基于活化能的煤自燃倾向性研究

对国内外主要煤自燃倾向性鉴定方法进行了分析和评价，指出了我国现行的煤自燃倾向性色谱吸氧鉴定法的不足之处，同时给出了煤自燃倾向性鉴定标准的基本原则．在煤自燃动力学基本方程基础上得到了煤绝热氧化方程，并设计了相应绝热氧化实验装置．通过理论和实验研宄，提出了能够反应煤自燃关键阶段，即低温氧化阶段动力学参数活化能E作为煤自燃倾向性鉴定指标，并测试了3个典型煤样的低温氧化活化能E．最后，通过现场煤自燃发火期与煤物理吸附氧量和低温氧化活化能E的对比，对该指标的实用性和科学性进行了检验．     

煤炭自燃标志性气体预测指标的实验研究

设计并研制了氧化热解实验模拟装置，通过对峰峰矿区小屯矿工作面采空区煤样的氧化热解模拟实验，绘制了各氧化热解气体CO2、O2、C2H6和CO等气体浓度随温度的变化曲线，并对其分析找出了该矿采空区煤炭自燃的标志性气体预测指标，从而为掌握工作面采空区煤炭自燃的规律和制定有效合理的煤炭自燃发火的防治措施提供依据，为煤矿的高效生产提供安全保障。     

环保型煤自燃阻化剂的阻化特性及机理研究

为了研究环保型煤自燃阻化剂(EFI)对煤炭自燃的阻化特性和机理,采用热重/差热扫描-傅里叶红外光谱(TG/DSC-FTIR)联用技术测试在EFI作用下,煤自燃过程中质量、特征温度、热效应、气体产生量和活化能等参数的变化规律.结果表明:在煤体表面形成液膜从而隔绝氧气、蒸发吸热以及销毁煤氧化过程中的羟基(—OH)和羧基(—COOH)等活性基团是EFI抑制煤自燃的主要机理.添加EFI后的煤样,由于产生更加复杂的结构,加热过程中CO2,H2O和CO的释放与DSC曲线放热峰均出现双峰或三峰,且将原煤的起始放热温度提高20～30℃,脱水脱附吸热量增加4倍.EFI的添加能够促进煤样CO2和H2O的产生而抑制CO的产生,20%添加量的EFI将能够将单位质量煤样的放热量降低4 004J,而且将煤样燃烧的活化能提高60kJ/mol.     

煤炭自燃标志性气体预测指标的实验研究

设计并研制了氧化热解实验模拟装置,通过对峰峰矿区小屯矿工作面采空区煤样的氧化热解模拟实验,绘制了各氧化热解气体CO2、O2、C2H6和CO等气体浓度随温度的变化曲线,并对其分析找出了该矿采空区煤炭自燃的标志性气体预测指标,从而为掌握工作面采空区煤炭自燃的规律和制定有效合理的煤炭自燃发火的防治措施提供依据,为煤矿的高效生产提供安全保障。     

咪唑类离子液体抑制煤自燃特性的研究

为了考察咪唑类离子液体对煤自燃特性的影响,开展热重-差热同步热分析试验测试.结果表明:离子液体对煤自燃的失重过程有明显的减弱作用,且不同离子液体的作用效果不同.效果最好的为[BMIM][BF4],抑制百分比约7.9%.同种阴离子([BF4]-)下,[BMIM]+的抑制效果比[EMIM]+强;同种阳离子([BMIM]+)下,[BF4]-的抑制效果比[NO3]-和[I]-强.差热结果显示:[BMIM][BF4]处理煤样峰值温度提高28℃,放热量明显变低.通过采用热动力学分析方法,计算出煤样自燃过程中的表观活化能(Ea)和指前因子(A),得出煤样增重阶段的活化能均高于对应失重阶段的活化能,说明煤在失重阶段更容易氧化自燃,[BMIM][BF4]处理煤的平均表观活化能高于其他煤样,说明其抑制效果较好.     

注氮惰化窒息燃烧煤炭氧浓度的实验研究

利用煤炭自燃实验系统,对龙固煤矿7煤煤样的自燃过程进行了模拟实验.实验研究了注氮情况下的煤氧化煤温、自燃状态与氧含量的变化关系,确定了龙固煤矿7煤煤样窒息的最低氧浓度,研究结果对使用注氮防治煤炭自燃技术的应用具有重要的现实指导意义.     

咪唑类离子液体抑制煤自燃特性的研究

为了考察咪唑类离子液体对煤自燃特性的影响,开展热重-差热同步热分析试验测试.结果表明:离子液体对煤自燃的失重过程有明显的减弱作用,且不同离子液体的作用效果不同.效果最好的为[BMIM][BF_4],抑制百分比约7.9%.同种阴离子([BF_4]~-)下,[BMIM]~+的抑制效果比[EMIM]~+强;同种阳离子([BMIM]~+)下,[BF_4]~-的抑制效果比[NO_3]~-和[I]~-强.差热结果显示:[BMIM][BF_4]处理煤样峰值温度提高28℃,放热量明显变低.通过采用热动力学分析方法,计算出煤样自燃过程中的表观活化能(E_a)和指前因子(A),得出煤样增重阶段的活化能均高于对应失重阶段的活化能,说明煤在失重阶段更容易氧化自燃,[BMIM][BF_4]处理煤的平均表观活化能高于其他煤样,说明其抑制效果较好.     

咪唑类离子液体抑制煤自燃特性的研究

为了考察咪唑类离子液体对煤自燃特性的影响,开展热重-差热同步热分析试验测试.结果表明:离子液体对煤自燃的失重过程有明显的减弱作用,且不同离子液体的作用效果不同.效果最好的为[BMIM][BF4],抑制百分比约7.9%.同种阴离子([BF4]-)下,[BMIM]+的抑制效果比[EMIM]+强;同种阳离子([BMIM]+)下,[BF4]-的抑制效果比[NO3]-和[I]-强.差热结果显示:[BMIM][BF4]处理煤样峰值温度提高28℃,放热量明显变低.通过采用热动力学分析方法,计算出煤样自燃过程中的表观活化能(Ea)和指前因子(A),得出煤样增重阶段的活化能均高于对应失重阶段的活化能,说明煤在失重阶段更容易氧化自燃,[BMIM][BF4]处理煤的平均表观活化能高于其他煤样,说明其抑制效果较好.     

煤自燃倾向性的氧化动力学测定方法研究

通过煤自燃过程中的绝热氧化升温速率、耗氧量、交叉点温度的综合分析研究,指出以煤自燃某一阶段的单一特征参数无法体现煤自燃过程的整体特性,提出了煤自燃倾向性的氧化动力学测定方法.该方法在测试程序升温条件下煤样温度70℃时煤样罐出气口氧气浓度和之后的交叉点温度的基础上,得出煤自燃倾向性的氧化动力学综合判定指数,根据该指数的大小判定煤自燃倾向性的强弱.对不同煤种的综合判定指数与绝热氧化、30℃物理吸氧量对比分析,结果表明氧化动力学综合判定指数更能够反映煤自燃的难易程度.     

高硫自燃煤层低温氧化气体衍生规律研究

煤炭氧化后,随着氧化进程的不同将依次释放出各种气体,这些气体的出现及释放量能准确反映煤炭氧化自燃程度.利用煤氧化升温实验装置,研究了王台矿15号煤层煤自燃氧化特性,以及自燃升温过程中产生氧化气体和碳氢类气体随温度的变化规律.确定了15号煤自燃指标气体,并进行了详细分析,所得结果能够指导煤自燃的早期预测预报与防治工作.     

Thermogravimetric study of the effect of a PVA oxygeninsulating barrier on the spontaneous combustion of coal

Coal samples in the air for three months were characterized by Thermogravlmetnc Analysts(TGA).The effect of a PVA oxygen-insulating barrier on the spontaneous combustion of coal was examined.The moisture loss activation energy,oxidation activation energy and combustion activation energy were calculated by an integral method using the Coats-Redfen formula.The results show that the tendency for spontaneous combustion of three coal samples(judged by the activation energy)falls in the order:CYW>YJL>SW.The oxidation activation energy and combustion activation energy of coal protected by the PVA oxygen-insulating barrier increased.A significant increase in the combustion activation energy was noted,especially for the CYW coal where the increase was 28.53 kJ/mol.Hence,oxidation of the protected coal samples was more difficult.The PVA oxygen-insulating barrier helps to prevent spontaneous combustion of the coal.     

Thermogravimetric study of the effect of a PVA oxygen-insulating barrier on the spontaneous combustion of coal

Coal samples in the air for three months were characterized by Thermogravimetric Analysis (TGA). The effect of a PVA oxygen-insulating barrier on the spontaneous combustion of coal was examined. The moisture loss activation energy, oxidation activation energy and combustion activation energy were calculated by an integral method using the Coats-Redfen formula. The results show that the tendency for spontaneous combustion of three coal samples (judged by the activation energy) falls in the order: CYWYJLSW. The oxidation activation energy and combustion activation energy of coal protected by the PVA oxygen-insulating barrier increased. A significant increase in the combustion activation energy was noted, especially for the CYW coal where the in-crease was 28.53 kJ/mol. Hence, oxidation of the protected coal samples was more difficult. The PVA oxygen-insulating barrier helps to prevent spontaneous combustion of the coal.     

煤自燃逐步自活化反应理论

为了深入了解煤自燃发生发展过程，对煤自燃过程进行了绝热氧化模拟，获得了煤自燃过程升温曲线，得出煤自燃过程活化能随温度升高而逐渐上升的规律，同时对煤低温氧化过程微观结构变化规律进行了红外光谱测试．在充分研究煤自燃过程宏观特性和微观结构变化之间关系的基础上，提出了煤自燃逐步自活化反应机理：煤结构中不同官能团（活性结构）治化需要的温度与能量不一样，先被活化而发生氧化反应的官能团释放能量使其它需要更高活化温度和能量的官能团活化而进一步与氧发生反应释放更多能量，煤自燃过程是不同官能团依次分步浙进活化而与氧发生反应的自加速升温过程．     

Prediction of oxygen concentration and temperature distribution in loose coal based on BP neural network

An effective method for preventing spontaneous combustion of coal stockpiles on the ground is to control the air-flow in loose coal. In order to determine and predict accurately oxygen concentrations and temperatures within coal stockpiles, it is vital to obtain information of self-heating conditions and tendencies of spontaneous coal combustion. For laboratory conditions, we de-signed our own experimental equipment composed of a control-heating system, a coal column and an oxygen concentration and temperature monitoring system, for simulation of spontaneous combustion of block coal (13-25 ram) covered with fine coal (0-3 mm). A BP artificial neural network (ANN) with 150 training samples was gradually established over the course of our experiment. Heating time, relative position of measuring points, the ratio of fine coal thickness, artificial density, voidage and activation energy were selected as input variables and oxygen concentration and temperature of coal column as output variables. Then our trained network was applied to predict the trend on the untried experimental data. The results show that the oxygen concentration in the coal column could be reduced below the minimum still able to induce spontaneous combustion of coal-6% by covering the coal pile with fine coal, which would meet the requirement to prevent spontaneous combustion of coal stockpiles. Based on the predic-tion of this ANN, the average errors of oxygen concentration and temperature were respectively 0.5% and 7 ~C, which meet actual tolerances. The implementation of the method would provide a practical guide in understanding the course of self-heating and spontaneous combustion of coal stockpiles.     

Spontaneous coal combustion producing carbon dioxide and water

Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30～100 ℃, water and carbon dioxide gas were formed and from about 105～150 ℃, carbon monoxide was produced. Using the DFT B3LYP method with a 6-311G basis set, the reaction system, where spontaneous combustion between coal and oxygen occurs and produces water and monoxide, has been studied, with the geometric configuration for all stagnation points on the potential reaction energy surface optimized. With a frequency analysis and an IRC method, transient formations were tested. Our results indicate that in the reaction of coal oxidization and spontaneous combustion producing carbon dioxide and water, oxygen molecules attack carbon atoms of the terminal of the propyl alcohol group on the lateral chain of benzene rings, which causes this propyl alcohol group to produce the acid (-CH2-CH2-COOH) group and water. This acid group continues its break up into carbon dioxide and the (-CH2-CH3) ethyl group. We have come to the conclusion that this water-and-carbon dioxide-production reaction is spontaneous, based on the observation of the energy released by the reaction.     

绝热氧化法研究煤的自燃特性

介绍了一种绝热氧化实验设备及其实验方法，利用该设备测试了3种煤样的低温氧化自热升温过程，成功实现了100g左右小煤样的煤自然发火过程模拟试验研究，获得了煤在绝热状态下的氧化升温曲线，建立了煤的绝热氧化产热量计算的数学模型，对实验过程中煤在绝热条件下的氧化产热量进行了计算，获得了不同温度段煤的绝热氧化升温速率和产热速率。     

煤粉与废线路板混合燃烧特性

利用热重方法研究了煤粉与废线路板的单独及混合燃烧特性.研究结果表明,煤粉与废线路板的混烧特性总体上表现得较为复杂,是两者共同作用的结果.废线路板单独燃烧时,热失重过程的TG曲线有两个明显的拐点,DTG曲线为双峰结构,在200～600℃范围内是剧烈失重过程;当废线路板与煤粉混合燃烧时,随着煤粉含量的增加,TG曲线变为一个拐点,DTG曲线转为单峰结构.利用Coats-Redfern方程求出了煤粉与废线路板单独和混合燃烧反应动力学参数,混合燃烧过程基本分为两个主要反应阶段,混合反应的反应级数在1～3.33之间,活化能在73.1～346MJ/mol之间,随着煤粉掺入量的增加,活化能降低.     

A new apparatus to establish the spontaneous combustion propensity of coals and coal-shales

Coal and coal-shale both tend to undergo spontaneous combustion under favourable atmospheric conditions. The Wits-Ehac index has been developed in South Africa since the late 1980's to test the spontaneous combustion liability of coal. However, in some cases, the Wits-Ehac index fails to produce tangible results when testing coal-shales. To overcome this problem, a new apparatus has been developed to test carbonaceous materials such as coal and coal-shale under chemical reactions with oxygen and an index has been obtained. This index is called the Wits-CT index. The equipment emulates the influence of oxygen adsorption on carbonaceous material for a period of 24 h without a heating system.The Wits-CT index uses the total carbon content of the sample and the temperature variations obtained from the samples during reaction with oxygen to predict the spontaneous combustion liability. Eighteen samples have been analyzed using both indices and the results are in-line. It was found that coals and coal-shales with higher values of the Wits-CT index are more liable to spontaneous combustion.Further research on different coal-shales is underway in order to establish an extensive database for coal and coal-shales, together with known incidences of self-heating.     

煤粉粒度对元宝山褐煤燃烧特性的影响

为了给实际工程应用中煤粉粒度的确定提供参考,采用热重分析的方法,研究煤粉粒度对元宝山褐煤燃烧特性的影响.对燃烧热重曲线特征参数分析表明,粒度减小,煤粉着火提前、燃尽时间缩短;粒度减小,可燃指数C和综合燃烧指数S增加,表明煤粉燃烧性能得到改善;用Coats-Redfern方法求解燃烧反应的动力学参数,燃烧反应动力学分析表明,元宝山褐煤的热天平燃烧反应为一级反应;在最大燃烧速度对应温度前后燃烧过程分成两个阶段;粒度减小,各段燃烧反应的表观活化能和质量平均表观活化能均降低.减小煤粉粒度对改善煤粉燃烧性能是有利的.