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本文研究了在半间歇操作条件下,在100°—130℃的温度范围内,采用异丙苯氢过氧化物为引发剂的异丙苯液相空气氧化反应动力学.根据烃类氧化的链式自由基反应机理以及对在氧化反应中异丙苯氢过氧化物分解方式的假设,导出该氧化反应在链稳定增长阶段的反应动力学模型.根据所获得的实验结果,确定了异丙苯液相氧化反应及氢过氧化物分解副反应的速率常数、表观活化能及反应速率常数的Arrhenius关系式.由反应动力学模型计算出的异丙苯和它的氢过氧化物浓度与实验结果吻合良好.文中还讨论了在半间歇操作中存在的诱导期以及反应温度对异丙苯转化率和异丙苯氢过氧化物选择率的影响.
In this paper, the kinetics of liquid phase air oxidation of cumene using cumene hydroperoxide as initiator in a semi-batch operation at 100 ° -130 ° C was investigated. Free radical reaction mechanism and the assumption of cumene hydroperoxide decomposition in the oxidation reaction, the reaction kinetic model of the oxidation reaction in the steady growth of the chain was deduced. Based on the experimental results obtained, the cumene Arrhenius relationship between liquid-phase oxidation reaction and hydroperoxide decomposition side reaction rate constants, apparent activation energy and reaction rate constants. Cumene and its hydroperoxide concentration calculated from the reaction kinetic model are in agreement with experiments The results are in good agreement.The effects of the induction period and reaction temperature on cumene conversion and cumene hydroperoxide selectivity were also discussed in the semi-batch operation.