硫酸氢钠催化合成乙酸乙酯动力学研究.pdf

硕硕 士士 学学 位位 论论 文文 论文题目论文题目 硫酸氢钠催化合成乙酸乙酯动力学研究硫酸氢钠催化合成乙酸乙酯动力学研究 作者姓名作者姓名 葛葛 文文 锋锋 指导教师指导教师 吴吴 嘉嘉 教教 授授 学科学科(专业专业) 化化 学学 工工 程程 所在学院所在学院 材料与化工学院材料与化工学院 提交日期提交日期 2009 年年 5 月月 A Thesis Submitted to ZheJiang University For Master’s Degree of Chemical Engineering Kinetics of the esterification of acetic acid with ethanol catalyzed by sodium acid sulfate By GE Wenfeng Supervised by Prof. Wu Jia Major in Chemical Engineering Institute of Chemical Engineering College of Material Science and Chemical Engineering ZheJiang University, HangZhou, P.R. China May 2009 浙 江 大 学 硕 士 学 位 论 文 浙 江 大 学 硕 士 学 位 论 文 I 摘摘 要要 乙酸乙酯是一种重要的有机化工原料， 同时也是一种环境友好的绿色溶剂， 在化学工业过程中有着广泛的应用，近年来国内和国外乙酸乙酯的产能与产量 都有迅速的增长。

乙酸乙醇酯化法一直是乙酸乙酯最重要的合成方法，特别是 在国内，酯化法生产乙酸乙酯工业装置的应用极为普遍由于传统的酯化催化 剂硫酸不具备环境友好特性，探寻高效且环境友好的新型酯化催化剂则是近年 来工业酯化过程的改进方向 在众多新型酯化催化剂中，硫酸氢钠作为酯化反应的催化剂具有反应活性 高、副反应少、催化剂易分离等优点，是一种优秀的酯化催化剂鉴于硫酸氢 钠催化酯化反应动力学的定量研究尚未见报道，本论文通过大量实验测得了硫 酸氢钠催化乙酸与乙醇酯化反应的动力学数据，并整理归纳导出了动力学方程 和动力学参数的定量表达式，为硫酸氢钠催化剂应用于乙酸乙酯的工业化合成 的化学工程设计提供定量计算依据 本论文的研究表明：在反应的中后期，无论是酯化反应还是它的逆反应— —乙酸乙酯水解反应，其表观动力学都可以表示为二级反应，反应速率常数可 用 Arrhenius 方程表征在本论文研究的温度范围（60-90℃）和催化剂浓度范 围（0.3%-2%）内，反应活化能 Ea=45.28kJ•mol-1，指前因子则为催化剂浓度的 线性函数 k0=39.048ω-0.0995m3•mol-1•s-1 在本论文对硫酸氢钠催化乙醇与乙酸酯化反应速率的研究中，观察到在反 应的初期，体系中水的含量对于酯化反应的反应速率有明显影响，水的存在不 仅作为酯化产物使逆反应速率加大，同时它还对催化剂的催化活性产生明显影 响。

本论文设计并实施了一系列实验研究水浓度对酯化反应速率的影响，通过 对实验数据的回归分析，得到了速率常数中的指前因子与水浓度之间的函数关 系式：k0 = [8.022 exp(-c水/0.439) + 1] (39.048 ω -0.0995) m3•mol-1•s-1论文还对 水浓度影响酯化反应速率的原因进行了初步的探讨 关键词关键词：乙酸乙酯；酯化反应；硫酸氢钠；催化动力学 浙 江 大 学 硕 士 学 位 论 文 浙 江 大 学 硕 士 学 位 论 文 II ABSTRACT Ethyl acetate (EA) is an important organic chemical and one of the environment friendly solvents. It was widely used in the chemical industry. Recently, the production capacity and output of ethyl acetate in the world has increased noticeably. The esterification of acetic acid with ethanol is the main methods of EA synthesis, and this method is widely used in Chinese industry. Because of the lack of the environment-friendliness of the traditional esterification catalyst, sulfuric acid, the research on improving industrial esterification processes has been focused on searching for the novel esterification catalysts effective and environment-friendly in recent years. Many studies on quite a few novel esterification catalysts have been reported. Within these catalysts, the sodium acid sulfate is an excellent one with advantages in following aspects: first, sodium acid sulfate has high catalyzing activity; second, the byproduct is ignorable; third, catalyst can be separated fast and easily. Whereas the quantitative study on of the kinetics of esterification reaction of ethanol and acetic acid with sodium acid sulfate as catalyst has not been reported, this thesis measured, through a series experiments, the rate data of esterification reaction of ethanol and acetic acid with sodium acid sulfate as catalyst, and concluded by inductive analysis the quantitative expressions of kinetic equation and kinetic parameters. This work provided a basis of quantitative calculation for chemical engineering design of the application of sodium acid sulfate catalyst to industrial synthesis of ethyl acetate. It was shown by this study that the apparent kinetics of both the esterification reaction and its reverse reaction, hydrolysis of ethyl acetate, appeared as the second order ones in the metaphase and anaphase with a rate constant following Arrhenius equation. Within the range of temperature () and that of concentration of catalyst () in the experiments, the activation energy Ea= 45.28 kJ•mol-1 and the pre-exponential factor k0=39.048ω-0.0995 m3•mol-1•s-1. 浙 江 大 学 硕 士 学 位 论 文 浙 江 大 学 硕 士 学 位 论 文 III It also was observed in this study that the rate in the prophase of esterification reaction was influenced obviously by the water concentration in the reaction system. Not only the existence of water increased the rate of reverse reaction as a product, but also influenced obviously the activity of catalyst. A series of experiments were designed and carried out to study the influence of water concentration on the rate of esterification reaction. Based on a statistical regression, an expression between the water concentration and pre-exponential factor of rate constant has been proposed to describe the influence quantitatively, k0 = [8.022exp(-cwater/0.439)+1](39.048ω-0.0995) m3•mol-1•s-1. The thesis also gave a preliminary discussion on the mechanism of the influence. Keywords: Ethyl acetate, esterification, sodium acid sulfate, catalytic kinetics 浙 江 大 学 硕 士 学 位 论 文 浙 江 大 学 硕 士 学 位 论 文 IV 目 录 目 录 摘 要. I ABSTRACT.错误！未定义书签。

错误！未定义书签 目 录.IV 第 1 章 文献综述.1 1.1 乙酸乙酯简介.1 1.2 乙酸乙酯产需现状简介.1 1.3 乙酸乙酯现有合成方法简介.4 1.3.1 乙酸乙醇酯化法.4 1.3.2 乙醛缩合法.5 1.3.3 乙醇脱氢歧化法.6 1.3.4 乙烯乙酸加成酯化法.6 1.4 新型酯化催化剂.7 1.4.1 酸性阳离子交换树脂.7 1.4.2 路易斯酸.9 1.4.3 硫酸氢盐.10 1.4.4 固体超强酸.11 1.4.5 杂多酸.12 1.4.6 小结.13 1.5 硫酸氢钠用于催化酯化反应.13 1.5.1 硫酸氢钠用于催化酯化反应进展综述.13 1.5.2 硫酸氢钠催化酯化反应的历程.15 1.5.3 质子酸催化酯化反应的动力学模型.15 1.6 论文课题的意义.18 第 2 章 硫酸氢钠催化剂性能评价实验.19 2.1 评价实验设计.19 2.1.1。