The microporous zeolitic imidazolate framework ZIF-4 has been synthesized, and its ethylene/ethane and propylene/propane separation potentials have been evaluated by single-component adsorption isotherms and breakthrough experiments of the respective binary mixtures. In all experiments, a higher selectivity for the paraffin is observed that is manifested by a steeper equilibrium isotherm as well as a later breakthrough in the fixed-bed adsorber experiments. Microporous adsorbents with paraffin selectivity are rare but highly interesting for cyclic adsorption processes such as pressure-swing adsorption (PSA).
Two zeolitic imidazolate frameworks, ZIF-9 and ZIF-71, are evaluated by adsorption experiments and molecular simulations with respect to their potential towards olefin/paraffin separation. Pure component adsorption isotherms are measured and compared to grand-canonical Monte-Carlo (GCMC) simulations. The experiments show that the adsorption of the paraffin is favorable over the olefin in both structures. Whereas [a]
Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n-pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.
ZIF-318, isostructural to ZIF-8 but built from the mixed linkers of 2-methylimidazole and 2-trifluoromethylimidazole can be activated for gases sorption and the separation of ethane/ethene mixtures.
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