The kinetics of the butyl tert-butyl ether (BTBE) synthesis reaction over Amberlyst™ 35 as the catalyst has been studied at 303–356 K in the liquid phase in two different reactor systems: batch and fixed-bed. Internal mass transfer effects were detected at temperatures above 333 K for catalyst particles larger than 0.25 mm. Particles smaller than 0.08 mm did not show mass transfer limitations under the whole assayed temperature range. The best kinetic model has been searched among a large number of kinetic equations resulting from the systematic combination of all possible elementary reactions, adsorbed species, and rate-determining step based, according to the Langmuir–Hinshelwood–Hougen–Watson and the Eley–Rideal formalisms. The significance of the temperature effect on the kinetic parameters and of the effect of the interaction between the catalyst and the reaction medium on the reaction rate has been checked. All proposed kinetic equations have been fitted to experimental rate data free from mass transfer limitations. The model discrimination procedure has been based on mathematical and physicochemical criteria. The resulting kinetic model is consistent with an Eley–Rideal type mechanism where one 1-butanol molecule adsorbs on one active site of the catalyst, it reacts with one isobutene molecule from the liquid phase to give one adsorbed BTBE molecule, which finally desorbs. The rate-determining step is the surface reaction. The catalyst activity is affected by the resin-medium interaction. 1-Butanol adsorption on the catalyst is more exothermic than BTBE adsorption, and isobutene adsorption is negligible.

中文翻译：

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离子交换树脂催化液相合成丁基叔丁基醚：通过深度模型判别的动力学模型

叔丁基叔胺的动力学在Amberlyst™35上，在303–356 K液相中，在两种不同的反应器系统（间歇式和固定床式）中研究了丁基醚（BTBE）在催化剂上的合成反应。对于大于0.25mm的催化剂颗粒，在高于333K的温度下检测到内部传质作用。小于0.08 mm的颗粒在整个测定的温度范围内均未显示出传质限制。根据Langmuir-Hinshelwood-Hougen-Watson和Eley-Rideal的说法，在所有可能的基本反应，吸附的物种和速率决定步骤的系统组合所产生的大量动力学方程式中，搜索了最佳动力学模型。形式主义。已经检查了温度对动力学参数的影响以及催化剂与反应介质之间的相互作用对反应速率的影响的重要性。所有拟议的动力学方程均已符合实验速率数据，且无传质限制。模型判别程序基于数学和物理化学标准。所得的动力学模型与Eley-Rideal型机理一致，在该机理中，一个1-丁醇分子吸附在催化剂的一个活性位点上，它与液相中的一个异丁烯分子反应，得到一个吸附的BTBE分子，该分子最终解吸。决定速率的步骤是表面反应。催化剂活性受树脂-介质相互作用的影响。