Influence mechanism of water mist containing dimethyl methylphosphonate on hydrogen-air explosions
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摘要: 为有效控制受限空间氢-空气爆炸强度，并揭示含甲基膦酸二甲酯（dimethyl methylphosphonate, O=P(CH3)(OCH3)2）的微米级水雾的抑爆机理，通过定容燃烧弹试验平台及Chemkin-Pro程序，开展了试验研究和化学动力学分析。结果表明：含O=P(CH3)(OCH3)2的细水雾可导致火焰锋面细胞状结构增多，促使火焰失稳传播；当Φ=0.8, 1.0和1.5时，含O=P(CH3)(OCH3)2的细水雾有效衰减了平均火焰传播速度(衰减率为24.2%~47.2%)并阻止了郁金香火焰形成，取而代之的是波纹状火焰。含O=P(CH3)(OCH3)2的细水雾通过降低层流燃烧速度降低升压速率，另一方面增强火焰的失稳特性提高升压速率，最终抑制效果(衰减率为41.0%~65.8%)取决于上述2种作用的耦合效应。含的O=P(CH3)(OCH3)2的细水雾通过降低H∙、O∙和OH∙的浓度实现爆炸的有效抑制，其中H∙、O∙和OH∙的浓度衰减80%以上。细水雾基于火焰前沿冷却效应和物理稀释效应实现爆炸抑制，O=P(CH3)(OCH3)2基于分解后产生的HOPO∙、HOPO2∙、HPO2∙、PO(OH)2∙和PO(H)(OH)∙，捕捉H∙和OH∙，生成H2和H2O等稳定化合物，从而中断氢-空气爆炸过程中的链式反应。Abstract: Hydrogen is a renewable, carbon-free energy carrier and an important chemical feedstock. However, its high burning velocity and low ignition energy render it more hazardous than conventional fuels. To effectively control the explosion intensity of hydrogen-air mixtures in confined spaces and elucidate the suppression mechanism of micron-sized water mist containing dimethyl methylphosphonate (O=P(CH3)(OCH3)2), a rectangular constant-volume combustion chamber was first constructed, and a schlieren optical system was employed to capture fine flame structures under the addition of the suppressant. Secondly, based on the kinetic models proposed by Jayaweera et al. and Jing et al., a coupled chemical kinetic mechanism for O=P(CH3)(OCH3)2 was developed and validated for accuracy. Lastly, the influence of O=P(CH3)(OCH3)2-containing fine water mist on flame instability structures, mean flame speed, explosion overpressure, and mean pressure rise rate was then investigated under different equivalence ratios, together with the chemical kinetic mechanism and pathways governing hydrogen-air deflagration suppression. Results indicate that water mist containing O=P(CH3)(OCH3)2 promotes the formation of cellular structures on the flame front, thereby inducing flame instability. At equivalence ratios of 0.8, 1.0, and 1.5, the O=P(CH3)(OCH3)2-laden water mist effectively reduces the average flame speed (with reductions ranging from 24.2% to 47.2%) and suppresses the formation of tulip flames, which are replaced by wrinkled flame structures. The mist suppresses the pressure rise rate by reducing the laminar flame speed, but simultaneously enhances flame instability, which tends to increase the pressure rise rate. The overall suppression performance (with pressure reduction ranging from 41.0% to 65.8%) results from the coupling of these two opposing effects. Additionally, the O=P(CH3)(OCH3)2-laden mist achieves effective explosion suppression by reducing the concentrations of H∙, O∙, and OH∙ radicals, with reductions exceeding 80%. The physical suppression arises from pre-flame cooling and dilution effects of the water mist, while the chemical suppression is attributed to the decomposition of O=P(CH3)(OCH3)2 into phosphorus-containing radicals such as HOPO∙, HOPO2∙, HPO2∙, PO(OH)2∙, and PO(H)(OH)∙. These species scavenge reactive H∙ and OH∙ radicals, promoting the formation of stable products like H2 and H2O, thereby interrupting the chain reactions in hydrogen-air explosions.
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图 3 耦合机制的层流燃烧速度有效性验证
Figure 3. Validation of coupling mechanismfor laminar burning velocity
图 5 含甲基膦酸二甲酯的细水雾对氢-空气火焰锋面演化的影响
Figure 5. Effect of water mist containing dimethyl methylphosphonate on the evolution of hydrogen-air flame front
图 6 含甲基膦酸二甲酯的细水雾对氢-空气火焰胞状不稳定性的影响
Figure 6. Effect of water mist containing dimethyl methylphosphonate on cell instability of hydrogen-air flame
图 7 含甲基膦酸二甲酯的细水雾对氢-空气平均火焰传播速度的影响
Figure 7. Effect of water mist containing dimethyl methylphosphonate on hydrogen-air flame front propagation speed
图 8 含甲基膦酸二甲酯的细水雾作用下氢-空气爆炸压力演化
Figure 8. Evolution of hydrogen-air explosion overpressure under the action of water mist containing O=P(CH3)(OCH3)2
图 9 含甲基膦酸二甲酯的细水雾作用下氢-空气爆炸平均压力上升速率
Figure 9. Average overpressure rise rate of hydrogen-air explosions under the action of water mist containing O=P(CH3)(OCH3)2
图 10 含O=P(CH3)(OCH3)2的细水雾与氢-空气混合物燃烧过程中自由基浓度的分布
Figure 10. Distribution of free radical concentration during combustion of water mist containing O=P(CH3)(OCH3)2 and hydrogen-air mixture
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