• Applied Chemistry for Engineering
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• v.20 no.1
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• pp.80-86
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• 2009

In this study, binderless zeolite BaX granule, an effective adsorbent for the separation of p-xylene was made. This adsorbent which has a sufficient strength, high specific surface area and selectivity to p-xylene was prepared by various steps, such as granulation process, calcination, binderless treatment, ion-exchange, and activation. In the granulation, the concentration of colloidal silica solution was controlled in order to confirm the effect of $SiO_2$ contents after binderless treatment. As a result, we confirmed that the compressive strength of granule after binderless treatment was increasing with increasing proportion of $SiO_2$ in the granule. And then Na-ion in granule was exchanged with Ba-ion by successive batch ion-exchange process. And then prepared adsorbents were tested for p-xylene separation by batch adsorption at $90^{\circ}C$. As a results of batch adsortion test, we confirmed that prepared adsorbents have a high selectivity to p-xylene. Also, it could be conformed that the prepared binderless zeolite BaX has a sufficient compressive strength (0.450 kgf), high specific surface area $(647.57m^2/g)$, high crystallinity (98.5% compared with zeolite NaX powder), and selectivity to p-xylene.

• Applied Chemistry for Engineering
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• v.16 no.1
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• pp.123-130
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• 2005

Zeolite X adsorbents with large surface area were prepared for using oxygen PSA adsorbent. Selective adsorption performance of nitrogen on the synthesized zeolite X adsorbent was improved by the cation exchange of adsorbent. The zeolite X which had over $650m^2/g$ surface area was synthesized at the conditions of $SiO_2\;:\;Na_2O\;:\;H_2O\;:\;Al_2O_3$ = 2.5 : 3.5 : 150 : 1 mole ratio, $98^{\circ}C$ temperature and 18 h synthesized time in 50 L reactor. The metal ions Li, Ag, Ca, Br, Sr, etc. were investigated for ion exchange with zeolite X. Ag ion was showed the highest ion exchange rate among these metal ions and all metal ions were exchanged with Na ion at equivalent rate. Compared with the NaX adsorbent, the ion exchanged zeolite X adsorbent remarkably improved its adsorption performance of nitrogen at the conditions of $10{\sim}40^{\circ}C$ temperature and 0~9 atm pressure. At an equilibrium pressure under 0.5 atm, adsorption performance of nitrogen on the ion exchanged zeolite adsorbent increased in the order of Ag > Li > Ca > Sr> Ba > K, whereas at an equilibrium pressure over 1 atm showed in the order of Li > Ag > Ca > Sr > Ba > K. Nitrogen/oxygen separation factor of Li ion exchanged zeolite X adsorbent was 13.023 at the partial pressure of nitrogen/oxygen gas mixture similar to air and $20^{\circ}C$ adsorption temperature.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.1
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• pp.49-58
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• 2018

For the immobilization of high-radioactive nuclides such as Cs and Sr by high-temperature thermal decomposition, this study was carried out to investigate the phase transformation with calcined temperature by using TGA (thermogravimetric analysis) and XRD (X-ray diffraction) in the Cs-adsorbed CHA (chabazite zeolite of K type)-Cs and CHA-PCFC (potassium cobalt ferrocyanide)-Cs zeolite system, and Sr-adsorbed 4A-Sr and BaA-Sr zeolite system, respectively. In the case of CHA-Cs zeolite system, the structure of CHA-Cs remained at up to $900^{\circ}C$ and recrystallized to pollucite ($CsAlSi_2O_6$) at $1,100^{\circ}C$ after undergoing amorphous phase at $1,000^{\circ}C$. However, the CHA-CFC-Cs zeolite system retained the CHA-PCFC-Cs structure up to $700^{\circ}C$, but its structure collapsed in $900{\sim}1,000^{\circ}C$, and then transformed to amorphous phase, and recrystallized to pollucite at $1,100^{\circ}C$. In the case of 4A-Sr zeolite system, on the other hand, the structure of 4A-Sr maintained up to $700^{\circ}C$ and its phase transformed to amorphous at $800^{\circ}C$, and recrystallized to Sr-feldspar ($SrAl_2Si_2O_8$, hexagonal) at $900^{\circ}C$ and to $SrAl_2Si_2O_8$ (triclinic) at $1,100^{\circ}C$. However, the BaA-Sr zeolite system structure began to break down at below $500^{\circ}C$, and then transformed to amorphous phase in $500{\sim}900^{\circ}C$ and recrystallized to Ba/Sr-feldspar (coexistence of $Ba_{0.9}Sr_{0.1}Al_2Si_2O_8$ and $Ba_{0.5}Sr_{0.5}Al_2Si_2O_8$) at $1,100^{\circ}C$. All of the above zeolite systems recrystallized to mineral phase through the dehydration/(decomposition) ${\rightarrow}$ amorphous ${\rightarrow}$ recrystallization with increasing temperature. Although further study of the volatility and leachability of Cs and Sr in the high-temperature thermal decomposition process is required, Cs and Sr adsorbed in each zeolite system are mineralized as pollucite, Sr-feldspar and Ba/Sr-feldspar. Therefore, Cs and Sr seen to be able to completely immobilize in the calcining wasteform/(solidified wasteform).

• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.265-270
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• 1991

Theoretical calculations on the stabilization energies of framework atoms in hydrolyses Co(Ⅱ )-exchanged zeolite A were made using some potential energy functions and optimization program. The protons which are produced by hydrolysis of $[Co(H_2O)_n]^{2+}$ ion in large cavity showed a tendency to attack the framework oxygen atom O(1) preferentially, and the oxygen atom O(4) within OH- ion was coordinated at Al atom. The weakness of bonds between T(Si, Al) and oxygen by attack of proton and too large coordination number around small aluminum atom will make the framework of Co(Ⅱ)-exchanged zeolite A more unstable. The stabilization energy of $Co_4Na_4$-A framework (- 361.57 kcal/mol) was less than that of thermally stable zeolite A($Na_{12-}$A: - 419.68 kcal/mol) and greater than that of extremely unstable Ba(Ⅱ)-exchanged zeolite A($Ba_{6-}$A: - 324.01 kcal/mol). All the data of powder X-ray diffraction, infrared and Raman spectroscopy of Co(Ⅱ)-exchanged zeolite A showed the evidence of instability of its framework in agreement with the theoretical calculation. Three different groups of water molecules are found in hydrated Co(Ⅱ )-exchanged zeolite A; W(Ⅰ) group of water molecules having only hydrogen-bonds, W(Ⅱ) group water coordinated to $Na^+$ ion, ans W(Ⅲ) group water coordinated to Co(Ⅱ) ion. The averaged interaction energy of each water group shows the decreasing order of W(Ⅲ)>W(Ⅱ)>W(Ⅰ).

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.248-251
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• 1995

The crystal structure of Ba46-X, Ba46Al92Si100O384 [a= 25.297(1) Å], has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd&bar{3}at 21(1) ℃. The crystal was prepared by ion exchange in flowing stream of 0.05 M Ba(OH)2 aqueous solution for 5 days. The crystal was then dehydrated at 380 ℃ and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices R1= 0.051 and Rw= 0.054 with 369 reflections for which I > 3σ(I). In this structure, all Ba2+ ions are located at the three different crystallographic sites: fourteen Ba2+ ions are located at site Ⅰ, the centers of the double six rings, two Ba2+ ions lie at site Ⅰ', in the sodalite cavity opposite double six rings(D6R's) and another thirty Ba2+ ions are located at site Ⅱ in the supercage. Two Ba2+ ions are recessed ca. 0.27 Å into the sodalite cavity from their three O(3) oxygen plane and thirty Ba2+ ions are recessed ca. 1.11 Å into the supercage from their three O(2) oxygen planes, respectively (Ba(1)-O(3) = 2.76(1) Å, O(3)-Ba(1)-O(3) = 180(0)°, Ba(2)-O(3) = 2.45(1) Å, O(3)-Ba(2)-O(3) = 108(1)°, Ba(3)-O(2)=2.65(1) Å, and O(2)-Ba(3)-O(2)=103.9(4)°).

• Journal of Power System Engineering
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• v.14 no.6
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• pp.13-19
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• 2010

이 논문에서는 디젤자동차용 LNT와 SCR 촉매의 NO, $NH_3$ 흡착 및 탈리의 기본 특성과 수열화 온도와 시간 및 정량화된 황피독 농도에 대한 de-$NO_x$ 촉매의 내구성을 평가하였다. LNT 촉매는 열적으로 열화됨에 따라 Pt 및 Ba의 소결 및 응집으로 활성이 떨어져 $NO_x$ 전환율은 감소하였다. 반면에 Pt의 비활성화로 중간생성물인 $NH_3$ 생성량은 증가하였으며, 이때 생성된 $NH_3$는 LNT+SCR 복합시스템의 SCR 촉매의 환원제 역할을 담당한다. 1.0 g/L 이상의 황이 피독된 LNT 촉매는 탈황을 하여도 질소 산화물 흡장물질(Ba) 의 성능이 회복이 되지 않아 $NO_x$ 전환율은 회복되지 않았으며, 탈황 후 Pt 재활성화로 인해 NO2 및 SCR 환원제인 $NH_3$ 생성량은 증가하였다. SCR 촉매의 $NO_x$ 전환율은 $700^{\circ}C$ 36h, $800^{\circ}C$ 24h로 수열화 시킨 촉매는 전이금속 입자 성장 및 zeolite 구조 파괴로 인하여 급격하게 떨어졌으며, 0.36 g/L 황 피독된 촉매는 zeolite가 가지는 강산성 특정으로 내피독성이 강하여 탈황시 $NO_x$ 전환율은 회복되었다.

• Korean Chemical Engineering Research
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• v.45 no.2
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• pp.160-165
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• 2007

The synthesis and the characterization of Low Silica X (LSX) zeolite for nitrogen adsorption have been studied. The performance of LSX zeolite for nitrogen adsorption was compared to that of the commercial zeolite. The $Na_2O/(Na_2O+K_2O)$ ratio in the gel and the crystallization time were fixed as the synthetic factor. The LSX zeolite was formed at the $Na_2O/(Na_2O+K_2O)$ ratio of 0.75. The formation of LSX zeolite was confirmed by XRD and SEM. The Si/Al ratio was investigated by using XRF and FT-IR. The synthesized LSX zeolite showed a lower Si/Al ratio than the NaY and NaX zeolites although they have a same faujasite structure. The Si/Al ratio of the LSX zeolite converged close to 1. 1A (Li, Na, K) and 2A (Mg, Ca, Ba) group elements were ion-exchanged to the LSX zeolite. As the charge density of cation rises, the amount of nitrogen adsorbed increased. $Li^+$ ion-exchanged LSX zeolite showed the highest nitrogen adsorption weight. When the Li/Al ratio was over 0.65, nitrogen adsorption increased remarkably. $Li^+$ ions located on the supercage (site III, III') in the LSX zeolite played a role as nitrogen adsorption sites. When the $Ca^{2+}$ ions were added to the LiLSX zeolite by ion-exchange method, the performance for nitrogen adsorption increased more. The performance for the nitrogen adsorption was the highest at the Ca/Al ratio of 0.26. Nitrogen adsorption capacity of LiCaLSX (Ca/Al=0.26) zeolite was superior to the commercial NaX zeolite.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.3
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• pp.169-176
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• 2021

This study aimed to fundamentally understand structural changes of zeolite under pressure and in the presence of different pressure-transmitting media (PTM) for application studies such as immobilization of heavy metal cation or CO₂ storage using pressure. High-pressure X-ray powder diffraction study was conducted on the zeolite-W (K_6.4Al_6.5Si_25.8O₆₄× 15.3H₂O, K-MER) to understand linear compressibility and the bulk moduli in different PTM conditions. Zeolite-w is a synthetic material having the same framework as natural zeolite merlinoite ((K, Ca_0.5, Ba_0.5, Na)₁₀ Al₁₀Si₂₂O₆₄× 22H₂O). The space group of the sample was identified as I4/mmm belonging to the tetragonal crystal system. Water, carbon dioxide, and silicone-oil were used as pressure-transmitting media. The mixture of sample and each PTM was mounted in a diamond anvil cell (DAC) and then pressurized up to 3 GPa with an increment of ca. 0.5 GPa. Pressure-induced changes of powder diffraction patterns were measured using a synchrotron X-ray light source. Lattice constants, and bulk moduli were calculated using the Le-Bail method and the Birch-Murnaghan equation. In all PTM conditions, linear compressibility of c-axis (𝛽^c) was 0.006(1) GPa^-1 or 0.007(1) GPa^-1. On the other hand, the linear compressibility of a(b)-axis (𝛽^a) was 0.013(1) GPa^-1 in silicone-oil run, which is twice more compressible than the a(b)-axis in water and carbon dioxide runs, 𝛽^a = 0.006(1) GPa^-1. The bulk moduli were measured as 50(3) GPa, 52(3) GPa, and 29(2) GPa in water, carbon dioxide, and silicone-oil run, respectively. The orthorhombicities of ac-plane in the water, and carbon dioxide runs were comparatively constant, near 0.350~0.353, whereas the value decreased abruptly in the silicone-oil run following formula, y = -0.005(1)x + 0.351(1) by non-penetrating pressure fluid condition.

• Journal of the Korean Institute of Gas
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• v.9 no.4 s.29
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• pp.17-25
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• 2005

The dealuminated and alkali/alkaline-earth metal exchanged Y-zeolites were prepared as a catalyst. Elemental compositions and structures of the prepared catalysts were analyzed by the various spectroscopic techniques such as inductively coupled plasma-atomic emission spectroscopy(ICP-AES), X-ray fluorescence(XRF) and X-ray diffraction(XRD), and the desorption behaviors of adsorbed species on the catalyst surfaces were investigated via NO-TPD experiment. Comparing with the composition of the starting material of NaY zeolite, the magnitudes of Si/Al ratio in catalytic materials were increased after dealumination. The Si/Al ratio of catalytic materials after dealumination followed by Cs and Ba cation exchange were additionally decreased. Dealumination to catalysts induced a destruction of basic frame due to a detachment of aluminum, which results in reducing framework structure, while increasing non-framework structure. This phenomenon becomes more serious with increasing time of steam treatment and even more significant for the cation exchanged catalysts. In NO-TPD experiments, the desorption peaks of NO which indicates an activity point of catalysts shifted to the low temperature region after dealumination and cation exchange. The desorption peaks of the NO-TPD profiles taken after steam treatment also shifted to the low temperature region as the steam treatment time increased. In dealuminated and cation exchanged Y-zeolites, the catalytic activities were more influenced by exchanged cation and the formation of non-framework structure.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.808-818
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• 1994

Effects of ceria additive on the activity and thermal aging behavior of supported Ru catalysts were investigated using Ru/${\gamma}$-$Al_2O_3$and Ru/$CeO_2$-${\gamma}$-$Al_2O_3$. The catalysts were characterized by $^{129}Xe$-NMR and $H_2$ chemisorption. The cataltic activity for conversion of CO, HC and $NO_x$ was measured using simulated automobile engine exhausts under lean, rich and stoichiometric conditions. For both fresh and aged catalysts, Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was more active than Ru/${\gamma}$-$Al_2O_3$ for all three pollutants. Results of $^{129}Xe$-NMR and $H_2$ chemisorption indicated that sintering of Ru particles occurred to the same extent for both catalysts during the thermal aging process. After thermal aging at 673K, however, the catalytic activity of the aged Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was substantially higher than that of the fresh one, while the activity of Ru/${\gamma}$-$Al_2O_3$ decreased after the thermal aging. This finding may suggest new active sites were created during the thermal aging, probably in the vicinity of the interface between Ru and Ce. For more quantitative investigation of the effect of a cation such as Ce on the thermal aging of Ru metal particles, Ru catalysts supported on cation-exchanged Y-zeolites were used as the model catalysts. The results indicated that when Ba, Ca, La, Y or Ce was used for the cation exchange, the exchanged cation did not affect the thermal aging behavior of Ru in Y-zeolite, as evidenced by $^{129}Xe$-NMR and EXAFS.