Coal Geology & Exploration
Abstract
Objective When used for the treatment of fire zones in deep coal mine goafs, low-oxygen and inertization techniques suffer from a scientifically blind spot, i.e., the fire prevention and control bottleneck caused by a high susceptibility to re-ignition of coals after being treated with high-temperature, low-oxygen (or inert) gas. To overcome this limitation, this study aims to systematically determine the mechanisms by which the evolution of the physical and chemical structures of coals after heat treatment under different atmospheres influences their spontaneous combustion and activation behavior. The purpose is to provide theoretical support for the treatment and safe opening of fire zones in a coal mine goaf. Methods This study investigated gas-bearing coals in the Zhujidong Coal Mine, Anhui Province. Using a series of techniques, such as the Fourier transform infrared spectroscopy (FTIR), specific surface area and pore size analyses, thermal conductivity tests, and thermogravimetric analysis, this study systematically investigated the evolution of the chemical functional groups and changes in the pore structures in coal samples after heat treatment under atmospheres of 13% O2, N2, and CO2. In combination with low-temperature oxidation experiments, this study monitored the release patterns of indicator gases such as CO and C2H4, oxygen consumption rates, and exothermic intensities of these coal samples. Additionally, variations in the activation energy for coal spontaneous combustion were quantitatively assessed through kinetic parameter-based inversion. Results and Conclusions FTIR analysis revealed that coal samples after heat treatment under different atmospheres exhibited significantly decreased ―OH content and noticeably increased contents of C―O and C=O. Among these, samples treated under a CO2 atmosphere showed the most prominent effect of functional group reconstruction. Pore structure analysis suggests that coal samples after heat treatment exhibited significantly increased pore volumes and micropore specific surface areas, as well as improved pore connectivity. Most especially, samples treated under a CO2 atmosphere exhibited the most developed pores with pore sizes ranging from 2 nm to 50 nm, with a micropore volume increasing by 0.3 μL/g and micropore specific surface area reaching up to 1.56 m2/g. These samples were followed by those treated under a N2 atmosphere and then those treated under a 13% O2 atmosphere in this regard. The test results of thermophysical properties and low-temperature oxidation characteristics revealed a generally enhanced thermal conductivity and low-temperature oxidation activity of coal samples after heat treatment, as manifested by significantly increased volume fractions of CO and C2H4, elevated oxygen consumption rates, and enhanced exothermic intensities. Kinetic analysis demonstrated that the apparent activation energy of the coal samples treated under 13% O2, N2, and CO2 atmospheres decreased by 8.3%, 17.6%, and 21.6%, respectively. Thermogravimetric analysis (TGA) further confirmed that the active temperature t3 of coal samples after heat treatment dropped by 2‒11 ℃. Furthermore, the mass loss rates in stages from t3 to t5 of the coal samples decreased in the order of those treated under CO2, N2, and 13% O2 atmospheres. These findings suggest that although heat treatment under inert atmospheres (especially CO2) can temporarily suppress oxygen, it could increase the tendency of coals to spontaneous combustion. In engineering, it is advisable to adopt N2 injection or N2-CO2 co-injection, supplemented by measures including temperature control, heat insulation, and fire suppression agents, to establish a multi-element fire prevention and re-ignition control system. This will help enhance the safety and long-term stability of the fire zones of coal mine goafs.
Keywords
spontaneous combustion of coal, pore structure, functional group, indicator gas, characteristic temperature point, coal mine goaf
DOI
10.12363/issn.1001-1986.25.04.0281
Recommended Citation
ZHANG Leilin, LI Wanting, WEN Chenchen,
et al.
(2025)
"Structural evolution and spontaneous combustion and activation mechanisms of coals treated under inert atmospheres in a coal mine goaf,"
Coal Geology & Exploration: Vol. 53:
Iss.
11, Article 10.
DOI: 10.12363/issn.1001-1986.25.04.0281
Available at:
https://cge.researchcommons.org/journal/vol53/iss11/10
Reference
[1] 唐跃刚,王绍清,王晓帅,等. 洁净煤地质内涵、现状与未来发展方向[J]. 煤田地质与勘探,2025,53(1):36−63.
TANG Yuegang,WANG Shaoqing,WANG Xiaoshuai,et al. Connotation,research status,and development directions of clean coal geology in China[J]. Coal Geology & Exploration,2025,53(1):36−63.
[2] 袁亮,张通,王玥晗,等. 深部煤炭资源安全高效开采科学问题及关键技术[J]. 煤炭学报,2025,50(1):1−12.
YUAN Liang,ZHANG Tong,WANG Yuehan,et al. Scientific problems and key technologies for safe and efficient mining of deep coal resources[J]. Journal of China Coal Society,2025,50(1):1−12.
[3] ONIFADE M,GENC B. A review of research on spontaneous combustion of coal[J]. International Journal of Mining Science and Technology,2020,30(3):303−311.
[4] 徐永亮,孙萌,王兰云,等. 矿井带式输送机火灾烟流特性及其预警防控综述[J]. 中国安全科学学报,2024,34(3):117−128.
XU Yongliang,SUN Meng,WANG Lanyun,et al. Review of fire smoke flow characteristics and early warning prevention and control of mine belt conveyor[J]. China Safety Science Journal,2024,34(3):117−128.
[5] 余明高,阳旭峰,郑凯,等. 我国煤矿瓦斯爆炸抑爆减灾技术的研究进展及发展趋势[J]. 煤炭学报,2020,45(1):168−188.
YU Minggao,YANG Xufeng,ZHENG Kai,et al. Progress and development of coal mine gas explosion suppression and disaster reduction technology in China[J]. Journal of China Coal Society,2020,45(1):168−188.
[6] LU Yi,SHI Shiliang,WANG Haiqiao,et al. Thermal characteristics of cement microparticle–stabilized aqueous foam for sealing high–temperature mining fractures[J]. International Journal of Heat and Mass Transfer,2019,131:594−603.
[7] 李树刚,张静非,林海飞,等. 双碳战略中煤气共采技术发展路径的思考[J]. 煤炭科学技术,2024,52(1):138−153.
LI Shugang,ZHANG Jingfei,LIN Haifei,et al. Thoughts on the development path of coal and gas co–mining technology in dual carbon strategy[J]. Coal Science and Technology,2024,52(1):138−153.
[8] 周博斐,张廷尧,周月桂. 高温低氧及富氧气氛下煤粉颗粒着火和燃烧特性数值分析[J]. 燃烧科学与技术,2021,27(6):653−658.
ZHOU Bofei,ZHANG Tingyao,ZHOU Yuegui. Numerical analysis of ignition and combustion characteristics of pulverized coal particles in low–oxygen and oxy–fuel atmospheres at high–temperature[J]. Journal of Combustion Science and Technology,2021,27(6):653−658.
[9] 甘青青,许江,蔡果良,等. 升温速率对热压型煤微结构演化规律及力学、渗流特性的影响[J]. 矿业科学学报,2024,9(5):786−796.
GAN Qingqing,XU Jiang,CAI Guoliang,et al. Effect of heating rate on microstructure evolution and mechanical-seepage characteristics of hot-pressed briquettes[J]. Journal of Mining Science and Technology,2024,9(5):786−796.
[10] 王双明,申艳军,孙强,等. “双碳”目标下煤炭开采扰动空间CO2地下封存途径与技术难题探索[J]. 煤炭学报,2022,47(1):45−60.
WANG Shuangming,SHEN Yanjun,SUN Qiang,et al. Underground CO2 storage and technical problems in coal mining area under the “dual carbon” target[J]. Journal of China Coal Society,2022,47(1):45−60.
[11] 梁杰,王喆,梁鲲,等. 煤炭地下气化技术进展与工程科技[J]. 煤炭学报,2020,45(1):393−402.
LIANG Jie,WANG Zhe,LIANG Kun,et al. Progress and technology of underground coal gasification[J]. Journal of China Coal Society,2020,45(1):393−402.
[12] XIAO Yang,REN Shuaijing,DENG Jun,et al. Comparative analysis of thermokinetic behavior and gaseous products between first and second coal spontaneous combustion[J]. Fuel,2018,227:325−333.
[13] TARABA B,PAVELEK Z. Study of coal oxidation behaviour in re–opened sealed heating[J]. Journal of Loss Prevention in the Process Industries,2016,40:433−436.
[14] DONG Liang,WANG Ziming,ZHANG Yadong,et al. Study on pyrolysis characteristics of coal and combustion gas release in inert environment[J]. Journal of Chemistry,2019,2019(1):1032529.
[15] 王双明,孙强,胡鑫,等. 不同气氛下富油煤受热裂隙演化及热解动力学参数变化[J]. 煤炭科学技术,2024,52(1):15−24.
WANG Shuangming,SUN Qiang,HU Xin,et al. Fissure evolution and variation of pyrolysis kinetics parameters of tar–rich coal during heat treatment under different atmosphere[J]. Coal Science and Technology,2024,52(1):15−24.
[16] TANG Yibo,XUE Sheng. Laboratory study on the spontaneous combustion propensity of lignite undergone heating treatment at low temperature in inert and low–oxygen environments[J]. Energy & Fuels,2015,29(8):4683−4689.
[17] ZHANG Yixin,DONG Jixiang,GUO Fanhui,et al. Effects of the evolutions of coal properties during nitrogen and MTE drying processes on the spontaneous combustion behavior of Zhaotong lignite[J]. Fuel,2018,232:299−307.
[18] LI He,SHI Shiliang,LIN Baiquan,et al. Effects of microwave–assisted pyrolysis on the microstructure of bituminous coals[J]. Energy,2019,187:115986.
[19] 叶正亮,郭曦蔓,尚博,等. 煤变质程度对微观结构与热解参数的影响及关联性分析[J]. 中国安全科学学报,2025,35(2):57−65.
YE Zhengliang,GUO Ximan,SHANG Bo,et al. Influence of coal metamorphism on microstructure and pyrolysis parameters:A correlation analysis[J]. China Safety Science Journal,2025,35(2):57−65.
[20] 张玉涛,杨杰,李亚清,等. 煤自燃特征温度与微观结构变化及关联性分析[J]. 煤炭科学技术,2023,51(4):80−87.
ZHANG Yutao,YANG Jie,LI Yaqing,et al. Correlation analysis between characteristic temperature and microstructure of coal spontaneous combustion[J]. Coal Science and Technology,2023,51(4):80−87.
[21] 张锦萍,李冬,张成,等. 低温热提质褐煤的理化结构演化及燃烧特性[J]. 煤炭学报,2015,40(3):671−677.
ZHANG Jinping,LI Dong,ZHANG Cheng,et al. Physical/chemical structure evolution and combustion characteristics of mild thermally upgraded lignite[J]. Journal of China Coal Society,2015,40(3):671−677.
[22] 王福生,张志明,武建国,等. 煤体结构对自燃倾向性影响研究[J]. 煤炭科学技术,2020,48(5):83−88.
WANG Fusheng,ZHANG Zhiming,WU Jianguo,et al. Study on influence of coal structure on spontaneous combustion tendency[J]. Coal Science and Technology,2020,48(5):83−88.
[23] 刘垚,王福生,董轩萌,等. 基于程序升温试验的煤自燃特性及微观机理研究[J]. 煤炭科学技术,2024,52(增刊1):94−106.
LIU Yao,WANG Fusheng,DONG Xuanmeng,et al. Study on the characteristics and microscopic mechanism of coal spontaneous combustion based on programmed heating experiment[J]. Coal Science and Technology,2024,52(Sup.1):94−106.
[24] XU Tao. Heat effect of the oxygen–containing functional groups in coal during spontaneous combustion processes[J]. Advanced Powder Technology,2017,28(8):1841−1848.
[25] 秦波涛,邵旭,李子威,等. 火成岩侵入对煤物化结构与低温氧化的影响机制[J]. 中国矿业大学学报,2025,54(1):186−201.
QIN Botao,SHAO Xu,LI Ziwei,et al. Mechanisms of igneous intrusion on coal physical and chemical structure and low–temperature oxidation[J]. Journal of China University of Mining & Technology,2025,54(1):186−201.
[26] 徐帅,张虹,刘雪景. 内构件调控下高温热解煤焦理化性质与燃烧动力学[J]. 科学技术与工程,2025,25(14):5976−5982.
XU Shuai,ZHANG Hong,LIU Xuejing. Properties and combustion kinetics of coalchar through high–temperature internals–regulated pyrolysis[J]. Science Technology and Engineering,2025,25(14):5976−5982.
[27] 刘和武,吕晓雪,侯晨亮,等. 动力变质作用对构造煤微纳米孔隙结构演化的影响机理[J]. 煤田地质与勘探,2024,52(12):1−12.
LIU Hewu,LYU Xiaoxue,HOU Chenliang,et al. Influence mechanisms of dynamic metamorphism on the evolution of micro/nano pore structures in tectonically deformed coals[J]. Coal Geology & Exploration,2024,52(12):1−12.
[28] 罗元培,张盛平,任文君,等. 连续外热式低阶煤热解–干熄焦反应实验研究[J]. 工程热物理学报,2025,46(4):1355−1367.
LUO Yuanpei,ZHANG Shengping,REN Wenjun,et al. Experimental study on continuous externally heated lowrank coal pyrolysis coupled with coke dry quenching[J]. Journal of Engineering Thermophysics,2025,46(4):1355−1367.
[29] 杨甫,程相强,李明杰,等. 富油煤原位热解多物理场演化规律数值模拟研究[J]. 煤田地质与勘探,2024,52(7):25−34.
YANG Fu,CHENG Xiangqiang,LI Mingjie,et al. Numerical simulations of the evolutionary patterns of multi–physical fields during the in–situ pyrolysis of tar–rich coals[J]. Coal Geology & Exploration,2024,52(7):25−34.
[30] 娄和壮,贾廷贵. 惰性气氛对煤自燃过程的竞争吸附差异性研究[J]. 中国安全科学学报,2020,30(4):60−67.
LOU Hezhuang,JIA Tinggui. Competitive adsorption difference during coal spontaneous combustion process in noble gas atmosphere[J]. China Safety Science Journal,2020,30(4):60−67.
[31] 文虎,李倬锋,张铎,等. 低温阶段煤吸附C2H4的吸附特性研究[J]. 中国安全科学学报,2024,34(1):94−105.
WEN Hu,LI Zhuofeng,ZHANG Duo,et al. Investigation of adsorption characteristics of C2H4 from coal in low–temperature stage[J]. China Safety Science Journal,2024,34(1):94−105.
[32] 张嘉勇,吕祖欣,崔啸,等. 正断层影响下采空区注CO2防灭火数值模拟研究[J]. 中国安全科学学报,2025,35(4):9−17.
ZHANG Jiayong,LYU Zuxin,CUI Xiao,et al. Numerical simulation of CO2 injection for fire prevention in a goaf affected by normal fault influence[J]. China Safety Science Journal,2025,35(4):9−17.
[33] 邓军,张敏,雷昌奎,等. 不同变质程度煤自燃特性及低温氧化动力学分析[J]. 安全与环境学报,2021,21(1):94−100.
DENG Jun,ZHANG Min,LEI Changkui,et al. Kinetic analysis of the low temperature spontaneous oxidation combustion of the coal seams due to the different metamorphism extents[J]. Journal of Safety and Environment,2021,21(1):94−100.
[34] YANG Yongliang,LI Zenghua,HOU Shisong,et al. The shortest period of coal spontaneous combustion on the basis of oxidative heat release intensity[J]. International Journal of Mining Science and Technology,2014,24(1):99−103.
[35] 于志金,晋策,汤旭,等. 岩浆侵入与接触距离对煤低温氧化过程热效应的影响[J]. 煤炭学报,2024,49(12):4873−4882.
YU Zhijin,JIN Ce,TANG Xu,et al. Influence of magma intrusion and contact distance onthermal effects of low–temperature oxidation processes in coal[J]. Journal of China Coal Society,2024,49(12):4873−4882.
[36] 徐永亮,刘泽健,步允川,等. 单轴应力下烟煤氧化–自燃灾变温度[J]. 工程科学学报,2021,43(10):1312−1322.
XU Yongliang,LIU Zejian,BU Yunchuan,et al. Catastrophic temperature of oxidation–spontaneous–combustion for bituminous coal under uniaxial stress[J]. Chinese Journal of Engineering,2021,43(10):1312−1322.
[37] 秦波涛,宋爽,戚绪尧,等. 浸水过程对长焰煤自燃特性的影响[J]. 煤炭学报,2018,43(5):1350−1357.
QIN Botao,SONG Shuang,QI Xuyao,et al. Effect of soaking process on spontaneous combustion characteristics of long–flame coal[J]. Journal of China Coal Society,2018,43(5):1350−1357.
[38] 周晓东,吴浩,刘景梅,等. TG–FTIR研究煤油共热解产物逸出行为[J]. 燃料化学学报(中英文),2024,52(4):525−537.
ZHOU Xiaodong,WU Hao,LIU Jingmei,et al. TG–FTIR study on escape behavior of products from co–pyrolysis of coal and residuum[J]. Journal of Fuel Chemistry and Technology,2024,52(4):525−537.
[39] ZHANG Duo,WANG Weifeng,DENG Jun,et al. Thermokinetic characteristics of Jurassic coal spontaneous combustion based on thermogravimetric analysis[J]. Combustion Science and Technology,2022,194(8):1527−1541.
[40] ZHAO Jingyu,DENG Jun,CHEN Long,et al. Correlation analysis of the functional groups and exothermic characteristics of bituminous coal molecules during high–temperature oxidation[J]. Energy,2019,181:136−147.
[41] HOU Xinran,GUO Liwen,WANG Fusheng. Inhibiting effects of three phosphates on coal spontaneous combustion[J]. International Journal of Coal Preparation and Utilization,2022,42(10):3054−3069.
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