对二甲苯二次氧化过程中液相反应的研究  

Study on Liquid-Phase Reaction in Secondary Oxidation Process of p-Xylene

作　　者：黄欢[1] 孙伟振[1] 赵玲[1] 陈筱金[2] 李华[2] 

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237 [2]中国石化上海石化股份有限公司涤纶部,上海200540

出　　处：《化学反应工程与工艺》2010年第1期1-6,共6页Chemical Reaction Engineering and Technology

基　　金：国家"863"高技术研究发展计划资助项目(2007AA04Z159)

摘　　要：通过半连续实验考察了对二甲苯(PX)二次氧化过程中的液相氧化,并对该过程进行了模拟计算。设计和进行了包含PX液相氧化、中断反应以及降温二次液相氧化三个阶段的实验;通过动力学实验测定和数据回归确定了基于芳烃氧化自由基链式反应机理的PX液相氧化动力学模型的参数;采用建立的PX液相氧化机理模型对PX分段氧化过程进行了预测。结果表明,对中断反应后的降温二次液相氧化间歇过程,采用第一阶段末期自由基浓度做初值时模型预测值与实验值符合良好;而假设自由基初值浓度为零时,PX液相氧化动力学模型对二次氧化的液相反应预测效果较差,其原因可能是中断降温后的氧化母液中存在过氧基团会使二次液相氧化反应极快地被再引发启动。The liquid-phase reaction in secondary oxidation process of PX was investigated by experiments and predicted by model. The secondary oxidation experiment which contains PX oxidation at higher temperature, interrupt stage and continuous oxidation at lower temperature were designed and performed. First, the model parameters of free radical reaction kinetics for PX liquid-phase oxidation were determined, and then the batch process of stage oxidation of PX was predicted using the obtained PX liquid-phase oxidation kinetic model. The results showed that the model predicted data fitted well with the experimental data when using free radical concentration of the end of first stage as the initial value. Whereas when initial free radicals were considered to be zero, the liquid reaction in PX secondary oxidation process could not be simulated with PX liquid-phase oxidation kinetic model satisfactorily. The possible reason was that reactions could be re-initiated instantaneously by peroxides in oxidation liquor.

关 键 词：对二甲苯 二次氧化 对苯二甲酸 自由基 模型预测 

分 类 号：TQ031.7[化学工程]