低共熔溶剂在木质纤维类生物质研究中的应用

低共熔溶剂(DESs)是一种新型绿色溶剂,具有蒸汽压低、合成过程简单、价格低廉、无毒、可生物降解等优点,被认为是最有发展潜力的生物质预处理试剂之一,在木质纤维类生物质领域中的研究应用逐年增加。综述了DESs在木质素、纤维素和半纤维素的溶解、改性以及利用等相关方面的研究进展,分析了DESs氢键供体和氢键受体种类、摩尔比、浓度、处理温度等条件对三大素溶解性能的影响,以及三大素在DESs中酯化、活化和降解等的研究现状。介绍了DESs预处理稻壳、玉米芯、农作物秸秆、木材等木质纤维类原料的研究现状,利用DESs预处理木质纤维类生物质主要是提取并获得高纯木质素组分,同时提高富纤维物质的葡萄糖得率和木糖得率,对DESs预处理木质纤维类生物质的机理进行了分析。重点介绍了利用DESs预处理纸浆等木质纤维类生物质制备纳米纤维素的研究进展。最后,提出了DESs在木质纤维类生物质领域研究的发展方向,以期为DESs应用于木质纤维类生物质资源化利用提供依据和参考。     

木质纤维生物质制备乙酰丙酸及其应用综述

随着资源的枯竭以及环境问题的日益严峻,可再生绿色资源的高值化利用日益受到重视。乙酰丙酸作为一种新一代生物质基绿色平台化合物,可用来制备燃料和高附加值的化学品。笔者详细介绍了木质纤维生物质制备乙酰丙酸的最新研究进展,重点介绍了乙酰丙酸的两条重要制备路径和各种催化体系的制备方法以及乙酰丙酸的应用。生产乙酰丙酸最原始的方法是在水溶液中进行。虽然液体酸制备乙酰丙酸具有反应效率高、反应时间短等优点,但也存在一些缺点,比如酸回收成本高、乙酰丙酸分离困难、对设备的要求高等,而固体酸的应用很好地克服了以上问题。固体酸催化剂制备过程需要考虑的是强酸位点的数量和酸位点的类型,这是生成目标化学品乙酰丙酸的关键因素。离子液体和γ-戊内酯作为绿色溶剂,也应用于乙酰丙酸的生产。此外,还对乙酰丙酸的衍生物5-氨基乙酰丙酸、γ-戊内酯和2-甲基四氢呋喃作了详细描述。最后分析了乙酰丙酸制备面临的可能挑战,提出了未来的研究方向,以期为广大研究者提供有益参考。     

5-羟甲基糠醛制备及其应用研究进展

5-羟甲基糠醛(HMF)被认为是最重要的生物质基平台分子之一,广泛应用于制备精细化学品、关键医药中间体、功能聚酯、溶剂和液体燃料等多功能化合物。目前,HMF的制备是生物质领域研究的热点,大量的研究使得制备HMF的原料和方法得到不断扩展。简单介绍了HMF的主要制备方法及其反应机理,系统综述了制备HMF的催化体系,包括催化过程中所使用的催化剂(无机酸、离子液体、金属氯化物、固体酸及其他催化剂)种类及制备HMF的溶剂体系。归纳了HMF重要衍生物的制备路径及应用,总结了目前研究中所存在的问题,并展望了未来的研究方向。     

湖北木质生物质能源研究

林木生物质能源是可再生能源的重要组成部分,其研究利用对解决湖北省能源、生态环境问题将起到十分积极的作用。本文介绍了湖北省林木生物质能源研究情况,涉及到能源树种种质资源库建设、树木果实榨取柴油、林木废弃物利用以及木纤维转化酒精等方面的研究。结合我省实际情况,提出了建议。     

木质生物质直接液化研究现状及趋势

木质生物质可以再生利用、能量密度相对较高、易运输和储存, 是实现大规模替代石化燃料的理想生物资源。直接液化是近年来迅速发展起来的一门新兴的生物质能利用技术, 具有反应条件较为温和、反应设备简单、产品可部分生物降解等特点, 发展潜力较大。阐述了木质生物质直接液化的分类, 总结了该技术的国内外研究状况, 探讨了木质生物质直接液化技术的发展趋势。     

水热液化制备5-羟甲基糠醛的碳稳定同位素分馏研究

对比了不同碳稳定同位素组成原料在水热液化制备5-羟甲基糠醛(5-HMF)过程中碳稳定同位素分馏特征,研究原料的碳稳定同位素组成对5-HMF产率的影响。结果表明：木薯淀粉水热液化制备的5-HMF的最大产率为33.90%,高于玉米淀粉的29.93%,杨木纤维素(P-C)最大产率为31.00%,高于玉米秸秆纤维素(CS-C)的30.76%,竹粉和杨木的最大产率分别为13.00%和13.80%,高于玉米秸秆和玉米芯(分别为11.60%和12.53%)。在反应时间为15 min时,不同原料的反应速率如下：木薯淀粉0.301 g/(L·min)大于玉米淀粉0.128 g/(L·min),P-C为0.513 g/(L·min)大于CS-C的0.386 g/(L·min),竹粉0.133 g/(L·min)大于杨木0.124 g/(L·min),大于玉米芯0.117 g/(L·min),大于玉米秸秆0.097 g/(L·min)。δ₍¹³C)值较小的原料(木薯淀粉、P-C、杨木、竹粉)反应过程中的δ₍¹³C)值在反...     

假木质素沉积及对纤维素酶解的影响研究进展

木质纤维素类生物质是地球上最丰富的可再生资源。为提高木质纤维素类生物质的转化率,提升纤维素酶的水解效率和可发酵性糖产量,降低纤维素酶的使用量和生物质转化成本,对木质纤维素类生物质进行预处理十分必要;然而,木质素、纤维素和半纤维素之间的天然屏障限制了纤维素酶对纤维素组分的酶解。木质纤维素类生物质预处理主要有物理法、化学法、物理化学法和生物法,目前更多采用质量分数小于4%的稀酸法(如盐酸、硫酸和硝酸等,120～210℃)、高温热水法、蒸汽爆破法和液相水热法等,不同预处理方法对木质素或大部分半纤维素的溶解和去除有利于提高纤维素酶的可及性。木质素对纤维素酶解具有明显抑制作用,通过预处理降低木质素含量有利于提高纤维素酶解效率。木质纤维经稀酸或高温热水等预处理后,Klason木质素相对含量反而会增加。在木质纤维素类生物质预处理过程中,木质素液滴可能以假木质素形式沉积于纤维素表面,使其比天然木质素更加抑制纤维素酶解。本研究首先概述生物质预处理过程中木质素液滴和假木质素的形成过程,提出假木质素产生的可能机制,并对其组成和性质进行综述;然后阐述木质素液滴和假木质素对木质纤维酶解的影响;最后总结假木质素形成的调控策略。假木质素的形成过程属于非均相反应过程,受传质扩散(分子水平)和流动(宏观统计水平)的影响,可从介尺度行为研究假木质素的形成机制,同时建立相关模型和理论实现其科学的定量描述和定向调控,这不仅有利于木质纤维素类生物质炼制工艺的发展,也有利于促进跨学科科学规模的形成。     

木质生物质能源技术的发展创新

阐述了木质生物质能源技术的发展及目前在我国的应用;指出了我国木质生物质能源未来的发展方向。     

香樟木屑真空热解蒸气催化前后产物对比分析(英文)

在两段式反应器上开展了对香樟木屑真空热解蒸气的在线催化提质研究。对比分析了催化前后各相产物产率和气体组成的变化,以及催化前后液相产物理化特性和化学组成。结果表明,催化后液相产物产率降低,但生物油出现分层,上层为油相,下层为水相。油相的H/C物质的量之比、pH值和高位热值(湿基)分别为1.712、4.93和37.15 MJ/kg;油相中烃类和轻质酚类等目标产物含量明显增加,而酸类、醛类和酮类等具有腐蚀性和不稳定性的化合物含量则显著降低,燃料品质较生物原油有显著提升;水相中仍含有少量腐蚀性和不稳定化合物,但其干基的高位热值达32.98 MJ/kg,除去水分后亦可将其用作替代燃料。热解蒸气中非目标产物在HZSM-5分子筛的活性位点上发生转化反应生成期望化合物,各类反应遵循碳正离子反应机理。     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

Determination of nitrobenzene oxidation products by GC and1H-NMR spectroscopy using 5-iodovanillin as a new internal standard

The nitrobenzene oxidation method was modified to obtain more reproducible data and more structural information about lignin, not only by gas chromatography (GC) but also by proton nuclear magnetic resonance (¹H-NMR) spectroscopy for quantitative determination of the oxidation products and to simplify the procedures. The nitrobenzene oxidation mixture was directly extracted after acidification without preextraction of by-products. The direct extraction made the extractive step easy and gave reproducible data. 5-Iodovanillin was selected as a new internal standard. The reason for this selection was that 5-iodovanillin did not exist in the nitrobenzene oxidation products from any plant species and had an aldehyde group whose peak did not overlap with the other aldehyde peaks on an¹H-NMR spectrum. Thus, the use of 5-iodovanillin enabled us to quantifyp-hydroxybenzaldehyde, vanillin, and syringaldehyde in oxidation products on the basis of¹H-NMR analysis as well as GC. Furthermore, more information about the condensed structure of lignin was derived by comparing the¹H-NMR and GC analyses.Part of this work was presented at the 42nd Annual Meeting of the Lignin Symposium, Sapporo, October 1997     

Estimation of the biomass of fine roots and mycorrhizal fungi: a case study in a Japanese red pine (Pinus densiflora) stand

As part of a study on soil carbon flow in forest ecosystems, the biomass of fine roots (2.0mm in diameter) and root-associated fungi, including ectomycorrhizal fungi, were estimated in the summer season in 1998 at a Pinus densiflora (Japanese red pine) stand in western Japan. Fine roots of pine were classified into three categories: class I roots (0.5–2.0mm in diameter), long class II roots (long roots with diameter 0.5mm; II_L), and short class II roots (short roots with diameter 0.5mm; II_S). Total biomass of fine roots (I + II_L + II_S) at this stand was estimated to be 91.0gm^–2, about 23% of which was class II roots (II_L + II_S). Ergosterol, which is a component of fungal membranes, was analyzed to estimate the biomass of root-associated fungi in roots. In the upper soil layers (from the surface to 13.4cm in depth), ergosterol contents in the class I, II_L and II_S roots were in the ranges 43.1–82.2, 126.1–196.3 and 271.2–321.0µgg^–1 root DW, respectively. The ergosterol content was converted to fungal biomass using the median (minimum–maximum) value of ergosterol concentration reported for ectomycorrhizal fungi. Root-associated fungal biomass in this stand was estimated to be 2.0 (0.5–9.6) gm^–2. The data suggest the biomass of ectomycorrhizal fungi in the P. densiflora stand is small compared with that in other forest ecosystems.     

A methodology for the description of border hedges and the analysis of variables influencing their distribution: a case study in western Kenya

This paper presents results from a survey of border hedges on farmland in western Kenya. The survey covered 160000 ha of high potential land in eastern Siaya District and Vihiga District of western Kenya. The survey attempted to widen the knowledge of the typology, the biomass and the parameters influencing the spatial distribution of hedge types. Spatial analysis was used to delimit hedge type sub-regions (using cluster analysis) and to identify the variables influencing the spatial distribution of hedge types (using discriminant analysis). It is demonstrated that a complex association of variables is influencing the subdivision of the two districts in hedge type sub-regions in which ethnicity, population density, area in woodlots and ecological variables like elevation, rainfall and soil fertility are important variables. These variables are influencing each other and are responsible for the contrasting situation in Vihiga and Siaya District. Border hedges have similar functions in both districts (demarcation of land, to prevent cattle from entering), nevertheless species composition and dimensions differ remarkably in both districts. Border hedges in Siaya District are poorly managed or not managed at all. In Vihiga District people are used to manage their hedges. Agroforestry techniques, for example techniques based on frequent pruning of border hedges, have a high chance in being successful in this district because no additional investment in labour or time is required. The spatial distribution in the amount of biomass is strongly correlated with the distribution in the per cent area ground cover of border hedges. This means that secondary data on the area in hedges derived from aerial photographs can serve as a useful indicator of the biomass present. As a result, the most difficult part of the field survey, the destructive sampling for the determination of the biomass, can be eliminated, making general surveys considerably easier. This revised version was published online in June 2006 with corrections to the Cover Date.     

Windbreaks in southern Patagonia,Argentina: A review of research on growth models, windspeed reduction, and effects oncrops

In Patagonia, where strong winds are a constraint to agricultural production, live windbreaks are often planted in agricultural fields to protect crops, livestock, and soils from wind hazards. The major factors that determine the efficacy of windbreaks are height, porosity, orientation, length, and location in the landscape. A review of the research on the effect of live windbreaks during 1993 through 2000 is presented in the paper. Porosity and distance from windbreak were found to have major effects on relative windspeed reduction. The greatest degree of protection was for dense windbreaks (windspeed reduction of 85%) at 1H (1H = a distance of one tree height, leeward of the windbreak). Different crops showed a differential yield response to wind stress. The production of garlic (Allium sativum) was not significantly affected by wind. Tulip (Tulipa sp.) bulb yield decreased on average by 25% between 2H and 17H. The production of lucerne (Medicago sativa) at 1H was 40% higher than lucerne grown in open conditions. In contrast, strawberry (Fragaria sp.)and cherry (Prunus avium) were more sensitive to the effect of the wind. Dendrometric models (diameter, site index, volume and crown dynamics) were developed to define the wood potential productivity that could be expected from different site qualities. The prediction of height growth as a function of age, allows the estimation of the area protected by the windbreak. An economic assessment based on realistic estimates of shelter benefits is required to encourage the development of windbreak systems that could also offer other benefits, including erosion control and timber production.This revised version was published online in November 2005 with corrections to the Cover Date.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate III: Successive treatment of acid hydrolysis lignin and a lignin model compound by phenolation and arylsulfonation*

The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO₃Na/C₉ C₆. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C₉. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both.     

泡桐速生丰产施肥技术研究进展

综述了近几十年来我国泡桐林施肥技术的研究概况,理清了未来的研究热点和方向,重点阐述了林木配方施肥的理论基础及立地养分效应配方施肥模型。综合国内外现有研究成果,提出了建立泡桐林施肥基础数据库、减小林木施肥所造成的环境污染、实现环境保护的新观点,并指出我国泡桐速生丰产林施肥的发展方向是按立地类型、分生长阶段的目标产量及效益下的测土配方施肥。     

People,trees and projects: a review of CARE's activities in West Africa

CARE, in collaboration with a range of government agencies, has been active for over 15 years in agriculture, agroforestry and natural resource management projects in West Africa. Many of these projects evolved from emergency food distribution activities during the drought years of the 1970s and 80s. A number of valuable lessons are now emerging, particularly in relation to agricultural and agroforestry activities in the Sahelo-Sudanian and Sahelian zones. In the context of CARE's orientation and capabilities as a non-governmental development agency, these lessons are used to construct a framework for prioritizing future agriculture and natural resource management activities in the region.