自燃煤低温氧化放热性实验研究
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摘要
煤层自燃严重影响着煤炭工业发展，给矿井生产带来极大安全隐患。由于实际条件下的煤自燃过程很难描述清楚，使得煤层自然发火预测预报技术的发展受到严重制约。
因此，了解煤自燃的条件、发展过程的影响因素对煤层自然发火防治具有重要的理论和工程应用价值。
本文根据煤自燃是由于煤样复合放出热量引起的机理，研究涉及的两个关键因素：（1）煤氧复合（2）放出热量，采用理论、实验相结合的研究方法，对自燃煤低温氧化放热性进行研究。通过自然发火实验与程序升温实验以及一系列热重实验分析可得出煤自燃过程中的五个特征温度，在临界温度时煤的失重速率达到最大值，小于临界温度时 ，随煤温升高，煤体氧化放热强度、CO产生率、耗氧速度和升温速度增加缓慢，超过临界温度后，增速加快；超过干裂温度后，急剧增加。
通过煤热重动力学参数测定，计算出煤的活化能，了解自燃煤由初始稳定状态变为活化分子所吸收的能量，从本质上描述煤的着火性能。
通过煤自燃过程数学模型，确定出煤自燃过程数值模拟所需的关键参数为煤的耗氧速度和放热强度及松散煤体内的氧气扩散系数和渗透系数，通过实验对其进行了研究和测试。提出了实际条件下煤体放热强度和耗氧速度的计算方法。
通过模拟试验的测试，可分析得出煤的实验最短发火期以及表征煤自燃极限外界条件的参数：下限氧浓度、上限漏风强度和最小浮煤厚度。
通过研究煤自燃低温氧化放热性，了解煤自燃的发生及发展过程。
Coal is rich and the first energy resource in China. But spontaneous fires of coal often take place in the coal field outcrops, coal pile and coal mines, which results in a lot of coal lost and the air polluted. Spontaneous combustion of coal is becoming to one of the main disaster along with the development of the fully mechanized long-wall top-coal caving technology in the 90’s.Therefore, it’s important to study the proess of spontaneous combustion of coal .
According to the mathematical the model, oxygen consumption rate and heat liberation intensity of coal, diffusion coefficient and osmotic coefficient of oxygen is confirmed for keyparameter to numerical simulation of spontaneous combustion of coal process, and these parameters are researched and test by experiment. The calculation method of oxygen consumption rate and heat liberation intensity is put forward on actual condition.
Through the analysis of the thermal gravity investigation, we have known there are five key point of temperature in the process of spontaneous combustion of coal .We can calculate activation energy.
Through the analysis of the simulation experiment, we can know the Period of coal spontaneous combustion, heat liberation intensity; oxygen consumption velocity and so on.
因此，了解煤自燃的条件、发展过程的影响因素对煤层自然发火防治具有重要的理论和工程应用价值。
本文根据煤自燃是由于煤样复合放出热量引起的机理，研究涉及的两个关键因素：（1）煤氧复合（2）放出热量，采用理论、实验相结合的研究方法，对自燃煤低温氧化放热性进行研究。通过自然发火实验与程序升温实验以及一系列热重实验分析可得出煤自燃过程中的五个特征温度，在临界温度时煤的失重速率达到最大值，小于临界温度时 ，随煤温升高，煤体氧化放热强度、CO产生率、耗氧速度和升温速度增加缓慢，超过临界温度后，增速加快；超过干裂温度后，急剧增加。
通过煤热重动力学参数测定，计算出煤的活化能，了解自燃煤由初始稳定状态变为活化分子所吸收的能量，从本质上描述煤的着火性能。
通过煤自燃过程数学模型，确定出煤自燃过程数值模拟所需的关键参数为煤的耗氧速度和放热强度及松散煤体内的氧气扩散系数和渗透系数，通过实验对其进行了研究和测试。提出了实际条件下煤体放热强度和耗氧速度的计算方法。
通过模拟试验的测试，可分析得出煤的实验最短发火期以及表征煤自燃极限外界条件的参数：下限氧浓度、上限漏风强度和最小浮煤厚度。
通过研究煤自燃低温氧化放热性，了解煤自燃的发生及发展过程。
Coal is rich and the first energy resource in China. But spontaneous fires of coal often take place in the coal field outcrops, coal pile and coal mines, which results in a lot of coal lost and the air polluted. Spontaneous combustion of coal is becoming to one of the main disaster along with the development of the fully mechanized long-wall top-coal caving technology in the 90’s.Therefore, it’s important to study the proess of spontaneous combustion of coal .
According to the mathematical the model, oxygen consumption rate and heat liberation intensity of coal, diffusion coefficient and osmotic coefficient of oxygen is confirmed for keyparameter to numerical simulation of spontaneous combustion of coal process, and these parameters are researched and test by experiment. The calculation method of oxygen consumption rate and heat liberation intensity is put forward on actual condition.
Through the analysis of the thermal gravity investigation, we have known there are five key point of temperature in the process of spontaneous combustion of coal .We can calculate activation energy.
Through the analysis of the simulation experiment, we can know the Period of coal spontaneous combustion, heat liberation intensity; oxygen consumption velocity and so on.
引文
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[8] Lopez D. Effect of low-temperature oxidation of coal on hydrogen-transfer capability.Fuel,1998，77(14): 1623~1628
[9] Wang H. Theoretical analysis of reaction regimes in low-temperature oxidation of coal. Fuel, 1999，78(9): 1073~1081
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[30] Takanohashi T.Iino M. Ivestigation of bituminous structure of Upper Freeport Coal by solvent swelling. Energy Fuels,1995,9:788~793
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[43] 何萍.唐修义.煤氧化过程中气体的形成特征与煤自燃指标气体选择.煤炭学报,1994,19(6): 635~643
[44] 舒新前.葛岭梅.神府煤煤岩组分的结构特征及其差异.燃料化学学报,1996,24(5): 427~431
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[47] 张玉贵.唐修义.何萍.煤分子结构与煤的自燃倾向性.煤矿安全,1989(7):1~5
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[50] 朱红.李虎林.欧泽深.等.不同煤阶煤表面改性的FTIR谱研究.中国矿业大学学报,2001,30(4)：366~370
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[2] 胡社荣.蒋大成.煤层自燃灾害研究现状与防治对策.中国地质灾害与防治学报,2002,11(4): 69~72
[3] 王省身.张国枢.矿井火灾防治.中国矿业大学出版社,1990
[4] 阿.阿.斯阔成斯基.煤内火灾.北京矿业学院编译室译.北京:煤炭工业出版社，1958
[5] 李增华.煤炭自燃的自由基反应机理.中国矿业大学学报.，1996，25(3):111~114
[6] Chen Xiaodong. On the fundamentals of diffusive self-heating in water containing combustible materials.Chemical Engineering and Processing , 1998，37(5):367~378
[7] Martin R R, Macphee J A, Younger C. Sequential derivation and the SIMS imaging of coal. Energy sources.，1989，11(1):1~8
[8] Lopez D. Effect of low-temperature oxidation of coal on hydrogen-transfer capability.Fuel,1998，77(14): 1623~1628
[9] Wang H. Theoretical analysis of reaction regimes in low-temperature oxidation of coal. Fuel, 1999，78(9): 1073~1081
[10] 彭本信.应用热分析技术研究煤的氧化自燃过程.煤炭工程师,1992，(2): 1~10
[11] 舒新前.煤炭自燃的热分析研究.中国煤田地质,1994,25(2): 25~29
[12] 路继根,李凡.用热重法研究我国四种煤显微组分的燃烧特性.燃料化学学报，1996,24(4): 329~334
[13] Garcia P. The use of differential scanning calorimetry to identify coals susceptible to spontaneous combustion. Thermochemical acta，1999，336(1~2): 41~46
[14] Tevrucht M L E .Griffiths P R. Activation energy of air-oxidized bituminous coals. Energy & Fuel, 1989,3(4):522~527
[15] Patil A O.Keleman S R. In-situ polymerization of pyrrole in coal. Ploymeric materials science and engineering,1995,72:298~302
[16] 钟蕴英.煤化学[M].中国矿业大学出版社,1989
[17] 刘剑.王继仁.孙宝铮.煤的活化能理论研究. 煤炭学报, 1999,24(3): 316～320
[18] 王晓华.宗志敏.秦志宏等.有机波谱法在分子煤化学领域中的研究进展.煤炭转化,2001, 24(1): 5~10
[19] 陶著.煤化学.北京:化学工业出版社,1984
[20] 郭崇涛.煤化学.北京:化学工业出版社,1994
[21] 刘艳华.车得福.李荫堂.等. X射线光电子能谱确定铜川煤及其焦中氮的形态. 西安交通大学学报,2001,35(7):661~665
[22] Shinn J H. Study of coal molecular structure. Fuel,1984,63(8): 83~86
[23] 王娜.孙成功.李保庆. 煤中低分子化合物研究进展. 煤炭转化,1997,20(3):19~23
[24] Schulten H R.rzec A. Radical hydrogenation of coal studied by field ionization
mass spectrometry. Fuel Processing technology, 1986,15(1):307~318
[25] Schulten H R.bbt B G, Frimmel F H. Time-resolved pyrolysis field ionization mass spectrometry of humic material isolated from freshwater. Environmental science and technology, 1987, 21(4): 349~357
[26] Krichko A A.hpirt M Y.Glazunov M P.etc. Sulfide-molybdenum catalyst for the liquefaction of coal. Solid fuel chemistry, 1988,22(5): 57~61
[27] Krichko A A.Gagarin S G. New ideas of coal organic matter chemical structure and mechanism of hydrogenation processes. Fuel, 1990,69(7):885~891
[28] Nishioka M. Test of the proposed two-phase model for high-volatile bituminous coal. Energy & Fuels,1990,4(1): 70~73
[29] Nishoka M. The associated nature of bituminous coal. Fuel, 1992,71(8):941~948
[30] Takanohashi T.Iino M. Ivestigation of bituminous structure of Upper Freeport Coal by solvent swelling. Energy Fuels,1995,9:788~793
[31] Given P H.Marzec A.Barton W A etc. The concept of a mobile or molecular phase within the marcromolecular network of coals: adebate. Fuel,1986,65(8):155~163
[32] 傅家谟.匡宗.干酪根地球化学[M]. 广州:广东科技出版社,1995
[33] Jasienko S.Bieganska C.Matuszewska A. Chemiai Fizyka Wegla. Poland: Wroclaw, 1995
[34] Carlson G A. Modeling of coal structure by using computer-aided molecular design. ACS symposium series, 1991:461~465
[35] 刘旭光.保庆.煤大分子结构的计算机模拟.煤炭转化, 1999,22(3):1~5
[36] X J Hou. Theoretical study on the reactivity of coal structure. Prospects for coal science in the 21st century. 1999:295-298
[37] P Strka. Chemical structure of maceral groups of coal. Prospects for coal science in the 21st century, 1999:113~116
[38] 葛岭梅.煤分子中活性基团氧化与煤的自燃机制探讨.西安矿业学院学报,1988,8(1):90~94
[39] 徐精彩.张辛亥.文虎.等. 煤氧复合过程及放热强测算方法. 中国矿业大学学报,2000,29(3): 253~257
[40] Itay M.Hill C R.Glasser D. Study of the low temperature oxidation of coal. Fuel Processing Technology, 1989,21(2):81~97
[41] Continillo G.Galiero G.Maffettone P L.etc. Characterization of chaotic in the spontaneous combustion of coal stockpiles. Symposium on combustion, 1996.1585~1592
[42] 贺敦良.徐精彩.煤炭表面反应热与自燃性探讨.煤矿安全,1990(6):31~36
[43] 何萍.唐修义.煤氧化过程中气体的形成特征与煤自燃指标气体选择.煤炭学报,1994,19(6): 635~643
[44] 舒新前.葛岭梅.神府煤煤岩组分的结构特征及其差异.燃料化学学报,1996,24(5): 427~431
[45] 舒新前.朱书全.王祖讷.等.神府煤煤岩组分的表面电位研究.中国科学(E辑),1996,26(4): 333~338
[46] 王晓华.葛岭梅.周安宁等.神府煤流化床低温氧化煤分子中活性基团的变化. 西安科技学院学报,2001,21(1): 40~43
[47] 张玉贵.唐修义.何萍.煤分子结构与煤的自燃倾向性.煤矿安全,1989(7):1~5
[48] 张玉贵.镜煤和丝炭自燃倾向性研究.煤矿安全,1991 (2):20~24
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