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煤热解动力学及其挥发分析出规律的研究

Study on the Kinetics and Devolatilization of Coal Pyrolysis

【作者】 降文萍

【导师】 曾凡桂;

【作者基本信息】 太原理工大学 , 矿产普查与勘探, 2004, 硕士

【摘要】 煤热解是煤转化过程中(气化、液化、燃烧)的初始阶段,研究煤的热解对煤的其它转化都有很重要的意义。本论文在煤结构及煤热解的TG/DTA、TG/MS及热解红外光谱的分析基础上,详细考察了九种不同变质程度的煤,以及经过酸洗脱灰,二硫化碳、苯、三氯甲烷、四氢呋喃和吡啶单独抽提和连续抽提方法处理后霍林河和义马煤的热解动力学特征和热解气体逸出规律。主要结论如下: (1)不同变质程度煤的结构特征及热解特性:煤化程度高的煤有较高的芳香氢含量,较高的芳香度;煤化程度高的煤热解失重量相对较小,初始热解温度和最大失重速率温度比煤化程度低的煤较高;随升温速率的增加,各种煤的失重量没有什么变化,但特征点温度都相应升高,最大失重速率也呈线性增加;用一级分段反应模型求得各种煤的动力学参数:表观活化能和频率因子,活化能在无水无灰基碳含量81%左右达到最大,同一升温速率不同温度段活化能与频率因子呈正相关线性关 太原理工大学硕士研究生学位论文系;煤化程度高的热效应强度比煤化程度低的煤低,对应温度也相应升高;高煤化程度煤的热解气体产物氧化物和CZ3轻质烃类逸出量比低煤化程度煤少,C犷C:芳烃类逸出量较多,温度也相对较高。 (2)酸洗脱灰处理后煤的结构特征及热解特性:酸洗脱灰能脱出煤中90%的矿物质,并且基本不影响煤的大分子结构;霍林河和义马酸洗脱灰后比原煤有较大的失重量,较高的特征点温度,较大的失重速率;脱灰后主要热解阶段的活化能比原煤较大;脱灰后所分析的各种气体产物都比原煤减少,对应温度比原煤提前。 (3)抽提处理后煤的结构特征及热解特性:随溶剂极性的增加,抽提率逐渐增加,连续抽提率一般小于单独抽提率;经毗陡抽提后残煤的芳香度比原煤增大;在150一900℃范围,抽提后残煤的热解失重量比原煤增加,主要热解阶段的活化能除毗健抽提残煤较小外,其它都和原煤相近;抽提后残煤的热解气体产物一般比原煤少,但四氢吠喃抽提后比较特殊,有部分产物超过了原煤。

【Abstract】 Coal pyrolysis is an initial process of all major coal conversion, like gasification and combustion, carbonization, therefore, research on pyrolysis is very important for coal conversion process. Based on analysis of coal structure and TG/DTA, TG/MS, Py-FTIR investigation of coal pyrolysis, the kinetics of pyrolysis and the emission of pyrolysis gases were studied on 9 kinds of different rank coals and Huolinhe, Yima coals demineralized by HF/HC1 and extracted by respective and successive ways with five kinds of solvent: CS2, Benzene, CHC13, THF and Pyridine. The main conclusions are as following:(1) The structure and pyrolytic characteristics of different rank coals: The higher rank coals are , the more aromatic hydrogenand aromaticity have they. The higher rank coals lost lower weight and have higher initial pyrolysis temperature, higher temperature at the highest weight loss rate. With increasing of the heating rate, the weight loss unchanges, the characteristic temperatures increase, the highest weight loss rates linearly increase with the heating rate. The apparent activation energies and pre-exponential factors are calculated in the different pyrolysis temperature stages by the first-order raction model. The apparent activation energy reaches the maximum value about Cdaf81% of coal. In the different stages of the same heating rate, the apparent activation energy positively relates to the pre-exponential factor. The higher rank coals have lower heat effect and higher temperature of the endothermic and exothermic peaks, lower content of C2.3 light hydrocarbons, lower content oxides, higher content C6-8 aromatic hydrocarbons than the lower rank coals, and the temperatures of the maximum value of these components are higher than the lower rank coals.(2) The structure and pyrolytic characteristics after demineralization: The demineralization by HF/HC1 can remove 90% minerals, and do not change the main coal structure. Afterdemineralization, Huolinhe and Yima coals gain more weight losses, higher characteristic temperatures, higher highest weight loss rate, higher apparent activation energy in the main pyrolysis stage than raw coal. The content of different components studied are lower than raw coal after demineralization, and the temperatures of the maximum value are lower.(3) The structure and pyrolysis characteristics after extraction: With increasing of the solvent polarity, the extraction yields increase, the successive extraction yields are lower than the respective, and the Pyridine extraction can cause aromaticity higher. In 15 0-900 C, the weight loss amount after extraction are more than the raw coal, and the apparent activation energy of the main pyrolysis stage is close to the raw coal except Pyridine extraction. After extration, yields of the gases are lower than the raw coal but THF extraction.

  • 【分类号】TQ533
  • 【被引频次】59
  • 【下载频次】2769
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