用于木质纤维素生物质预处理,探索其在燃料乙醇制备中的可行性,为实现经济可行、经济有效的木质纤维素生物质酶解预处理技术和生物燃料生产提供基础信息。【方法】以银腺杨、日本落叶松、刚竹和柳枝稷为试验材料,采用微波液化法对其进行液化处理,将液化产物分为纤维素、半纤维素和木质素组分,并对纤维素纤维组分进行综合表征。【结果】化学分析结果表明,纤维素纤维具有较高的葡聚糖含量;红外光谱显示,木质素和半纤维素的信号逐渐减弱,说明半纤维素和木质素经液化处理后有效脱除;XRD分析结果表明,纤维素纤维结晶度高、表面积大。【结论】相比原木质纤维素生物质,银腺杨、日本落叶松、刚竹和柳枝稷4种原材料纤维素纤维的酶解糖化效率均有不同程度提升(最高酶解转化率可达70%),液化固体产物--纤维素纤维在制备燃料乙醇中具有广阔的潜力和前景。     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

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

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.Part of this report was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003     

竹材催化转化制备乙酰丙酸(酯)研究进展

中国竹资源丰富,但在实际生产过程中其加工剩余物并未得到充分利用,而乙酰丙酸（酯）作为环境友好且可持续的化学品具有广阔的应用前景,在化工生产过程中利用竹材制备乙酰丙酸（酯）具有很大的潜力。文章回顾了竹材制备乙酰丙酸（酯）的催化转化方法,对近年来竹材催化转化制备乙酰丙酸（酯）的研究进行了综述。从催化转化机理、产物收率、影响因素等角度对Brønsted酸、离子液体、固体酸以及金属盐等4种催化体系的特点进行了分析和对比,概括总结了不同转化方法的优势和不足,并根据现有转化方法中仍存在着的产品高效分离困难、催化剂污染较大以及副产物难以利用等问题,对未来研究方向提出展望,以期为今后的研究提供参考。     

杉木粉液化与液化产物树脂化的研究

以硫酸为催化剂、苯酚为液化剂采用溶剂热法对杉木粉进行液化,用杉木粉液化产物制备出酚醛树脂;考察了反应温度、反应时间、液比(苯酚-木粉的质量比)和催化剂用量对杉木粉液化效率的影响,并初步探讨了液化产物残渣率对所制酚醛树脂性能的影响。实验结果表明,杉木粉液化的最佳工艺条件是:反应温度160℃,液化时间12 h,液比值3,催化剂用量3%,在此条件下残渣率约为10%。液化产物残渣率的测定表明,升高反应温度、延长反应时间、增加液比和催化剂用量可以降低残渣率,提高液化效率;液比值为0.5~1.5时残渣率随液比增加而显著降低,催化剂用量为0.5%~2%时液化效率的变化明显。红外光谱结果表明,由液化产物所合成的酚醛树脂中羟甲基含量较高。液化产物残渣率低时制备的酚醛树脂残碳率较高。     

Reaction behavior of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

Reaction of Japanese beech (Fagus crenata) in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose, was investigated. Although both lignin and polysaccharides such as cellulose and hemicelluloses can be liquefied at a treatment temperature of around 100°C, the liquefaction of polysaccharides mainly occurs at the beginning of the treatment with [C2mim][Cl]. Cellulose crystallinity in the wood was gradually broken down as the treatment continued. The solubilized polymers were depolymerized to low molecular weight compounds. The results indicate that [C2mim][Cl] is an effective solvent and reagent for the liquefaction of wood components and subsequent depolymerization of them. Part of this report was presented at the 58th Annual Meeting of the Japan Wood Research Society, Tsukuba, April 2008     

Preparation and Characterization of the Phenolated Wood Using Sulfuric Acid as a Catalyst Ⅱ. FT-IR and GPC Characterization

By means of gel permeation chromatography analysis, the molecular weight of liquefied wood under different reaction conditions was investigated to trace the change in the structural characteristics of the liquefied wood. The insoluble residues were analyzed by Fourier transform infrared to investigate the liquefaction order of three main wood components. The results indicate that both reaction temperature and reaction time could affect the molecular characteristics of the liquefied wood obtained. The molecular weight of liquefied Chinese Fir wood is higher than that of liquefied Poplar wood under most of reaction conditions. During wood liquefaction, lignin is liquefied firstly. Hemicellulose is liquefied in the middle stage and cellulose is the most difficult to be liquefied.     

Influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

The influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), has been systematically studied. The wood samples were treated with [C2mim][Cl] at 120°C under various atmospheres such as oxygen, nitrogen, and carbon dioxide, both dried and humidified. The percentage of residue after the treatment shows that oxygen considerably accelerates the liquefaction of wood in [C2mim][Cl], and humidity hardly affects liquefaction under any atmosphere. Gel permeation chromatography (GPC) and high performance liquid chromatography (HPLC) analyses on the solubilized compounds in [C2mim][Cl] indicate that oxygen and humidity enhance the depolymerization of the wood component. Thus, the reaction atmosphere was revealed to influence, and 1be capable of controlling, the reaction of wood in [C2mim][Cl].     

Morphological changes in sugi (Cryptomeria japonica) wood after treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride

We investigated morphological changes in wood tissues of sugi (Cryptomeria japonica) resulting from treatment with the ionic liquid 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which dissolves cellulose. Treatment with [C2mim][Cl] caused dissociation and distortion of tracheids in latewood, but not in earlywood. This difference was due to the difference in swelling behavior of the cell wall between earlywood and latewood. Many pit membranes in bordered pits were broken by treatment with [C2mim][Cl]. In addition, some chemical changes in wood components, such as cellulose and lignin, occurred before significant disruption or destruction of the cell wall. Our results show that the reaction of wood liquefaction by [C2mim][Cl] treatment is not homogeneous, both from chemical and morphological viewpoints.     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.     

超声波-微波对杉木锯屑液化的强化效应研究

以正辛醇为溶剂、浓硫酸为催化剂,探讨了超声波-微波（UW-MW）辅助对杉木锯屑液化的强化作用,考察了工艺参数的影响,并对液化产物进行了表征分析。研究结果表明：超声波-微波具有很好的传质传热强化效应,与传统液化相比,杉木锯屑超声波-微波辅助液化反应时间从60 min缩短至20 min,液化率提高了5.24%。在溶剂与锯屑质量比值6、催化剂H₂SO₄浓度0.6 mol/L时,杉木锯屑液化率达到64.30%;适当添加γ-戊内酯可提高液化率,γ-戊内酯用量40%时液化率达81.17%。液化过程中,少量熔融状物质沉积在残渣（SR）表面,阻碍了原料的进一步液化;纤维素与半纤维素的降解产物主要为小分子糖类等物质,富集在水相产物（WS）中;木质素的降解产物主要由芳香族等物质组成,分布在生物油（BO）产物中。     

Sorption and thermodynamic properties of wood of <Emphasis Type="Italic">Pinus canariensis</Emphasis> C. Sm. ex DC. buried in volcanic ash during eruption

The hygroscopicity and thermodynamic properties of Pinus canariensis wood buried in volcanic ash, dating from 1100 BC, were studied and compared with recently felled juvenile and mature wood of the same species. The sorption isotherms were obtained by the saturated salt method at 35 and 50 °C. The isotherms were fitted using the Guggenheim–Anderson–de Boer model. The thermodynamic parameters were determined following the Clausius–Clapeyron integration method. To understand the behaviour of each type of wood, the chemical composition, infrared spectra and X-ray diffractograms were determined for each sample. The mature wood has a higher sugar content and lower extractive content than the juvenile and the buried wood. For both temperatures, the isotherm of the mature wood is above the isotherm of the juvenile wood and this, in turn, is above the isotherm of the buried wood, primarily influenced by the higher cellulose and hemicellulose contents and lower extractives content in the mature wood, resulting in a higher number of accessible –OH groups. Degradation of the buried wood due to high temperatures explains why its isotherms are below the isotherms of the recent wood. The energy involved in the desorption process is greater than in adsorption. Similarly, more energy is involved in the mature wood than in the juvenile wood, and the energy involved in the juvenile wood is greater than in the buried wood.     

森林资源的化学利用

本文阐述了利用森林资源生产化学产品的必要性和重要意义,讨论了作为化工原料的可行性。对化学利用的方法、主要产品及其用途,需要解决的技术问题、利用现状和可能的发展作了简单介绍。针对我国的具体情况,就开展化学利用的研究提出了初步建议。     

Effect of acetylation on the chemical composition of hornbeam (Carpinus betulus L.) in relation with the physical and mechanical properties

Common hornbeam (Carpinus betulus L.) is a highly underused wood species despite its great hardness, strength, wear-resistance and toughness. It is mainly used as firewood in Hungary because of its wood defects, irregular shape and low-dimensional stability. These wood defects and small breast height diameter result in a low yield. It is non-durable outdoors as it tends to turn grey, crack and be attacked by wood-decaying organisms. Indoors it lasts for hundreds of years. One technology that could improve the stability and durability properties is acetylation. Hornbeam was acetylated with the Accoya® method under industrial conditions. The aim of this research was the assessment of acetylation affecting the chemical properties of hornbeam wood and how these are related to the change in physical and mechanical properties. Main wood constituents (cellulose, hemicellulose, Klason lignin, extractives and ash content) were determined and compared. Chemical parameters related to the degradation of structural polymers were also evaluated (total phenolic and soluble carbohydrate contents, pH and buffering capacity, furfural, levulinic acid, formic acid, acetic acid). Structural changes in acetylated wood and in the Klason lignin fraction were also assessed using FTIR spectroscopy.