Pyrolysis of cyclohexane was conducted with a plug flow tube reactor in the temperature range of 873-973 K. Based on the experimental data, the mechanism and kinetic model of cyclohexane pyrolysis reaction were propos...Pyrolysis of cyclohexane was conducted with a plug flow tube reactor in the temperature range of 873-973 K. Based on the experimental data, the mechanism and kinetic model of cyclohexane pyrolysis reaction were proposed. The kinetic analysis shows that overall conversion of cyclohexane is a first order reaction, of which the rate constant increased from 0.0086 to 0.0225 to 0.0623 s-1 with the increase of temperature from 873 to 923 to 973 K, and the apparent activation energy was determined to be 155.0±1.0 kJ mol-1. The mechanism suggests that the cyclohexane is consumed by four processes：the homolysis of C-C bond （Path I）, the homolysis of C-H bond （Path II） in reaction chain initia- tion, the H-abstraction of various radicals from the feed molecules in reaction chain propagation （Path III）, and the process associated with coke formation （Path IV）. The reaction path probability （RPP） ratio of XPath I：XPath II ： XPath III ： XPath IV was 0.5420：0.0045：0.3897：0.0638 at 873 K, and 0.4336 ： 0.0061 ： 0.4885 ： 0.0718 at 973 K, respectively.展开更多
A mathematical mechanism of the n-pentane pyrolysis process based on free radical reaction model was presented.The kinetic parameters of n-pentane pyrolysis are obtained by quantum chemistry and the reaction network i...A mathematical mechanism of the n-pentane pyrolysis process based on free radical reaction model was presented.The kinetic parameters of n-pentane pyrolysis are obtained by quantum chemistry and the reaction network is established. The solution of the stiff ordinary differential equations in the n-pentane pyrolysis model is completed by semi implicit Eular algorithm. Then the pyrolysis mechanism based on free radical reaction model is built,and the computational efficiency increases 10 times by algorithm optimization. The validity of this model and its solution method is confirmed by the experimental results of n-pentane pyrolysis.展开更多
The sonolytic degradation of 2-chlorobiphenyl was investigated. Mass spectroscopy was used to detect the products of sonolytic degradation of 2-chlorobiphenyl. The results show that the products of sonolytic degradati...The sonolytic degradation of 2-chlorobiphenyl was investigated. Mass spectroscopy was used to detect the products of sonolytic degradation of 2-chlorobiphenyl. The results show that the products of sonolytic degradation, such as biphenyl, ethyl benzene, diethylbiphenyl, dibutylbiphenyl, phenol, propylphenol and di-tert-butyl phenol are produced by thermolysis and hydroxyl free radical reactions, in which biphenyl counts for almost 40%（mole fraction） of the mother compound and others are at trace level. Rapid accumulation of chloride ion shows quick dechlorination, and 78% organic chlorine is converted into chloride ion. Free radical scavengers, bicarbonate and carbonate, decrease the reaction rate of sonolytic degradation of 2-chlorobiphenyl significantly, and the pseudo 1st order rate constant of sonolytic degradation of 2-chlorobiphenyl decreases linearly with the natural logarithm of the concentration of the added free radical scavenger, showing that the pyrolysis and hydroxyl free radical reaction are the two major pathways for the sonolytic degradation of 2-chlorobiphenyl, in which the hydroxyl radical concentration is estimated to be 1×10-10 （mol/L.）展开更多
基金supported by the Natural Science Foundation of Zhejiang Province(Y4110276)for financial support
文摘Pyrolysis of cyclohexane was conducted with a plug flow tube reactor in the temperature range of 873-973 K. Based on the experimental data, the mechanism and kinetic model of cyclohexane pyrolysis reaction were proposed. The kinetic analysis shows that overall conversion of cyclohexane is a first order reaction, of which the rate constant increased from 0.0086 to 0.0225 to 0.0623 s-1 with the increase of temperature from 873 to 923 to 973 K, and the apparent activation energy was determined to be 155.0±1.0 kJ mol-1. The mechanism suggests that the cyclohexane is consumed by four processes：the homolysis of C-C bond （Path I）, the homolysis of C-H bond （Path II） in reaction chain initia- tion, the H-abstraction of various radicals from the feed molecules in reaction chain propagation （Path III）, and the process associated with coke formation （Path IV）. The reaction path probability （RPP） ratio of XPath I：XPath II ： XPath III ： XPath IV was 0.5420：0.0045：0.3897：0.0638 at 873 K, and 0.4336 ： 0.0061 ： 0.4885 ： 0.0718 at 973 K, respectively.
文摘A mathematical mechanism of the n-pentane pyrolysis process based on free radical reaction model was presented.The kinetic parameters of n-pentane pyrolysis are obtained by quantum chemistry and the reaction network is established. The solution of the stiff ordinary differential equations in the n-pentane pyrolysis model is completed by semi implicit Eular algorithm. Then the pyrolysis mechanism based on free radical reaction model is built,and the computational efficiency increases 10 times by algorithm optimization. The validity of this model and its solution method is confirmed by the experimental results of n-pentane pyrolysis.
文摘The sonolytic degradation of 2-chlorobiphenyl was investigated. Mass spectroscopy was used to detect the products of sonolytic degradation of 2-chlorobiphenyl. The results show that the products of sonolytic degradation, such as biphenyl, ethyl benzene, diethylbiphenyl, dibutylbiphenyl, phenol, propylphenol and di-tert-butyl phenol are produced by thermolysis and hydroxyl free radical reactions, in which biphenyl counts for almost 40%（mole fraction） of the mother compound and others are at trace level. Rapid accumulation of chloride ion shows quick dechlorination, and 78% organic chlorine is converted into chloride ion. Free radical scavengers, bicarbonate and carbonate, decrease the reaction rate of sonolytic degradation of 2-chlorobiphenyl significantly, and the pseudo 1st order rate constant of sonolytic degradation of 2-chlorobiphenyl decreases linearly with the natural logarithm of the concentration of the added free radical scavenger, showing that the pyrolysis and hydroxyl free radical reaction are the two major pathways for the sonolytic degradation of 2-chlorobiphenyl, in which the hydroxyl radical concentration is estimated to be 1×10-10 （mol/L.）
