Changes in the reaction regime during low-temperature oxidation of coal in confined spaces

A study of the initial stage of the low-temperature oxidation of coal is important, not only for the prevention for fires in coal industry, but also in reducing emissions of hazardous gases. A batch reactor was introduced and a series of simulated experiments of coal oxidation was carried out in this paper. The time-dependent rates of CO emission and oxygen consumption during oxidation experiments of coal samples with different particle size ranges were obtained simultaneously from the measurements of CO and O₂ concentration in the reactor. The experimental results show that the rate of CO emission presents three stages in the duration of coal oxidation. Based on the rates of oxygen consumption, the reaction order and reaction rate were obtained from the reaction rate equation. These results indicate that the reaction regime switches during coal oxidation in confined spaces. The initial decrease of reaction rate is due to the decrease of the active sites in coal. While the decrease of reaction rate in the following period of coal oxidation is attributed to the reaction-inhibition mechanism of oxidation products. And it is mainly represented by the chemisorption sequence of coal oxidation. The oxidative activity of coal can be restored when the oxidation products are evacuated. A mechanism of low-temperature oxidation of coal in confined spaces was also suggested.     

The relationship between oxygen consumption rate and temperature during coal spontaneous combustion

Spontaneous combustion is a major natural disaster in coal production. In the process of exploring coal self-ignition, a series of hypotheses have been put forward, most scholars agree that the current coal-oxygen compound theory. Oxygen consumption rate reflects the status of coal spontaneous combustion, and it is also one of the parameters necessary for numerical simulation of coal spontaneous combustion. In this paper, a coal heating and oxidation experiment was designed, Experimental device consists of heating and oxidation furnace, gas chromatograph, temperature control and data acquisition systems and other equipment components. Three coal samples whose weight each is 5 g were selected for the study. By experiment, oxygen concentration at the inlet and outlet of temperature oxidation furnace was measured. Oxygen consumption rate is calculated in the heating process of coal according to air flow. In the Cartesian coordinate system, the temperature as abscissa and the oxygen consumption rate for the longitudinal coordinates, drawing the relationship between oxygen consumption rate and temperature plot. And then regression analysis was used to analyze the relationship between oxygen consumption rate and coal temperature during the heating and oxidation process of coal. The results show that the oxygen consumption rate and temperature of coal were linear relationships both before and after the critical temperature when the coal temperature is less than 180 °C. Before the critical temperature oxygen consumption rate is low, however it increases rapidly when coal temperature reaches a critical temperature. The result is important for the prevention and treatment of spontaneous combustion of coal.     

煤氧复合热效应的影响因素分析

煤的氧化放热是引起煤自燃的主要原因。煤氧复合热效应与耗氧速率和表面反应热有关。通过分析得出 ,q(z,n,CO2 ,T,d5 0 ) =h(Z) .g(n) .f (CO2 ) .I(T) .Ψ (d5 0 )。其中主要影响因素为煤结构、温度、氧浓度及粒度。根据威斯化学结构模型、本田化学结构模型及煤分子中包含的 7种表面活性结构 ,推出煤自燃表面分子结构模型 ,并分析其表面活性结构的种类、数量、活泼性 ,它们随煤体不同而千差万别 ;表面活性结构随温度变化的氧化活泼性及反应过程不同 ,造成煤表面氧化反应热 H不同。外在主要影响因素—煤的温度、氧浓度、粒度不同造成了耗氧速率 VO2 不同 ,使煤的放热强度不同。对此 ,通过 XK型煤自然发火实验台及 XKS程序升温实验台进行了实验分析     

Experimental study on oxygen consumption rate of residual coal in goaf

In order to research the actual oxygen consumption rate of residual coal in goaf, the heating and oxidizing experiment was conducted respectively on five types of single particle size of coal samples and one hybrid particle size of coal samples by using self-developed CSC-B2 test system. This study measured inlet and outlet oxygen concentration of the oxidation tank, and calculated the oxygen consumption rate of each coal sample at different temperatures. For the residual coal in the same goaf, which is regarded as a hybrid particle size of coal consisting of a variety of single granularity of coal, its oxygen consumption rate is the mass weighted average of the rate of each particle size of coal. Accordingly, this paper established the equation of oxygen consumption rate of hybrid particle size of coal samples, taking into account temperature, granularity and oxygen concentration. Then comparison between the calculated value and the actually measured value of oxygen consumption rate of hybrid particle size of coal samples at different temperatures was conducted. And the results reveal that the calculated value basically coincide with the actually measured one. Moreover, the results prove that the established calculation formula for oxygen consumption rate can be used to accurately calculate the actual oxygen consumption rate of residual coal samples. The achievement of this research is of theoretical and practical significance for learning about the characteristics of coal spontaneous combustion and forecasting the self-ignition of residual coal in goaf.     

煤自燃发火潜伏期不同温度下耗氧特性的研究

为了探究地层温度的升高对采空区自燃倾向性的影响,对处于自燃潜伏期的煤展开耗氧特性和CO释放特性的研究。通过对长平矿3#煤分别进行20~60℃的封闭耗氧实验,得到了自燃潜伏期不同温度下煤的氧浓度以及CO浓度随时间变化的曲线。对氧浓度变化曲线和CO浓度变化曲线进行拟合分析得到了不同温度下煤的氧气消耗和CO生成速度,同时得到了氧浓度衰减系数和CO浓度增长系数。封闭耗氧实验结果表明:从20~60℃氧气消耗速度逐渐增大并且氧浓度衰减系数呈指数增长,CO浓度增长系数也逐渐增大并且同样呈指数增长,煤的窒熄带氧浓度临界值从20~60℃逐渐由16.8%降低到12.4%。为探究不同温度下采空区煤的自燃发火危险性,将封闭耗氧实验结果的参数应用到采空区CFD数值模拟仿真中,模拟得到随着温度升高采空区窒熄带临界氧浓度位置由200 m增长到380 m。结果表明:常温下不易自燃的煤在较高的环境温度下表现出了较强的氧气消耗和CO释放能力,并且采空区自然氧化带随着温度的升高动态变宽,增大了采空区的自燃发火危险性。     

不同粒径易自燃煤常温氧化实验研究*

为探究易自燃煤在常温条件下的氧化特性,自行设计煤常温封闭氧化实验装置,采用实验研究与回归分析2种方法,分析易自燃煤发生氧化反应的气体变化过程,探究3种粒径煤样在20 ℃有限空间内的耗氧与产气特征。结果表明:易自燃煤样在16 d常温封闭氧化过程中,容器内O2体积浓度呈指数衰减、CO和CO2体积浓度呈指数增长的变化规律;在0.06~0.83 mm范围内,粒径越大,易自燃煤耗氧速率越大,CO和CO2产生速率则先增大后减小;介于中间的粒径为0.13~0.25 mm易自燃煤氧化反应最强烈,更容易发生氧化。研究结果对揭示生产环境温度下煤粒粒径对煤自燃的影响有一定的意义。     

电厂烟气对采空区防火效果实验研究

为考察电厂烟气对采空区防灭火效果的影响,采用吸附实验装置和热重分析仪开展了不同气体氛围下煤吸附O2的实验研究,研究了不同气氛下煤的着火活化能。结果表明:将惰性气体N2和烟气注入井下,均可有效地减小常温常压下煤对氧气的吸附量,即具有抑制煤自燃氧化反应的作用。其中,烟气对减小煤吸附氧气量的效果优于N2,使同忻矿和高海矿煤样吸附氧气量分别减少了27%和35%。TG实验数据表明,煤样在烟气氛围下燃烧时低温氧化阶段的增重率略小于在空气氛围下燃烧时的增重率,而其着火点大于在空气氛围下燃烧时的着火点。同时,发现煤样在烟气中燃烧时的着火活化能大于在空气中燃烧时的着火活化能,说明煤在烟气氛围下燃烧时对O2的吸附量变小,活化能增大,增加了煤自燃的困难程度。     

煤自燃预测气体及活化能变化研究

为了研究煤在低温阶段的自燃活化能及气体产生规律,基于耗氧量与煤温间的计算模型,利用煤氧化动力学测试系统,分析了3种不同自燃性煤的低温氧化表征。结果表明:1)随着煤自燃倾向性增强,煤的耗氧量和耗氧速率逐渐增大,且其耗氧速率急剧增大的拐点温度逐渐升高;2)不同自燃性煤活化能变化规律存在显著差异,利用阶段耗氧量拐点计算出铜川和大同煤样温度分别为203℃、228℃时,活化能快速减小,开始进入自发氧化阶段;晋城煤样活化能经历先减小后增大的过程,其中过渡温度段91~135℃时,活化能最小;同时拟合出活化能(E)与指前因子(A)关系式满足动力补偿效应,验证了机理函数的合理性;3)依据复合气体CO_2/CO、CH_4/C_2H_6、C_2H_4/C_2H_6、C_3H_8/C_2H_6随温度的变化趋势,结合煤低温氧化特性,可预测煤样的氧化进程和煤体温度。     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

不同变质程度煤自燃特性及低温氧化动力学分析

为了研究不同变质程度煤在低温氧化自燃过程中的特性,以及煤样变质程度对煤自燃过程的影响,利用程序升温试验系统研究了不同变质程度煤在低温氧化阶段气体与特征温度变化规律。通过计算其耗氧速率、放热强度,分析了耗氧速率、放热强度与温度之间的对应关系。同时分析了煤样变质程度对CO、CO₂气体及耗氧速率、放热强度的影响规律。根据程序升温的试验条件和阿伦尼乌斯公式建立了CO与温度的计算模型,分析了该方程的线性回归直线斜率,计算了不同变质程度煤低温氧化活化能,分析并印证了煤样变质程度与活化能之间的关系。根据不同煤质工业分析指标试验结果,进一步阐述了各煤种主要煤质工业分析指标的差别,分析了主要指标与煤程序升温试验自燃氧化参数的相关性,同时分析了主要工业分析指标对各特征参数的影响。结果表明:煤在低温氧化自燃过程所产出的CO和CO₂气体释放量、耗氧速率及放热强度均随温度升高而呈指数级增长;随煤样变质程度增加,CO和CO₂气体、耗氧速率、放热强度变化较小;煤的变质程度越高,特征温度和活化能越大;煤样自燃的可能性越小,危险性越小;结合煤样工业分析与活化能发现,水分、灰分、挥发分含量与活化能呈负相关。     

单轴应力对煤自燃特性参数和导热系数的影响研究

为探究单轴应力作用下煤氧化和传热特性,利用自制荷载加压煤自燃特性参数测定装置对炉体内长焰煤煤样进行程序升温。结合程序升温过程中煤临界温度Tc和Tg,对其进行阶段划分:阶段1为30℃~Tc;阶段2为Tc~Tg。计算了不同单轴应力下2个阶段煤表观活化能和平均耗氧速率。根据能量守恒得出程序升温过程煤导热系数随温度的变化,进一步分析煤导热系数与单轴应力的关系。结果表明:阶段1单轴应力为4 MPa时为临界轴压,煤表观活化能最大,平均耗氧速率最小;阶段2煤表观活化能和平均耗氧速率随单轴应力增大均呈抛物线变化,单轴应力为2.7 MPa时为临界轴压,煤表观活化能最大,平均耗氧速率最小;阶段1和2煤导热系数随温度升高均先减小后增大,并且煤导热系数随单轴应力增大呈三次函数变化。     

“U+I”型采煤工作面瓦斯抽采与浮煤自燃耦合研究

为了研究“U+I”型工作面进风量和顶板巷抽采负压对工作面瓦斯浓度与采空区氧化带宽度的影响,协调瓦斯抽采和浮煤自燃之间的关系。以2306综放面为工程背景,基于“U”型冒落岩层孔隙率分布公式和流体通用控制方程建立采空区数值模拟解算模型。采用CFD软件对不同进风量、不同抽采负压下的工作面瓦斯浓度和采空区氧化带宽度进行模拟,结果表明:随着工作面风量的增加,工作面和顶板巷瓦斯浓度减小,但工作面处浓度减幅逐渐变小而顶板巷浓度减幅几乎不变;提高顶板巷抽采负压,对减少工作面瓦斯浓度效果明显,顶板巷自身瓦斯浓度先增加再减小,采空区进风侧氧化带宽度变窄,回风侧和采空区中部氧化带宽度增加,总体上增加了采空区浮煤自燃的危险性但影响程度有限。     

Evaluation of the spontaneous combustion characteristics of coal of different metamorphic degrees based on a temperature-programmed oil bath experimental system

Research on the micro- and macrocharacteristics of different metamorphic degrees of coal helps improve the control and protection techniques used during spontaneous combustion. Nine coals with different properties were thoroughly investigated in this study. Fourier transform infrared spectroscopy and a self-designed temperature-programmed oil bath experimental system were adopted to analyze the molecular structure and macrocharacteristic parameters of the spontaneous combustion of coal. Additionally, the influence of particle size on spontaneous combustion was considered. Various functional groups were employed as microcharacteristic parameters to capture the principal active groups in oxidation. The gas production rate, oxygen consumption rate, gas concentration, heat energy release rate, and characteristic temperatures were evaluated as macrocharacteristic parameters to investigate the changes in coal during oxidation. The results establish that the microcharacteristics of coal molecules determine the degree of spontaneous combustion based on intrinsic properties and that changes in the macrocharacteristics of the spontaneous combustion of coal reflect the microstructural changes. The contents of the hydroxyl groups, carbonyl groups, alkyl ether and aryl ether in the coal molecules gradually decrease with the metamorphic increase. Oxygen-containing functional groups have higher reactivities and easily react with oxygen, causing the macroparameters, such as the oxygen consumption rate, the gas generation rate and the heat energy release rate, to consistently decrease with the increase of the metamorphic degree. Small-particle-size coal molecules have more active aliphatic hydrocarbons, oxygen-containing functional groups and a larger specific surface area, increasing the chances of adsorbing the oxygen of active groups and promoting the reaction between coal and oxygen. The experimental results indicate that coal samples with higher metamorphic degrees or larger sizes exhibit lower tendencies toward spontaneous combustion. Evaluation of the spontaneous combustion of coal based on a temperature-programmed oil bath experimental system is of great practical importance for preventing the spontaneous combustion of coal during storage, processing and utilization and can serve as a convenient reference for production safety in mining applications.     

空气湿度对煤自燃特性影响的试验研究

为研究空气湿度对煤自燃特性的影响,运用程序升温试验台,在不同环境湿度条件下,对黄陵2号矿4#煤层煤样进行程序升温,分析不同温度下的气体成分,计算煤样在不同温度和湿度条件下的耗氧速率、CO和CO_2产生率,以及煤氧化的表观活化能。结果表明:与在干燥的空气中氧化相比,煤在加湿空气中的耗氧速率、CO和CO_2产生率升高,活化能降低,表明加湿有利于煤自燃;随空气湿度增加,煤体的耗氧速率、cO和CO_2产生率先升高后降低,活化能先降低后增加,表明存在一个最容易使煤氧化自燃的临界空气湿度;黄陵2号矿4#煤层煤样的临界相对湿度为25%左右。     

采空区不同瓦斯抽采方法与自燃合理平衡的数值模拟

为了研究和解决西铭矿在生产中由于瓦斯抽采方法的不同可能引起采空区自燃以及瓦斯爆炸等重大安全隐患问题,构建了高位巷、埋管和高低位钻孔瓦斯抽采方法下的非均质多孔介质三维模型。利用非线性渗流定律、通用控制方程和自定义的函数进行解算,结果表明:高位巷、高低位钻孔抽采流量与抽采氧气浓度近似呈正比函数关系,埋管抽采流量与氧化带宽度呈指数函数关系;高位巷、高低位钻孔随着抽采流量的增加抽采效率反而降低,抽采总量增加,埋管抽采位置在距工作面35m处、抽采流量为20m3/min能很好解决上隅角瓦斯超限问题。根据模拟结论:采用立体联合瓦斯抽采方法既能满足抽采要求又能有效控制采空区自燃现象。     

Limiting explosible concentration of hydrogen–oxygen–helium mixtures related to the practical operational case

This paper presents data on the limiting (minimum) concentrations of hydrogen in oxygen, in the presence of added helium, at elevated temperature and pressure related to the practical operational case. A 5 L explosion vessel, an ignition sub-system and a transient pressure measurement sub-system were used. Through a series of experiments carried out using this system, the limiting concentrations of hydrogen in oxygen and helium at different initial pressures and temperatures for the practical operational case were studied, and the influence of ignition energy and initial temperature on the limiting concentration of hydrogen in oxygen and helium was analyzed and discussed. The variation of ignition energy within the studied range is found to have a significant effect on the limiting concentration of hydrogen in oxygen and helium at lower initial temperature. However, when the ignition energy is higher than 32 mJ, the limiting hydrogen concentration remains almost changeless as the initial temperature increases from 21 °C to 90 °C. The limiting explosible concentration of hydrogen–oxygen–helium mixture decreases as the ignition energy increases when the initial temperature is lower. When the initial temperature is higher, the ignition energy has little effect on the limiting hydrogen concentration of hydrogen–oxygen–helium mixtures. When the initial temperature reaches 90 °C, the limiting hydrogen concentration remains almost changeless with an increase in ignition energy. The limiting explosible concentration of hydrogen in the mixtures, at the initial temperature of 21 °C and the ignition energy of 0.5 mJ, is 8.5% and that of oxygen is 11.25%.     

氧浓度对煤低温氧化热效应影响规律研究

为了准确掌握氧浓度对煤低温氧化热效应的影响,采用C80微量量热仪研究低温阶段煤氧化的自热过程,根据单升温速率的非等温动力学分析方法,得到不同氧浓度下煤样的活化能。研究结果表明:氧浓度对实验初始阶段的热流曲线和放热量的影响较小,随着温度的升高,氧浓度对热流曲线和放热量影响逐渐变得明显,放热趋势随着氧浓度的增大而增强;煤样的初始放热温度随着氧浓度的增大而降低;活化能随着氧气浓度的降低呈阶梯式上升;总放热量和氧浓度服从线性方程y=ax+b;与21%（空气气氛）氧浓度相比,15%,10%和5%氧浓度下煤的放热量分别降低了约19%,33%和46%,表明降低氧浓度对煤样的氧化放热具有明显的减缓作用。因此可以加强采空区的密闭性检测、注入惰性气体,使采空区的氧浓度尽可能地低,对采空区煤自热升温的防治有着理论指导意义。     

极限平衡区顶煤自燃三维非均质动态数值模拟

为探究极限平衡区内顶煤自燃规律,利用Fluent软件对顶煤自燃进行数值模拟研究。通过对顶煤移动变形及自燃特点的分析,确定顶煤自燃过程的模拟为三维非均质动态模拟,并建立数学模型,给出相关参数及边界条件的确定方法。以恒大矿某工作面为例,对其顶煤的自燃过程进行数值模拟,并分析工作面风量及煤体耗氧速度与自然发火期之间的关系。结果表明:对计算区域进行模拟所得到的速度场、氧浓度场及温度场与现场观测结果及理论结果比较吻合;工作面风量对煤体自然发火期影响较小,而对高温区域中心点位置影响较大;煤体耗氧速率与自然发火期近似成负指数函数关系。     

基于20L球形爆炸装置的甲烷煤尘混合爆炸实验

利用实验室自行设计的20L球形爆炸装置,对煤尘及甲烷煤尘混合物的爆炸特性进行了研究。结果表明:无论有无甲烷,煤尘的最大爆炸压力随煤尘浓度增加呈现先升高后降低的变化趋势,并且均在在煤尘浓度为600g/m3时均达到最大值。同时,甲烷的加入明显提高了煤尘最大爆炸压力值,而且随着甲烷浓度的增加,最大爆炸压力增幅先增加后降低,在甲烷5%时增幅最大。煤尘的爆炸持续时间随煤尘浓度增加呈现先降低后升高的特点,甲烷存在时有同样规律,但是有甲烷时爆炸持续时间明显降低,而且随着甲烷含量的增加,煤尘的爆炸持续时间降低幅度不断增加,在甲烷5%以后趋于稳定。实验结果对生产实践有一定的指导作用。     

贫氧环境对煤低温氧化特性影响研究

浅埋藏煤层开采过程中,由于地表裂隙导致的漏风,使其经常处于变化的氧浓度场中。针对这一实际情况,利用煤氧化动力学测定系统,对煤样在21%,18%,14%,10.5%,5%,3%氧浓度下,进行程序升温试验。测得了不同温度下指标气CO,C2H4,C2H6,C3H8浓度,并分析了其随温度变化规律,测量并计算了不同氧浓度下交叉点温度以及升温速率;对氧浓度大小影响指标气产量和其随温度变化幅度原因,以及温度特征影响效果进行必要的机理分析。结果表明:不同氧浓度下指标气CO,C2H4,C2H6在70 ℃左右有明显产量变化,分别在120 ℃,125 ℃,120 ℃处开始大量释放,C3H8则在温度达到125 ℃左右开始大量释放;120 ℃前,各氧浓度下煤样温度按相同规律变化,120 ℃后,氧浓度越大则对应的升温速率越大,温度也越高;氧浓度不同影响了煤中脂肪烃侧链氧化产生-OH的过程,继而造成指标气产量与温度变化差异。