煤氧化自燃过程中一氧化碳产生机理研究

In response to the practical problem of CO abnormal transfinite in many mines currently, the project proceeds from the CO generation mechanism study in the process coal oxidation and spontaneous combustion. The transient characteristics in the CO generative process that based on the time resolved spectroscopy technology would be studied. The variety and reconfiguration characteristics of transient species would be ascertained in the CO generative process. The dynamic and real-time change mechanism in the CO generative process would be revealed. The time resolved spectroscopy online quantitative analysis system in the CO generative process would be established. The function relationship between CO quantity generated and specific surface area of coal in the broken and oxidized process would be studied, and the mathematic model of corresponding relation between the two factors would be built. The mutual quantitative deduction method between the specific surface area of coal and CO quantity generated would be concluded. The generating course and evolution regularity of intermediate products and free radicals which affect CO generating in the process of coal oxidation and spontaneous combustion would be studied. The probability of elementary reactions dissimilation in the CO generation mechanism on coupling effects would be analyzed. The key elementary reactions which should be promote or inhibit the generation of CO would be ascertained. The most probable mechanism function of CO generating in the process of coal oxidation and spontaneous combustion would be concluded, and the chemical reaction kinetics model would be founded. Finally the chemical reaction kinetics mechanism of CO generating in the process of coal oxidation and spontaneous combustion would be revealed. The project results can make contributions to seeing material breakthroughs of CO generation mechanism study in the process of coal oxidation and spontaneous combustion.

针对当前许多矿井CO异常超限的实际问题，项目从煤氧化自燃过程中CO产生机理入手，研究基于时间分辨光谱技术的CO产生过程的瞬态特性，探明CO产生过程中瞬变中间体的种类及构型变换特性，揭示CO产生过程的动态实时变化机理，建立CO产生过程中的时间分辨光谱在线定量分析技术体系；研究煤破碎氧化过程中比表面积与CO产生量之间的函数关系，建立描述煤破碎氧化过程中比表面积与CO产生量之间对应关系的数学模型，提出煤比表面积与CO产生量之间的相互定量推演方法；研究煤氧化自燃过程中影响CO产生的中间产物和自由基的生成历程与演化规律，考察多因素耦合影响下CO产生机理中基元反应异化的或然性，探明促进和抑制CO产生的关键基元反应，确定煤氧化自燃产生CO的最概然机理函数，建立CO产生机理的化学反应动力学模型，揭示煤氧化自燃产生CO的化学反应动力学机理。预期能够为煤氧化自燃过程中CO产生机理的研究取得实质性突破做出贡献。

针对我国当前许多矿井CO异常超限的现状，项目从煤氧化自燃过程中一氧化碳产生机理入手，对CO、CH4、C2H6等10中矿井混合极性气体进行了红外光谱谱图采集，通过对特征吸收峰峰面积、波数区间、极性气体浓度之间的相关性研究，对矿井极性气体的特征吸收峰及其波数区间进行了提取，对特征吸收峰的波数区间进行了优化，从而提高了矿井极性气体的红外光谱定量分析的精度和准确性。采集并分析了煤无氧升温过程中CO产生及变化规律的时间分辨红外光谱谱图，揭示了煤无氧升温过程中CO的产生和变化规律，建立了描述CO生成量与煤质量分数之间函数关系的方程。建立了专门针对CO等煤矿灾害气体特性的红外光谱分析新技术，开发了红外光谱分析新装备，通过研究傅立叶变换红外光谱气体定性定量分析机理，对CO等矿井多组分极性气体特征吸收峰进行了提取；分析了不同测试条件对气体红外吸收谱线的影响规律，揭示了不同气体吸收谱图中吸收峰重叠特征，提出了重叠谱线分离方法，掌握了基于本底直接消除的红外光谱分析方法，最终为煤矿井下环境气体的快速、精确、实时地分析和监测提供技术支撑。针对目前许多矿井开采过程中回风隅角CO异常超限的问题，对煤层中CO产生及来源规律进行了现场试验研究。建立了有氧环境下煤比表面积增长与CO生成量之间定量关系的数学推导式，掌握了低温氧化对CO生成量的影响规律。对定容燃烧反应器中瓦斯爆炸反应动力学机理的计算模型进行了推导、细化和求证，研究结果中的方程组的解（温度参数和组分摩尔分数参数）准确的描述了定容定质量绝热反应体系中瓦斯爆炸反应动力学的变化过程和变化情况。对激波诱导瓦斯爆炸反应动力学机理的数学模型进行了推导、细化和求证。计算模型中的控制方程组解释了激波管内各反应组分的流动特性沿轴向距离或随时间变化的函数关系，控制方程组的解描述了激波诱导瓦斯爆炸反应动力学的变化过程和变化情况。