High-temperature pulsed field gradient nuclear magnetic resonance self-diffusion measurements of n-alkanes in MFl-type zeolites

Abstract

The coefficients of intracrystalline self-diffusion of the n-alkanes from propane to n-alkanes from propane to n-hexane adsorbed in zeolite ZSM-5 are studied by means of the pulsed field gradient (PFG) NMR method with field gradient amplitudes up to 25 T m–1 over a temperature range from –20 to +380 °C. The diffusivities are found to decrease monotonically with increasing chain lengths. They are in satisfactory agreement with the results of quasielastic neutron scattering and MD simulations as well as with non-equilibrium measurements by the frequency response and single-step adsorption technique. However, in comparison with zero-length-column (ZLC) desorption and permeation studies, these data, though exhibiting the same trends of chain length dependence, are ca. two orders of magnitude larger. As expected, the diffusivities are intermediate between those for zeolite NaX and NaCaA, exhibiting, however, the smallest activation energies. This indicates that the differences in the potential energies of the adsorbate molecules on their intracrystalline trajectories are in general smaller than in zeolites NaCaA and NaX.