• Title/Summary/Keyword: Zeolite ion exchange

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브란운관의 후면유리 폐기물을 이용한 제올라이트 합성

  • Jang, Yeong-Nam;Bae, In-Guk;Chae, Su-Cheon;Ryu, Gyeong-Won
    • Journal of the Korean Professional Engineers Association
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    • v.34 no.2
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    • pp.167-173
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    • 2001
  • Through alkaline hydrothermal activation processes, Na-A type zeolite was synthesized as a single phase withfunnel-glass waste from a television tube factory. The autoclaving was performed in a closed teflon vessel in therange of 80~95"C. The silica-rich solution as a starting material was hydrothermally synthesized with quartz in INNaOH by heating 350"C under the pressure of 1,500 atm. NaA102 was made from NaOH and Al(OH)3 by heating95"c for 2~3 hours and the molar ratios of it were Na20/A1203=1.4 and H20Ha20=8. The equi-dimensional Atype zeolite (1 ~2 U) was formed by the simple mixing of'the silica-rich solution, glass waste and NaA102 for I~3hours-heating at 80"C. The characterization of the reaction product shows Na-A as a single phase. The synthesizedzeolite has cube-dodecahedral form and Ca2+ ion exchange capacity of the Na-A was in the range of 215~220mequivalent/100 g.20mequivalent/100 g.

Adsorption and Catalytic Characteristics of Acid-Treated Clinoptilolite Zeolite (산처리한 Clinoptilolite Zeolite 의 흡착 및 촉매특성)

  • Chon Hakze;Seo Gon
    • Journal of the Korean Chemical Society
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    • v.20 no.6
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    • pp.469-478
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    • 1976
  • Clinoptilolite zeolite samples were treated with hydrochloric acid, sulfuric acid and phosphoric acid of different strength and the adsorption characteristics and crystal structures of the original and acid-treated clinoptilolites were studied. By treating with hydrochloric acid, the adsorbed amount increased to 5-fold for nitrogen, to 3-fold for benzene, but for methanol no significant change was observed. As acid strength increased further, there were declines both in adsorption capacity and crystallinity. The results showed that the increase of adsorbed amount was caused by the rearrangement of the pore entrance and cation exchange. A method for determination of clinoptilolite content in natural mineral based on benzene adsorption on acid-treated sample is proposed. By this method, the original sample used in this study was found to contain approximately 40% of clinoptilolite. Using pulse technique in micro-catalytic reactor system, the catalytic activities of hydrochloric acid-treated clinoptilolites in cumene cracking and toluene disproportionation reactions were measured. For cumene cracking reaction, the maximum conversion was observed for the 0.5 N hydrochloric acid-treated sample. It is instructive to note that the maximum benzene adsorption was also observed for the sample treated with 0.5 N HCl. This suggest that the conversion rate was determined mainly by the rate of transport of reactants and the products through the pore structure. In the toluene disproportionation reaction, the same trend was observed. But the rate of deactivation was high for samples with strong acid sites. Since catalyst having higher activity was deactivated more easily, the conversion maximum was shifted to the sample treated with higher concentration of acid, -1N. The catalytic activity of $Ca^{2+} and La^{3+} ion exchanged samples for the toluene disproportion was much lower than that of acid-treated samples. Introduction of Ca^{2+} and La^{3+}$ into the pore structure apparently decreases the effective pore diameter of acid-treated clinoptilolite thus limiting the diffusion of reactants and products.

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Single-crystal Structure of Partially Dehydrated Partially Mg2+-exchanged Zeolite Y (FAU), |Mg30.5Na14(H2O)2.5|[Si117Al75O384]-FAU

  • Kim, Hu-Sik;Ko, Seong-Oon;Lim, Woo-Taik
    • Bulletin of the Korean Chemical Society
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    • v.32 no.10
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    • pp.3696-3701
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    • 2011
  • The single-crystal structure of partially dehydrated partially $Mg^{2+}$-exchanged zeolite Y, ${\mid}Mg{30.5}Na_{14}(H_2O)_{2.5}{\mid}$ [$Si_{117}Al_{75}O_{384}$]-FAU per unit cell, ${\alpha}$ = 25.5060(1) ${\AA}$, dehydrated at 723 K and $1{\times}10^{-4}$ Pa, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd$\bar{3}$ m at 100(1) K. The structure was refined using all intensities to the final error indices (using only the 561 reflections with $F_{\circ}$ > $4{\sigma}(F_{\circ})$) $R_1$ = 0.0377 (Based on F) and $R_2$ = 0.1032 (Based on $F^2$). About 30.5 $Mg^{2+}$ ions per unit cell are found at four different crystallographic sites. The 14 $Mg^{2+}$ ions occupy at site I at the center of double 6-ring (Mg-O = 2.231(3) ${\AA}$, O-Mg-O = $89.15(11)^{\circ}$ and $90.85(11)^{\circ}$). Four $Mg^{2+}$ ions are found at site I' in the sodalite cavity; the $Mg^{2+}$ ions are recessed 1.22 ${\AA}$ into the sodalite cavity from their 3-oxygen plane (Mg-O = 2.20(3) ${\AA}$ and O-Mg-O = $92.3(14)^{\circ}$). Site II' positions (opposite single 6-rings in the sodalite cage) are occupied by 2.5 $Mg^{2+}$ ions, each coordinated to an $H_2O$ molecule (Mg-O = 2.187(20) ${\AA}$ and O-Mg-O = $114.2(16)^{\circ}$). The 10 $Mg^{2+}$ ions are nearly three-quarters filled at site II in the supercage, being recessed 0.12 ${\AA}$ into the supercage (Mg-O = 2.123(4) A and O-Mg-O = $119.70(19)^{\circ}$). About 14 $Na^+$ ions per unit cell are found at one crystallographic site; the $Na^+$ ions are located at site II in the supercage (Na-O = 2.234(7) ${\AA}$ and O-Mg-O = $110.5(4)^{\circ}$).

Two Crystal Structures of Dehydrated Ag$^+$ and K$^+$Exchanged Zeolite A, $Ag_{12-x}K_x$-A, x = 1.3 and 2.7

  • Kim, Yang;Song, Seong-Hwan;Park, Jong-Yul;Kim, Un-Sik
    • Bulletin of the Korean Chemical Society
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    • v.9 no.6
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    • pp.338-341
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    • 1988
  • Two crystal structures of fully dehydrated silver and potassium exchanged zeolite A, stoichiometries of $Ag_{9.3}K_{{2.7}^-}A$ (${\alpha}$ = 12.282(2) ${\AA}$) and $Ag_{10.7}K_{{1.3}^-}{\AA}$ (${\alpha}$ = 12.287(2) A) per unit cell, have been determined from 3-dimensional x-ray diffraction data gathered by counter methods. All structures were solved and refined in the cubic space group Pm3m at 21(1)$^{\circ}C$ . The crystals of $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$ were prepared by flow method using exchange solutions in which mole ratios of $AgNO_3$ and $KNO_3$ were 1:10 and 1:5, respectively, with total concentration of 0.05M. The structures of the dehydrated $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$ were refined to yield the final error indices $R_1$ = 0.037 and $R_2$ = 0.040 with 321 reflections, and $R_1$ = 0.042 and $R_2$ = 0.043 with 371 reflections, repectively, for which I > 3${\sigma}$(I). In both structures, eight $Ag^+$ ions are found nearly at 6-ring centers and each $Ag^+$ ion is nearly in the (1 1 1) plane at its O(3) ligands. The 8-ring sites are preferentially occupied by $K^+$ ions in both structures. 1.3 and 1.7 reduced silver atoms per unit cell were found inside of sodalite units of $Ag_{9.3}K_{{2.7}^-}A$ and that of $Ag_{10.7}K_{{1.3}^-}A$, respectively. These reduced silver species were presumably formed from the reduction of $Ag^+$ ions by oxide ions of residual water molecule or of the zeolite framework. These two crystals may be presented as hexasilver cluster in 21.7% and 28.3% of sodalite unit cells for $Ag_{9.3}K_{{2.7}^-}A$ and $Ag_{10.7}K_{{1.3}^-}A$, repectively.

Sorption and Ion Exchange Characteristics of Chabazite: Competition of Cs with Other Cations (차바자이트의 흡착 및 이온 교환 특성: Cs 및 다른 양이온과의 경쟁)

  • Baek, Woohyeon;Ha, Suhyeon;Hong, Sumin;Kim, Seonah;Kim, Yeongkyoo
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.2
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    • pp.59-71
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    • 2016
  • To investigate the sorption characteristics of Cs, which is one of the major isotopes of nuclear waste, on natural zeolite chabazite, XRD, EPMA, EC, pH, and ICP analysis were performed to obtain the informations on chemical composition, cation exchange capacity, sorption kinetics and isotherm of chabazite as well as competitive adsorption with other cations ($Li^+$, $Na^+$, $K^+$, $Rb^+$, $Sr^{2+}$). The chabazite used in this experiment has chemical composition of $Ca_{1.15}Na_{0.99}K_{1.20}Mg_{0.01}Ba_{0.16}Al_{4.79}Si_{7.21}O_{24}$ and its Si/Al ratio and cation exchange capacity (CEC) were 1.50 and 238.1 meq/100 g, respectively. Using the adsorption data at different times and concentrations, pseudo-second order and Freundlich isotherm equation were the most adequate ones for kinetic and isotherm models, indicating that there are multi sorption layers with more than two layers, and the sorption capacity was estimated by the derived constant from those equations. We also observed that equivalent molar fractions of Cs exchanged in chabazite were different depending on the ionic species from competitive ion exchange experiment. The selectivity sequence of Cs in chabazite with other cations in solution was in the order of $Na^+$, $Li^+$, $Sr^{2+}$, $K^+$ and $Rb^+$ which seems to be related to the hydrated diameters of those caions. When the exchange equilibrium relationship of Cs with other cations were plotted by Kielland plot, $Sr^{2+}$ showed the highest selectivity followed by $Na^+$, $Li^+$, $K^+$, $Rb^+$ and Cs showed positive values with all cations. Equilibrium constants from Kielland plot, which can explain thermodynamics and reaction kinetics for ionic exchange condition, suggest that chabazite has a higher preference for Cs in pores when it exists with $Sr^{2+}$ in solution, which is supposed to be due to the different hydration diameters of cations. Our rsults show that the high selectivity of Cs on chabazite can be used for the selective exchange of Cs in the water contaminated by radioactive nuclei.

Stabilization Behavior of Heavy Metals in the EAF Dust-clay Body Mixtures at Various Sintering Conditions (점토계소지내에서 전기로 더스트 중금속의 소성 온도별 안정화거동)

  • Kwon, Yong-Joon;Kim, Yoo-Taek;Lee, Gi-Gang;Kim, Young-Jin;Kang, Seung-Gu;Kim, Jung-Hwan
    • Journal of the Korean Ceramic Society
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    • v.39 no.8
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    • pp.728-734
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    • 2002
  • Stabilization behavior of Cr, Cd, Cu, Pb, Fe and Zn heavy metals in the EAF dust was investigated by adding EAF dust to clay or white clay, respectively, up to 50 wt% with 10 wt% intervals and sintering at temperatures between 200 and $1200^{\circ}C$ with $200^{\circ}C$ intervals with an aid of ICP-AES followed by TCLP test to evaluate heavy metal cation exchange capacity of the clay or the white clay. The clay or the white clay had a better Cr ion exchange capacity than that of zeolite. The TCLP leaching test for the sintered specimens showed that Cr and Fe were rarely detected for all the specimens and the concentration of Cd and Zn decreased with increasing sintering temperature and decreasing EAF dust contents respectively. When the clay or the white clay were mixed with EAF dust, cation exchange may occur between the clay and the EAF dust so that the first stabilization of the mixtures containing semistabilized heavy metals may happen. Stabilization of heavy metals in the ceramic bodies was further completed probably due to the eutectic reaction caused by the sintering of semi-stabilized mixtures. It was conceivable that the white clay rather than the clay may be a better stabilizer for the EAF dust containing heavy metals.

Dissolution Conditions of Solid Radioactive Wastes Generated from NPP for the Analysis of Radionuclides Using a Closed-vessel Microwave Acid Digestion System (원전 발생 고체 방사성폐기물 내 핵종 분석을 위한 극초단파 산분해 장치를 이용한 용액화 조건)

  • 표형열;이정진;전종선;이창헌;지광용
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2004.06a
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    • pp.158-166
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    • 2004
  • The optimal conditions are obtained for the decomposition of solid radioactive wastes, including ion exchange resin, zeolite, active charcoal, and sludge from nuclear power plant. In the process of decomposing the radioactive wastes were used the microwave acid digestion method with mixed acid. The solution after acid digestion by the following method was colorless and transparent. Each solution was analyzed with ICP-AES and AAS and the recovery yield for 5 different elements added the simulated radioactive wastes were over 94%. As an effective pre-treatment, the proposed microwave acid digestion conditions concerning the chemical trait of each radioactive waste are expected to be generally applied to above-mentioned radioactive wastes from nuclear power plant hereafter.

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Determination of major and minor elements in low and medium level radioactive wastes using closed-vessel microwave acid digestion (밀폐형 극초단파 산분해법을 이용한 중${\cdot}$저준위 방사성폐기물의 성분 원소 분석)

  • Lee Jeong-Jin;Pyo Hyung-Yeal;Jeon Jong-Seon;Lee Chang-Heon;Jee Kwang-Yong;Ji Pyung-Kook
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.2 no.4
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    • pp.231-238
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    • 2004
  • The conditions are obtained for the decomposition of solid radioactive wastes, including ion exchange resin, zeolite, charcoal, and sludge from nuclear power plant. In the process of decomposing the radioactive wastes was used the microwave acid digestion method with mixed acid. The solution after acid digestion by the following method was colorless and transparent. Each solution was analyzed with ICP-AES and AAS and the recovery yield for 5 different elements added into the simulated radioactive wastes were over $94{\%}$. The elemental analysis of destructive low and medium level radioactive wastes by the proposed microwave acid digestion conditions concerning the chemical characteristics of each radioactive waste are expected to be useful basic data for development of optimal glass formulation.

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Removal Characteristics of Heavy Metals in Acid Mine Drainage (AMD) Using Porous Starfish Ceramics (II) - Treatment of AMD in a Column Reactor System (불가사리 소재 다공성 세라믹을 이용한 산성광산배수 내 중금속의 제거특성(II) - 컬럼연속 실험을 통한 산성광산배수의 처리특성)

  • Lee, Yonghwan;Yim, Soobin
    • Journal of the Korean GEO-environmental Society
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    • v.15 no.12
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    • pp.25-34
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    • 2014
  • The objective of this study was to investigate the removal characteristics and the elimination mechanism of heavy metals in Acid Mine Drainage (AMD) using spherical-type porous Zeolite-StarFish ceramics (porous ZSF ceramics) packed in a continuous column reactor system. The average removal efficiencies of heavy metals in AMD were Al 98.7, As 98.7, Cd 96.0, Cu 89.1, Fe 99.5, Mn 94.4, Pb 96.3 and Zn 80.8 % during 110 days of operation time. The average removal capacity of porous ZSF ceramics for heavy metals were measured to be Al 21.76, As 1.52, Cd 1.27, Cu 3.41, Fe 44.83, Mn 3.48, Pb 2.36 and Zn $3.76mg/kg{\cdot}day$. The analysis results of mechanism using SEM, EDS and XRD exhibited that the porous ZSF ceramics could act as a multi-functional ceramics for the removal of heavy metals in AMD through the reactions of precipitation, adsorption and ion-exchange. The experimental results of column reactor system displayed that the porous ZSF ceramics would be a consistently efficient agent for the removal of heavy metals in AMD for a long term.

The Crystal Structure of an Iondine Sorption Complex of Dehydrated Calcium and Silver Exchanged Zeolite A ($Ag^+$이온과 $Ca^{2+}$이온으로 치환한 제올라이트 A를 탈수한 후 요오드를 흡착한 결정구조)

  • Bae, Myung-Nam;Kim, Yang;Kim, Un-Sik
    • 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).

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