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秸秆发酵渣的催化热解及其与酚醛树脂的共热解研究
马蕊
学位类型硕士
导师宋文立 ; 王泽
2016-07
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业化学工程
关键词生物质 发酵渣 酚醛树脂 催化 热解
摘要

近年来,随着石油、煤炭等化石燃料日益短缺,生物质能的开发利用倍受青睐。其中富木质素类生物质来源广泛,却尚未得到有效利用,其主要工业来源包括造纸黑液及木质纤维素发酵渣等,然而不论何种生物质物料,其热解液不可避免的存在组成复杂、热值偏低的弊端。因此,通过催化热解或与塑料共热解方式对热解液进行提质,成为生物质热解相关研究领域中的热点方向。另一方面,逐年增加的大量电子垃圾的无害化处理和再利用是关系环境、能源、材料等诸多领域的重要内容。因此,作为电路板主要成分的酚醛树脂的热解特性研究具有重要价值。鉴于此,本论文通过热重及PY-GC/MS手段对酚醛树脂和玉米秸秆发酵渣的热解转化特性进行了分析比较,进一步考察了两者的共热解特性、以及秸秆发酵渣的催化热解特性、并通过Coats-Redfern方法对两者的转化控制机制及活化能进行了动力学分析和比较。研究发现:酚醛树脂热稳定性及热解起始温度较高,热解产物主要由苯酚、甲基苯酚、二甲基苯酚等烷基酚及其衍生物构成,并含有少量芳烃及特殊结构产物;玉米秸秆发酵渣的起始热解温度较低,主要产物涵盖小分子酸、烷基酚、烷氧基酚、芳烃等多种组分,其中2,3-二氢苯并呋喃及烷氧基酚是玉米秸秆发酵渣的特征性产物。玉米秸秆发酵渣与酚醛树脂的共热解协同作用对芳烃有抑制作用,但对烷基酚具有显著的促进效应;烷氧基酚含量随热解温度升高呈极大值变化,且协同作用下低温时烷氧基酚受到促进但高温时受到抑制;气体产物在协同作用下CH4及CO含量有所增加,但H2含量显著降低。考察了三种催化剂对玉米秸秆发酵渣的催化热解行为,结果显示,ZSM-5和Y型分子筛作用下,主要芳烃组分含量均显著提高,且ZSM-5具有更高的催化活性;烷基酚含量显著降低,但苯酚含量有所增加,其中Y型分子筛作用效果尤为突出;SAPO-34和ZSM-5作用下烷氧基酚含量低温时较高而高温时有所减低;SAPO-34对所有产物的作用均很微弱。动力学分析显示,酚醛树脂在转化率25%-75%范围内的热解过程主要受扩散机制控制,而秸秆发酵渣热解过程远比酚醛树脂热解过程更为复杂,其在转化率10%-50%范围内的热解过程同样主要受扩散机制控制;在50%-75%的高转化率范围内的转化机制难以准确描述,相对而言二级反应控制机制与实验结果相关性较高,活化能更低

其他摘要

With depletion of coal and petroleum fossil fuels, the utilization of biomass as an important resource of renewable energy is urgently demanded. Among the biomass materials, the resource of lignin rich biomass, including the black liquid and the lignocellulose fermentation residue is abundant, but has not been utilized high efficiently. However, whatever the type of biomass is, the unavoidable shortcomings of the pryolytic liquid such as the complexity of the composition and the low heat value extremely restricted the application of the pyrolytic liquid. The two methods of catalytic pyrolysis and co-pyrolysis with plastics were thereby frequently used for upgrading of the pyrolytic liquid. On another hand, waste circuit board discarded every year in large amount is an important issue related to environment, energy, and materials. Therefore, the pyrolysis of phenolic resin, as a major component of circuit, is a potential way to recover energy materials (fuel gas and char) and other high value chemicals. Based on the above reasons, the individual pyrolysis of phenolic resin and corn straw fermentation residue, the co-pyrolysis of their mixture, and the catalytic pyrolsis of the fermentation residue were investigated, through the TG and Py-GC/MS method. Additionally, kinetic analyses were conducted on the individual pyrolytic behaviors of the two materials of phenolic resin and fermentation residue with a similar phenolic structure by the Coats-Redfern method. Some of the major results are as follows:The initial pyrolytic temperature of phenolic resin is higher, indicating a higher stability of the material. The pyrolytic liquid product mainly consists of phenol, methylphenol, dimethylphenol, and their derivatives, accompanied with a low amount of aromatics and some special structure related products. On the contrary, the initial pyrolytic temperature is rather low and the products are broadly scattered in the types of small acids, alkyl phenols, alkoxy phenols, aromatics, etc. Particularly, 2,3-dihydro-benzofuran is a major and specific product from pyrolysis of fermentation residue. Under the synergistic effect by co-pyrolysis of fermentation residue and phenolic resin, the formation of aromatics is restricted while alkyl phneols are more generated; the content of alkoxy phenol appears a maximum value varied with increasing temperature, and the formation of alkoxy phenol is promoted at low temperatures but hindered at high temperatures; the gas products of CH4 and CO are more generated, while the formation of H2 is hindered severely.Under the catalysis of ZSM-5 and Y zeolite, the content of aromatics is increased and comparatively the effect of ZSM-5 is more distinct, while the content of alkyl phenols is decreased, except that phenol is more generated, and comparatively the effect of Y zeolite is more remarkable. Under the influences of SAPO-34 and ZSM-5, alkoxy phenols are more generated at lower temperatures but are reduced at higher temperatures. Comparatively, Y zeolite has a strongest effect in promoting the conversion of alkoxy phenols, while the influence of SAPO-34 is weakest to all product components. Kinetic analysis illustrated that the pyrolysis of phenolic resin is a diffusion controlled process in the conversion range of 25% - 75%. The pyrolysis of fermentation reside is much more complex than that of phenolic resin, and thus the whole process has to be analyzed by stages: in the conversion range of 10%-50%, the pyrolysis of fermentation residue is also predominantly controlled by diffusion process; in the higher conversion range of 50% to 75%, no mechanic function was found qualified in description of the reaction stage, while relatively a second order reaction model has a higher correlation level with the experimental results, with a much lower activation energy value.

语种中文
文献类型学位论文
条目标识符http://ir.ipe.ac.cn/handle/122111/22943
专题研究所(批量导入)
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马蕊. 秸秆发酵渣的催化热解及其与酚醛树脂的共热解研究[D]. 北京. 中国科学院研究生院,2016.
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