超声波作用下甲苯的均相催化氧化

S. Melnyk, V. Reutskyi, Y. Melnyk
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摘要

研究了超声作用下醋酸钴(II)催化分子氧在液相中催化甲苯氧化的规律。发现氧化过程的温度和压力之间有密切的关系。该关系式决定了反应速率、反应产物组成和甲苯极限转化值。结果表明,无论在反应初始阶段还是在烃转化率较高的阶段,声化学反应速率与无超声作用的甲苯氧化反应速率之比均随反应温度的升高而增大。同时,在温度为430 ~ 438 K、压力为0.4 MPa的条件下,超声波作用下甲苯氧化反应速率有所提高。在所有其他条件下,声化学反应速率低于无超声作用的甲苯氧化速率。揭示了常温下均相甲苯催化氧化反应速率对压力的极度依赖。结果表明,在超声作用下,反应速率随压力的增加而降低,反应温度越高反应速率越明显。一般情况下,声化学反应速率低于甲苯催化氧化的速率。结果表明,超声对所有反应产物的浓度都有影响。超声化学反应与不经超声处理的甲苯氧化反应的产物浓度之间的关系取决于温度和压力。确定了超声作用下氧化产物定量组成的主要变化是苯甲酸和苯甲醇浓度的增加/减少。甲苯催化氧化反应初期声化学反应速率的降低和较高烃类转化率时声化学反应速率的增加、反应产物选择性的变化以及超声波对甲苯极限转化率的影响表明,空化作用影响了催化剂-中间体配合物转化规律的变化。
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Homogeneous catalytic oxidation of toluene under the ultrasonic action
The regularities of toluene catalytic oxidation with molecular oxygen catalyzed by cobalt (II) acetate in a liquid phase under the ultrasonic action have been researched. It was found a close relationship between the temperature and pressure of the oxidation process. The relationship determines the reaction rate, the reaction products composition, and the toluene limiting conversion value. It was found that the ratio between a sonochemical reaction rate and a toluene oxidation reaction rate without ultrasonic action increases with increasing the reaction temperature both at the process initial stage and higher values of hydrocarbon conversion. Simultaneously, an increase in the rate of toluene oxidation reaction under the ultrasonic action was detected only at a temperature of 430–438 K and a pressure of 0.4 MPa. Under all other conditions the rate of sonochemical reaction is lower than the toluene oxidation rate without ultrasonic action. An extreme reaction rate dependence of the homogeneous catalytic toluene oxidation on pressure at constant temperature was revealed. It is established that the reaction rate decreases with pressure increasing under the ultrasonic action more significantly the higher the reaction temperature is. In general the sonochemical reaction rate is lower than the rate of catalytic toluene oxidation. It was shown that ultrasound affects the concentrations of all reaction products. The relationship between the product concentrations obtained in the sonochemical reaction and in the toluene oxidation reaction without ultrasonic treatment depends on temperature and pressure. It is established that the main changes in the quantitative composition of oxidation products are to increase/decrease the benzoic acid and benzyl alcohol concentrations under the ultrasonic action. The decrease in the sonochemistry reaction rate of toluene catalytic oxidation at the reaction initial stage and its simultaneous increase at higher values of hydrocarbon conversion, as well as changes in the reaction products selectivities, and the ultrasonic effect on the toluene limiting conversion indicate that the cavitation affects on the changes in the regularities of catalyst-intermediate complexes transformations.
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