• Clean Technology
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• v.24 no.1
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• pp.41-49
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• 2018

Y zeolites with different extra-framework cations, such as $Na^+$, $N^+$, $Ca^{2+}$, and $Cu^{2+}$, with different charge and ionic radius have been investigated to greatly enhance a working capacity (W) of $CO_2$ adsorption at $25^{\circ}C$ and a $CO_2/CO$ selectivity factor (S). A sample of NaY with a very small amount of 0.012% $Ca^{2+}$ was fully reversible for seven times repeated $CO_2$ adsorption/desorption cycles, thereby forming no surface carbonates unlikely earlier reports. Although at pressures above 4 bar, 2.00% CaY, 1.60% CuY and 1.87% LiY all showed a $CO_2$ adsorption very similar to that measured for NaY, they gave a significant decrease in the adsorption at lower pressures, depending on the metal ion. At 0.5 ~ 2.5 bar, the extent of $CO_2$ adsorption was in the order NaY > 1.60% CuY > 2.00% CaY > 1.87% LiY. All the $Na^+-based$ metals-exchanged zeolites have a FAU (faujasite) framework and a Si/Al value near 2.6; thus, there is no discernible difference in the framework topology, framework chemical compositions, effective aperture size, and channel structure between the zeolite samples. Therefore, the distinctive behavior in the adsorption of $CO_2$ with a character as a weak Lewis acid is associated with the site basicity of the zeolites, and the interaction potentials of the cations. Different trend was shown for a CO adsorption due to weaker quadrupole interactions. Adsorption of $CO_2$ and CO on samples of CaY with 0.012 to 5.23% Ca disclosed a significant dependence on the Ca loading. The $CO_2$ adsorption increased when the cation exists up to ca. 0.05%, while it decreased at higher Ca amounts. However, values for both W and S could greatly increase as the bare zeolite is enriched by $Ca^{2+}$ ions. The 5.23% CaY had $W=2.37mmol\;g^{-1}$ and S = 4.37, and the former value was comparable to a benchmark reported in the literature.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.3
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• pp.251-258
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• 2020

Single crystal of fully dehydrated and partially Ca²⁺-exchanged zeolites A (|Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA) was brought into contact with Se in fine pyrex capillary at 523 K for 5 days. Crystal structure of Se-sorbed |Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA has been determined by single-crystal X-ray diffraction techniques at 294 K in the cubic space group $Pm{\bar{3}}m$ (a = 12.2787(13) Å). The crystal structure of yellow |Ca₄Na₄Se₄|[Si₁₂Al₁₂O₄₈]-LTA has been refined to the final error indices of R₁/wR₂ = 0.0960/0.3483 with 327 reflections for which F_o > 4s(F_o). In this structure, 4 Na⁺ and 4 Ca²⁺ ions fill every 6-ring site: These ions are all found at three crystallographic positions, on 3-fold axes equipoints of opposite 6-rings. Selenium atoms are found at three crystallographically distinct positions: 2 Se atoms per unit cell at Se(1) are located opposite 6-rings in the sodalite cavity (Se(1)-Na(1) = 2.53(5) Å) and 1 at Se(2) opposite 4-rings (Se(2)-O(1) = 2.76(10) Å) and 1 at Se(3) opposite 6-rings in the large cavity (Se(3)-Na(1) = 2.48(5) Å). Two molecular of Se₂ (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5) ) Å) are found in all sodalite cavity and large cavity. Other clusters such as Se₄ and Se₈ could be existed in large cavity. The inter-selenium distances turned out to be longer that of gases Se₂ molecule.