Thermodynamic and kinetic studies on alkoxylation of camphene over cation exchange resin catalysts
Thermodynamic and kinetic studies on alkoxylation of camphene over cation exchange resin catalysts
复制标题
阳离子交换树脂催化剂下莰烯烷氧基化的热力学和动力学研究
DOI：
10.1002/aic.14786
复制
发表时间：
2015-06-01
期刊：
影响因子：
3.7
通讯作者：
Yang, Gaodong
中科院分区：
文献类型：
--
作者：
Nie, Huiqin;Xu, Ruyin;Yang, Gaodong
以无水大孔阳离子交换树脂和强酸性阳离子交换树脂为催化剂，研究了顺丁烯二酸与2-甲基-1，3-丙二醇的烷氧基化反应。在250 mL搅拌釜式反应器中考察了催化剂种类、溶剂、反应物摩尔比、反应温度和催化剂重复使用性等因素对反应的影响，优化了反应条件。用CNOAC基团贡献法修正了液相的非理想性，给出了333-370 K的热力学平衡常数。通过三种不同的方法（高斯03，常数，和温度的函数）计算的焓变进行了比较。最后一种方法计算的值（−74.6 ± 3.3 kJ/mol）比第二种方法计算的值（−30.2 ±1.2 kJ/mol）更接近理论值（−75.73 kJ/mol）。采用基于活性的Langmuir-Hinshelwood-Hougen-Watson模型对实验数据进行拟合，得到活化能为29.14 kJ/mol。在5 L反应釜中对优化的反应条件进行了验证。© 2015美国化学工程师学会AIChE J，61：1925-1932，2015
The alkoxylation of camphene with 2-methyl-1,3-propanediol was studied using anhydrous macroporous and strong acid cation exchange resins as catalysts. The effects of various parameters, such as catalyst type, solvent, molar ratio of reactants, reaction temperature, and reusability of catalysts, were investigated in a 250 mL stirred tank reactor to optimize the reaction conditions. The UNIFAC group contribution method was used to correct liquid nonideality, giving the thermodynamic equilibrium constant at 333–370 K. The enthalpy changes calculated by three different methods (Gaussian 03, constant, and a function of temperature) were compared. The value (−74.6 ± 3.3 kJ/mol) calculated by the last method was closer to the theoretical value (−75.73 kJ/mol) than that given by the second method (−30.2 ±1.2 kJ/mol). A Langmuir–Hinshelwood–Hougen–Watson model based on activity was used to fit experimental data and the activation energy was 29.14 kJ/mol. The optimized reaction conditions were also verified in a 5 L reaction kettle. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1925–1932, 2015