We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identify...We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identifying and quantifying the oxidation species. Major products, cyclic olefins, and oxygenated products including reactive hydroperoxides and high oxygen compounds were detected. Compared with n-alkanes, a narrow low-temperature window （-80 K） was observed in the low-temperature oxidation of cyclohexane. Besides, a kinetic model for cyclohexane oxidation was developed based on the CNRS model [Combust. Flame 160, 2319 （2013）], which can better capture the experimental results than previous models. Based on the modeling analysis, the 1,5-H shift dominates the crucial isomerization steps of the first and second O2 addition products in the low-temperature chain branching process of cyclohexane. The negative temperature coefficient behavior of cyclohexane oxidation results from the reduced chain branching due to the competition from chain inhibition and propagation reactions, i.e. the reaction between cyclohexyl radical and O2 and the de- composition of cyclohexylperoxy radical, both producing cyclohexene and HO2 radical, as well as the decomposition of cyclohexylhydroperoxy radical producing hex-5-en-l-al and OH radical.展开更多
A new oxidation kinetics model is established for high-temperature oxidation. We assume that the interface reaction is fast enough and the oxidation rate is controlled by diffusion process at high temperature. By intr...A new oxidation kinetics model is established for high-temperature oxidation. We assume that the interface reaction is fast enough and the oxidation rate is controlled by diffusion process at high temperature. By introducing the growth stress gradient we modify the classical oxidation parabolic law. The modified factor of the oxidation rate constant is a function of growth strain, environment oxygen concentration, and temperature. The modeling results show that the stress gradient effect on the oxidation rate cannot be ignored. Growth strain will dominate whether the stress gradient effect promotes or slows down the oxidation process. The stress gradient effect becomes weaker at higher temperature. This effect is amplified at higher concentrations of environmental oxygen. Applied mechanical loads do not affect the oxidation rate. This model is available for high temperature oxidation of metals and alloys.展开更多
基金supported by the National Natural Science Foundation of China(No.91641205,No.51622605,No.91541201)the Shanghai Science and Technology Committee(No.17XD1402000)
文摘We report the investigation on the low-temperature oxidation of cyclohexane in a jet-stirred reactor over 500-742 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry （SVUV-PIMS） was used for identifying and quantifying the oxidation species. Major products, cyclic olefins, and oxygenated products including reactive hydroperoxides and high oxygen compounds were detected. Compared with n-alkanes, a narrow low-temperature window （-80 K） was observed in the low-temperature oxidation of cyclohexane. Besides, a kinetic model for cyclohexane oxidation was developed based on the CNRS model [Combust. Flame 160, 2319 （2013）], which can better capture the experimental results than previous models. Based on the modeling analysis, the 1,5-H shift dominates the crucial isomerization steps of the first and second O2 addition products in the low-temperature chain branching process of cyclohexane. The negative temperature coefficient behavior of cyclohexane oxidation results from the reduced chain branching due to the competition from chain inhibition and propagation reactions, i.e. the reaction between cyclohexyl radical and O2 and the de- composition of cyclohexylperoxy radical, both producing cyclohexene and HO2 radical, as well as the decomposition of cyclohexylhydroperoxy radical producing hex-5-en-l-al and OH radical.
基金Project supported by the National Basic Research Program (973) of China (No 90505015)the National Natural Science Foundation of China (Nos 90816006 and 10732050)
文摘A new oxidation kinetics model is established for high-temperature oxidation. We assume that the interface reaction is fast enough and the oxidation rate is controlled by diffusion process at high temperature. By introducing the growth stress gradient we modify the classical oxidation parabolic law. The modified factor of the oxidation rate constant is a function of growth strain, environment oxygen concentration, and temperature. The modeling results show that the stress gradient effect on the oxidation rate cannot be ignored. Growth strain will dominate whether the stress gradient effect promotes or slows down the oxidation process. The stress gradient effect becomes weaker at higher temperature. This effect is amplified at higher concentrations of environmental oxygen. Applied mechanical loads do not affect the oxidation rate. This model is available for high temperature oxidation of metals and alloys.
