During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experi...During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.展开更多
Burning of p-xylene and solvent during oxidation is the critical side reaction.In this paper the burning mechanism is analyzed and the kinetics model is developed on the basis of the radical chains reaction mechanism....Burning of p-xylene and solvent during oxidation is the critical side reaction.In this paper the burning mechanism is analyzed and the kinetics model is developed on the basis of the radical chains reaction mechanism.Model parameters were determined by data fitting of the CO x transient response curves.The experimental results showed that, the CO x generating rates increased remarkably with increasing Co/Mn ratio and catalyst concentration.As compared with the main reaction, the burning rate was more sensitive to the change of the ratio of cobalt vs manganese, but less to bromine concentration.展开更多
基金Supported by the Natural National Science Foundation of China (20080672) and the Research Fund for the Doctoral Program of Higher Education of China (200803351111).
文摘During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.
基金国家自然科学基金项目 (No 2 0 0 760 3 9)中国石油化工股份有限公司资助项目 (No X5 0 0 0 2 9)~~
文摘Burning of p-xylene and solvent during oxidation is the critical side reaction.In this paper the burning mechanism is analyzed and the kinetics model is developed on the basis of the radical chains reaction mechanism.Model parameters were determined by data fitting of the CO x transient response curves.The experimental results showed that, the CO x generating rates increased remarkably with increasing Co/Mn ratio and catalyst concentration.As compared with the main reaction, the burning rate was more sensitive to the change of the ratio of cobalt vs manganese, but less to bromine concentration.