余吾煤业原煤和构造煤X射线光电子能谱测试

为了分析余吾煤业原煤和构造煤的X射线光电子能谱,对比研究了原煤和构造煤样品表面元素碳、氧、氮元素的结构归属和相对含量,获得了样品的结构特征差异。碳结构主要以C-H和C-C形式存在,氧元素以C-O、C=O和COO-形式存在,N-5和N-6是主要的氮结构表现形式。与原煤相比,构造煤的表面元素表现为碳元素含量增加、氧元素含量减少及氮元素含量不变,体现了应力作用下煤体含氧官能团含量减少、煤化程度升高以及对氮元素含量影响较小的特征。     

溴水脱硫对煤自燃特征温度及活性基团的影响

以山西柳湾和两渡的炼焦精煤为研究对象,利用热重分析(TG-DTG)、X射线光电子能谱(XPS)和红外光谱(FTIR)等测试技术,研究了室温环境下溴水脱硫对煤自燃特征温度与煤活性基团的影响.结果 表明:随着脱硫次数增加,煤进入氧化增重阶段的起始温度向高温区偏移,煤进入快速燃烧阶段与达到最大失重速率的温度点均向低温区偏移,即煤的氧化自燃进程加快.煤的发热量呈下降趋势,但最多仅降低原煤发热量的3.4％.煤表面C元素、N元素和S元素含量随着脱硫次数的增加而规律性地减少,而O元素含量呈增加趋势,煤中硫醇、硫醚、噻吩、芳碳、碳氢键碳与质子化吡啶等官能团相对含量逐渐降低,砜、亚砜、羧基、羰基、吡啶、吡咯与氮氧化物等含氧官能团相对含量逐渐增加,说明脱硫后煤中各元素以更高的价态存在,溴水脱硫是一个氧化过程.IR光谱显示芳香族官能团和脂肪烃官能团中的C— H键伸缩振动锋均变弱,含氧官能团中的C=O双键和酚羟基中的C—O—H键伸缩振动峰均变强,说明煤中C—H键含量减少,C=O双键和C O H键含量增大,这与TG-DTG和XPS的分析结果相一致,说明脱硫后煤中的C元素、S元素和N等元素被氧化,煤的氧化程度变高.     

煤自燃氧化放热效应的影响因素分析

任何一种煤都具有氧化放热性是煤自燃的根本原因,煤自燃氧化放热效应的主要影响因素包括煤分子结构、温度、氧浓度和松散煤松粒度。通过总结前人提出的煤化学结构模型,参照现代研究的成果,提出了描述煤自燃的煤分子化学结构模型。从煤分子结构上看,主要是煤分子中的非芳香结构侧链、桥链与氧发生反应,煤的氧化放热效应主要取决于煤表面活性分子种类、数量和空间结构特性。氧化放热强度和耗氧速率分别是描述煤氧化放热效应和煤氧复合速度的主要指标,利用化学动力学理论和煤低温自然发火实验测算出不同煤温时的氧化放热强度,利用程度升温实验测算出不同氧浓度时的耗氧速率,从定性和定量两个方面分析了氧浓度、温度和松散煤体粒度对煤氧化放热效应的影响。     

煤基质表面官能团对二氧化碳及甲烷吸附性能作用规律的研究进展

强化煤层气CH_4开采的深部煤层封存CO_2技术能够有效减少CO_2的排放。由于煤基质具有的吸附性能是煤体吸附CH_4及封存CO_2的主要机理,且煤基质表面官能团对于煤体CO_2和CH_4吸附能力具有潜在的影响,因此本文阐述了表面官能团对煤体CO_2和CH_4吸附性能的作用及机理,归纳了煤基质表面官能团的修饰及表征方法,指出了煤基质表面官能团对CO_2和CH_4吸附作用规律的研究趋势。分析表明:影响煤体CO_2和CH_4吸附性能的官能团主要包括含氧和含氮官能团;整体上,含氧官能团有利于CO_2吸附,含氧官能团对CH_4的吸附作用仍存在一定争议,含氮官能团均有利于提升煤体CO_2和CH_4吸附能力;官能团表征方法包括化学分析法、程序升温脱附、X射线光电子能谱、傅里叶变换红外光谱和核磁共振波谱。为了深入研究煤基质表面官能团对其吸附性能的作用规律,后续需开展以下工作:建立更为真实的煤体结构模型,提高理论模拟研究工作的预测精度;强化实验科学研究,弥补目前主要以理论模拟为研究手段的不足;优化煤体预处理方法,提高现有官能团表征方法用于煤基质官能团分析的精确度。     

煤自燃的分子结构模型探讨

煤自燃主要是由于煤表面活性结构与氧之间相互作用的结果 .通过对煤、氧分子结构特性的分析 ,并根据类似有机结构与氧发生化学反应的条件及过程分析 ,探讨了煤分子表面易于氧化自燃的活性结构 ,归纳出 7种在常温常压下就能与氧发生化学反应的煤分子表面活性基团及其氧化反应热 ,利用煤自然发火实验对推断出的活性基团氧化反应热进行了验证 .在威斯化学结构模型和本田化学结构模型的基础上 ,提出了能够对煤自燃进行描述的煤分子结构模型 ,对煤自然发火机理及其过程的研究具有一定的参考价值 .     

热提质褐煤预氧化后自燃特性变化及其自由基原位分析

针对不同温度热提质褐煤新鲜样及其自然环境中储存一定时间后的预氧化样,利用订制的自燃测定实验装置测得各样品的自燃倾向性差异,采用X-band电子自旋共振波谱仪进行自由基动态原位分析,研究预氧化对热提质褐煤自燃特性的影响。结果表明,热提质温度升高,新鲜样的自燃倾向性降低。但随着储存时间延长,105~500℃热提质褐煤发生预氧化,自燃倾向性不同程度地增加,400℃热提质后的预氧化样与原煤一样易自燃。在自燃氧化过程中,与新鲜样不同,预氧化样的吸氧量增加,自由基浓度也增加。预氧化不仅使热提质褐煤自由基增加;且在自燃的加速氧化阶段后期,不断产生自由基,维持氧化自热升温。而400℃热提质褐煤新鲜样在自燃氧化初期消耗大量小分子自由基,损失达80%,因不能持续产生活性自由基难以维持自燃氧化反应进行。     

热提质褐煤预氧化后自燃特性变化及其自由基原位分析

针对不同温度热提质褐煤新鲜样及其自然环境中储存一定时间后的预氧化样，利用订制的自燃测定实验装置测得各样品的自燃倾向性差异，采用X-band电子自旋共振波谱仪进行自由基动态原位分析，研究预氧化对热提质褐煤自燃特性的影响。结果表明，热提质温度升高，新鲜样的自燃倾向性降低。但随着储存时间延长，105~500℃热提质褐煤发生预氧化，自燃倾向性不同程度地增加，400℃热提质后的预氧化样与原煤一样易自燃。在自燃氧化过程中，与新鲜样不同，预氧化样的吸氧量增加，自由基浓度也增加。预氧化不仅使热提质褐煤自由基增加；且在自燃的加速氧化阶段后期，不断产生自由基，维持氧化自热升温。而400℃热提质褐煤新鲜样在自燃氧化初期消耗大量小分子自由基，损失达80%，因不能持续产生活性自由基难以维持自燃氧化反应进行。     

富氧多孔炭的合成及其在电化学储能中的作用

多孔炭在电化学储能器件中具有不可或缺的作用。本文主要介绍了富氧多孔炭材料的物理化学特性、表面含氧官能团的种类及表征方法;总结了富氧多孔炭常见的合成方法并分析了各种方法的优缺点;以超级电容器和锂/钠离子电池为例,阐述了近年来富氧多孔炭材料在储能应用方面的研究进展,探讨了含氧官能团在储能过程中的作用机理;指出了富氧多孔炭应用于电极材料时高比容量与高导电性能相互制约的问题,提出理性设计多孔炭结构中含氧官能团的类型及数量,可以在保持多孔炭电化学稳定性的同时,为多孔炭提供丰富的氧化还原活性位,提高其与电解质的亲和性,从而提升储能器件的能量密度;并展望了含氧官能团原位表征技术的开发与材料先进结构组分的设计等富氧多孔炭储能电极的未来发展方向。     

双氧水对新疆伊犁煤的氧化行为研究

本文采用双氧水（H2O2）作为氧化剂,研究了新疆伊犁煤的氧化特性。通过比较双氧水加入比例和氧化温度,探究新疆伊犁煤表面酸性含氧官能团随氧化剂加入比例的变化规律以及双氧水加入比例对氧化煤抽提率的影响。结果发现：双氧水加入比例越大,温度越高,煤样氧化后失重越大;双氧水氧化增加了煤表面的酸性含氧官能团含量;随着双氧水加入比例增大其氧化煤抽提率有明显的增加。     

褐煤物化结构对水分复吸的影响

阐述了褐煤中水分的赋存形态及其在受热过程中的转化行为。分析了不同提质干燥过程中褐煤物化结构的变化,探讨了褐煤物化结构与水分脱除及复吸的关系。结果表明:褐煤表面丰富的孔结构和大量亲水性含氧官能团是其水分较高的主要原因。干燥提质过程中,孔结构坍塌和交联反应的剧烈程度对于抑制复吸非常重要。加热过程中褐煤表面活性含氧官能团的数量、形成和分解行为直接影响褐煤的持水和吸氧能力,含氧官能团的分解会使煤的疏水性增加,自燃倾向性降低。最后说明褐煤提质的关键是水分的高效安全脱除,脱水煤表面氧化和水分复吸的抑制,并提出了抑制提质褐煤复吸水分的可能途径是依据不同组成、结构褐煤的水分赋存和脱除行为,针对性地改善干燥操作条件,调节样品孔径分布、比表面积和表面含氧官能团的存在形态及数量。     

Numerical simulation and application experiment of the spontaneous combustion tendency of a coal stockpile covered with pulverized coal

In this paper, we developed a new method for preventing the spontaneous combustion of a coal stockpile covered by pulverized coal. This technique is based on the numerical-simulation analysis of endothermic/exothermic balance in coal stockpile. Depth and height are confirmed to be the main factors influencing the endothermic/exothermic balance in coal stockpiles and the hot-spot region is easily formed at a coal stockpile height of 1-1.5 m and a depth of 2-3 m, where there is the highest tendency for spontaneous combustion. The numerical simulation and the 120-day application test both confirm that the diffusion process of oxidation can be prevented and the coal oxidation reaction can be hindered by covering the surface of the hot region with pulverized coal. As a result, the coal spontaneous combustion is prevented effectively.     

Moisture readsorption and low temperature oxidation characteristics of upgraded low rank coal

This study investigated the behavior of upgraded low rank coal produced by a coal-oil slurry dewatering process regarding moisture readsorption, low temperature oxidation, and spontaneous combustion. The upgraded low rank coal had higher heating values than raw coal. It also showed lower moisture readsorption than raw coal and had less susceptibility to low temperature oxidation and spontaneous combustion. This seemed to result from the coating of the asphalt on the surface of the coal, which covered fine pores and suppressed the active functional groups from reacting with moisture and oxygen in the air. The increasing upgrading pressure negatively affected the moisture readsorption, low temperature oxidation, and spontaneous combustion.     

A comparison of spontaneous combustion susceptibility of coal according to its rank

This study investigated spontaneous combustion susceptibility of coal according to the rank. To estimate the spontaneous combustion susceptibility of coal, both crossing-point temperature (CPT) measurement and gas analysis by using gas chromatography (GC) were performed. For the experiment, Eco coal and Kideco coal, Indonesian lignite, and Shenhua coal that is Chinese bituminous coal were used. The lignite such as Eco coal and Kideco coal contains more functional groups that easily react to oxygen more so than Shenhua coal. For this reason, the lignite is more easily oxidized than bituminous coal at low temperature, which results in high O₂ consumption, increase in CO and CO₂ generation, and low CPT. Although the CPT of Eco coal and Kideco coal is identical to each other as they are the lignite, Kideco coal has a lower initial oxidation temperature (IOT) and maximum oxidation temperature (MOT) than those of Eco coal. This means that although each coal has the same rank and CPT, spontaneous combustion susceptibility of coal may vary because the initial temperature of the coal at which oxidation begins may be different due to the substances that participate in oxidation.     

煤表面对氧分子物理吸附的微观机理

应用量子化学的理论和方法研究煤这种非晶体物质的物理吸附机理,从微观上揭示其吸附机理和吸附过程,定量研究煤对氧分子发生物理吸附过程中吸附量和放出热量的关系,从而揭示煤炭氧化自燃初始反应的本质.从煤表面对多个氧分子吸附优化后的平衡几何构型可以看出,煤表面吸附5个以下的氧分子时,1个氧分子在煤表面含氮的侧链吸附,其余的氧分子被苯环所吸附.煤表面吸附6个氧分子以上时,苯环对氧分子的吸附减弱,被吸附的氧分子偏向侧链端,在煤表面侧链部位吸附了大量的氧分子,这也证明了在煤的氧化自燃过程中侧链首先被氧化的结论的正确性.煤表面对氧分子的吸附量与吸附能呈线性关系.     

Detection of natural oxidation of coking coal by TG-FTIR—mechanistic implications

The natural oxidation/weathering of coal continues to be a subject of interest both scientifically and industrially, in part due to the complexity of the molecular processes at hand as well as to the commercial implications involved. It is widely recognized that coking can be adversely affected by weathering whereas, combustion processes appear to be enhanced as result of oxidation.Combustion techniques are commonly used in the analysis of coal, and organic compounds in general, for the determination of elemental hydrogen, carbon and nitrogen. For oxygen, the method in common practice involves the determination by difference from directly determined values for moisture, ash, sulphur, hydrogen, carbon and nitrogen. This has led us to consider the use of thermogravimetry coupled to gas analysis by infrared spectroscopy (TG-FTIR) to measure organic oxygen in coal directly. Although this technique, developed by Solomon and coworkers, has been extensively used by our group and others, it appears not to have been considered for this particular purpose.Recently, we have shown that TG-FTIR is capable of measuring all the organic oxygen in both fresh and oxidized coal by simultaneous measurement of the three main oxygen-containing gases H₂O, CO and CO₂ evolved during rapid pyrolysis. This gives us a way of measuring quantitatively the oxygen introduced into the coal matrix during oxidation and at least a partial capability of establishing oxygen speciation.We have found, using TG-FTIR, that the early stages of coal oxidation results in the appearance of O-containing functional groups not present in the original coal. The nature of these functional groups is directly related to the oxidation reaction mechanism. These results will be presented and discussed in detail.     

Evaluation of the susceptibility of coal to spontaneous combustion by a TG profile subtraction method

It is imperative to have an in-depth understanding of the intrinsic reaction between coal and oxygen during low-temperature oxidation, as the reaction is the main source responsible for the self-heating and spontaneous combustion of coal. As low-temperature oxidation of coal involves a series of physical and chemical process and many parallel reactions, it is difficult to directly investigate the intrinsic reaction between coal and oxygen by conventional analytical method. Thermogravimetric analysis (TGA) was used to investigate the intrinsic reaction between coal and oxygen based on the mass change. By means of the subtraction analysis method of TGA, the TG-subtraction curves were obtained by subtracting the TG-N₂ curves from the TG-air curves. The results indicate that a TG-subtraction curve can better reflect the intrinsic reaction of coal oxidation than a TG-air curve by eliminating the influence of evaporation of water and thermal decomposition of inherent oxygen-containing groups. In terms of the rate of mass increase, the intrinsic reactions can be divided into three stages: slow oxidation stage, advanced oxidation stage and rapid oxidation stage. The activation energy at each of the stages, obtained by Coats and Redfern’s model, can be used to as a technical parameter to evaluate the proneness of coal spontaneous combustion. The optimum experiment conditions were also developed to study low-temperature coal oxidation with the subtraction method of TGA.     

The effect of moisture content and air-drying on spontaneous combustion characteristics of two Turkish lignites

The results of an experimental study aimed at evaluating the spontaneous combustion characteristics of two Turkish lignites moistured and air-dried at varying times are discussed. The spontaneous combustion characteristics of the coals were determined using Crossing Point Methods adapted to our laboratories conditions. The content of three predominant oxygen functional groups (carboxyl, hydroxyl, and carbonyl) of untreated, moisten and air-dried coal samples were also determined with wet chemical methods. The content of oxygen functional groups in moisten coal samples do not differ significantly that of untreated coal samples, for realized in vacuum desicator to moistured of coal samples. The liability of spontaneous combustion of the two coals was reduced when moisture content increased with increase in contacted time to water vapour. The moisten coal samples was dried in laboratory during 24 and 48 h time period. The concentration of oxygen contain functional groups of drying coal samples increased with increase of contact time with air and decrease of particle size. The liability of spontaneous combustion of the air-dried coal samples increased with increase of contacted time with air and with decrease of moisture content.     

DEACTIVATION OF DRIED SUBBITUMINOUS COAL

Deep drying of inherent moisture from subbituminous coal produces a dried product which is friable and very reactive to oxygen in air. The major problems in handling dried coal, which are unique to deep drying of low-rank coal, are: (1) avoidance of spontaneous combustion, (2) prevention of moisture reabsorption, and (3) control of dust. Atlantic Richfield has developed, and successfully demonstrated, technologies which solve all three problems. However, this paper will be confined to the spontaneous combustion problem

Low-temperature 'oxidation may result in spontaneous combustion' of the coal during storage or transit. The increased reactivity to low-temperature oxidation of dried coal is due to two factors: (1) the reduction in moisture content, and (2) the increase in temperature. A laboratory technique was developed to measure the coal reactivity to low-temperature oxidation at temperatures near ambient. Laboratory data was then used to develop a pseudo-first order kinetics model for dried subbituminous coal as a function of temperature and moisture content. The influence of particle size was also determined

A one-dimensional spontaneous heating model was formulated to evaluate the effects of wind velocity, coal pile porosity, thermal conductivity of crushed coal, and geometry of coal piles on the dried coal's tendency to spontaneous combustion. This model was validated against two large-scale spontaneous heating tests. Each test consumed about 800 pounds of dried coal.

Based on a selected combination of three deactivation methods and predictions of the computer model, a special product treatment procedure was developed and successfully demonstrated in pilot plant tests in 1983. Dried coal stockpiles (about 100 tons per pile) were monitored for four months under severe weather conditions with no evidence of either moisture reabsorption or spontaneous combustion.     

烟煤化学链反应特性及机理分析

在固定床反应器中添加铁基载氧体Fe4Al6和铜基载氧体Cu4Al6，进行巨野(JY)烟煤化学链燃烧实验，通过气相色谱(GC)、红外光谱(FT-IR)等分析了JY煤化学链反应特性及表面官能团演变规律。结果表明，相对于Al2O3，Fe4Al6或Cu4Al6为床料时，JY煤中CO2含量分别提高了52.25%和59.16%，最大碳转化速率分别提高了8.93%和30.36%，Cu4Al6反应效果更好。添加Cu4Al6后，JY煤表面官能团演变进程加快，Cu4Al6对脂肪烃结构、芳香碳骨架和芳香族CH的转化均有明显促进作用。煤中脂肪烃?CH3和?CH2稳定性低、反应速率快，是化学链燃烧初期气相产物主要来源；芳香碳骨架和芳香族?CH稳定性高、反应活性低，反应速率较缓慢，是化学链燃烧中后期气相产物主要来源。