张铎 唐瑞 王振 邓军 张辛亥 蒋志刚 陈曦

摘 要：為有效防治红庆河矿煤层自然发火灾害，利用同步热分析仪测试了该矿不粘煤在4种不同升温速率（5，10，15，20 K/min）下样品质量随温度的变换规律，采用atava推断法和Popescu法对数据进行了动力学分析。结果表明相同温度下，升温速率越小，煤的反应程度越高;确定了红庆河煤自燃升温过程中8个特征温度点及其阈值。据此将自燃升温过程划分为5个阶段：水分蒸发及气体脱附、吸氧增重、热分解失重、燃烧阶段和燃尽阶段。研究发现第Ⅰ阶段的最概然机理函数符合二维扩散Jander方程，明确了该阶段氧化动力学模式。进而计算出4种不同升温速率下的活化能分别为：64.35，110.91，70.42，59.72 kJ/mol，指前因子分别为3.51×1014，1.29×1021，3.41×1015，1.23×1014 s-1.活化能和指前因子动力学计算结果揭示了不同升温速率条件下，第Ⅰ阶段煤氧复合反应的程度不同，这为研究煤自燃分级预警方法和主动防控技术提供了重要的理论依据。关键词：煤自燃;热分析;动力学;活化能;指前因子;特征温度

中图分类号：TD 752

文献标志码：A

文章编号：1672-9315（2020）06-0974-07

DOI：10.13800/j.cnki.xakjdxxb.2020.0606开放科学（资源服务）标识码（OSID）：

Thermodynamics characteristics of spontaneous combustion of

Hongqinghe coal based on thermogravimetric analysis

ZHANG Duo1，2，TANG Rui1，WANG Zhen3，DENG Jun1，2，

ZHANG Xin-hai1，JIANG Zhi-gang4，CHEN Xi4

（1.College of Safety Science and Engineering，Xian University of Science and Technology，Xian 710054，China;

2.Postdoctoral Research Mobile Station in Mining Engineering，Xian University of Science and Technology，Xian 710054，China;

3.Xian Railway Engineering Staff University，Xian 710065，China;

4.Technology Center，Sichuan Coal Industry Group Limited Company，Chengdu 610091，China）

Abstract：In order to effectively prevent and control the mine spontaneous combustion disaster of Hongqinghe coal mine，the dynamic characteristics of the coal spontaneous combustion were

examined.Simultaneous thermal analysis technology was used to test the change of sample quality with temperature at four different heating rates（5，10，15，20 K/min）of non-stick coal of Hongqinghe Mine.The atava inference method and the Popescu method were used to calculate the kinetics.The results show that at the same temperature，the smaller the heating rate，the higher the degree of coal reaction.Eight characteristic temperature points during the spontaneous combustion temperature rise of Hongqinghe coal were identified with characteristic temperature thresholds given.Therefore，the process of coal spontaneous combustion heating was divided into five stages：water evaporation and gas desorption，oxygen absorption weight gain，thermal decomposition weight loss，combustion stage and burnout stage.It is found that the most probable mechanism function of the low-temperature oxidation stage of the Hongqinghe coal mine conforms to the two-dimensional diffusion Jander equation，and the oxidation kinetic model at this stage was determined.

The activation energy at four different heating rates were calculated to be 64.35，110.91，70.42，59.72 kJ/mol.The pre-finger factors are 3.51×1014，1.29×1021，3.41×1015，and 1.23×1014 s-1，

respectively.The activation energy and pre-finger factor kinetic calculation results reveal that the energy barrier of the first stage coal-oxygen composite reaction is different under

different heating rate conditions，this provides  theoretical and practical significance for the study of coal spontaneous combustion classification early warning method and active prevention and control technology.

Key words：coal

spontaneous combustion;thermogravimetric analysis;thermodynamics;activation energy;preexponential factor;characteristic temperature

0 引 言

2019年BP Statistical Review of World Energy数据表明，2018年中国一次能源消费总量为33.05亿吨油当量，其中煤炭为19.13亿吨油当量，占比为57.89%;中国煤炭产量为18.29亿吨油当量，占世界煤炭总产量的46.70%[1]。研究表明煤自燃灾害与煤炭开采密切相关[2-3]，每年都有大量煤炭资源被火灾烧毁。煤火灾害还可能导致生态破坏、人员伤亡和经济损失等严重问题[4-6]。红庆河矿不粘煤因低硫、低磷、低灰分的特点而将其归于“优质煤”之列。……