不同压力下氨-氢混合燃料泄漏自燃的化学动力特性分析

Analysis of chemical kinetic characteristics for autoignition of ammonia-hydrogen blended fuel under different leakage pressures

  • 摘要:
    目的 高压氢气泄漏自燃属于氢能安全利用中的重要危险因素之一,掺混氨气被认为是一种具有应用前景的抑制手段,而泄漏压力是影响自燃行为的关键参数,故探究泄漏压力对于氨-氢混合燃料自燃行为的化学动力学调控作用显得尤为重要。
    方法 利用Ansys Chemkin-Pro软件,根据Otomo化学反应机理,在初始温度为1 000~1 600 K、当量比为1的条件下,探究不同泄漏压力(6 MPa、8 MPa、10 MPa、12 MPa)对氨-氢混合燃料的点火延迟时间(Ignition Delay Time, IDT)敏感性、自由基浓度、自由基生成速率及化学反应路径的影响。
    结果 当泄漏压力由6 MPa提高到12 MPa时,IDT明显缩短,在1 000 K处下降幅度达到了约44.2%。敏感性分析结果表明,链分支反应H+O2=O+OH(R1)始终起到最强的促进作用,三体反应H+O2(+M)=HO2(+M)(R13,M代表反应的中间体)起抑制作用;泄漏压力升高使各个关键反应的敏感性系数绝对值增大,但由于促进着火的主导反应总体作用强于抑制反应,体系整体反应活性增强。进一步分析自由基浓度可知,泄漏压力增大时,高活性自由基H、O、OH的摩尔分数分别上升约47.72%、66.33%、17.05%,中间自由基HO2的摩尔分数减少约41.40%。由化学反应路径分析可知,泄漏压力增大使得自由基OH的摩尔分数在大多数含氮反应路径中所占的比例增大,自由基H、O摩尔分数的贡献比例减小,体系更加依赖自由基OH主导的氧化过程来推进着火。
    结论 泄漏压力增大,H/O子体系反应活性提高,自由基生成增多,自由基分配路径改善,氨-氢混合燃料IDT明显减小,自燃倾向得到提升。研究成果可为不同压力工况下氨-氢混合燃料的安全储运与泄漏防护设计提供理论指导。

     

    Abstract:
    Objective Autoignition induced by high-pressure hydrogen leakage is a critical hazard in the safe utilization of hydrogen energy. Ammonia blending serves as a promising suppression strategy for this hazard, while leakage pressure serves as a key parameter governing autoignition behaviors. Therefore, exploring how leakage pressure chemically regulates the autoignition characteristics of ammonia-hydrogen blended fuel is of vital significance.
    Methods Using Ansys Chemkin-Pro software and the Otomo chemical reaction mechanism, simulations are performed at initial temperatures ranging from 1 000 K to 1 600 K and an equivalence ratio of 1. The influences of leakage pressure (6 MPa, 8 MPa, 10 MPa, and 12 MPa) are examined. These include effects on IDT sensitivity, radical concentrations, radical formation rates, and chemical reaction pathways of the ammonia-hydrogen blended fuel.
    Results IDT shortens remarkably as leakage pressure rises from 6 MPa to 12 MPa, with a reduction of approximately 44.2% at 1 000 K. Sensitivity analysis reveals that the chain-branching reaction H+O2 = O+OH (R1) consistently exerts the strongest promoting effect. In contrast, the three-body reaction H+O2(+M) = HO2(+M) (R13) (where M denotes the third body in the reaction) plays an inhibitory role. Elevated leakage pressure increases the absolute sensitivity coefficients of all critical reactions. Since the overall contribution of dominant ignition-promoting reactions outweighs that of inhibitory reactions, the global reactivity of the system improves. Further analysis of radical concentrations indicates that, with rising leakage pressure, the mole fractions of highly reactive radicals H, O, and OH increase by roughly 47.72%, 66.33%, and 17.05%, respectively. Meanwhile, the mole fraction of the intermediate radical HO2 decreases by about 41.40%. Chemical pathway analysis demonstrates that higher leakage pressure enlarges the proportion of OH radicals in most nitrogen-containing pathways and reduces the contribution ratios of H and O radicals. Consequently, the system relies more on oxidation processes dominated by OH radicals to drive autoignition.
    Conclusion Increased leakage pressure improves the reactivity of the H/O subsystem, elevates radical production, and optimizes radical distribution pathways. These variations markedly reduce the IDT of ammonia-hydrogen blended fuel and increase its autoignition propensity. The research findings provide theoretical guidance for the safe storage, transportation, and leakage protection design of ammonia-hydrogen blended fuels under variable pressure operating conditions.

     

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