The intrinsic kinetics of the methanol dehydration to dimethyl ether over the laboratory-synthesized and commercial γ-alumina is studied. A set of kinetic models admitting different mechanisms of the reaction is developed. The developed kinetic models, as well as the kinetic models of the methanol dehydration presented in the literature, are experimentally verified. It is shown that the kinetic model admitting Langmuir–Hinshelwood mechanism with associative methanol adsorption is the only model which describes intrinsic methanol dehydration rate over either laboratory or commercial γ-alumina catalyst. The estimated activation energies are 121 and 128 kJ/mol, methanol adsorption heats are 45 and 70 kJ/mol, and methanol adsorption entropies are 72 and 131 J/(mol × K) for the laboratory and commercial samples, respectively. The laboratory-synthesized γ-alumina may be successfully used for modeling and scaling the process that utilizes the commercial γ-alumina catalysts.

中文翻译：

---

实验室和商业γ-氧化铝上甲醇脱水制二甲醚的内在动力学：比较研究

研究了在实验室合成和商业化的γ-氧化铝上甲醇脱水生成二甲醚的内在动力学。开发了一套允许不同反应机制的动力学模型。所开发的动力学模型以及文献中提出的甲醇脱水动力学模型均经过实验验证。结果表明，承认具有关联甲醇吸附的 Langmuir-Hinshelwood 机理的动力学模型是描述实验室或商业 γ-氧化铝催化剂上固有甲醇脱水速率的唯一模型。对于实验室和商业样品，估计的活化能分别为 121 和 128 kJ/mol，甲醇吸附热为 45 和 70 kJ/mol，甲醇吸附熵分别为 72 和 131 J/(mol × K)。