• Bulletin of the Korean Chemical Society
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• v.16 no.10
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• pp.923-929
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• 1995

Four crystal structures of M3-A (M3Na9-xHx-A, M=Rb or K and x=1 or 0), Rb3Na8H-A(a=12.228(1) Å and R1=0.046), Rb3Na9-A (a=12.258(3) Å and R1=0.058), K3Na8H-A (a=12.257(3) Å and R1=0.048) and K3Na9-A (a=12.257(3) Å and R1=0.052), have been determined by single crystal x-ray diffraction technique in the cubic space group Pm3^m at 21 ℃. In all structures, each unit cell contained three M+ ions all located at one crystallographically distinct position on 8-rings. Rb+ ions are 3.12 and 3.21 Å away respectively from O(1) and O(2) oxygens, about 0.40 Å away from the centers of the 8-rings, and K+ ions are 2.87 and 2.81 Å apart from the corresponding oxygens. These distances are the shortest ones among those previously found for the corresoponding ones. Eight 6-rings per unit cell are occupied by eight Na+ ions, each with a distance of 2.31 Å to three O(3) oxygens. The twelfth cation per unit cell is found as Na+ opposite 4-ring in the large cavities of M3Na9-A and assumed to be H+ for M3Na8H-A. With these noble non-framework cationic arrangements, larger M+ ions preferably on all larger 8-rings and the compact Na+ ions on all 6-rings, the bond angles in the 8-rings of M3-A, 145.1 and 161.0 respectively for (Si,Al)-O(1)-(Si,Al) and (Si,Al)-O(2)-(Si,Al), turned out to be remarkably stable and smaller, by more than 12 to 17°, than the corresponding angles found in the crystal structures of zeolites A with high concentration of M+ ions. It is to achieve these remarkably relaxed 8-rings, the main windows for the passage of gas molecules, with simultaneously maximized cavity volumes that M3-A have been selected as one of the efficient zeolite A systems for gas encapsulation.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.423-429
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• 2008

Currently, Ash-free clean coal producing process by solvent extraction is under development. The produced ash-free clean coal can be directly combusted in a gas turbine which results in substantial improvement of power generation efficiency. However, the clean coal produced by the solvent extraction still contain trace amount of alkali metal which may cause corrosion on turbine blades during the direct combustion. In present work ${\alpha},{\beta}$-metal (Zr and Ti) phosphates and H-Y zeolite were synthesized and their ion exchange characterizations were investigated for the application on alkali metal removal for clean coal production. $Na^+$ ion removal capacities of the metal phosphates and H-Y zeolite were measured and compared in both aqueous solution (100 ppmw, $Na^+$) and coal dissolved N-methyl-2-pyrrolidone (NMP, 12 ppmw $Na^+$) at elevated temperature. In aqueous solution, the ${\beta}$ form metal phosphates showed very high ion exchange capacities compared to ${\alpha}$ form. ${\beta}$ form metal phosphates also showed higher $Na^+$ removal capacities than H-Y zeolite. In ion exchange medium of NMP, all the ${\alpha}$ form metal phosphates showed over 90% of $Na^+$ ion removal efficiency in the temperature range of 200 to 400 while that of H-Y zeolite decreased as a half when the temperature was over 350. In addition, the regenerated metal phosphates by acid treatment showed no sign of degradation in $Na^+$ removal efficiency. Among the metal phosphates used, $Zr_{0.75}Ti_{0.25}(HPO_4)_2$ showed the best performance in $Na^+$ removal and is expected to be the most suitable inorganic ion exchanger for the alkali metal removal process.

• Korean Journal of Crystallography
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• v.4 no.2
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• pp.54-62
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• 1993

The crystal shnture of dehydrated fully Cd2+-exchanged zeolite A evacuated at 2 × 10-6 Torr and 650℃ (a:12.189(2) A) and of its iodine sorption corrplex (a:12.168(2)A) have been netsmlmn by single uystal x-ray diffraction techliques in the cubic space group hkTn at 21(1)℃. The strutures were refined to final error indices, Ri:0.057 and R2 =0.063 with 186 reflections and Rl:0.082 and R2:0.085 with 181 reflections, respectively, for which 1>3σ(In both structure, six lie at two distinguished threefold axes of unit cell ten the crystal structure of an iodine sorption complex of Cd6-A four Cd2+ ions are recessed 0.69(1) A into the large cavity to complex each with from the (111) plane of 0(3), whereas two Cd2+ ions recessed 0.68(1) A into the sodalite unit Awximately 4.0 l3ions per nit cell are sorbed. Each bridge between a Cd2+ ion and 8-ring oxygens ((I-I-I)= 117(1) ˚ and 0(1)-I(1)-I(2)=172(1)). The near linear I-I-0 angle and its interatomic distance (I-0=3.57(3) A) are indicative of a weak charge transfer interacticn between the frarrework oxygen and iodine. The existence of In3 inside the large cavity indicates that the If ions and H ions may be produced by reaction of In vapor with water molecules which maybe associated with Cd2+ ions in partially dehydrated Cd6-A In3- ions may be produced by the combination of I- and I2.

• Journal of Soil and Groundwater Environment
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• v.8 no.2
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• pp.55-61
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• 2003

The objective of this study was to investigate the characteristics of nitrate removal by conducting the column test in order to see the performance of surfactant modified zeolite (SMZ) as a permeable reactive barrier material. The prediction of nitrate removal was tested using the one-dimensional advective-dispersive model fitted to the experimental breakthrough curve. A methodology for scaling up to in-situ permeable reactive barrier was also proposed. The breakthrough of nitrate in the column packed with SMZ was well predicted using linear equilibrium adsorption model. The breakthrough time and half-life obtained by breakthrough experiment with variation of flowrates were decreased with the increase of flowrates. When 10㎥/day of groundwater containing the 50 mg/l of nitrate is to be treated to satisfy the potable water quality criteria (10 mg/l) by SMZ reactive barrier, 300 tons of SMZ and about 6 years of breakthrough time will be required, suggesting that 165 million wons are needed as barrier material expenses in each 6 years besides the initial design and construction expenses and the minimal monitoring and maintenance expenses.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.145.2-145.2
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• 2011

메탄 하이드레이트는 낮은 온도와 높은 압력 조건에서 물분자들의 격자구조에 메탄가스분자가 포획되어 수소결합으로 형성되는 외관상 얼음과 비슷한 결정성 화합물이다. $1m^3$의 메탄 하이드레이트는 표준상태에서 $172m^3$의 메탄가스와 $0.8m^3$의 물로 분해되며, $-10^{\circ}C{\sim}-20^{\circ}C$의 온도에서는 하이드레이트 입자표면에서 생성되는 얼음막으로 인하여 상압에서도 안정하게 존재하는 자기보존 효과를 가지고 있다. 따라서 이와 같은 특징을 천연가스 수송 및 저장의 방법으로 이용할 경우 $-162^{\circ}C$의 초저온을 만들고 유지시키기 위하여 고가의 설비를 필요로 하는 기존의 LNG 수송방법을 대체할 수 있다. 특히 연간 천연가스 소비량을 0.4 ~ 1.0 million ton으로 가정했을 때, 하이드레이트 수송방법은 LNG 수송에 비해 18 ~ 25% 정도의 비용을 절약할 수 있는 경제적인 방법으로 알려져 있다. 그러나 하이드레이트를 인공적으로 제조할 경우 물분자와 가스분자의 반응율이 낮기 때문에 하이드레이트가 생성되기까지 많은 시간이 소요되며, 하이드레이트에 포획되는 가스분자의 양도 적다. 따라서 본 연구에서는 이와 같은 문제점을 해결하기 위하여 다공성 물질인 천연 제올라이트와 제올라이트 13X를 이용하여 제올라이트 혼합유체를 제조하였으며, 메탄가스와 반응시켜 하이드레이트를 생성시키는 실험을 수행하였다. 그 결과, 하이드레이트 생성 시 천연 제올라이트와 제올라이트 13X 모두 0.01 wt%의 혼합비율에서 가장 좋은 효과를 나타내었으며, 하이드레이트에 포획된 가스의 양은 같은 과냉도 조건에서 천연제올라이트와 제올라이트 13X 혼합유체를 이용하여 하이드레이트를 생성 시켰을 때, 증류수보다 각각 4배, 5배 높음을 보였다. 또한 낮은 과냉도에서 하이드레이트 생성 시 제올라이트, 제올라이트13X 혼합유체에서 하이드레이트 생성시간이 증류수에서 하이드레이트를 생성시킬 때보다 빨라짐을 확인하였다.

• Korean Journal of Crystallography
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• v.6 no.2
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• pp.118-124
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• 1995

The crystal structure of an iodine sorption complex of vacumm-dehydrated Ag+ and Ca2+ exchanged zeolite A(a=12.174(3)Å) has been determined at 21℃ by single-crystal X-ray diffraction techniques in the cubic space group Pm3m. The crystal was prepared by flow method for three days using exchange solution in solution in which mole ratio of AgNO3 and Ca(NO3)2 was 1:150 with total concentration of 0.05 M. The complex was prepared by dehydration at 360℃ and 2×10-6 Torr for 2 days, followed by exposure to about 14.3 Torr of iodine vaporat 80℃ for 24 hours. Full-matrix least-squares refinement converged to the final error indices of R1=0.082, R2=0.068 using 122 reflections for which I > 3σ(I). Two Ag+ ions, 1.1 Ag+ ions, and 4.45 Ca2+ ions per unit cell are located on three different three-fold axes associated with 6-ring oxygens. Two Ag+ ions per unit cell are in the large cavity, 1.399(4)Å from the (111) plane of three oxygens. Another 1.1 Ag+ ions are found at opposite sites. Six iodine molecules are sorbed per unit cell. Each I2 molecule approaches a framework oxide ion axially (O-I=3.43(2)Å, I-I=2.92Å, I-I-O;166.1(3)°), by a charge transfer complex interaction. Two Ag+ ions make a close approach to the iodine molecules (Ag-I ; 2.73(2)Å).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.14 no.3
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• pp.223-234
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• 2016

This study aimed to the adsorption-removal of high- radioactive iodide (I) contained in the initially generated high-radioactive seawater waste (HSW), with the use of AgX (Ag-impregnated X zeolite). Adsorption of I by AgX (hereafter denoted as AgX-I adsorption) was increased by increasing the Ag-impregnated concentration in AgX, and its concentration was suitable at about 30 wt%. Because of AgCl precipitation by chloride ions contained in seawater waste, the leaching yields of Ag from AgX (Ag-impregnated concentration : about 30~35 wt%) was less than those in distilled water (< 1 mg/L). AgX-I adsorption was above 99% in the initial iodide concentration ($C_i$) of 0.01~10 mg/L at m/V (ratio of weight of adsorbent to solution volume)=2.5 g/L. This shows that efficient removal of I is possible. AgX-I adsorption was found to be more effective in distilled water than in seawater waste, and the influence of solution temperature was insignificant. Ag-I adsorption was better described by a Freundlich isotherm rather than a Langmuir isotherm. AgX-I adsorption kinetics can be expressed by a pseudo-second order rate equation. The adsorption rate constants ($k_2$) decreased by increasing $C_i$, and conversely increased by increasing the ratio of m/V and the solution temperature. This time, the activation energy of AgX-I adsorption was about 6.3 kJ/mol. This suggests that AgX-I adsorption is dominated by physical adsorption with weaker bonds. The evaluation of thermodynamic parameters (a negative Gibbs free energy and a positive Enthalpy) indicates that AgX-I adsorption is a spontaneous reaction (forward reaction), and an endothermic reaction indicating that higher temperatures are favored.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.2
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• pp.117-124
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• 2023

X-ray diffraction analysis, X-ray fluorescence analysis, thermal differential and thermos gravimetric analysis, cation exchange capacity analysis, and Cesium (Cs), Strontium (Sr) adsorption experiments were performed to investigate the physical and chemical properties of natural zeolite from Guryongpo in Korea. As a result of X-ray diffraction analysis, minerals such as mordenite, heulandite, clinoptilolite, and illite are contained, and as a result of X-ray fluorescence analysis, elements such as SiO₂, Al₂O₃, CaO, K₂O, MgO, Fe₂O₃ and Na₂O are contained, and the cation exchange capacity was 148.6 meq/100 g. As a result of thermal differential and thermos gravimetric analysis, it was confirmed that the thermal stability was excellent up to 600 ℃. As a result of the adsorption equilibrium experiment over time, the equilibrium was reached within 30 min. for Cesium (Cs) and within 8 hr. for Strontium (Sr), and the adsorption rates of Cesium (Cs) and Strontium (Sr) were 80% and 18%, respectively. As a result of the single-component isothermal adsorption experiment, in conformed to the Langmuir model, and the maximum Cesium (Cs) adsorption amount was 131.5 mg/g, which was high, while the Strontium (Sr) maximum adsorption amount was 29.5 mg/g, which was low. In the case of the natural zeolite used in this study, the content of minerals including 8-rings such as clinoptilolite, heulandite, and mordenite is high, showing high selectivity for Cesium (Cs).

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.76-82
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• 1993

Two crystal structures of fully dehydrated Ca(II) and Tl(I) exchanged zeolite A, $Ca_{5.6}Tl_{0.8}-A (a = 12.242(2){\AA})\;and\;Ca_{1.4}Tl_{9.2}-A (a = 12.191(1){\AA})$, have been determined by single-crystal X-ray diffraction methods in the cubic space group Pm3m at 21(1)$^{\circ}C$. All crystals were ion exchanged in flowing streams of mixed $Ca(NO_3)_2\;and\;TINO_3$ aqueous solution with total concentration of 0.05M. All crystals were dehydrated at 360$^{\circ}C$ under $2{\times}10^{-6}\;torr$ for two days. The structures of the dehydrated $Ca_{5.6}Tl_{0.8}-A$ and $Ca_{1.4}Tl_{9.2}-A$ were refined to the final error indicies, $R_1$ = 0.072 and $R_2$ = 0.076 with 179 reflections for I > 3$\sigma$(I), and $R_1$ = 0.048 and $R_2$ = 0.043 with 226 reflections for I > 3$\sigma$(I), respectively. In each structure, Ca(II) ions are located on threefold axes associated with three 6-ring oxygens. $Ca^{2+}$ ions prefer to 6-ring sites and $Tl^+$ ions prefer to 8-ring sites when total number of exchanged cations per unit cell is more than 8.

• Korean Journal of Crystallography
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• v.8 no.2
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• pp.127-131
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• 1997

The crystal structure of a bromine sorption complex of vacuum-dehydrated Ag+ and Ca2+ exchanged zeolite A(a=12,234(1) Å) has been determined by single-crystal X-ray diffraction methods in the cubic space group Pm3m. The crystal was prepared by flow method using exchange solution in which mole ratio of AgNo3 and Ca(NO3)2 was 1:150 with a total concentration of 0.05M. The crystal was dehydrated at 360℃ and 2 ×10-6 Torr for 2days, followed by exposure to 180 Torr of Br2 vapor for 20min. full-matrix least-squares refinements converged to the final error indices of R1=0.111 and R2=0.101 using 90 reflections for which I>3o(I). About 3.1 Ag+ ions and 4.45 Ca2+ ions lie on the two crystallographically nonequivalent three-fold axes associated with 6-ring oxygens. A total of six bromine molecules are sorbed per unit cell. Each bromine molecule approaches a framework oxide ions axially (Br-Br-O=171(2)', O-Br=3.25(6) Å; and Br-Br=2,61(8) Å by a charge-transfer interaction.