乙酸正戊酯酯化反应动力学探讨与催化精馏模拟

doi:10.16085/j.issn.1000-6613.2017-2333

化工进展 ›› 2018, Vol. 37 ›› Issue (11): 4143-4149.DOI: 10.16085/j.issn.1000-6613.2017-2333

乙酸正戊酯酯化反应动力学探讨与催化精馏模拟

李洪^1,2,3, 肖财春^1,2,3, 吴艳^1,2,3, 李鑫钢^1,2,3, 高鑫^1,2,3

1 天津大学化工学院, 天津 300072;
2 精馏技术国家工程研究中心, 天津 300072;
3 天津化学化工协同创新中心, 天津 300072

收稿日期:2017-11-17 修回日期:2018-03-19 出版日期:2018-11-05 发布日期:2018-11-05
通讯作者: 高鑫,副教授,主要从事传质与分离工程、化工分离过程强化及非常规化石能源的炼制方面的研究工作。E-mail:gaoxin@tju.edu.cn。
作者简介:李洪(1980-),女,特聘研究员。
基金资助:
国家重点研究发展计划（2018YFB0604905）及国家自然科学基金（21776202，21336007，21690084）项目。

Study on esterification kinetics of n-amyl acetate synthesis and catalytic distillation simulation

LI Hong^1,2,3, XIAO Caichun^1,2,3, WU Yan^1,2,3, LI Xingang^1,2,3, GAO Xin^1,2,3

1 School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2 National Engineering Research Center of Distillation Technology, Tianjin 300072, China;
3 Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China

Received:2017-11-17 Revised:2018-03-19 Online:2018-11-05 Published:2018-11-05

摘要/Abstract

摘要： 在间歇釜式反应器中，以NKC-9阳离子交换树脂为催化剂，对乙酸和正戊醇催化合成乙酸正戊酯的酯化过程进行了研究。实验考察了不同催化剂用量及反应温度对乙酸转化率的影响，同时测定了实验条件下乙酸正戊酯酯化反应的反应动力学数据。采用拟均相模型对实验数据进行关联，得到了平衡常数和反应速率常数的计算式。在本实验条件下，该酯化反应为吸热反应，反应热及正、逆反应活化能分别为8.339kJ/mol、50.191kJ/mol和41.852kJ/mol，平衡常数及正、逆反应速率常数与温度的关系式分别为：K=54.2173e^-8338.8/RT，k₁=95402.5e^50191/RT，k₂=1759.6e^41852.2/RT。结合测定的动力学方程，建立了基于严格数学模型的过程模拟计算方法，对乙酸正戊酯催化精馏酯化过程进行过程模拟优化。优化后的操作条件为精馏段板数3、反应段板数9、提馏段板数14、进料位置7、混合进料酸醇摩尔比1.1∶1，此时塔釜乙酸正戊酯摩尔分数与正戊醇转化率达到99%以上。

关键词: 酯化, 乙酸正戊酯, 离子交换树脂, 动力学, 模拟

Abstract: The n-amyl acetate synthesis from the esterification reaction of acetic acid and n-amyl alcohol over an acidic cation exchange resin catalyst, NKC-9, was studied in a batch reactor. The effects of catalyst dosage and reaction temperature on the conversion of acetic acid were investigated. And the kinetic data of the esterification reaction was measured under optimal reaction conditions. The pseudo-homogeneous kinetic model was used to correlate the experimental data and determine the equation of equilibrium constant and reaction rate constant. As evidenced by the experimental results that under the operating conditions of this investigation the esterification reaction was endothermic, and the enthalpy of reaction, activation energies of the forward and reverse reactions were 8.339kJ/mol, 50.191kJ/mol and 41.852kJ/mol, respectively. The equations of equilibrium constant and forward and reverse reaction rate constant with temperature were obtained respectively as K=54.2173e^-8338.8/RT,k₁=95402.5e^50191/RT, and k₂=1759.6e^41852.2/RT. Combined with the reaction kinetics measured, a simulation program based on the rigorous mathematical model was established, and the catalytic distillation process of n-amyl acetate synthesis was simulated. 3 Trays in rectifying section, 9 trays in reaction section, 14 trays in stripping section, feed location of 7th tray and feed molar ratio of acid to alcohol of 1.1:1 were the optimized operating conditions, under which the bottom n-amyl acetate purity and n-amyl alcohol conversion were both obtained over 99%.

Key words: esterification, n-amylacetate, ion exchange resin, kinetics, simulation

中图分类号:

TQ032.4

李洪, 肖财春, 吴艳, 李鑫钢, 高鑫. 乙酸正戊酯酯化反应动力学探讨与催化精馏模拟[J]. 化工进展, 2018, 37(11): 4143-4149.

LI Hong, XIAO Caichun, WU Yan, LI Xingang, GAO Xin. Study on esterification kinetics of n-amyl acetate synthesis and catalytic distillation simulation[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4143-4149.

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乙酸正戊酯酯化反应动力学探讨与催化精馏模拟

Study on esterification kinetics of n-amyl acetate synthesis and catalytic distillation simulation

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