PFG NMR self-diffusion of small hydrocarbons in high silica DDR, CHA and LTA structures

被引:109
作者
Hedin, Niklas [1 ]
DeMartin, Gregory J. [1 ]
Roth, Wieslaw J. [1 ]
Strohmaier, Karl G. [1 ]
Reyes, Sebastian C. [1 ]
机构
[1] ExxonMobil Res & Engn Co, Corp Strateg Res, Annandale, NJ 08801 USA
关键词
self-diffusion; PFG NMR; ZSM-58; chabazite; ITQ-29;
D O I
10.1016/j.micromeso.2007.05.007
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy was used to measure and rationalize the intracrystalline self-diffusion coefficients of small hydrocarbons in high silica DDR (ZSM-58, Si/Al = 190), pure silica chabazite (Si-CHA) and ITQ-29 (Si-LTA) structures. The self-diffusivities of methane, ethane, ethylene and propylene were measured on these materials at 301 K and 101.3 kPa. A clear correlation is shown between the size of the 8-ring windows and the size of the molecules on the measured self-diffusivities. Window sizes were obtained from X-ray diffraction measurements: [3.65 x 4.38 angstrom] for ZSM-58, [3.70 x 4.17 angstrom] for Si-CHA and [4.00 x 4.22 angstrom] for Si-LTA. An increase in self-diffusivity with window size and a decrease with molecular size were clearly observed. The magnitudes of these effects are shown to be very large. For example, at 301 K and 101.3 kPa, the. self-diffusivities of methane were 1.6 x 10(-8) cm(2)/S, 10.7 x 10(-8) cm(2)/s and 142.0 x 10(-8) cm(2)/s in ZSM-58, Si-CHA and Si-LTA, respectively; an increase in self-diffusivity of nearly 2 orders of magnitude that is primarily due to window size effects. Similarly, at 301 K and 101.3 kPa, the self-diffusivities of methane, ethylene, ethane and propylene in Si-LTA were 142.0 x 10(-8) cm(2)/s, 21.4 x 10(-8) cm(2)/s, 20.9 x 10(-8) cm(2)/s and 0.0047 x 10(-8) cm(2)/s, respectively; a decrease in self-diffusivity with molecular size of more than 4 orders of magnitude. These findings contribute to a fundamental understanding of self-diffusion in microporous materials and have important implications for kinetic based separation schemes in which diffusion plays a key role. (c) 2007 Elsevier Inc. All rights reserved.
引用
收藏
页码:327 / 334
页数:8
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