PSA USING SUPERIOR ADSORBENTS

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volume. A comparison with the same plot of the isosteric heat of adsorption for N2 on for Li94.5Na1.5-X-1.0, which is essentially horizontal, shows that the energetic heterogeneity of the Li94.2Na0.7Ag1.1-X-1.0 zeolite is due entirely to the incorporation of the approximately one Ag per unit cell. The plots of the heats of adsorption for O2 and Ar were horizontal with coverage, indicating the interaction between the silver clusters and these guest molecules is much less than with the N2. The approximately constant heat of adsorption with increasing coverage for the Li94.5Na1.5-X-1.0 is consistent with previously reported results,25 and likely indicates an energetically homogeneous surface. Cation Site Location. For the X zeolites, the cation site designations are conventionally designated as SI (the center of the hexagonal prism), SI’ (opposite SI but located in the cubooctahedron), SII (single six-ring in the supercage), SII’ (opposite SII but inside the cubooctahedron), and SIII (near the four-ring windows in the supercage).4 Several studies have been employed in order to locate extraframework Li+ cations in X, Y and A zeolites using solid state NMR and neutron diffraction methods.26,27 It was found that the Li+ ions fully occupy all 32 SI’ sites and all 32 SII sites. The SIII sites were then occupied with the remaining Li+ ions, 22 for Li86-X-1.25 and 32 for Li96-X-1.0. No occupancy of the SI sites was observed. Coe reported an occupancy “threshold” of 64 cations.10 Mixed LixNay-X zeolites which contained less Li+ than this threshold amount did not show any increase in the N2 adsorption capacity over that of the fully Na+- exchanged materials. This indicated that only those Li+ ions located in the SIII cation sites were interacting with the N2 molecules. This result is interesting because, even though the SI and SI’ sites are sterically inaccessible to the N2 molecules, the SII sites are not; and other cations, such as Ca2+, do interact with N2 when located in the SII positions. 61

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