Propane oxidation in supercritical water was investigated at iso-thermal iso-baric conditions using a batch reactor facility. Mixtures were comprised of 0.014 % propane by volume with an equivalence ratio of 0.8 and a total density of 222 mg/mL or 610 mg/mL. Reaction times ranged from 8 to 30 min for a temperature of 375ºC at 220 or 400 bar, or 400ºC at 220 bar. Major reaction products were CO and CO and minor products were propene, acetone, ethene, ethanol, methane, methanol and hydrogen. New detailed chemical kinetic models were developed by combining and refining existing models using genetic optimization. Model predictions exhibited excellent agreement with experimental observations, and indicated that rates of H-abstraction and OH addition reactions involving alkanes and alkenes are affected by the supercritical water environment. Model accuracy was highly sensitive to the rates of CHOH = CHO + OH and CH + HO = CH + HO.

中文翻译：

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低温超临界水中丙烷氧化动力学的实验和模型研究


使用间歇式反应器设施在等温等压条件下研究了超临界水中的丙烷氧化。混合物由体积百分比为 0.014% 的丙烷组成，当量比为 0.8，总密度为 222 mg/mL 或 610 mg/mL。对于 375℃、220 或 400 bar 的温度或 400℃、220 bar 的反应时间，反应时间为 8 至 30 分钟。主要反应产物是CO和CO，次要产物是丙烯、丙酮、乙烯、乙醇、甲烷、甲醇和氢气。通过使用遗传优化组合和完善现有模型，开发了新的详细化学动力学模型。模型预测与实验观察结果非常吻合，并表明涉及烷烃和烯烃的 H 夺取和 OH 加成反应的速率受到超临界水环境的影响。模型精度对 CHOH = CHO + OH 和 CH + H2O = CH + H2O 的比率高度敏感。