An experimental and modeling study of propane oxidation kinetics in low temperature supercritical water

IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL
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Abstract

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 CO2 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 CH3O2H = CH3O + OH and CH3 + H2O2 = CH4 + HO2.

低温超临界水中丙烷氧化动力学的实验和模型研究
在等温等压条件下,使用间歇式反应器设备对超临界水中的丙烷氧化进行了研究。混合物中丙烷的体积含量为 0.014%,当量比为 0.8,总密度为 222 mg/mL 或 610 mg/mL。反应时间为 8 至 30 分钟,温度为 375 摄氏度,压力为 220 或 400 巴,或温度为 400 摄氏度,压力为 220 巴。主要反应产物为一氧化碳和二氧化碳,次要产物为丙烯、丙酮、乙烯、乙醇、甲烷、甲醇和氢气。通过遗传优化组合和改进现有模型,建立了新的详细化学动力学模型。模型预测结果与实验观察结果非常吻合,并表明涉及烷烃和烯烃的氢萃取反应和羟基加成反应的速率受到超临界水环境的影响。模型的准确性对 CH3O2H = CH3O + OH 和 CH3 + H2O2 = CH4 + HO2 的速率高度敏感。
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来源期刊
Journal of Supercritical Fluids
Journal of Supercritical Fluids 工程技术-工程:化工
CiteScore
7.60
自引率
10.30%
发文量
236
审稿时长
56 days
期刊介绍: The Journal of Supercritical Fluids is an international journal devoted to the fundamental and applied aspects of supercritical fluids and processes. Its aim is to provide a focused platform for academic and industrial researchers to report their findings and to have ready access to the advances in this rapidly growing field. Its coverage is multidisciplinary and includes both basic and applied topics. Thermodynamics and phase equilibria, reaction kinetics and rate processes, thermal and transport properties, and all topics related to processing such as separations (extraction, fractionation, purification, chromatography) nucleation and impregnation are within the scope. Accounts of specific engineering applications such as those encountered in food, fuel, natural products, minerals, pharmaceuticals and polymer industries are included. Topics related to high pressure equipment design, analytical techniques, sensors, and process control methodologies are also within the scope of the journal.
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