Impacts of char structure evolution and inherent alkali and alkaline earth metallic species catalysis on reactivity during the coal char gasification with CO2/H2O

In this work, we studied the effects of char structural evolution and alkali and alkaline earth metallic species (AAEMs) catalysis on the reactivity during the char gasification with CO₂, H₂O, and their mixture. The gasified chars with different carbon conversion levels were prepared, and their physicochemical structures were characterized via nitrogen adsorption and FT‐Raman techniques. The concentrations of AAEMs in different modes were obtained by the sequential chemical extraction method. The reactivities of the raw and gasified chars were analyzed by the thermogravimetric analysis. The gasification atmospheres had varied effects on the physicochemical structure of coal char. The gasified char obtained in the CO₂ atmosphere had a lower aromatic condensation degree compared with that obtained in the H₂O atmosphere, irrespective of the temperature. The impact of the atmospheres on the specific surface area of the char varied with the temperature because H₂O and CO₂ have different routes of development of pore structure with coal char. A large specific surface area facilitates the exposure and dispersion of more AAEMs on the surface of the channel, which is conducive to their contact with the gasification agent to play the catalytic role. Thus, the reactivity of the gasified char is well correlated with its specific surface area at different gasification temperatures. In the absence of AAEMs, the chemical structure of coal char becomes the dominant factor affecting the reactivity.     

Aluminium/tin (IV) oxide thermite composite: sensitivities and reaction propagation

ABSTRACT

Thermites are energetic composites made of metal and oxidizer particles that react according to an exothermic reaction and release large amounts of energy. Many possible metal and oxidizer couples exist in the literature. Here, the performance of the aluminum reducing metal and tin (IV) oxide (SnO₂) combination was reported as a function of the fuel/oxidizer mass ratio. The Al/SnO₂ energetic composite, in stoichiometric conditions, was insensitive to impact, sensitive to friction and extremely sensitive to electrostatic discharge. The combustion velocity was determined to be close to 600 m/s. Changing the stoichiometry affected both the sensitivity thresholds to the friction test (160 N to > 360 N) and flame propagation velocity (480–588 m/s) of the Al/SnO₂ composite. These results are reported for the first time.     

辛置煤矿10#煤综采工作面防灭火技术研究与应用

针对辛置煤矿10#煤综采工作面煤层自然发火的特点,采用现场实测分析及注胶防灭火的方法,对工作面煤体漏风情况、回采巷道内风流温度、CO及CH4浓度进行了监测,并应用了注胶防灭火的技术。针对工作面煤体内多处漏风严重,应用粉煤灰、高分子胶体注胶技术进行防治后,各监测点风流温度及煤层温度均得到有效降低,保证了工作面安全推进。     

采用绝热式自燃测试方法分析煤的自燃倾向

对煤的自燃倾向进行快速有效鉴别,有助于对煤的自燃倾向采取分级分类管理从而有效防治煤矿火灾,因而采用绝热式自燃测试方法对煤的自燃倾向进行准确分析很有必要。简要介绍绝热式自燃测试方法的测试原理及其仪器结构,模拟煤炭自燃的物理过程,通过采用包括反应器、气体预热铜管和跟踪温度控制方式等综合绝热措施以实现300 g煤样的自然发火实验,记录煤样从40℃上升到70℃的升温速率(或前30 h的升温速率),测试煤样的自燃特性曲线并分析曲线特征。即建立煤绝热氧化产热速率计算模型,结合实验数据计算所得的煤在绝热氧化条件下的升温速率和产热速率可鉴定煤自燃倾向性的强弱。采用绝热式自燃测试方法对不同煤的自燃倾向分析后表明,无烟煤和部分烟煤的自燃倾向较低,褐煤的自燃倾向较高,故而在煤矿开采时需特别注意褐煤的自燃倾向。     

Thermogravimetric kinetics on catalytic combustion of bituminous coal

The catalytic combustion and non-isothermal kinetics of bituminous coal by CeO₂, Fe₂O₃, and NiO were investigated. The exothermic characteristics during catalytic combustion of bituminous coal were determined. Based on the Coats-Redfern method by introducing the function of kinetics mechanisms, the activation energies and pre-exponential factors of catalytic combustion of bituminous coal were estimated iteratively by regression. It is found that the catalysts promoted the transport of oxygen to the coal or char surface and effectively improved the combustion characteristics of bituminous coal. Under the same experimental conditions, the exothermic values were significantly increased and the catalysts of composite oxides exhibited higher exothermic values than pure metal oxide catalysts. The metal oxides significantly reduced the activation energies of bituminous coal combustion. SEM analysis presented that combustion residues became more porous with the addition of the catalyst.     

珲春地区高瓦斯矿井煤自然发火标志气体研究

为了探究珲春地区高瓦斯矿井煤自然发火情况，选取该地区板石煤矿22、23a和八连城煤矿18#、26#共4个煤层进行程序升温特性实验，分析了CO及烃类气体产生量随温度的变化规律，优选自然发火标志气体，测算煤自燃临界温度。结果表明，板石22、23a和八连城18#、26#四个煤层的自燃临界温度分别为101.0℃、97.6℃、121.0℃、169.1℃。CO和C2H4的初现温度大约在30℃与80～120℃，且产生量随温度单调递增，可作为煤自燃预测预报的主要参考指标|而同时，为了保证检测的全面与准确，还可以将规律性良好的其他烃类气体、烯烷比和链烷比进行辅助参考。     

水热法制备Sr_2FeNiO_6催化剂及其催化性能研究

采用水热法制备双钙钛矿催化剂Sr_2FeNiO_6,考察不同浓度KOH溶液(4 mol·L~(-1)、6 mol·L~(-1)、8 mol·L~(-1)、10 mol·L~(-1)、12 mol·L~(-1)、14 mol·L~(-1))对催化剂性能的影响,利用X射线衍射、比表面积测定、程序升温还原和扫描电镜等对样品进行性能表征,并以催化甲烷燃烧为目标,考察催化剂催化性能。结果表明,矿化剂KOH浓度对样品性能影响较大,当浓度为10 mol·L~(-1)时,起燃温度最低,T_(10%)为430℃;浓度为8 mol·L~(-1)时,样品比表面积最大,为19.0 m~2·g~(-1),完全燃烧温度最低,T_(90%)为610℃。     

Evolution mechanism of active groups and thermal effects of Chinese lignite in low-temperature oxidation

Abstract

The evolution of active groups at low temperature was examined using Chinese lignite by infrared technology and X-ray photoelectron spectroscopy (XPS). The results showed that the hydroxyl, aliphatic ether, methylene, and methyl groups played important roles in the low-temperature oxidation of lignite below 200?°C. Carbonyl and carboxyl groups were important intermediates. Thus, a multi-step evolution mechanism involving the hydroxyl, aliphatic ether groups, and alkane was reasoned to describe the low-temperature oxidation of lignite. In addition, according to the oxidation kinetics experiment and the evolution laws of the active groups, the ratios of the reaction lines were determined considering the accuracy of thermal effects. The thermal effects and the heat release intensities of each temperature interval were obtained based on the evolution mechanism and the reaction ratios. The shortest spontaneous combustion period of lignite was calculated and compared with the experimental value, which proved that the reasoned evolution mechanism of the active groups and the calculations of the thermal effects were reliable.     

小庄煤矿液态CO2防灭火技术实践

针对小庄煤矿40203综放工作面采空区出现自然发火隐患问题,分析了该工作面自然发火原因、液态CO 2防灭火机理及施工工艺,成功实施了液态CO 2防灭火技术在现场的应用。在向40203综放工作面采空区灌注液态CO 2后,采空区出水温度由灌注前的36℃降至26.5℃,上隅角袋子墙内CO浓度由灌注前的0.0067%降至0.0051%,上隅角采空区19 m处CO浓度由灌注前的0.0072%降至0.0053%,采空区出水温度和CO浓度显著下降并维持稳定。实践表明,该技术成功遏制了采空区遗煤进一步氧化升温,消除了采空区自然发火隐患,保证了工作面的安全回采,也为矿井防灭火工作积累了可借鉴的实践经验。     

Pb-TKX-50燃烧催化剂的合成及热分解性能

以二氯乙二肟、二甲基甲酰胺、叠氮化钠、盐酸羟胺和硝酸铅等为原料,合成了1,1-二羟基-5,5′-联四唑羟胺铅盐(Pb-TKX-50)燃烧催化剂,研究了Pb-TKX-50对推进剂机械感度的影响以及与推进剂组分的相容性;利用差示扫描量热法和热重法研究了Pb-TKX-50在不同升温速率下的热分解过程,计算其表观活化能(E K和E O)和指前因子(A K),得到其热分解动力学参数、热分解机理函数、热爆炸温度和热力学性质。结果表明,在推进剂配方中加入Pb-TKX-50燃烧催化剂,可以改善其撞击感度和摩擦感度,且与推进剂组分的相容性良好;Pb-TKX-50的主峰分解温度相对于TKX-50的主峰分解温度显著提高,说明其热稳定性显著提高。Ozawa法和Kissinger法得到Pb-TKX-50的表观活化能分别为181.45 kJ/mol和182.49 kJ/mol,且热分解过程符合Avrami-Erofeev方程;Pb-TKX-50的自加速分解温度和爆炸临界温度分别为500.53 K和544.33 K,表明其热稳定性良好;Pb-TKX-50催化剂的热分解自由能(ΔG^≠)为158.87 kJ/mol,活化焓(ΔH^≠)为187.03 kJ/mol,活化熵(ΔS≠)为52.98 kJ/mol。