热重红外光谱法考察木质生物质综纤维素热转化特性

热重红外光谱联用考察了木质生物质纤维素、半纤维素以及综纤维素的热转化特性,并与微晶纤维素和木聚糖等模型化合物进行了对比分析。应用三维扩散模型计算了活化能、指前因子等热转化动力学参数,拟合效果良好。通过分析气相产物三维IR图谱,在最大失重速率附近,观察到了H₂O,CO,CO₂,CH₄和含氧化合物的明显特征峰。讨论了主要气体产物可能的生成途径,发现其产量顺序为CO₂>H₂O>CO≈CH₄。综合分析得出,综纤维素的热转化过程是纤维素主导下、纤维素和半纤维素综合作用的结果。     

超临界水中纤维素气化制氢的实验研究

在500～650℃、20-35 MPa条件下,对超临界水- 纤维素混合物进行气化反应实验,发现压力、温度、反应停留时间、物料浓度等参数对纤维素的气化率和气态产物的组成都有明显影响,得出上述因素的影响规律。结果表明纤维素在超临界水中具有较高的气化率,生成以H2和CO2为丰要成份的气态产物。     

木质纤维素类生物质超低酸水解试验及产物分析研究

在自行设计的木质纤维素类生物质超低酸水解装置上,结合以木聚糖和定量滤纸为模化物得到的半纤维素和纤维素水解的最佳工况,对白松、速生杨和玉米秸秆这三种在我国分布较为广泛的木质纤维素类生物质原料进行了高压液态水和超低酸水解相结合的两步水解研究,分别得到41．78％、57．84%和53．44％的原料转化率和39．28％、42．83％和23．82％的总还原糖转化率,并以HPLC定性了糖类产物,对产物中的低聚糖和单糖含量傲了对比,最后对速生杨水解残渣做了分析。     

纤维素热解过程的分子动力学模拟

本文利用 PM3 方法对生物质主要组分纤维素进行了结构优化并得到了一系列的结构参数.对不同力场下,聚合度为 9 的纤维素单链热分解进行了分子动力学方法模拟研究,得到不同力场下的模拟过程中参数.通过与相关生物质热解实验结果对比,利用 Amber 力场模拟得到的结果与实验值吻合较好.基于 Amber 力场并结合量子力学对纤维素单元热解过程进行了研究,模拟得到纤维素单元分子链在加热过程中的主要分解温度范围、断键顺序以及一次热解的基团,并对一次产物进行了分析.     

一维棒状纳米纤维素及光谱性质

采用稀酸预处理纤维素浆粕,结合高压均质的物理方法,制备出一维棒状纳米纤维素.通过傅里叶红外光谱(FTIR),X射线衍射(XRD),热重分析(TGA),原子力显微镜(AFM)和透射电镜(TEM)等方法对纳米纤维素光谱性能和形貌结构进行了表征.结果表明,制得的纳米纤维素与纤维素浆粕具有相同的红外特征官能闭,但分子内氢键缔合作用被部分破坏.纳米纤维素与纤维素浆粕同属于纤维素I的晶形类型,结品度从59%提高至70%,仍保持结晶区与无定形区共存的状态.纳米纤维素的分解温度为330℃,热稳定性低于纤维素浆粕,失重温度从292℃持续至500℃,有两个明显失重阶段.纳米纤维素长度为数百纳米,宽度为数十纳米的棒状形态,易产生团聚现象.     

纤维素、木质素含量对生物质热解气化特性影响的实验研究

本文采用化学方法测定了六种生物质中纤维素和木质素的含量,通过热重研究了实际生物质及用纤维素、木质素按一定比例混合模拟生物质的热解和气化特性,并结合电子扫描电镜(SEM)对焦样进行了微观形貌分析.结果表明:在本文所选择的生物质中纤维素的含量高于木质素,两者一般在55%～85%和10%～35%.生物质热解分为纤维素热解和木质素分解两个阶段,应于气化过程中挥发份析出和焦炭气化.在热解过程中,首先纤维素发生热解呈现快速失重过程,接着木质素缓慢热解.实验发现生物质中纤维素含量越高,热解反应速率就越大;反之,木质素含量越高,热解反应速率越小.通过对焦形貌与气化研究,发现气化特性与生物质中纤维素和木质素的含量有着密切联系.因此纤维素、木质素含量是影响生物质热解气化特性的重要因素之一.     

基于热重红外联用分析的生物质热裂解机理研究

利用热重红外联用技术在线分析研究了白松在不同升温速率下的热裂解行为,结果表明木材的热裂解可归结于纤维素、半纤维素和木质素三种主要组分的热裂解。白松的热裂解产物主要有酸类、醇类、醛类、酮类、酯类、水分和小分子气体等。在线红外分析结果表明白松热裂解过程中先析出游离水,随后发生解聚和脱水反应,主要的苷键和碳碳键断开形成各种烃类、醇类、醛类和酸类等物质,随后,这些大分子物质又二次降解为一氧化碳为主的气体产物。     

纤维素和甲醇共催化热解制备对二甲苯

本文对纤维素和甲醇在不同金属氧化物改性的ZSM5催化剂作用下共催化快速热解实现一步制备可再生对二甲苯的过程进行了研究. 结果表明,镧改性的ZSM5催化剂是生产生物基对二甲苯的有效催化剂. 对二甲苯的选择性和产率主要由催化剂酸性、反应温度和甲醇含量决定. 在20%La₂O₃-ZSM5(80)催化剂作用下,纤维素与33wt%甲醇共催化快速热解获得对二甲苯的最高收率和对二甲苯/二甲苯的最高比率分别为14.5 C-mol%和86.8%. 本文详细研究了催化热解过程中催化剂的失活,基于产物的分析和催化剂的表征提出了由纤维素制备对二甲苯的可能反应途径.     

三维金属有机骨架/石墨烯水凝胶均相降解纤维素为小分子酸的研究

通过在三维还原氧化石墨烯孔径中原位生长ZIF-8纳米粒子,制备了三维金属有机骨架/石墨烯催化剂.这种ZIF-8/rGO纳米复合材料同时具有介孔和微孔,并且拥有高比表面积和大量催化位点,是生物质转化的理想催化剂.将纤维素溶解于氢氧化钠水溶液中,在水热条件下,使用这种催化剂,纤维素可以被充分降解转化.纤维素转化率可以达到100%,其主要产物是甲酸,产率最高可达93.66%.催化剂还可以被回收,重复使用依然具有很好的催化效果.     

纤维素拉曼光谱的单体仿真方法研究

纤维素是由葡萄糖组成的大分子多糖,是世界上最丰富、最便宜、最容易获得的天然聚合物。纤维素作为最古老最丰富的天然高分子在研究中备受关注,纤维素的可控性取决于其分子量、大小和结构,而拉曼光谱具有“指纹特性”,可以对不同的纤维素纤维进行鉴别,也能对历史老化的纺织纤维材料进行鉴别。然而纤维素作为大分子多糖对其做理论仿真较为困难,该研究提出采用基本单元模拟大分子光谱这一方案,使用纤维素单体仿真拉曼光谱来分析纤维素大分子的光谱性质。使用Gaussian 16软件基于密度泛函理论,在B3LYP/6-31g(d, p)的基组条件下,计算了不同外电场(-0.01～0.03 a.u.)下的纤维素单体的拉曼光谱,以及纤维素双链节的拉曼光谱。研究表明,在无外电场作用下,纤维素单体的拉曼光谱主要在449、 597、 842、 1 127、 1 361、 1 395和3 005 cm^-1处有特征峰,对其做振动分析,结果表明这些拉曼峰分别是由环(C6—C4—O20)伸缩振动、 C—C—H扭曲振动、环(C4—O20—C2)伸缩振动、糖苷键(C2—O1—C8)的伸缩振动、 CH₂     

Formation of reaction intermediates and primary volatiles during acid-catalysed fast pyrolysis of cellulose in a wire-mesh reactor

This study aims to understand the fundamental reaction mechanisms during fast pyrolysis of the acid-impregnated cellulose in a wire-mesh reactor at 40–450 °C and 20 °C/s, via quantifying key compounds in the reaction intermediates and primary volatiles. Acid impregnation reduces the onset reaction temperature of cellulose pyrolysis. During acid-catalysed cellulose pyrolysis, 1,6-anhydro-β-d-glucofuranose (AGF), levoglucosenone (LGO) and 5-hydroxymethylfurfural (5-HMF) are identified as major products in the primary volatiles, and the formation of levoglucosan is greatly suppressed. At temperatures < 100 °C, acid catalyses hydrolysis reactions to produce glucose, which is further dehydrated to AGF at 120 °C. At temperatures > 160 °C, acid enhances the dehydration of glucose, levoglucosan and AGF to produce 5-HMF and LGO as major primary products. Once produced, those products can be easily released into the vapour phase, as either aerosols via thermal ejection or vapours via evaporation. As the pyrolysis temperature increases to 240 °C, aromatic compounds can be identified in the primary volatiles, indicating condensation reactions also play important roles during acid-catalysed cellulose pyrolysis under the conditions. As a result, char formation becomes the favoured pathway during acid-catalysed cellulose pyrolysis at temperatures > 300 °C.     

Pyrolysis of cellulose and lignin

X-ray and UV-induced photoelectron spectroscopy (XPS and UPS) and scanning electron microscopy (SEM) have been performed to characterise the pyrolysis of cellulose and lignin and their interaction with methanol. Clean highly oriented pyrolitic graphite (HOPG) was also analysed as a reference material. Asymmetric C1s core level fits and valence band XPS of the samples indicate a graphitic-like structure after the pyrolysis at 1200 °C. Due to the low polar contents in pyrolysed cellulose and lignin, an interaction with methanol under high vacuum conditions could not be identified. From a technical viewpoint a temperature of 1200 °C is attainable without high costs. Therefore, the pyrolysis of wood-based polymers containing high amounts of cellulose and lignin are potential low-cost materials for various applications. If it is possible to generate graphite in complex structures made of wood-based polymers, a cheap and energy-efficient method will become available for producing bipolar plates for fuel cells. Technical problems like form instability and foaming are discussed as well as further development and possible modifications of the ground material to achieve optimal compositions.     

Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

Rapid catalytic oxidation of CO to CO(2) - On the development of a new approach to on-line oxygen isotope analysis of organic matter

A new approach to on-line oxygen isotope analysis has been developed which utilises existing elemental analyser and mass spectrometry technology to produce a sample of carbon dioxide gas for oxygen isotople analysis. The method relies on on-line high temperature pyrolysis of the sample over a carbon source followed by a rapid, non-contributive partial catalytic oxidation over nickel powder at between 550 and 600 degrees C. Initial results demonstrate both good precision (better than 0.2 per thousand) and accuracy for both cellulose and silver nitrate samples. Copyright 1999 John Wiley & Sons, Ltd.     

傅里叶红外光谱法研究GAP/AP混合体系的快速热裂解

用T-Jump/FTIR在线联用分析技术,研究了GAP/AP混合体系在模拟燃烧条件下快速加热高温高压的热裂解。结果表明,GAP/AP混合体系的主要热裂解气相产物的组成发生了变化,说明组分之间存在相互作用。压力对GAP/AP混合体系气相产物有明显的影响,表明混合体系组分GAP和AP之间的相互作用是通过AP分解气相产物进行的,混合体系不但存在气相之间的反应,也存在气相/凝聚相反应。而温度并没有影响AP对GAP的作用。用T-Jump/FTIR在线分析技术能够实现模拟燃烧条件下含能材料实时气体产物分析,为从微观反应的角度探索含能材料的快速高压热裂解及其组分之间的相互作用提供一条技术途径。     

A Nonequilibrium Approach to Temperature Calibration for Tungsten Filament Atomic Spectrometry

A nonequilibrium approach to voltamperometric temperature measurement for tungsten filament atomizers was developed to facilitate the transfer of thermal conditions between instruments that possess different power supply regulation modes and filaments. Large differences in the equilibrium and instantaneous temperatures were found during the pyrolysis and atomization steps of cadmium atomic absorption spectroscopy (AAS) analysis. By using the instantaneous temperature, the pyrolysis and atomization behaviors of cadmium were shown to be equivalent regardless of the power supply regulation mode. The pyrolysis conditions optimized for a 15-V filament were readily and accurately transferred to a 12-V filament by applying the nonequilibrium voltamperometric temperature model.