草酸酯树脂催化水解研究-化学工程专业论文.docxVIP

万方数据 万方数据 摘 要 草酸（Oxalic acid）是一种应用广泛的有机化工产品。近年来，制药行业及 稀土加工行业进入了快速发展期，对于草酸的需求量不断增加。通过草酸酯水解 制备草酸的绿色生产工艺受到了人们的广泛关注，该工艺对环境无污染，反应条 件温和，具有广阔的发展前景。开展有关草酸酯水解过程研究具有重要的意义。 本文对以 Amberlyst-15 为催化剂的草酸二甲酯和草酸二乙酯水解过程进行了研 究。 建立了高效液相色谱分析法对草酸二乙酯水解体系中各物质进行检测。通过 对影响产品分离因素的考察，确定了合适的分析条件。 进行了 Amberlyst-15 离子交换树脂催化下草酸酯水解过程的研究。研究发现， Amberlys-15 的加入显著提高草酸二乙酯的水解速率，也能在一定程度上加快草 酸二甲酯水解进程。根据草酸二乙酯水解过程中浓度的变化以及产物选择性随转 化率的变化规律，确定草酸二乙酯水解为可逆连串反应，草酸单乙酯为水解中间 产物。在考察了树脂用量、水酯比和温度的影响后发现：草酸酯水解初速率均与 单位酯质量下的树脂质量呈正比。高水酯比对草酸的生成更有利。水解反应速率 随着温度的升高而明显增大，草酸的选择性随温度的提高而增加。 结合草酸二甲酯自催化水解研究结果以及催化剂用量对水解初速率影响，提 出了包括离子交换树脂催化作用以及产物草酸的催化作用的反应动力学模型。 通过实验数据拟合水解动力学参数。模型计算与实验数据的平均相对误差 0.06，表明在我们所考察的树脂用量范围内，草酸的催化作用不能忽略；获得 的水解动力学模型适用于树脂催化下草酸酯水解过程速率的描述。此外，根据 van’t Hoff 方程，对草酸二乙酯水解反应的标准反应焓进行估算，得到的 与 分别为 4.95 kJ/mol、6.34 kJ/mol，即草酸二乙酯的两步水解反应均为微吸热 反应。 关键词：草酸酯， 草酸， 离子交换树脂，水解动力学，Amberlyst-15 ABSTRACT Oxalic acid is a widely used organic chemical product. With the development of pharmaceutical and rare earth industries, the demand of oxalic acid is growing rapidly. Hydrolysis of oxalate, as a green technique to produce Oxalic acid, has attracted wide attention. The hydrolysis could conduct under the mild reaction conditions, and the whole process did not produce pollutants. Therefore, it has important significance to investigate the process and kinetics of oxalate hydrolysis. Diethyl oxalate hydrolysis with ion-exchange-resin was studied in this work, as well as the hydrolysis process of methyl oxalate. A RP-HPLC method was developed to determine concentrations of diethyl oxalate and oxalic acid in the process of hydrolysis. The effects of separation conditions, such as mobile phase compositions, flow rate and pH were studied, and the appropriate analysis conditions were determined. The comparison between the autocatalytic and ion-exchange-resin catalyzed hydrolysis of oxalate showed that Amberlyst-15 significantly improved the rate of diethyl oxalate hydrolysis, and accelerated the initial hydrolysis rate of methyl ox