Low-temperature oxidation of coal at elevated pressures

A mathematical model is presented to describe steady-state mass transfer and oxidation processes in coal at low temperatures in a fixed-bed flow reactor. The model incorporates the effects of partial pressure of oxygen, temperature and coal particle size, and accounts for the rate of coal oxidation and the composition of oxygenated products at high pressures. This is an important development since previous models did not include the effect of pressure in their formulation. It is found that, when the partial pressure of oxygen increases the rate of oxygen consumption increases accordingly. However, the influence of partial pressure of oxygen on the rate of oxidation is less pronounced when the pressure surpasses 1 MPa. In addition the model predicts that, for a constant partial pressure of oxygen, higher rates of oxygen consumption occur at lower total pressures. The same trends are also found for the concentration of oxygenated products at the reactor outlet. It is suggested that, the variation of partial pressure of oxygen leads to different concentration levels of oxygen at the surface and within the pores of coal particles, substantially affecting the rate of oxidation.     

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。     

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。     

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。     

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。     

预氧化浸水煤体表面结构变化及复燃特性*

为研究预氧化长期浸水煤体孔隙结构变化及贫氧复燃特性,以长焰煤原煤（RC）、浸水煤(S200)、预氧化200浸水煤(O200I200)、预氧化300浸水(O300I200)煤为研究对象,采用N2吸附、电镜扫描、热重实验手段,在21%,15%,10%,5%氧浓度下进行实验分析。结果表明:浸水后煤样比表面积增大,低温氧化最大质量变化率（DTG）较高,促进低温氧化过程煤氧复合反应;预氧化浸水煤样平均孔径增加,初始放热温度较小,总放热量增加,其中O200I200煤样热参数相对较大。随氧浓度增加,各煤样着火点温度减小,活化能增加,O200I200煤样的这2个参数较小;随氧浓度降低,煤样初始放热温度增加,最大放热量与总放热量减小。O200I200煤体孔隙较发达,锁水能力较强,持续升温后氧化能力较强,更易复燃。     

Experimental study on CO and CO2 emissions from spontaneous heating of coals at varying temperatures and O2 concentrations

Laboratory experiments were conducted to investigate carbon monoxide (CO) and carbon dioxide (CO₂) emissions from spontaneous heating of three U.S. coal samples in an isothermal oven at temperatures between 50 and 110 °C. The oxygen (O₂) concentration of an oxygen/nitrogen (N₂) mixture flowing through the coal sample was 3, 5, 10, 15, and 21%, respectively. The temperature at the center of the coal sample was continuously monitored, while the CO, CO₂, and O₂ concentrations of the exit gas were continuously measured. The results indicate that the CO and CO₂ concentrations and the CO/CO₂ ratio increased when the initial temperature was increased. As the inlet O₂ concentration increased, the CO and CO₂ concentrations increased, while the CO/CO₂ ratios tended to converge to the same value. The ratio of CO/CO₂ was found to be independent of coal properties, approaching a constant value of 0.2. The maximum CO production rate correlated well with the maximum coal temperature rise. The apparent order of reaction for coal oxidation was estimated to be between 0.52 and 0.72. The experimental results in this study could be used for early detection and evaluation of a spontaneous heating in underground coal mines.     

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。     

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     

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.     

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.     

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.     

The influence of oxygen concentration on the composition of gaseous products occurring during the self-heating of coal and wood sawdust

This article deals with an assessment of the influence of oxygen concentration on the composition and amount of combustion products generated in the course of heating coal particles and wood sawdust at 150 °C. This was done both with normal air and at 15% oxygen in the air in an isothermal furnace. The generated gases were analyzed by a Fourier Transform infrared spectrometer. Results show that under both conditions, the same substances are formed: water, carbon dioxide, carbon monoxide and aliphatic hydrocarbons. However, the quantities changed. At 21% oxygen, the concentrations of carbon monoxide and methane were higher than at 15% oxygen both in coal and wood. The oxygen concentration was also found to affect the rates of release of CO and CO₂. The rate of release of CO was higher at 21% oxygen, but that of CO₂ was higher at 15%, indicating two different mechanisms. In all cases, the concentrations of these gases were higher for coal than for wood. The results have implications for the specification of safe conditions of storage of coal and wood substances and the selection of safety measures.     

煤低温恒温氧化过程反应特性的试验研究

为进一步揭示煤低温氧化机理、指导煤矿安全开采过程中的煤自燃火灾防治工作,根据CO,CO2是煤低温氧化的主要气体产物这一反应特性,同时CO是判断煤自燃程度的重要指标性气体这一工程实际,采用恒温试验方法研究某烟煤在30℃,50℃和70℃解吸附和解吸附后再氧化过程中的CO,CO2气体产物的产生特性。研究结果表明,新鲜煤中就存大量活泼的络合物,并且这种络合物在高于常温的情况下就可以自身发生分解,产生的主要气体产物为CO2,在较高的温度下,CO的生成量才逐渐增加;在煤的低温氧化阶段,煤与氧气发生的化学反应并不强烈,气体产物CO和CO2主要由络合物分解产生。因此,在煤自燃火灾防治时要及时控制煤在低温情况下,由于络合物分解放热而使煤温逐渐升高从而导致自燃发生。     

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.     

真三轴加卸载煤样声发射长程相关性特征

为模拟井下应力条件,设计固定轴压卸围压试验,得到煤样破裂过程的声发射结果,并计算不同初始围压及不同卸载速率条件下声发射时间序列的长程相关性特征,以期对煤岩体的破裂做出预警。研究结果表明:不同初始围压及不同卸载速率下声发射实验结果类似,根据声发射累计计数可将声发射变化过程分为线性增长期、平静期以及指数增长期,可以很好地反应煤样的破裂过程;随初始围压和卸载速率的增大,声发射时间序列的Hurst指数随之增大,正相关性增强;Hurst指数与分形维数的动态变化与煤样的失稳破裂过程良好对应,且不同初始围压及卸载速率下,Hurst指数与分形维数的动态变化规律类似,说明其声发射时间序列的宏观产生机制具有内在统一性,可将接近破裂荷载时Hurst指数的增大与分形维数的减小作为煤样失稳破裂的前兆信息。     

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。     

注CO2置换/驱替煤中甲烷定量化研究

煤层注CO2促排瓦斯主要包含气体置换和流动驱替两种作用机理,但在注气过程中哪种机理占主导地位,能否将这两种机理剥离开还需要进一步研究。为了研究注CO2促排煤中甲烷的机理及其主导地位,进行了低应力载荷条件下分层预压成型煤样注CO2置换/驱替煤层甲烷的实验。实验结果表明:在置换和驱替最初246 min内,出气口没有检测到CO2气体,注入的CO2气体全部驻留在煤体中,没有随气流排出,宏观表现为仅有置换作用而没有驱替作用。在之后的1 180 min内,注入的CO2气体一部分继续驻留在煤体中,另一部分随气体流出,宏观表现为既有置换作用又有驱替作用,置换作用减弱,驱替作用增加的过程。在注气实验后期,随着注气时间的增加,煤体中CO2逐渐吸附平衡,驱替作用开始逐渐占据主导地位。截止到实验结束时,整个阶段过程中,置换作用累计贡献率为53.32%,驱替作用累计贡献率为46.68%,置换作用累计贡献率大于驱替作用累计贡献率,随着注气不断进行驱替作用累计贡献率会逐渐上升,会出现超过置换作用累计贡献率的现象。     

不同煤层煤氧化自燃性实验分析

为研究不同煤层煤自然发火特征的异同性及规律,以淮南矿区1号、3号、6号、13号煤层为研究对象,通过自然发火实验,对不同煤层煤的自然发火期周期、煤样70℃时放热强度和R70值进行分析。研究结果表明:4个不同煤层煤样自燃性由强到弱依次为:3煤>6煤>1煤>13煤;变质程度相近的4个煤层,3煤自然发火期最短,这与煤体中硫分和水分含量高有关;13煤变质程度较高,且前期放热强度、耗氧速率增长缓慢,其自燃性较弱;4个不同煤层煤的耗氧速率、CO,CO2产生率,以及C2H4/C2H6值随煤温升高具有相似的变化规律;煤中CH4气体大量解吸出现于煤温60℃之前,煤中灰分在80~120℃开始逐渐吸热融化,解析和融化均会抑制煤氧接触并且减小煤氧反应放热总量。