The liquid-phase catalytic oxidation of 2,6-dimethylnaphthalene (2,6-DMN) to 2,6-naphthalenedicarboxylic acid (2,6-NDA) were carried out over Co/Mn/Br catalysts in acetic acid solvent. Considering the complex free-radical oxidation mechanism of 2,6-DMN, detailed reaction pathways for the oxidation of 2,6-DMN to the main 2,6-NDA product and byproducts were elucidated. Then, a detailed fractional kinetic model was proposed to describe the liquid-phase oxidation of 2,6-DMN to 2,6-NDA with side reactions involved. Furthermore, the kinetic model parameters were determined by a nonlinear optimization method, minimizing the difference between the experimental data and calculated values. Several key factors such as substrate concentration, reaction temperature and catalyst concentration, influencing the reaction rate were investigated systematically. Finally, semicontinuous experiments were carried out at different reactant feed rates and temperatures to evaluate the reliability of the derived fractional kinetic model. The determined fractional kinetic model can provide fundamental data for the industrial process optimization and scale-up of 2,6-DMN oxidation to 2,6-NDA.

中文翻译：

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2,6-二甲基萘催化氧化为2,6-萘二甲酸的动力学及机理

在乙酸溶剂中，在Co / Mn / Br催化剂上将2,6-二甲基萘（2,6-DMN）液相催化氧化为2,6-萘二甲酸（2,6-NDA）。考虑到2,6-DMN的复杂自由基氧化机理，阐明了将2,6-DMN氧化为主要的2,6-NDA产物和副产物的详细反应途径。然后，提出了详细的分数动力学模型来描述2,6-DMN液相氧化为2,6-NDA并涉及副反应。此外，通过非线性优化方法确定动力学模型参数，以最大程度地减少实验数据和计算值之间的差异。系统研究了底物浓度，反应温度和催化剂浓度等几个关键因素对反应速率的影响。最后，在不同的反应物进料速率和温度下进行了半连续实验，以评估导出的分数动力学模型的可靠性。所确定的分数动力学模型可以为工业过程优化和将2，6-DMN氧化扩大为2,6-NDA提供基础数据。