烟煤低温氧化过程中CO生成特性及溯源分析

    Characteristics and source tracing analysis of CO generation during low-temperature oxidation of bituminous coal

    • 摘要: CO作为预测煤炭早期自燃的重要标志气体,主要来源于采空区遗煤自燃。在华北地区,烟煤储量丰富,且由于变质程度较低,更易发生自燃,在低温下更容易氧化产生CO气体。例如,在某些矿井的采空区,尽管未出现煤自燃燃烧迹象,但工作面CO体积分数持续超限,导致早期煤自燃预测和预警工作的误判。针对这一问题,通过实验研究、理论分析相结合的方法,对2种不同变质程度烟煤(气煤、焦煤)在氮气和空气氛围下开展破碎实验,来模拟工作面开采破碎过程,分析CO体积分数和煤样温度变化规律;通过低温水浴−气相色谱实验、低温液氮吸附实验、傅里叶红外光谱实验,从宏观与微观2个角度分析CO异常来源及生成特性。结果表明:在空气环境中,气煤和焦煤破碎生成的CO体积分数均呈指数上升趋势,最高分别达到55.62×10−6和17.83×10−6;而在氮气环境中,二者破碎生成的CO体积分数均未超过2×10−6;在低温水浴氧化过程中,气煤和焦煤生成的CO体积分数最高分别达到2 295×10−6和527×10−6。低温液氮吸附实验结果显示:气煤在低温水浴过程中,平均孔径从11.381 nm增至17.586 nm,比表面积增加35.8%(由2.179 m2/g增至2.961 m2/g),内部大孔比例由18%增至23%,微孔比例由12%降至3%;焦煤的平均孔径从11.615 nm增至14.694 nm,比表面积增加37.9%(由2.803 m2/g增至2.867 m2/g),大孔比例由12%增至20%,微孔比例由23%降至7%。傅里叶红外光谱实验进一步分析了低温条件下脂肪烃等官能团的氧化反应过程,发现CO主要来源于羰基的受热分解。

       

      Abstract: Carbon monoxide (CO), as a crucial indicator gas for predicting the early spontaneous combustion of coal, is mainly derived from the spontaneous combustion of residual coal in gobs. In North China, bituminous coal reserves are abundant, and due to their low metamorphism degree, such coal is more prone to spontaneous combustion and tends to oxidize to produce CO gas at low temperatures. For instance, in the gobs of some coal mines, even though there are no signs of coal spontaneous combustion, the CO concentration at the working face continuously exceeds the limit, which leads to misjudgments in the prediction and early warning of early coal spontaneous combustion. To address this problem, a combined method of experimental research and theoretical analysis was adopted. Crushing experiments were carried out on two types of bituminous coal with different metamorphism degrees (gas coal and coking coal) under nitrogen and air atmospheres to simulate the crushing process during working face mining, and analyze CO volume fraction and coal sample temperature changes. Furthermore, low-temperature water bath-gas chromatography experiments, low-temperature nitrogen adsorption experiments, and Fourier transform infrared spectroscopy (FTIR) experiments were conducted to analyze the abnormal sources and generation characteristics of CO from both macroscopic and microscopic perspectives. The results show that: in an air atmosphere, the volume fractions of CO generated by the crushing of gas coal and coking coal both exhibited an exponential growth trend, reaching maximum values of 55.62×10−6 and 17.83×10−6, respectively, whereas in a nitrogen atmosphere, the volume fractions of CO generated by the crushing of both coals did not exceed 2×10−6; during the low-temperature water bath oxidation process, the maximum volume fractions of CO produced by gas coal and coking coal reached 2 295×10−6 and 527×10−6, respectively; the results of low-temperature nitrogen adsorption experiments indicated that during the low-temperature water bath process, the average pore diameter of gas coal increased from 11.381 nm to 17.586 nm, and the specific surface area increased by 35.8% (from 2.179 m2/g to 2.961 m2/g), the proportion of macropores in gas coal increased from 18% to 23%, and the proportion of micropores decreased from 12% to 3%; the average pore diameter of coking coal increased from 11.615 nm to 14.694 nm, and the specific surface area increased by 37.9% (from 2.803 m2/g to 2.867 m2/g), the proportion of macropores in coking coal increased from 12% to 20%, and the proportion of micropores decreased from 23% to 7%; Fourier transform infrared spectroscopy experiments further analyzed the oxidation reaction process of functional groups such as aliphatic hydrocarbons under low-temperature conditions, revealing that CO is mainly derived from the thermal decomposition of carbonyl groups.

       

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