Determination of Kinetic Constants for Titanium-based Ethylene Trimerization Catalysis

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• 作者：Henk Hagen
• 刊名：Industrial & Engineering Chemistry Research
• 出版年：2006
• 出版时间：May 10, 2006
• 年：2006
• 卷：45
• 期：10
• 页码：3544 - 3551
• 全文大小：210K
• 年卷期：v.45,no.10(May 10, 2006)
• ISSN：1520-5045

文摘

For two titanium-based ethylene trimerization catalysts, [(Me₃SiC₅H₃CMe₂C₆H₃Me₂)TiCl₃] (1) and[(Me₃SiC₅H₃C(CH₂)₅C₆H₃Me₂)TiCl₃] (2), the entropies and enthalpies of activation for the ethylene trimerizationreaction (k₁) as well as the catalyst deactivation reaction (k_d) have been determined. Using a combination of,on the one hand, experimental pressure and temperature data and, on the other hand, vapor-liquid equilibriumcalculations, the 1-hexene concentration as a function of time was estimated and these data were fitted to akinetic model to obtain the thermodynamic data. A best fit was obtained for a combination of a propagationreaction that is first order in the ethylene concentration and a catalyst deactivation reaction that is secondorder in the catalyst concentration. The measured entropies and enthalpies of activation are in good agreementwith the previously reported calculated ones.