ZHANG Xin-hai,BAI Ya-e,LI Ya-qing,et al.Kinetics and segmentation law of coal oxidation at elevated temperature[J].Journal of Xi'an University of Science and Technology,2017,(04):474-478.[doi:10.13800/j.cnki.xakjdxxb.2017.0404]





Kinetics and segmentation law of coal oxidation at elevated temperature
张辛亥12白亚娥12李亚清12马 腾12
1.西安科技大学 安全科学与工程学院,陕西 西安 710054; 2.教育部 西部矿井开采及灾害防治重点实验室,陕西 西安 710054
ZHANG Xin-hai12BAI Ya-e12LI Ya-qing12MA Teng12
1.College of Safety Science and Engineering,Xi'an University of Science and Technology,Xi'an 710054,China; 2.Key Laboratory of Western Mine Exploration and Hazard Prevention,Ministry of Education,Xi'an 710054,China
煤自燃 热分析实验 分段性 活化能 补偿效应
Key words:coal spontaneous combustion thermogravimetric analysis experiments divided segments activation energy kinetic compensation effect
TD 75
为了研究煤的自燃特性,选取石圪台煤矿22203采煤工作面煤样为研究对象,采用热分析技术,对煤氧化升温过程中质量及动力学参数变化规律进行了探讨。结果表明:煤的失重呈阶段性变化规律,可分为低温失重、吸氧增重、缓慢化学反应和燃烧阶段; 通过采用改进的KAS法计算煤升温氧化动力学参数,可知在温度达到燃点前,随着温度升高反应活化能增加,说明不断有难燃结构参与到反应。超过燃点温度,在燃烧阶段初期,活化能基本保持不变,而指前因子出现峰值,表明有大量活性结构被激活,准备参与到燃烧反应中。在燃烧阶段中后期,活化能随温度的增加逐步减小,表明该阶段有芳香环的破坏形成更易于反应的活性结构; 动力学参数的补偿效应存在显著分段性,说明在煤氧反应过程中前后反应不同,其整体反应存在不止一个反应机理。研究结果对防治煤自燃提供理论依据。
Abstract:In order to research on spontaneous combustion of coal,thermogravimetric analysis is employed to study laws of mass loss of coal sample from Shigetai coal mine 22203 working face.During oxidation at elevated temperature,kinetics of the process is studied.The results showed that lows of sample mass loss and kinetics remarkably among different temperature segments.Accordingly,the reaction process of coal in air at elevated temperature is divided into 4 segments:low temperature heat loss,oxygen adsorption weight gaining,low rate chemical reaction and combustion.The modified KAS method is employed to calculate activation energy of coal.It can been known from the results that the activation energy increases as temperature rises to combustion point,indicate that more and more less reactive structures of coal involves in the reaction.When temperature crosses the combustion point,at the beginning of combustion the activation energy keeps almost constant while the pre-exponential factor have a peak.It indicate that more and more reactive structures were appeared to prepare for the combusion reaction.As temperature continues to rise,the activation energy decreases slowly.The main reason is that the aromatic core of the coal may break down to produce large amount of reactive structures.The kinetic compensation effect has a significant segments,indicating that the Shigetai coal's combustion mechanisms are different in the ealy stage and in the later stage during its burning,and there are more than one mechanism through the whole reaction.The results provide a theoretical basis for the prevention and control of coal spontaneous combustion.


[1] 胡荣祖,高胜利,赵凤起,等.热分析动力学[M].北京:科学出版社,2008. HU Rong-zu,GAO Sheng-li,ZHAO Feng-qi,et al.Thermal analysis kinetics[M].Beijing:Science Press,2008.
[2] 张辛亥,白亚娥,李青蔚,等.基于活化能指标研究不同变质程度烟煤自燃特性[J].矿业安全与环保,2016,43(1):5-7. ZHANG Xin-hai,BAI Ya-e,LI Qing-wei,et al.Based on activation energy studying the spontaneous combustion tendency of different metamorphic grade of coal[J].Mining Safety and Environmental Protection,2016,43(1):5-7.
[3] 屈丽娜,刘星魁,张红元.煤自燃阶段动力学参数及特征温度点的实验研究[J].西安科技大学学报,2015,35(5):597-601. QU Li-na,LIU Xing-kui,ZHANG Hong-yuan.Experimental study of stage characteristic parameters and temperature on coal spontaneous combustion[J].Journal of Xi'an University of Science and Technology,2015,35(5):597-601.
[4]王继仁,邓存宝,单亚飞,等.煤的自燃倾向性新分类方法[J].煤炭学报,2008,33(1):47-49. WANG Ji-ren,DENG Cun-bao,SHAN Ya-fei,et al.A new classifying method of the spontaneous combustion tendency[J].Journal of China Coal Society,2008,33(1):47-49.
[5] Aboyade A O,Carrier M,Meyer E L,et al,Model fitting kinetic analysis and characterisation of the devolatilization of coal blends with corn and sugarcane residues[J].Thermochimica Acta,2012,530:95-106.
[6] 战 婧,王 寅,王海晖.煤氧化增重现象中的控制反应及其动力学解析[J].化学学报,2012,70(8):980-988. ZHAN Jing,WANG Yin,WANG Hai-hui.A study of the phenomenon of mass increased by coal oxidation prior to 400 ℃:governing mechanism and the associated chemical kinetics[J].Acta Chimica Sinica,2012,70(8):980-988.
[7]周俊虎,平传娟,杨卫娟,等.用热重红外光谱联用技术研究混煤热解特性[J].燃料化学学报,2004,32(6):658-662. ZHOU Jun-hu,WANG Chuan-juan,YANG Wei-juan,et al.Experimental study on the pyrolysis characteristic of coal blends using TGA-FTIR[J].Journal of Fuel Chemistry and Technology,2004,32(6):658-662.
[8]Scaccia S.TG–FTIR and kinetics of devolatilization of Sulcis coal[J].Journal of Analytical and Applied Pyrolysis,2013,104:95-102.
[9]Starink M J.The determination of activation energy from linear heating rate experiments:a comparison of the accuracy of isoconversion methods[J].Thermochimica Acta,2003,404:163-176.
[10]Starink M J.Activation energy determination for linear heating experiments:deviations due to neglecting the low temperature end of the temperature inte-gral[J].Journal of Material Science,2007,42:483-489.
[11]Vyazovkin S,Burnham A K,Criado J M,et al.ICTAC kinetics committee recommendations for performingkinetic computations on thermal analysis data[J].Thermochimica Acta,2011,520:1-19.


 QU Li-na,LIU Xing-kui,ZHANG Hong-yuan.Experimental study of stage characteristic parameters and temperature on coal spontaneous combustion[J].Journal of Xi'an University of Science and Technology,2015,(04):597.[doi:10.13800/j.cnki.xakjdxxb.2015.0512]
 MA Li,XIANG Qi,REN Li-feng.Experimental study on the primary/secondary oxidation characteristics of inhibited coal sample[J].Journal of Xi'an University of Science and Technology,2015,(04):702.[doi:10.13800/j.cnki.xakjdxxb.2015.0605]
[3]邓 军,任立峰,艾绍武,等.综放面间歇式开采注氮对采空区氧化自燃区域的影响研究[J].西安科技大学学报,2017,(04):467.[doi:10.13800/j.cnki.xakjdxxb.2017.0403]
 DENG Jun,REN Li-feng,AI Shao-wu,et al.Influence of nitrogen injection on oxygenated spontaneous combustion zone in gob of fully mechanized caving face[J].Journal of Xi'an University of Science and Technology,2017,(04):467.[doi:10.13800/j.cnki.xakjdxxb.2017.0403]
[4]邓 军,雷昌奎,曹 凯,等.煤自燃预测的支持向量回归方法[J].西安科技大学学报,2018,(02):175.[doi:10.13800/j.cnki.xakjdxxb.2018.0201]
 DENG Jun,LEI Chang-kui,CAO Kai,et al.Support vector regression approach for predicting coal spontaneous combustion[J].Journal of Xi'an University of Science and Technology,2018,(04):175.[doi:10.13800/j.cnki.xakjdxxb.2018.0201]
[5]邓 军,邢 震,马 砺.多元回归分析在煤自燃预测中的应用[J].西安科技大学学报,2011,(06):645.
 DENG Jun,XING Zhen,MA Li.Application of multiple regression analysis in coal spontaneous combustion prediction[J].Journal of Xi'an University of Science and Technology,2011,(04):645.
[6]邓 军,李保霖,程方明,等.煤自燃特征信息的模糊聚类与模式识别[J].西安科技大学学报,2011,(05):505.
 DENG Jun,LI Bao-lin,CHENG Fang-ming,et al.Fuzzy clustering and pattern recognition of characteristic information in coal spontaneous combustion[J].Journal of Xi'an University of Science and Technology,2011,(04):505.
[7]程方明,常助川,李 贝,等.基于热棒降温技术的自燃煤堆热迁移行为数值模拟[J].西安科技大学学报,2019,(04):0.[doi:10.13800/j.cnki.xakjdxxb.2019.0404]
 CHENG Fang-ming,CHANG Zhu-chuan,LIBei,et al.Numerical simulation on thermal migration behavior of spontaneous combustion coal pile based on heat pipe cooling technology[J].Journal of Xi'an University of Science and Technology,2019,(04):0.[doi:10.13800/j.cnki.xakjdxxb.2019.0404]


基金项目:国家自然科学基金(U1361129) 通讯作者:张辛亥(1971-),男,陕西蓝田人,教授,E-mail:zhangxinh71@126. com
更新日期/Last Update: 1900-01-01