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纤维素快速热裂解机理试验研究 Ⅱ. 机理分析 总被引:12,自引:12,他引:12
针对在热辐射反应器上得到的纤维素热裂解实验结果,对左旋葡聚糖、1-羟基-2-丙酮以及乙醇醛等一次产物的生成机理进行了分析研究。在气相产物快速析出并急冷的条件下,乙醇醛和1-羟基-2-丙酮二种产物的生成与LG的生成呈现出竞争反应。基于这一结果,我们建立了竞争反应动力学模型,并分别对乙醇醛和1-羟基-2-丙酮进行了模拟,得出二种产物的生成具有相似的动力学行为,表明这两种竞争化合物具有相同的初始反应。分析认为,纤维素的热裂解通过活性纤维素这一反应前体以异裂和均裂两种热解途径进行分解,其中转糖基作用下糖苷键的异裂断开形成了包括LG以及其同分异构体的脱水糖;缩醛结构的开环以及环内C—C键的断裂形成乙醇醛、1-羟基-2-丙酮以及CO等其它小分子化合物。在Brodio-shafizadeh模型的基础上提出了反应机理模型,并按照该模型对高辐射源温度下纤维素热裂解LG的生成进行了模拟,计算结果与实验数据吻合较好。 相似文献
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生物质三组分热裂解行为的对比研究 总被引:33,自引:9,他引:33
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。 相似文献
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中孔分子筛MCM—41的合成与表征 总被引:7,自引:5,他引:7
以白炭黑和正硅酸乙酯为硅源,十二、十六烷基三甲基铵为模板剂,用水热法和室温直接法合成出中孔分子筛MCM-41,考察了对合成的影响因素,用红外光谱、吸附、孔分布、热分析等手段对这两种产物进行了表征。 相似文献
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利用热裂解-气相色谱-质谱联用分析烟用咖啡颗粒的热裂解特性。分别于150、200、250、300、350℃对烟用咖啡颗粒进行热裂解分析,同时针对不同水分含量和粒径的咖啡颗粒在同一温度下进行热裂解成分分析。结果显示,随着温度的升高,热裂解产物逐渐增多,释放物质的种类逐渐也逐渐增多,在250℃时咖啡颗粒生成关键致香成分占比较高。不同水分含量和粒径的咖啡颗粒在250℃裂解时,水分越高,裂解产物中烟碱含量占比越高,烟气越充足;粒径越小,裂解产物中咖啡因和烟碱的总量越大,香气质量也越高。该试验为咖啡颗粒在卷烟中应用时的温度设计和香气品质改善提供理论依据。 相似文献
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采用热失重分析法(TGA)和在线热裂解气相色谱-质谱法(Py-GC-MS)研究了黄芩浸膏热裂解性质。在氦气氛围中,将黄芩浸膏分别在300,450,600,750,900℃下进行热裂解,并以气相色谱-质谱法对其裂解产物进行定性和半定量分析,并用黄芩浸膏进行了卷烟加香试验。结果表明:①在热失重曲线图中不能较明显地看出黄芩浸膏的较大失重点;②黄芩浸膏在上述温度下检测到的主要挥发性热裂解产物分别为12,18,28,42,40种;③600℃以下,黄芩浸膏热裂解产物主要是醛类、酮类、酯类和呋喃类物质;有害物质的量随着温度的升高而提高;900℃时,则主要为苯、甲苯、萘等有害成分;④黄芩浸膏具有提高卷烟香气质量、改善余味、柔和烟气的作用。 相似文献
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烤烟烟叶和烟梗的热裂解产物的研究 总被引:3,自引:0,他引:3
为了加深理解梗丝在卷烟叶组配方中的作用,对比研究了烤烟叶片和烟梗的化学组成以及它们在不同温度下的热裂解产物。一个改进后的热裂解装置被用来模拟卷烟的燃烧行为。采用热裂解仪研究了烤烟叶片和烟梗在大气环境中于300 ℃、600 ℃和900 ℃下的热裂解行为,并采用气相色谱-质谱联用仪对它们的热裂解产物进行分析。结果表明,烤烟烟叶和烟梗的热裂解产物种类随着热裂解温度的增加而增多;在相同热裂解温度条件下,烟叶的热裂解产物种类明显多于烟梗的热裂解产物。 相似文献
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A pure model compound for polyacrylonitrile, 1,3,5,7-tetracyanoheptane, was shown to discolour thermally in a similar manner to the polymer. This and other evidence is presented to support the view that thermal degradation of polyacrylonitrile is a free radical reaction involving tertiary hydrogen atoms. 相似文献
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John W-P. Lin Les P. Dudek 《Journal of polymer science. Part A, Polymer chemistry》1985,23(5):1589-1597
Thermal treatment of novel poly(copper 2,3,9,10,16,17,23,24-octacyanophthalocyanine), PCOCP, has been carried out at different temperatures in an inert atmosphere. As polyacrylonitrile, the polymer can be thermally cyclized through the cyano groups to produce semiconductive and conductive materials. Polymeric copper octacyanophthalocyanine material with a conductivity as high as 5–8 (Ω cm)-1 was prepared. Weight loss, electrical data, infrared, and photoacoustic results of the thermally treated copper octacyanophthalocyanine polymer are discussed. 相似文献
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Influence of electron beam pre-irradiation on the thermal behaviors of polyacrylonitrile 总被引:1,自引:0,他引:1
Thermal treatment of polyacrylonitrile pre-irradiated by electron beam was performed to investigate the radiation effects on thermally activated reactions. Thermal properties were characterized by differential scanning calorimetry and thermogravimetric analyses. Pre-irradiation lowers the onset temperature of reactions and alleviated the heat evolution process. Char yields (800 °C) of polyacrylonitrile increase significantly with increasing irradiation dose. FTIR was used to monitor the thermal reaction. The results reveal that the thermal reactions can be regulated by pre-irradiation dose. FTIR and UV-visible absorption spectra of pre-irradiation polyacrylonitrile illustrate the formation of -HCN-NCH- conjugation across the polymeric chains as a function of dose, which could improve the thermal behaviors of polyacrylonitrile. 相似文献
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Thermally stimulated discharge has been used in the past to diagnose and estimate the magnitude of electrical polarization in polymers. Nevertheless, molecular characterization of operative phenomena by this technique alone is often a difficult task. In the present work, infrared attenuated total reflection spectroscopy has been used to investigate the origin of thermally stimulated discharge currents near 200°C in externally unpolarized films of polyacrylonitrile (PAN). Spectroscopic analysis of thermally degraded films reveals some unsaturation of the PAN backbone and possibly the generation of cyanide ions. Opposite surfaces in a solvent-cast film give different spectra, indicating a gradient in chemical degradation products across the film thickness. Data suggest that nonuniform generation of charged species and unsaturated bonds gives rise to internal potentials in PAN. The origin of thermally stimulated currents in PAN near 200°C is thus believed to be associated with the onset of chemical degradation. 相似文献
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Titania thin film was deposited successfully on polyacrylonitrile (PAN) fiber by the sol‐gel process with the assistance of tetraethyl silicate (TEOS) at low temperature. It was found that the densification and crystallization of the film was a result of the post‐treatment in boiling water because of the hydrolysis of the Si‐O‐Ti bonds and dissolution of the silica component formed in the film. XRD patterns revealed the existence of anatase phase in the continuous titania layer. The product, titania coated polyacrylonitrile fiber (TiO2/PAN), showed a high photocatalytic property and good repetition on the photodegradation of methylene blue (MB). The proposed method is expected to be used for the preparation of novel photo‐catalysts based on thermally sensitive substrates. 相似文献
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E. A. Karpushkin A. K. Berkovich M. V. Artemov V. G. Sergeev 《Polymer Science Series A》2014,56(5):681-686
Rheological properties of dispersions of carbon nanotubes in dimethylsulfoxide solutions of polyacrylonitrile are studied at different concentrations of the components. The viscosity values of all the studied dispersions are substantially dependent on shear rate. For a number of systems, the energies of activation of viscous flow are determined. The relationship of viscosity and the energy of activation of flow to the compositions and possible structural features of dispersions is discussed. The concentration regime where a thermally reversible mixed network exists with crosslinks formed by physical contacts of the polymer with nano-tubes is characterized. 相似文献
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XIE De-Min SU Zhong-Min SHI Zhong-Liang WANG Rong-ShunDepartment of Chemistry Northeastern Normal University Changchun Jilin China 《中国化学》1994,12(3):206-212
The molecular structures of thermally structurized polyacrylonitrile (PAN), that is, polypyridinopyridine (PPyPy) series have been investigated by using quantum chemistry semiem-pirical MNDO, CNDO/2-CO methods. The changing regularities of structural stability and electronic properties are pointed out. The analyses of the energy band structures indicate that the energy gaps will become smaller, intrinsical conductivities will increase when the quasi-one-dimentional (1D) series of PPyPy molecule widen toward two-dimention (2D), which is consistent with the experimental results of polymerization degree (PD) and electrical conductivity increase with the increasing of pyrolyzed temperature. 相似文献
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Yu. N. Sazanov V. A. Lysenko P. Yu. Sal’nikova G. N. Gubanova T. P. Maslennikova T. E. Sukhanova G. N. Fedorova 《Russian Journal of Applied Chemistry》2013,86(9):1410-1416
Composite materials based on polyacrylonitrile with carbon nanofillers (technical-grade carbon, thermally expanded graphite, carbon nanotubes) were synthesized. A carbonization of film and fiber composite samples in the temperature range 20–1000°C provided a noticeable increase in the thermal stability of fibers and a rise in the electrical conductivity of the composite material. Dependences of the degree of carbonization on the concentration of nanostructures, type of material, and nature of modifier were determined. Differential-thermal and X-ray diffraction analyses revealed the formation of oriented nucleus structures of turbostratic carbon in the temperature range 450–550°C. 相似文献
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Various natural and modified polysaccharides (i.e. arabic gum, tragacanth gum, xanthan gum, sodium alginate, chitosan, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose) were modified using ceric-initiated graft polymerization of acrylonitrile under inert atmosphere. Grafting was confirmed using spectral (FT-IR) proofs. The grafting parameters were determined by conventional methods. Thermal characteristics of the homopolymer-free copolymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere. The major thermal transitions as well as the activation energy of the major decomposition stages were investigated. The polyacrylonitrile (PAN)-grafted polysaccharides were recognized to be thermally stable more than the corresponding non-grafted substrates, although they begin to decompose at relatively lower temperatures than the non-grafted counterparts. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
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Nandini Chatterjee Sunanda K. Palit Mrinal M. Maiti 《Journal of polymer science. Part A, Polymer chemistry》1995,33(17):2875-2879
Finely powdered blends of poly(vinyl chloride) (PVC) and polyacrylonitrile (PAN) have been thermally degraded at 275°C for 24 h in an inert atmosphere to effect complete de-hydrochlorination of PVC to a conjugated polyene structure and simultaneous internal polymerization of nitrile groups in PAN to a conjugated polyimine sequence. The room temperature d.c. conductivity of the degraded blends showed clear synergistic behavior. A maximum conductivity has been observed with a blend of 60 PAN/40 PVC which is about 4 orders of magnitude over the linearly weighted average conductivity of the individual degraded homopolymers. The results have been interpreted in terms of a possible donor-acceptor interaction between the degraded homopolymers leading to mutual doping and, hence, an enhanced electrical conductivity. © 1995 John Wiley & Sons, Inc. 相似文献