生物质主要组分低温热解研究

利用热重分析仪和裂解气质联用仪进行生物质主要组分低温热解特性研究。热重实验结果表明,生物质主要组分的热稳定性为：纤维素>木质素>半纤维素。半纤维素主要热解温度在210℃～320℃,而纤维素和木质素的主要热解温度分别在310℃～390℃和200℃～550℃。裂解气质联用实验考察不同温度对生物质主要组分低温热解产物的影响。半纤维素热解产物主要有乙酸、1-羟基-丙酮和1-羟基-2-丁酮,纤维素热解产物主要包括左旋葡聚糖和脱水纤维二糖,而木质素热解产物主要是邻甲氧基苯酚。     

钾元素对生物质主要组分热解特性的影响

采用热重-红外联用仪对松木及生物质主要化学组分半纤维素、纤维素、木质素的热解特性及钾元素对其热解特性的影响进行了研究.结果表明,半纤维素、纤维素、木质素发生热解的主要温度分别为200~350 ℃、300~365 ℃和200~600 ℃;半纤维热解产物中CO、CO₂较多;纤维素热解产物中LG和醛酮类化合物最多;木质素热解主要形成固体产物,气体中CH₄相对含量较高.三种组分共热解过程中发生相互作用使热解温度提高、固体产物增加,气体中CO增加而CH₄减少.添加K₂CO₃后半纤维素和纤维素热解温度区间向低温方向移动,固体产率提高.K对纤维素作用最明显,CO、CO₂气体与固体产物产率明显增加,醛酮类和酸类物质的产率降低;木质素受K影响相对较小,热解固体产物略有增加,挥发分中H₂O和羰基物质增加;三组分共热解减弱了钾元素的催化作用.     

低品质生物质的热解及低温催化气化研究

利用TG及小型固定床反应器对不同来源的三种低品质生物质--禽畜粪便样品的热解特性及其低温催化气化过程进行了研究。结果表明,各种粪便的主要热解温度为473K~823K。猪粪与禽粪中的有机组分及矿物质组分性质的不同,导致了它们的热解行为存在着较大的差异。在其主要热解区间内,猪粪的热解经历两个明显的失重过程,表明猪粪中的有机成分包括半纤维素、纤维素和木质素。鸡粪中的主要有机组分为纤维素,导致其有一个明显的热解失重过程。鸡粪中含有大量的CaCO₃,在热解过程中受热分解以CaO的形式存在于鸡粪半焦中。禽畜粪便的低温催化气化过程可以将热解焦油全部转化为小分子气相产物和碳,气相产物中有效组分(H₂和CO)产率明显增加。每克猪粪(daf.)低温催化气化过程氢的产量为960mL,鸡粪的氢气产率为680mL/(g鸡粪(daf.))。     

无机矿物质盐对生物质热解特性的影响

生物质灰中碱金属盐的存在对生物质热解行为起着重要的催化作用。选取典型的农业废弃物花生壳作为实验的研究对象,首先分析了不同脱灰方法（水洗和酸洗（5%盐酸和5%硫酸））对生物质热解特性的影响,并采用ICP-AES测试分析不同洗涤方法的脱灰效果;为了进一步考察碱金属盐对生物质热解的影响,采用添加金属盐（K2CO3和CaCO3.M gCO3）分析了脱灰样的热解特性。结果表明,酸洗明显减少了生物质样内的碱金属含量,加快了生物质的热解速度,热解温度升高,少量金属盐的增加有利于生物质的热解。     

烘焙预处理对稻壳燃料品质及热解特性的调控机制研究

研究493–573 K惰性烘焙和有氧烘焙对稻壳元素构成、组分分布、芳香结构、孔隙结构、热解特性和反应动力学的影响规律。结果表明,烘焙温度对生物质燃料品质影响最为明显,氧化剂的加入可以增加生物质燃料品质对温度变化的敏感性。烘焙温度的升高促使生物质中含氧结构逐渐解离,当烘焙条件为573 K的烟气气氛时,样品的H/C和O/C比明显降低(0.188和0.259)。多种氧化剂能够协同调控生物质的官能团结构、活性芳香结构和孔隙结构,温度的升高促使稻壳中羟基减少、活性芳香结构占比逐渐降低和轻质挥发分的解离,在573 K烟气烘焙后活性结构占比达到最小值1.79、比表面积达到最大值295.78 m²/g。稻壳的热解动力学参数可以通过Coats-Redfern近似函数求解,烘焙可以有效提高生物质发生热解的温度和活化能(14.84→28.82 kJ/mol)。相较于惰性气氛和贫氧气氛,烟气气氛能够更加节能、高效地提高生物质的燃料品质和存储稳定性。     

烟草及其主要组分的热分析质谱研究

采用热分析质谱技术研究国产烤烟,白肋烟以及烟草的主成分纤维素,木质素,果胶的热解及热解产物。研究结果表明:烟草热解分为三个阶段,大分子物质分解引起的失重为最主要的失重阶段。果胶,木质素,纤维素的分解主要发生在200至450℃之间。烟气中羧酸类物质,醚类物质,酯类物质生成温度较低,主要来自于纤维素和果胶的分解,而苯系物和酚类物质则需要较高的热解温度,主要来自于木质素的分解。     

基于TG-FTIR的生物质催化热解试验研究

运用热重－傅里叶红外光谱联用技术(TG-FTIR)，以麦秸为研究对象，探讨催化与非催化条件下生物质的热解挥发分析出特性，分析研究热解温度、催化剂种类对生物质热解主要析出产物的影响。通过热重TG和DTG曲线，获得了相关热解特性参数及动力学参数。结果表明，添加NiO和CaO存在两个失重峰，并促进麦秸热解反应进行，降低表观活化能，其中NiO对提高热解析出产率作用更显著。通过红外光谱对热解产物实时测量的分析表明，CO与CO2的析出与失重峰基本一致，而CH4的析出滞后于前两者。添加NiO和CaO有利于减少热解产物中的CO2的浓度，促进挥发分产物CO、CH4的生成。其中CaO更有利于生物质在温度800℃以下的热解性能改善，而NiO在800℃以上具有更好的催化作用。     

利用Py-GC/MS研究温度和时间对生物质热解的影响

以稻壳为原料,采用Py-GC/MS装置对其在不同热解条件下进行快速热解,并对热解气进行在线检测分析,考察了热解温度和时间对生物质热解性质的影响.结果表明,低于450 ℃,随着温度的升高,生物质热解产物种类及其产率均增加,但低温条件下产物种类较少,有利于产物的分离提纯;高于450 ℃,生物质热解产物种类基本稳定,仅在产率上有所变化,当550 ℃时,收率最大.随着热解温度的升高,其对应的最佳热解时间缩短,且生物质低温热解时间延长时热解比高温解热时间缩短时热解更充分.     

生物质化学组分在空气和合成气下的热重行为研究

在热重分析仪上,分别在空气和合成气气氛下,对生物质三种化学组分（纤维素、半纤维素和木质素）的热重行为进行了研究,考察了两种不同气氛下生物质及其三种组分的热化学转化温度区间分布;同时通过合成样品（以不同比例混合的三种组分的混合物）热重曲线的实验值和理论计算值的对比分析,考察了生物质化学组分在不同气氛下热重行为的相互作用。结果表明,在空气和合成气气氛下生物质各种化学组分发生热化学反应从难到易的顺序为木质素 > 纤维素 > 半纤维素,这是由其不同的化学结构决定的,但不同气氛下各组分的具体热重行为存在一定差别。在合成气气氛下木质素及半纤维素在与纤维素的共热解过程中存在明显的协同作用,而在空气气氛下半纤维素及纤维素在与木质素的共燃烧过程中存在一定的协同作用,这与各组分在不同气氛下所处的热化学反应温度区间具有一定的关系。     

生物质三组分热裂解行为的对比研究

在热天平上对比研究了生物质中的纤维素、半纤维素和木质素三种主要组分的热失重规律。结果表明，作为半纤维素模型化合物的木聚糖热稳定性差，在217℃～390℃发生明显分解；纤维素热裂解起始温度最高，且主要失重发生在较窄温度区域，固体残留物仅为6.5%；木质素表现出较宽的失重温度区域，最终固体残留物高达42%。在红外辐射机理试验台上对比研究了三组分热裂解产物随温度的变化规律。三组分热裂解生物油产量随温度变化先升后降。纤维素生物油产量在峰值上最高，但纤维素生物油热稳定性差，高温时挥发分的二次分解最明显；木聚糖和木质素生物油产量较低，表现出较好的热稳定性。三组分热裂解焦炭产量随温度升高而降低，最终纤维素热裂解焦炭产量为1.5%，而木聚糖和木质素分别为22%和26%。三组分热裂解气体产物随温度升高而增长，但在气体组成分布上因三组分的结构上的差异而不同。     

Thermogravimetric analysis of composites obtained from sintering of rice husk-scrap tire mixtures

Summary The disposal of used automotive tires has caused many environmental and economical problems to most countries. We propose the use of rice husk as filler for increasing the value of recycled tire rubber. Thermal degradation of both components and their sintering mixtures is presented in this paper. Thermal decomposition of rice husk occurs in various steps in the temperature range between 150 and 550°C. This complex process is the result of the overlapping of thermal decomposition of the three major constituents common in all lignocellulosic materials, i.e., hemicellulose, lignin and cellulose. Hemicellulose is degraded at temperatures between 150 and 350°C, cellulose from 275 to 380°C and lignin from 250 to 550°C. The degradation process of major constituents of scrap tires or their composites is observed at temperatures between 150 and 550°C. For composites, the addition of rice husk (maximum 25%) produces an increase in the mass loss rate. This effect is higher as the amount of rice husk increases. However, the degradation initial temperature of elastomeric matrix is not affected with addition of rice husk. Apparent kinetic parameters were also studied by the isoconversional Friedman method. We observed that the addition of rice husk produces a decrease in apparent activation energy for low conversions (up to 0.6). For higher conversions this decrease was not so clearly observed.     

Influence of the interaction of components on the pyrolysis behavior of biomass

There has been much interest in the utilization of biomass-derived fuels as substitutes for fossil fuels in meeting renewable energy requirements to reduce CO₂ emissions. In this study, the pyrolysis characteristics of biomass have been investigated using both a thermogravimetric analyzer coupled with a Fourier-transform infrared spectrometer (TG-FTIR) and an experimental pyrolyzer. Experiments have been conducted with the three major components of biomass, i.e. hemicellulose, cellulose, and lignin, and with four mixed biomass samples comprising different proportions of these. Product distributions in terms of char, bio-oil, and permanent gas are given, and the compositions of the bio-oil and gaseous products have been analysed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC). The TG results show that the thermal decomposition of levoglucosan is extended over a wider temperature range according to the interaction of hemicellulose or lignin upon the pyrolysis of cellulose; the formation of 2-furfural and acetic acid is enhanced by the presence of cellulose and lignin in the range 350-500 °C; and the amount of phenol, 2,6-dimethoxy is enhanced by the integrated influence of cellulose and hemicellulose. The components do not act independently during pyrolysis; the experimental results have shown that the interaction of cellulose and hemicellulose strongly promotes the formation of 2, 5-diethoxytetrahydrofuran and inhibits the formation of altrose and levoglucosan, while the presence of cellulose enhances the formation of hemicellulose-derived acetic acid and 2-furfural. Pyrolysis characteristics of biomass cannot be predicted through its composition in the main components.     

生物质组分及温度对闪速热解挥发分的影响

生物质是一种可再生、污染小的自然资源，它可以直接燃烧产生热能，也可以转化为气体、液体燃料或化工原料。生物质热转化技术近年来受到国内外学者的广泛重视。而热转化过程中，热解是第一步，与生物质组分、热解温度、滞留时间等因素有关。热重仪（TGA）是一种研究热解机理常用的方法，它适用于慢速程序升温的热解研究。研究发现，热解条件及生物质种类对反应表观活化能与表观频率因子等动力学参数有很大影响。层流炉闪速加热设备，已经用于煤的热解研究。本文利用自己设计的以热等离子体为热源的层流炉系统，对椰子壳、棉花秆和稻壳粉末进行了闪速热解实验研究及模型理论分析，探讨了生物质化学组分、热解温度和滞留时间对挥发分的影响，为生物质闪速热解提供了一定的基础数据。     

氯化钙催化纤维素热裂解动力学研究

用差示热重分析仪对氯化钙纤维素热裂解动力学催化影响进行了研究。结果表明，氯化钙对焦炭的形成具有强烈的促进效果，使热裂解最终残留物产率从5％提升到10％以上，氯化钙的存在影响到热失重初始阶段活性纤维素的生成，使热重曲线向低温侧移动，并在低温段产生了小的失重速率峰。通过热重分析发现，氯化钙催化条件下纤维素热裂解动力学参数被分为了三段，分别对应于活性纤维素的生成、炭化和活性纤维素转化为挥发分产物三个区间，并依次成为整体失重过程的控制步骤。结合Broido-Shafizadeh机理分析以及与纯纤维素热裂解动力学参数的对比，氯化钙对这三个主要反应步骤都产生了促进效果，其中以催化焦炭的生成最为明显，在促进焦炭化的过程中，降低了气体产物的生成比率。     

蔗渣的热解与燃烧动力学特性研究

利用热重分析仪对蔗渣在不同升温速率下的热解、燃烧失重特性进行了研究。采用Friedman法对反应过程中可能存在的反应机理进行初步判断，蔗渣热解过程由其主要组分半纤维素、纤维素和木质素热解的三个独立的平行反应来描述，相应的反应活化能分别为203.92 kJ·mol-1、238.50 kJ·mol-1和77.11 kJ·mol-1； 蔗渣燃烧过程分为两段，第一段类似于其热解过程，第二段由木质素热解和残焦燃烧共同组成的连续反应，反应活化能为255.57 kJ·mol-1和159.11 kJ·mol-1。通过非线性回归法拟合获得的曲线与实验曲线基本一致，证实了蔗渣的热解、燃烧过程中存在着上述假定的反应机理。     

The fire retardant behavior of various chlorides on cellulose

TG, DTA, and TMA data on the pyrolysis of α-cellulase powder in air is reported together with the modified pyrolysis behavior of the cellulose impregnated with between 2–3% (w/w) of calcium, potassium, sodium and zinc chlorides. The lower temperature of onset of the pyrolysis (as shown by TG and TMA), the increased peak areas of the DTA exotherms, and the elimination of an initial endotherm present in the pure cellulose, all suggest an increased flammability for the impregnated samples. Other properties of the impregnated celluloses however favor a fire retardancy effect; these are an increase in the temperature of the first exothermic peak on the DTA, a reduction in the maximum rate of mass loss, a reduction in the% mass loss occurring in the first mass loss period, and an increase in the% ash remaining at 800°C. The relative effect of the various chlorides is examined and shown to correlate with other data already published.     

Thermal kinetics and morphological investigation of alkaline treated rice husk biomass

Agro waste bio mass are creating challenges for environment in term of air pollution due to improper disposal. Rice milling is the process in which rice husk is produced as by-product. The agro-waste rice husk has tremendous potential to be used either in its raw form or in ash form. The inherent component of this waste cellulose provides enhanced properties in a reinforced composite when used as filler. Rice husk is the hard outer layer and covering rice seed, which makes reinforcement challenging in its original form. Fiber surface treatment significantly improves adhesion with matrix and various thermo chemical properties of filler as well as of composites. NaOH treatment is cost-effective and it ensures the adhesion with matrix by removal of hemicellulose and lignin. The chemical treatment of agro-waste (rice husk) is performed with 5% alkali solutions of NaOH in water. Results are compared with the properties of untreated rice husk for thermal and morphological characterizations. In the present work, we are trying to quantify the impact of chemical treatment on rice husk thermal decomposition and its kinetics. Thermogravimetric analysis and kinetics study of thermal degradation, provide key input towards pyrolysis pattern of rice husk, while FTIR and SEM analysis provide the prospects of this bio filler using a reinforcing agent to develop green composite and productive disposal. The FTIR data helps to find the possibilities of blending different bio fillers and natural fibers to find suitable reinforcing substances. The average activation energy of treated fiber is noted as 137.95 by KAS method and 108.08 by FWO method as compared to 55.56 by KAS method & 54.26 by FWO method for untreated rice husk.