Nonuniform Chain-Length-Dependent Diffusion of Short 1-Alcohols in SAPO-34 in Liquid Phase

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• 作者：Julien Cousin Saint Remi ; Gino V. Baron ; Joeri F. M. Denayer
• 刊名：The Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：May 16, 2013
• 年：2013
• 卷：117
• 期：19
• 页码：9758-9765
• 全文大小：346K
• 年卷期：v.117,no.19(May 16, 2013)
• ISSN：1932-7455

文摘

Liquid-phase diffusion of 1-alcohols in SAPO-34 was explored by batch experimentation. The uptake of pure and binary mixtures of 1-alcohols, dissolved in tert-butanol, was obtained for C1鈥揅8 1-alcohols at temperatures between 25 and 80 掳C, concentrations varying between 0.5 and 10 wt %, and crystal sizes between 7.5 and 20 渭m. The experimental uptake data were fitted with an intracrystalline diffusion model and a linear driving force model. The intracrystalline diffusion coefficient showed a nonuniform stepwise decrease with chain length, ranging from 10^鈥?2 m²/s for methanol to 10^鈥?0 m²/s for 1-pentanol. No effect of the external concentration on the intracrystalline diffusion coefficient was observed. Variation of the crystal size showed that the intracrystalline diffusion is the rate-limiting step. On the basis of the Arrhenius equation, the activation energies of diffusion of ethanol, 1-propanol, and 1-butanol were determined, being, respectively, 27.8, 47.8, and 47.2 kJ/mol. Co-diffusion occurred in the uptake of binary mixtures of methanol/ethanol, methanol/1-propanol, and ethanol/1-propanol, where mutual effects could be noticed. From this experimental work, it could be concluded that the small dimensions of the SAPO-34 framework generate a very sterically hindered diffusion of 1-alcohols into the crystals, resulting in a chain-length-dependent behavior, interesting to obtain efficient kinetic-based separations.