甲烷-氧气混合物火焰中氟利昂 227ea 的降解机理计算

Павел Сергеевич Копылов, В.В. Агафонов, Сергей Николаевич Копылов, О.В. Фомина
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引用次数: 0

摘要

На основании известных кинетических данных выполнен расчет механизма превращения C3F7H в пламени смеси метан - кислород.Показано, что C3F7H в пламени смеси СН4 / О2 деструктурирует в реакциях с H, О и ОН без регенерации.В богатой смеси стадии с участием С3F7H и С2F4 в основном протекают за счет взаимодействия с атомарным водородом и ответственны за ингибирование горения метана в кислороде.Полученная схема качественно описывает всю известную экспериментальную картину, наблюдаемую при горении смесей СН4 / O2 / С3F7H。通式为 СnF2n+1H 的氟化碳氢化合物被广泛用作气体灭火剂。然而,这些物质具有显著的全球变暖潜势,根据《关于消耗地球臭氧层物质的蒙特利尔议定书基加利修正案》,必须在 2036 年前将其生产量淘汰 85%。由于不可能完全放弃在灭火中使用含氟烷烃,减少其消耗量的一种方法是通过与其他灭火剂混合来提高其灭火效率。如果知道 СnF2n + 1H 型化合物在火焰中的转化机理,就有可能采用这种方法。本研究是氟化碳氢化合物在火焰中转化机理研究的继续,专门研究七氟丙烷(氟利昂 227ea,C3F7H)。根据中间物质浓度的已知实验数据,并只考虑动力学参数已知的基本反应,计算了 C3F7H 在不同成分的甲烷和氧气混合物火焰中的转化机理。结果表明,在СН4 / О2混合物的火焰中,C3F7H在与 H、O 和 OH 的反应中分解而不再生,这驳斥了迄今为止普遍存在的经典观点,即火焰中初始试剂的转化是沿着分子路径进行的。在富混合物中,涉及 С3F7H 和 С2F4 的阶段主要是通过与原子氢的相互作用发生的,是抑制甲烷在氧气中燃烧的原因。在化学计量混合物中,特别是在贫混合物中,С3F7H 和 С2F4 与原子氢反应的作用减弱,而有 O 和 OH 参与的氧化过程的作用增强,也就是说,在贫混合物中,抑制作用减弱。由此得出的方案定性地描述了在СН4 / O2 / С3F7H混合物燃烧过程中观察到的全部已知实验情况,可用于制造基于氟利昂 227ea 的高效气体灭火组合物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
CALCULATION OF DEGRADATION MECHANISM OF FREON 227EA IN THE FLAME OF METHANE-OXYGEN MIXTURE
На основании известных кинетических данных выполнен расчет механизма превращения C3F7H в пламени смеси метан – кислород. Показано, что C3F7H в пламени смеси СН4 / О2 деструктурирует в реакциях с H, О и ОН без регенерации. В богатой смеси стадии с участием С3F7H и С2F4 в основном протекают за счет взаимодействия с атомарным водородом и ответственны за ингибирование горения метана в кислороде. Полученная схема качественно описывает всю известную экспериментальную картину, наблюдаемую при горении смесей СН4 / O2 / С3F7H. Fluorinated hydrocarbons with the general formula СnF2n+1H are widely used as gaseous fire extinguishing agents. However, these substances have a significant global warming potential, and their production must be phased out by 85 % by 2036 under the Kigali Amendment to the Montreal Protocol on Substances that Deplete the Earth’s Ozone Layer. Since it is impossible to completely abandon the use of fluorinated alkanes in fire extinguishing, one way to reduce their consumption is to increase their fire extinguishing efficiency by creating mixtures with other agents. The implementation of this approach is possible if the mechanism of transformation of compounds of the type СnF2n + 1H in a flame is known. This work is a continuation of the study of the mechanism of transformation of fluorinated hydrocarbons in a flame and is devoted to the consideration of heptafluoropropane (freon 227ea, C3F7H). Based on known experimental data on the concentrations of intermediate substances and taking into account only those elementary reactions whose kinetic parameters are known, the mechanism of the conversion of C3F7H in the flame of mixtures of methane with oxygen of various compositions was calculated. It has been shown that C3F7H in the flame of a СН4 / О2 mixture destructs in reactions with H, O and OH without regeneration, which refutes the hitherto widespread classical idea that the transformation of initial reagents in a flame proceeds along a molecular path. In a rich mixture, the stages involving С3F7H and С2F4 mainly occur through interaction with atomic hydrogen and are responsible for inhibiting the combustion of methane in oxygen. In a stoichiometric and especially in a lean mixture, the role of reactions of С3F7H and С2F4 with atomic hydrogen decreases, and the role of oxidative processes with the participation of O and OH increases, i.e. in a lean mixture, the inhibition effect weakens. The resulting scheme qualitatively describes the entire known experimental picture observed during the combustion of СН4 / O2 / С3F7H mixtures and can be used in the creation of highly effective gas fire extinguishing compositions based on freon 227ea.
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