生物质三组分真空热解特性及液化产物成分分析

以微晶纤维素、木聚糖和碱性木质素分别作为生物质3组分(纤维素、半纤维素和木质素)的模型物,利用傅立叶变换红外光谱技术(FT-IR)对生物质3组分结构进行了表征,并对3组分进行了真空热解特性分析,同时利用气质联用技术(GC-MS)对3组分真空热解液化后的生物油进行了成分分析,初步探讨了各组分的真空热解液化机理。研究结果表明,纤维素含有吡喃环、β-糖苷键等特征结构,真空热解时失重区间较窄(250~400℃),真空热解油产率较高(73.79%),产物主要有2,5-二甲基呋喃(9.32%)、2,6-二甲氧基苯酚(5.72%)和左旋葡聚糖(17.04%)等;木聚糖中存在β-糖苷键、阿拉伯糖侧链等结构,支链多,热稳定性差,真空热解油主要含有乙酸(10.11%)、羟基丙酮(18.42%)和糠醛(13.15%)等;木质素中含有较多的芳香族类物质结构,热解缓慢,失重区间较宽(185~550℃),热解终了时固体残留物较多,为29.67%,真空热解油中苯酚(16.24%)、愈创木酚(20.37%)等酚类物质较多。     

杏壳半纤维素的结构表征与热解产物特性

【目的】研究杏壳半纤维素的结构组成、微观形貌以及其热解特性和产物生成规律,为杏壳热化学利用提供理论基础。【方法】采用碱抽提和乙醇纯化方式分离杏壳半纤维素,基于红外光谱、核磁共振、扫描电子显微镜对其结构组成和微观形貌进行表征,利用热重分析、热重红外连用分析杏壳半纤维素的热解特性。【结果】从杏壳中分离出半纤维素的得率为29.44%,红外光谱特征吸收峰主要集中在1 620～600 cm^-1范围内,半纤维素成分以吡喃环结构的木糖为主。核磁共振图谱表明,杏壳半纤维素是以β-D-吡喃木糖形成的木聚糖为主链,在木糖基的C-2位连接4-O-甲基-α-D-葡萄糖醛酸,C-3位连有α-L-呋喃阿拉伯糖。扫描电子显微镜分析显示,半纤维素存在团聚现象,微观形态呈堆砌状的近似球形结构,半纤维素结构有一定的破坏。杏壳半纤维素的主要热解温度范围为210～380℃,在240℃出现一个肩状峰,在308℃出现最大失重尖峰,失重过程在600℃左右结束,800℃时热解残炭量为25.33%。杏壳半纤维素热解时各产物析出量在310℃时达到最高,小分子气体产物主要有CO_2、CO、CH_4,且CO_2和CO量远高于CH_4。【结论】杏壳半纤维素得率为29.44%,是以β-D-吡喃木糖形成的木聚糖为主链,呈堆砌状的近似球形结构,热解产物以CO_2、CO及乙酸、糠醛、丙酮等为主。     

基于TG-FTIR技术的油茶壳及其三组分热解特性研究

以油茶壳为原料,分离提取纤维素、半纤维素和木质素。利用TG-FTIR研究了油茶壳及其三组分在不同升温速率下的热解特性。结果表明:油茶壳及其三组分的热解过程都大致包括干燥、热裂解和炭化3个阶段,随着升温速率的增加,TG/DTG曲线向高温侧移动。热解挥发分主要为H_2O,CO_2,CO和CH_4,以及一些醛类、酸类、酮类、醇类和酚类等有机物。半纤维素对CO_2和CO的产出贡献最大,高温区木质素也产生较多的CO,纤维素的CH_4析出峰强度最高。采用Kissinger法对油茶壳及其三组分热解动力学特性进行研究,计算得到了反应活化能和频率因子。     

基于热重红外的硫酸盐法黑液热解特性分析

为了深入地探讨黑液热解的反应机理以及黑液热解过程中产物的释放规律,采用热重-红外联用(TG-FT-IR)技术对竹子和桉木混合硫酸盐法制浆黑液固形物(BLS)的热裂解过程进行了研究。TG-FT-IR结果显示,BLS热解产物的释放主要集中在500~2 000 s,热解产物主要是CO2、CH4、H2O、CO、醇酚类化合物和醛酮类化合物。BLS的整个热解过程可分为3个阶段,第1阶段的失重主要是原料中结合水的挥发引起的,此阶段的最大失重速率出现在105℃;第2失重阶段主要发生在173~518℃,失重率约为25.19%,主要产物是CO2、CH4、H2O、醇酚类化合物、醛酮类化合物以及少量的CO,此阶段CO2的生成量最大;第3阶段主要发生在722~1 000℃,失重率接近39.05%,产物主要是CO,其它小分子产物的产率都很低。     

基于TG-FTIR和Py-GC-MS分析的椰壳热解特性研究

采用热重-红外光谱(TG-FTIR)和裂解-气相色谱-质谱联用(Py-GC-MS)技术对椰壳粉的热失重、热裂解行为及其裂解产物进行了研究。在对N2和空气气氛下椰壳的TG和DTG曲线进行分析的基础上,采用三维红外光谱对热解过程中气体产物进行在线检测,结果表明:N2气氛下,椰壳的最大失重峰温度(Tm)为347.8℃,固体残余量为32.0%,主要的气体产物是CO2;而空气气氛下椰壳的热解更完全,固体残余量仅为6.5%,且最大热失重温度为282.1℃,释放的气体除了CO2,还有CO、H2O和CH4等。Py-GC-MS分析结果表明:酚类化合物是主要的裂解产物,当温度为400℃时共检测到39种裂解产物,其中酚类化合物12种(GC含量40.0%);当温度为700℃时共检测到56种裂解产物,其中酚类化合物18种(GC含量45.8%)。     

乙酸预处理对木质纤维素结构及性能的影响

对木质纤维素进行乙酸预处理及三段磨浆,分析了不同试样的化学组分,并进行了结构表征。结果显示,经乙酸预处理及三段磨浆后,相思木木片表面出现大量坍塌、裂纹及孔洞,纤维间的结合也变得更为疏松,木片超微结构受到不同程度的破坏。试样中半纤维素含量显著降低,纤维素及木质素所占比例相对增加,纤维素的结晶度指数有所降低。核磁共振波谱(P31NMR)分析结果表明,经预处理及磨浆后,试样中木素的脂肪族羟基含量降低,酚羟基含量增加,酚型/非酚型木素值增加,S/G(紫丁香基/愈创木基型木素)值增加,且随着预处理温度的升高,酚型/非酚型值下降,S/G值增加。热重-红外(TG-IR)分析结果表明,经预处理及磨浆后,DTG曲线在280℃左右少一个肩峰,半纤维素的降解产物木聚糖的特征吸收峰大幅降低,纤维素降解产物的特征吸收峰强度略微增强,木质素热解产物的特征吸收峰强度略有下降。为探讨预处理及磨浆对木质纤维素孔结构的影响,采用低温氮气吸附法(BET)对试样进行分析,结果显示,试样的比表面积增大,大孔所占比例减小,介孔所占比例增加。     

生物质三组分在聚乙二醇辅助热解液化过程中的协同作用

将三大组分的模型化合物微晶纤维素、木聚糖和木质素进行不同配比得到合成生物质,对不同配比的合成生物质样品进行热重(TG)分析,研究了其溶剂辅助热解液化行为,并得出三大组分在溶剂辅助热解液化过程中的协同作用。研究发现:温度低于350℃时,半纤维素对纤维素的降解有一定的促进作用;而高于350℃时,则有明显的抑制作用;半纤维素和纤维素均对木质素的降解起到抑制作用。采用极端顶点法选取典型配比的合成生物质,运用热裂解-色谱-质谱联用技术(Py-GC/MS)探究了合成生物质的溶剂辅助热解液化产物分布,得出了生物质各组分对溶剂辅助热解液化产物分布的影响。结果表明:合成生物质中的木质素含量较高会促进酸类物质的生成,纤维素和半纤维素的溶剂辅助热解液化产物对木质素溶剂辅助热解生成酚类化合物有一定的抑制作用;对于酯类化合物来说,合成生物质溶剂辅助热解液化都生成了较多的酯类物质,生物质三组分不同的配比促进了酯类化合物的生成。     

杨木粉与纤维素热解特性的对比研究

利用热重红外联用的分析方法对杨木粉和纤维素的热解失重特性和产物生成特性进行了对比研究。结果表明,杨木粉与纤维素热解失重的主要阶段在210～400℃范围内,裂解速率均约在350℃时达到最大。由于纤维素与杨木粉组成成分不同,杨木粉发生热失重的时间更早过程更长,而结构单一的纤维素在热失重过程中反应更为剧烈,分解速度较快裂解更完全。在线红外分析结果表明,杨木粉和纤维素热解产生的气体主要为CO2、CO、H2O及饱和小分子烷烃类,由于杨木粉中还有除纤维素以外的组分,使其热裂解过程变得更为复杂。     

树叶组成的热解反应及热稳定性的理论解析

采用多组分平行反应模型并结合非线性最小二乘拟合技术,对树叶在惰性氛围中的热重(TG)试验结果进行动力学过程的解析,理论上跟踪各组分的热解特性和规律。结果表明:随着温度的提升,树叶经历脱水、挥发油类物质析出、半纤维素、纤维素以及木质素的依次降解并形成焦炭(即固定碳)等过程。温度150℃后树叶的热失重速率(DTG)曲线的变化特征主要由半纤维素、纤维素以及木质素的热解叠加而成,与木材中主要成分的热解现象相似。半纤维素热解几乎完全生成气体,对碳形成的贡献很小;纤维素则稍有不同。木质素对固定碳的含量贡献最大。相应地,半纤维素和纤维素的份额对应工业分析中的挥发分含量,而固定碳含量则取决于木质素所占的比例。工业分析中挥发分的含量高意味着对应材料的热稳定性差,即可燃性强;对于固定碳的含量来说则正好相反。研究结果为评估植物的热稳定性以及防火树种的筛选提供了重要的依据。     

澳洲坚果壳活性炭制备的热解特性研究

以澳洲坚果壳为原料,磷酸为活化剂,利用同步热重-差热分析仪(TG-DTA)对澳洲坚果壳的热失重、热效应以及热解机理进行探讨.实验结果表明:不同条件下的澳洲坚果壳的热分析曲线都有两个失重阶段和相应的吸热峰或放热峰.澳洲坚果壳热解温度在200～410 ℃之间,800 ℃时残余量接近零.以磷酸为活化剂浸渍12和24 h的磷酸-澳洲坚果壳炭化和活化温度区间为130～400 ℃,800 ℃时残余量分别为34.431 %和17.743 %.磷酸-澳洲坚果壳较佳的活化温度在400 ℃左右,浸渍时间选择24 h为宜.同时随着浸渍时间的增加,DTG峰值温度呈现向低温推移的趋势,由未浸渍的363.63 ℃降至为243.71 ℃和238.37 ℃.磷酸浸渍对澳洲坚果壳有明显促进炭化作用,使其在130 ℃左右就开始热解炭化,研究结果为澳洲坚果壳活性炭制备提供理论依据.     

Browsing Damage on Pine (Pinus sylvestris and P. contorta) by a migrating moose (Alces alces) Population in Winter: Relation to Habitat Composition and Road Barriers

In Scandinavia, moose (Alces alces L.) sometimes cause severe browsing damage to economically-important pine. Moose-vehicle accidents have spurred construction of fences along roads, and these may interfere with moose migration between summer and winter ranges, or the road alone may be a barrier. If this happens and moose build up along roads, landowners may suffer economically. Therefore, this study investigated whether roads, fences or other factors influence the use of young pine stands by moose. Eighty stands along roads in northern Sweden were evaluated in which individually-browsed branches were counted on 9972 pines. Moose browsing was not significantly related to birch (Betula pendula Roth, B. pubescens Ehrh.) density, nor did it differ between pines (Pinus contorta Douglas or P. sylvestris L.). However, increased pine density, site productivity and proximity to a highway were associated with increased browsing. Further large-scale studies are needed to understand moose habitat selection and the effects of roads.     

Effects of Root Freezing on the Physiology and Growth of Picea glauca,Picea mariana and Pinus banksiana Seedlings Under Different Soil Moisture Regimes

The root systems of 2-yr-old Picea glauca, Picea mariana and Pinus banksiana seedlings were submitted to various frost temperatures during an artificial frost to induce different levels of root damage. Frost-damaged and control seedlings were placed in a greenhouse under high and low soil moisture regimes. Seedling growth and physiology were evaluated periodically. Seedling survival was reduced when root damage reached levels of 60-80%. Root systems of all three species showed partial to total recovery by the end of the experiment. In general, root freezing damage caused reductions in seedling growth, with these reductions becoming less significant over time. Root damage had little to no effect on black spruce and jack pine seedling physiology, while white spruce CO 2 uptake decreased with increasing root damage. Shoot nitrogen content of all three species decreased slightly with increasing root damage.     

Stand Structure in Pine,Spruce and Deciduous Forests: A Comparison Between Finnish and Russian Karelia

This study investigated the stand structure in pine, spruce and deciduous forests in the border district of Finland and Russia. A total of 46 mature forest stands was selected as pairs, the members of each pair being as similar as possible with respect to their forest site type, age, moisture and topography. The stands were then compared between the two countries by means of basal areas and number of stems. The proportions of dominating tree species were 2-12% lower, and correspondingly the proportions of secondary tree species higher, in Russian forests. The density of the forest stock was also higher in each forest type in Russia. The forests in the two countries differed most radically in terms of the abundance of dead trees. The amount was two to four times higher in Russian deciduous and spruce forests, and in pine forests the difference was 10-fold. The stand structures indicated that Russian coniferous stands, in particular, were more heterogeneous than intensively managed pine and spruce stands in Finland.     

Growth and Terminal Bud Formation in Picea abies Seedlings Grown with Alternating Diurnal Temperature and Different Light Qualities

The root collar diameter and the height:diameter ratio are of particular importance in container-grown seedlings where a high density in the containers may produce spindly seedlings. Temperature regimes and light quality are known to affect plant growth. The aim of this study was to identify responses in Picea abies (L.) Karst. seedlings grown with light providing different red:far-red ratios and under temperature regimes with alternating day (DT) and night temperature (NT) from negative (DT < NT) to positive (DT > NT) difference (DIF) between DT and NT. Experiments were conducted in controlled environment chambers and in a daylight phytotron. Only limited thermoperiodic responses appeared in P . abies seedlings with respect to seedling height and dry weight accumulation. The formation of terminal buds, however, was clearly delayed in seedlings grown at negative DIF. The results indicate a requirement for day extension light that is high in far-red, to prevent terminal bud formation under natural short-day conditions. An extended study should be conducted to clarify the minimum level of light intensity and the optimal light quality needed to prevent terminal bud formation under natural short-day conditions.     

CAD与建筑设计的关系

本文分析了CAD在设计中引起的正面和负面影响,并进行了系统的阐述,从而使设计者在应用中能够保持客观的态度。     

Natural Regeneration in Clear-cuts: Effects of Scarification,Slash Removal and Clear-cut Age

The effects of soil scarification (mounding), slash removal and clear-cut age on the natural regeneration in clear-cuts was evaluated using data from four sites in southern Sweden. The treatments were carried out during a good seed and establishment year for birch ( Betula pubescens Ehrh. and B. pendula Roth). Scarification had the strongest positive effect on the density of naturally regenerated seedlings, especially in birch, but also in pine ( Pinus sylvestris L.) and spruce [ Picea abies (L.) Karst]. Slash removal had a positive effect on birch density. No statistically significant effect of clear-cut age was found. In addition, no statistically significant interactions between clear-cut age and scarification or slash removal were found. The ingrowth of field vegetation was the fastest in areas that were not scarified, less rapid in areas scarified on old clear-cuts, and the slowest after scarification in fresh clear-cuts. In conclusion, it may be possible to control the density of birch during a good establishment year for birch. If birch is desired, the best combination of treatments is to remove the slash and scarify; otherwise, these treatments should be avoided.     

Risk Perception Among Non-industrial Private Forest Owners

Based on an enquiry, risk perception among non-industrial private forest owners is described in relation to climate change and forestry hazards. Of the respondents, 11% took action to remedy the effects of climate change. Out of a given set, hazards were ranked according to each respondent's experience of recent substantial financial loss to the estate and in relation to his or her willingness to make investments aimed at risk reduction. For each hazard, the respondent assessed the risk in four classes ranging from very high to negligible risk. Six hazards were considered most problematic in all three aspects: browsing damage, falling timber prices, damage by wind, spruce bark beetle, root rot and pine weevil. A majority of the respondents claimed to take action to reduce the risk associated with at least one hazard, while 35% did not know whether they did. Excluding climate change, the need for decision support was the largest in relation to damage by wind owing to a combination of perceived high risk and a high level of ignorance in relation to whether risk-reducing measures were taken.     

Interactions in decomposition and N mineralization between tropical legume residue components

In situ produced plant residues contain a mixture of different plant components of varying quality. To assess synergistic or antagonistic interactions occurring during the decomposition and mineralization of such mixtures, individual plant parts (stems, leaves, leaf litter and roots) or the mixture of stems, leaves and leaf litter of the agroforestry species pigeonpea (Cajanus cajan) or of crop residues of peanut (Arachis hypogaea) or of the weed hairy indigo (Indigofera hirsuta) were incubated in pots for 19 weeks. Periodically, remaining plant residues were sieved out (>2 mm), weighed and N content as well as soil mineral N determined. Above- and below-ground residues of peanut decomposed fastest and showed the largest N release in agreement with their high N concentration and low-acid detergent fibre (ADF) : N ratio. Hairy indigo was hypothesized to be of lower quality than pigeonpea because of its high-polyphenol content. However, it decomposed faster than pigeonpea, largely because of the higher N and lower lignin concentration of its components. Ranking of individual plant components for N mineralization resulted in the following pattern, leaves > leaf litter > roots > stems. In mixtures of the different plant components a similar species order in decomposition was obtained, e.g. peanut > hairy indigo > pigeonpea. The amount of N released from the mixture was dominated by stem material that comprised 46–61% of the mixture. The interactions in mixtures were relatively small for peanut (generally high-quality components) as well as for pigeonpea (low proportion of high-quality components, i.e. N rich leaf material). However, a positive interaction occurred during later stages of N mineralization in the mixture of hairy indigo as it had a significant proportion of N rich components and absence of highly reactive polyphenols. Thus, for plants with low to intermediate chemical quality attributes, manipulating plant composition (e.g. by varying harvest age, affecting stem and leaf proportions) will be important to obtain significant interactions during decomposition when its components are mixed.     

Pasture production and tree growth in a young pine plantation fertilized with inorganic fertilizers and milk sewage in northwestern Spain

The use of organic waste materials such as milk sewage as an organic fertilizer could have the dual advantages of organic-waste disposal and reduced dependence on inorganic fertilizers. The effects of fertilization with (1) conventional mineral fertilization, (2) milk sewage sludge at 40 kg N ha⁻¹ target rate and (3) no fertilization on pasture production and tree growth were examined in an experiment consisting of two pasture mixtures under a one-year-old Pinus radiata plantation with a density of 2500 trees ha⁻¹. The two pasture mixtures were: (1) Dactylis glomerata L. var. saborto (25 kg ha⁻¹) + Trifolium repens L. group Ladino (4 kg ha⁻¹) + Trifolium pratense L. var. Marino (1 kg ha⁻¹); (2) Lolium perenne L. var. Tove (25 kg ha⁻¹) + Trifolium repens L. group Ladino (4 kg ha⁻¹) + Trifolium pratense L. var. Marino (1 kg ha⁻¹). The experiment began in the spring of 1995 using a randomized block design with three replicates in Castro Riberas de Lea (Lugo, Galicia, north-western Spain). Plot size was 12 × 8 m², with a 1 m buffer strip between plots. Two-year data showed that fertilization with either material had a positive effect on pasture production, with no significant difference between the two fertilization treatments. Tree growth in the milk sewage sludge plot was significantly higher than in the control plots. Inorganic fertilization increased pasture production, but affected tree growth negatively. The results show that milk sewage sludge could be used as a fertilizer in silvo-pastoral systems. This revised version was published online in June 2006 with corrections to the Cover Date.