过渡金属对煤自燃影响的实验研究

    Experimental study on the influence of transition metals on coal spontaneous combustion

    • 摘要: 为了分析过渡金属对煤自燃特性的影响,选用煤中含量较高的Fe、Mn、Cu三种金属离子的化合物添加到煤中进行实验研究。首先,利用热重分析法、差示扫描量热法分析了煤的着火温度、质量变化、表观活化能、放热量参数;其次,根据氧化过程中指标性气体的释放情况来分析三种金属离子对煤自燃的影响;最后,通过红外光谱测试分析了三种金属离子对煤低温氧化过程中活性基团的影响。实验结果表明:添加Fe2+和Cu2+后,分别使煤样的着火点温度降低了23 ℃和20 ℃,并降低了煤氧反应的活化能,且增加了煤样的氧化放热量324.1 J/g和42.6 J/g,说明Fe2+对煤自燃的促进作用最强,Cu2+对煤自然氧化前期影响明显,而Mn2+对自燃过程中的特征温度、放热量和气体释放量影响较小。通过红外光谱测试得到Fe2+和Cu2+加速了煤低温氧化过程中-COOH、-CH3、-CH2-和-OH活性结构的反应,而Mn2+的催化作用较弱。这是由于Cu2+氧化性活性强于Mn2+,Fe2+在催化反应的同时会还原成氧化性更强的Fe3+来促进煤氧反应。研究结果可为煤自燃防治提供理论支撑。

       

      Abstract: In order to analyze the influence of transition metals on the spontaneous combustion characteristics of coal,the compound of three metal ions,Fe,Mn and Cu,with high content in coal,are selected to add to the coal for experimental research.Firstly,the parameters of ignition temperature,quality change,apparent activation energy and heat release of coal are analyzed by thermogravimetry and differential scanning calorimetry.Then,the influence of three metal ions on coal spontaneous combustion is analyzed by the release of indicator gas in the oxidation process.Finally,the influence of three metal ions on active groups in the low-temperature oxidation process of coal is analyzed by infrared spectroscopy.The experimental results show that Fe2+and Cu2+reduce the ignition temperature of coal samples by 23 ℃ and 20 ℃ respectively,reduce the activation energy of coal oxygen reaction,and increase the oxidation heat release of coal samples by 324.1 J/g and 42.6 J/g,indicating that Fe2+has the strongest promotion effect on coal spontaneous combustion,and Cu2+ has a significant impact on the early stage of coal natural oxidation.However,Mn2+has little effect on characteristic temperature,heat release and gas release during spontaneous combustion.The infrared spectrum test show that Fe2+and Cu2+ accelerated the reaction of the active structures of -COOH,-CH3,-CH2- and -OH during the low-temperature oxidation of coal,while the catalytic effect of Mn2+ is weak.This is because Cu2+ has stronger oxidizing activity than Mn2+,and Fe2+will be reduced to Fe3+with stronger oxidizing ability to promote the coal oxygen reaction at the same time of catalytic reaction.The results of this study can provide theoretical support for the prevention and control of coal spontaneous combustion.

       

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