• Journal of the Korean Chemical Society
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• v.57 no.1
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• pp.12-19
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• 2013

The single-crystal structure of fully dehydrated partially $Li^+$-exchanged zeolite Y, ${\mid}Li_{50}Na_{25}{\mid}[Si_{117}Al_{75}O_{384}]$-FAU, was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 100(1) K. Ion exchange was accomplished by flowing stream of 0.1 M aqueous $LiNO_3$ for 2 days at 293 K, followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. The structure was refined using all intensities to the final error indices (using only the 801 reflections with ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2=0.043/0.140$. The 50 $Li^+$ ions per unit cell are found at three different crystallographic sites. The 19 $Li^+$ ions occupy at site I' in the sodalite cavity: the $Li^+$ ions are recessed 0.30 ${\AA}$ into the sodalite cavity from their 3-oxygens plane (Li-O = 1.926(5) ${\AA}$ and $O-Li-O=117.7(3)^{\circ}$). The 20 $Li^+$ ions are found at site II in the supercage, being recessed 0.23 ${\AA}$ into the supercage (Li-O = 2.038(5) ${\AA}$ and $O-Li-O=118.7(3)^{\circ}$). Site III' positions are occupied by 11 $Li^+$ ions: these $Li^+$ ions bind strongly to one oxygen atom (Li-O = 2.00(8) ${\AA}$). About 25 $Na^+$ ions per unit cell are found at four different crystallographic sites: 4 $Na^+$ ions are at site I, 5 at site I', 12 at site II, and the remaining 4 at site III'.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.642-645
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• 2007

석탄, 폐기물 등 다양한 시료의 가스화 반응을 통해서 발생되는 합성가스는 CO, $H_2$, $CO_2$가 주성분으로 가스엔진, 가스터빈 등의 연료로 사용하여 발전하거나 합성반응을 통해 다양한 화학원료로의 전환이 가능하다. 합성가스를 가스엔진, 가스터빈, 연료전지등의 연료로 사용하는 경우는 고효율 발전이 가능하여 기존 연소방식의 발전과 비교하여 단위 전력 생산량 당 $CO_2$의 배출량이 감소 되며, 여기에 $CO_2$ 분리공정을 적용하면 $CO_2$ 배출량 감소효과를 극대화 할 수 있다. 화석연료의 연소 및 가스화 반응을 통해서 발생하는 이산화탄소의 분리에 대한 많은 연구가 진행되고 있으나, 본 연구에서는 흡착방식을 이용한 합성가스 내의 이산화탄소 분리를 위하여 흡착제를 이용한 이산화탄소의 흡착, 탈착 성능 분석 연구를 수행하였다. 합성가스내의 이산화탄소를 분리하기 위한 흡착제로는 NaX 계열의 zeolite를 이용하였으며, 가스화 반응을 통해 발생한 합성가스를 흡착제에 통과시켜 이산화탄소의 선택적 흡착 여부를 확인하였다. 또한 TPD(Temperature Programmed Desorption)방법을 이용하여 흡착제의 이산화탄소 흡착 성능을 분석하였다.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.339-344
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• 1994

The crystal structure of a methanol sorption complex of dehydrated partially Co(II)-exchanged zeolite A, $Co_4Na_4-A{\cdot}6.5CH_3OH$ (a = 12.169(1) $\AA)$, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm$\bar3$m at $21(1)^{\circ}C. $Co_4Na_4$-A was dehydrated at $360^{\circ}C\;and\;2{\times}10^{-6}$ torr for 2 days, followed by exposure to about 104 torr of methanol vapor at $22(1)^{\circ}C$ for 1 hr. The structure was refined to final error indices, $R_1$ = 0.061 and $R_2$ = 0.060 with 147 reflections, for which I > $3\sigma(I).$ In this structure, four $Co^{2+}$ ions and 1.5 $Na^+$ ions per unit cell lie at 6-ring positions: the $Na^+$ ions are recessed 0.44 $\AA$ into the sodalite unit and the Co(II) ions extend ca. 0.55 $\AA$ into the large cavity. 2.5 $Na^+$ ions lie in an 8-oxygen ring plane. The 6.5 methanol molecules are sorbed per unit cell. The 6.5 methanol oxygens, all in the large cavity, associate with the 4 $Co^{2+}$ ions and 2.5 $Na^+$ ions.

• Journal of the Mineralogical Society of Korea
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• v.16 no.3
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• pp.201-213
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• 2003

The adsorption property and ability of domestic zeolites for some heavy metal ions (Ag, Pb, Cr, Cu, Zn, Mn), which may cause a serious environmental problem in industrial wastewater, were evaluated on ore unit through a series of adsorption experiments together with careful examinations of mineral composition and properties of the zeolites. Though the adsorption behavior basically took place in the form of a cation exchange reaction, the higher CEC value does not necessarily to imply the higher adsorption capacity for a specific heavy metal. A general trend of the adsorption selectivity for heavy metals in the zeolites is determined to be as follow: $Ag\geq$Pb>Cr,Cu$\geq$Zn>Mn, but the adsorption properties of heavy metal ions somewhat depend on the species and composition of zeolite. Clinoptilolite tends to adsorb selectively Cu in case of Cr and Cu, whereas heulandite prefers Cr to Cu. A dominant adsorption selectivity of the zeolite ores for Ag and Pb is generally conspicuous regardless of their zeolite species and composition. The zeolite ores exhibit a preferential adsorption especially for $Ag^{+}$ so as not to regenerate when treated with $Na^{+}$ . In the adsorption capacity for heavy meta ions, the zeolites differ in great depending on their species: ferrierite>clinoptilolite>heulandite. Considering the CEC value of mordenite, the mordenite-rich ore appears to be similar to the clinoptilolite ore in the adsorption capacity. The adsorption capacity for heavy metals is not positively proportional to the CEC values of the zeolites measured by the exchange reaction with ammonium ion. In addition, the adsorption capacity roughly tends to depend on the zeolite contents, i.e., the grade of zeolite ore, but the trend is not consistent at all in some ores. These may be caused by the adsorption selectivity for some specific heavy metals, the presence of possible stacking micro-faults and natural cations such as K hardly to exchange in the zeolite. Considering the economic availability and functional effectiveness as natural zeolite resources, clinoptilolite ores could be applicable to utilize the domestic zeolites for the removal of heavy metals.

• Journal of the Korean institute of surface engineering
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• v.26 no.6
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• pp.285-290
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• 1993

A series of samples were prepared by treating natural zeolite from Kampo area with HCl and NaOH. And, the adsorption characteristics of some liquid samples were investigated by the Diamond-Kinter method. The adsorption amount of all liquid investigated was more effective in acid treatment than in alkali treatment. In the case of n-, iso-C3H7OH, thed adsorption amount of n-form which has smaller molecular size was larger. Similar tenedncy was observed in n-, iso-C4H9OH, but the amount was lower than n-, iso-C3H7OH. In CHCl3 and CCl4, that of CHCl, which is smaller molecular size and has polarity, was far lager. From the view of the molecular size, adsorption amount of C6H5CH3 and p-C6H4(CH3)2 showed the characteristics of surface activity rather than chemical treatment.

• Bulletin of the Korean Chemical Society
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• v.19 no.4
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• pp.466-470
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• 1998

Catalytic hydrogenation of carbon dioxide for the simultaneous synthesis of methanol and dimethyl ether (together called oxygenates) over a combination of methanol synthesis and methanol dehydration catalysts has been studied. Various methanol synthesis and methanol dehydration catalysts were examined for this reaction. The addition of promotors like $Ga_2O_3\; and\; Cr_2O_3$ to Cu/ZnO catalyst gave much more enhanced yield on the formation of oxygenates. From the results, the promotional effect of $Cr_2O_3$ has been explained in terms of increase in the intrinsic activity of Cu while that of $Ga_2O_3$ being increase in the dispersion of Cu. Among the methanol dehydration catalysts examined, the solid acids bearing high population of intermediate-strength acid sites were found to be very effective for the production of oxygenates. HY zeolite which contains strong acid sites produce small amount of hydrocarbons as by-products. However, CuNaY zeolite in which the presence of strong acid sites are minimum gives very high oxygenates yield without the formation of hydrocarbons.

• Journal of Energy Engineering
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• v.6 no.1
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• pp.26-33
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• 1997

Highly crystalline Cu-ZSM5 was prepared without using organic templates. Several ion exchange treatments between Na$\^$＋/ and Cu$\^$2＋/ brought about excess loading of copper ions on the ZSM5 zeolite and the resultant zeolite was active for the decomposition of NO. This indicates that the copper ions excessively loaded on the ZSM5 zeolite are effective for the NO decomposition. When oxygen was added to a reactants, the conversion of NO decreased. NO, O$_2$TPD experiments explained that the active sites for NO decomposition and the adsorption sites of O$_2$, were the same. O$_2$, at the surface of ZSM5 zeolite was desorbed incompletely after pretreatment at 500$^{\circ}C$, and CU-ZSM5 pretreated with H$_2$at 500$^{\circ}C$ showed promoted activity at the start of reaction. Thus, it seems clear that O$_2$, adsorbed ai the surface of catalyst inhibits the catalytic activity.

• Journal of radiological science and technology
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• v.29 no.3
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• pp.147-155
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• 2006

The crystal structures of fully dehydrated $K_3Na_8H-A(R_1=0.0478,\;R_2=0.0458\;and\;a=12.257(1){\AA})$ have been studied by single-crystal x-ray diffraction methods in the cubic space group. Pm3m in order to understand the structure of the zeolite as a gas storage medium and the mechanisms based on the encapsulation and decapsulation processes of gas molecules. In the crystal structures of dehydrated $K_3Na_8H-A$, three $K^+$ ions per unit cell are located on the 8-oxygen ring(0.0, 0.4531, 0.4531) and eight $Na^+$ ions per unit cell are located near the centers of 6-oxygen rings. Each $K^+$ ions on the 8-ring is $2.87(2){\AA}$ and $2.79(1){\AA}$ away from two kinds of framework oxygen atoms. These values are more realistic than previously known values in $K_{12}Na-A$. The exact positions of $K^+$ ions are ca. $0.8{\AA}$ away from the centers of the 8-rings which are previously reported as the preferred location of $K^+$ ions. Because the zeolites frameworks are stabilized as the results, more effective controls of gas molecules at encapsulation, decapsulation, and storage are achieved. Additionally, the available storage volumes are also maximized and more volume of gases can be stored in the materials. Therefore, oxygen storage bottles in hospital can be minimized and portable oxygen bottles for patients in emergency can be developed by using the materials.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.534-539
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• 2010

The adsorptive removal of organic sulfur compounds including tert-butylmercaptane(TBM), tetrahydrothiophene(THT) and dimethylsulfide(DMS) in methane was investigated over NaY and copper-exchanged NaY(CuNaY) zeolites at 303 K and atmospheric pressure. In the ternary adsorption system, the preferential adsorption of THT over other sulfur compounds on NaY and the concurrent adsorption of all sulfur compounds on CuNaY were achieved, which could be explained by the breakthrough curve, the temperature-programmed desorption, and the apparent activation energy for desorption. The sulfur uptake capacity of CuNaY(2.90~3.20 mmol/g) was much higher than that of NaY(0.70~0.90 mmol/g). A comparative study indicated that the $Cu^{1+}$ sites and acidity of CuNaY were probably responsible for the strong interaction with sulfur atom and high sulfur uptake abilities.

• Korean Journal of Crystallography
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• v.15 no.2
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• pp.59-68
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• 2004

Three crystal structures of dehydrated partially $Co^{2+}-exchanged$ zeolite A treated with 0.6 Torr of K at $300^{\circ}C$ (for 12 hrs, 6 hrs, and 2 hrs) vapor have been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m at 21(1)$^{\circ}C(a=12.181(1)\;{\AA},\;a=12.184(1)\;{\AA},\;and\;a=12.215(1)\;{\AA})\;respectively)$. Their structures were refined to the final error indices, R(weight) of 0.090 with 10 reflections, 0.091 with 82 reflections, and 0.090 with 80 reflections, respectively, for which $1>\sigma(I)$. In each structure, all four $Co^{2+}$ and four $Na^+$ ions to be reduced by K atoms. The cobalt and sodium atoms produced are no longer found in the zeolite. K species are found at five different crystallographic sites: three $K^+$ ions lie at the planes of 8-rings, filling that position, ca. 11.5 K^+$ ions lie on threefold axes, ca. 4.0 in the large cavity and ca. 4.0 in the sodalite cavity, and ca. 0.5 $K^+$ ion is found near a 4-ring. ca. three $K^0$ atoms are found deep into the large cavity on threefold axes. In these structures, crystallographic results show that cationic tetrahedral $K_4$ (and/or triangular $K_3$) clusters have formed in the sodalites of zeolite A. The $K_4$ and/or $K_3$ clusters coordinate trigonally to three oxygens of a six-oxygen ring. The partially reduced ions of these clusters interact primarily with oxygen atoms of the zeolite structure rather than with each other. ca. 14.5K species are found per unit cell, more than the twelve $K^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of $K^0$ has occurred. The three $K^0$ atoms in the large cavity are closely associated with three out of four $K^+$ ions in the large cavity to form $K_7^{4+}$ clusters. The $K_7^{4+}$ cluster not interacts primarily with framework oxygens.