强酸性阳离子交换树脂催化酯化丙烯酸和甲醇合成丙烯酸甲酯的反应动力学

doi:10.3724/SP.J.1095.2013.30102

摘要/Abstract

摘要： 以丙烯酸和甲醇为原料，强酸性阳离子交换树脂Amberlyst-15为催化剂，对苯二酚为阻聚剂，合成丙烯酸甲酯。考察了醇酸摩尔比、催化剂用量和温度对反应过程的影响，在实验范围内，随着温度或者催化剂用量的增加，反应速率加快，丙烯酸的转化率也不断提高。醇酸摩尔比的增加能提高丙烯酸的转化率，反应速率出现先增加后减缓的现象。与此同时，建立该催化酯化反应的Pseudo-Homogeneous（PH）的理想和非理想以及Langmuir-Hinshelwood（LH）反应动力学模型，辨识得到相应反应动力学方程。经比较，采用活度替代物质的量浓度的LH模型的平均相对偏差(MRD)最小，计算值为1.466%，最适合实际反应。

关键词: 丙烯酸甲酯, 强酸性阳离子树脂, 反应动力学, 催化酯化

Abstract: The methyl acrylate was synthesized from acrylic acid and methanol by using strong-acid cation exchange resin, Amberlyst-15, as catalyst and the hydroquinone as polymerization inhibitor. Effects of molar ratio of methanol to acrylic acid, amounts of catalyst and reaction temperature on esterification rate of acrylic acid were investigated. It was found that the reaction rate and the fractional conversion of acrylic acid increased with increasing the temperature or the catalyst′s amounts, while the reaction rate increased first and then decreased with the increase of the molar ratio of methanol to acrylic acid. In the meanwhile, the kinetics of the esterification of acrylic acid with methanol was established on the basis of ideal and non-ideal state of Pseudo-Homogeneous(PH) and Langmuir-Hinshelwood(LH), with the identification of relevant parameters to obtain the equation of reaction rate. By comparison, the LH model, which uses activity instead of concentration, has the lowest multireference single- and doubleexcitation(MRD) of 1.446%, and is therefore best fit for the reaction.

Key words: methyl acrylate, strong-acid cation exchange resin, chemical kinetics, esterification and catalysis

中图分类号:

O623.6

潘佳佳, 张贝克, 卢秉南. 强酸性阳离子交换树脂催化酯化丙烯酸和甲醇合成丙烯酸甲酯的反应动力学[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.30102.

PAN Jiajia, ZHANG Beike*, LU Bingnan. Kinetic Study of the Esterification of Acrylic Acid with Methanol Catalyzed by Strong-acid Cation Exchange Resin[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.30102.

参考文献

[1] GAO Hongpei,BAI Baochen. Factors Affecting Methacrylate Reaction[J]. Chem Eng Equipm,2011,(3):60-61(in Chinese).

高红培，白宝忱. 浅谈丙烯酸甲酯反应的影响因素[J]. 化学工程与装备,2011,(3):60-61.

[2] DENG Wenyu,ZHOU Xiaoyi,MIN Ruiying. The Synthesis of Methyl Acrylate by the Esterification of Acrylic Acid[J]. J Sichuan Univ,1984,(2):7-18(in Chinese).

邓文煜，周效懿，闵瑞英. 丙烯酸酯化合成丙烯酸甲酯[J]. 成都科技大学学报,1984,(2):7-18.

[3] ZHANG Xin,GUO Ping,SONG Yang,et al. The Choice of the MA React Temperature[J]. Guangdong Chem Ind,2011,(6):60-61(in Chinese).

张新，郭萍，宋阳,等. 丙烯酸甲酯反应温度的选择[J]. 广东化工,2011,(6):60-61.

[4] DENG Yong. Research and Practice to Improve the Conversion Rate of Methacrylate Reactor Acrylic[J]. Acrylic Chem Appl,2007,20(4):27-31(in Chinese).

邓勇. 提高丙烯酸甲酯反应器丙烯酸转化率的研究与实践[J]. 丙烯酸化工与应用,2007,20(4):27-31.

[5] Malshe V C,Chandalia S B. Kinetics of the Liquid Phase Esterification of Acrylic Acid with Methanol and Ethanol[J]. Chem Eng Sci,1977,32(12):1530-1531.

[6] Qu Y X,Peng S J,Wang S,et al. Kinetic Study of Esterification of Latic Acid with Isobutanol and n-Butanol Catalyzed by Ion-exchange Resins[J]. Chinese J Chem Eng,2009,17(5):773-780.

[7] LU Bo,SHEN Qingyang,CHEN Zhirong,et al. Kinetics of MMA Synthesis from MAA and Methanol with Resin Acid as the Catalyst[J]. Chem Reaction Eng Technol,1995,11(4):332-341(in Chinese).

鲁波，沈庆扬，陈志荣,等. 甲基丙烯酸催化酯化反应动力学模型研究[J]. 化学反应工程与工艺,2007,20(4):27-31.

[8] TANG Xun,XIA Tao,ZHANG Changli,et al. Synthesis of n-Butyl Acrylate by a Novel Catalyst[J]. Chem Reag,2002,24(5):301-302(in Chinese).

唐薰，夏涛，张长利,等. 催化合成丙烯酸正丁酯[J]. 化学试剂,2002,24(5):301-302.

[9] ZHOU Xueyong. Theoretical Analysis of Fluid-solid Adsorption Equilibrium Constants Calculated by Langmuir equation[A]. International Year of Chemistry in China-the Chinese Chemical Society on Thermal Analysis Kinetic and Thermal Dynamics Conference as Jiangsu Province, the Third Thermal Analysis Technology Seminar Proceedings[C]. Nanjing,2011:189-192(in Chinese).

周学永. 由Langmuir方程计算液-固吸附平衡常数的理论分析[A]. “国际化学年在中国”——中国化学会第三届全国热分析动力学与热动力学学术会议暨江苏省第三届热分析技术研讨会论文集[C]. 南京,2011:189-192.

[10] Fredrik S,Pekka O,Tapio S,et al. Dynamic Modelling of Catalytic Liquid-phase Reactions in Fixed Beds-Kinetics and Catalyst Deactivation in the Recovery of Anthraquinones[J]. Chem Eng Sci,2006,61(14):4528-4539.

[11] Guido S,Yolanada A,Nikhil Dube,et al. Esterification of Acrylic Acid with Methanol by Reactive Chromatography:Experiments and Simulations[J]. Chem Eng Sci,2006,61(16):5296-5306.

[12] Schwarzer S,Hoffmann U. Experimental Reaction Equilibrium and Kinetics of the Liquid-phase Butyl Acrylate Synthesis Applied to Reactive Distillation Simulation[J]. Chem Eng Technol,2002,25(10):975-980.

[13] Marco M,Bernardo N,Davino G,et al. Kinetics of Liquid-Phase Esterification Catalyzed by Acidic Resins[J]. Ind Eng Chem Res,1997,36(1):3-10.

[1]	王路飞, 甄蒙蒙, 沈伯雄. 贫电解液下电催化剂对调控锂硫电池性能的研究进展[J]. 应用化学, 2023, 40(2): 188-209.
[2]	王东升,闻新,李云辉,唐涛. 纳米二氧化硅表面接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物以及对聚甲基丙烯酸甲酯复合材料阻燃性能和透明性的影响[J]. 应用化学, 2018, 35(12): 1427-1433.
[3]	程金华, 姜鸿基. 无水FeCl₃存在下丙烯酸甲酯的单电子转移活性自由基聚合动力学[J]. 应用化学, 2017, 34(1): 40-45.
[4]	李艳, 巩士磊, 车影, 靳利娥, 闫果兰. Fenton反应考察抗坏血酸清除羟基自由基能力及动力学[J]. 应用化学, 2015, 32(8): 948-954.
[5]	张玥, 彭阳峰. 解草酯的合成及动力学[J]. 应用化学, 2015, 32(4): 416-421.
[6]	陈敏, 邓之俊, 张丽本, 李小刚. 碱性离子液体催化金属调节的甲基丙烯酸甲酯的电子转移活化原子转移自由基聚合[J]. 应用化学, 2014, 31(05): 553-559.
[7]	白云刚, 张贵宝, 李百祥, 李悦生. 碳酸乙烯酯溶剂中丙烯腈的聚合行为[J]. 应用化学, 2012, 29(09): 990-994.
[8]	仲玉, 沈珺, 魏荣卿, 刘晓宁. 洗滤-萃取法去除ATRP法制备PMMA-b-PLLA-b-PMMA嵌段聚合物中的Cu离子[J]. 应用化学, 2011, 28(03): 254-257.
[9]	王文, 林美娟, 沈永鑫, 黄丽梅. 有机相CdTe量子点/铕/聚甲基丙烯酸甲酯复合体系的发光性质[J]. 应用化学, 2011, 28(02): 142-148.
[10]	张凯, 黄春保, 沈慧芳, 陈焕钦. 氯丁胶乳乳液接枝甲基丙烯酸甲酯的反应动力学[J]. 应用化学, 2010, 27(10): 1144-1148.
[11]	李高亮, 何辉. N,N-二甲基羟胺与HNO₂的反应动力学[J]. 应用化学, 2010, 27(08): 916-923.
[12]	唐龙祥, 范保林, 屈龙, 刘春华, 王平华. 负载型原子转移自由基聚合配体的合成及应用[J]. 应用化学, 2010, 27(08): 882-886.
[13]	徐惠,刘小育,范宗良,张斯凡,苟国俊. HAP/P(MMA-St)复合微球的制备及其吸附性能[J]. 应用化学, 2010, 27(03): 276-279.
[14]	毕于铁, 任洪波, 张林, 王鲜, 尚承伟. PMMA/SiO₂透明块体材料的热性能分析与微观结构表征[J]. 应用化学, 2009, 26(10): 1244-1246.
[15]	马建华. 琥珀酸-壳聚胺-Cu（Ⅱ）配合物清除超氧阴离子自由基的性能[J]. 应用化学, 2008, 25(9): 1119-1121.