• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3303-3310
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• 2012

Two single crystals of fully dehydrated partially $Li^+$-exchanged zeolite X were prepared by the exchange of Na-X, $Na_{92}Si_{100}Al_{92}O_{384}$ (Si/Al = 1.09), with $Li^+$ using aqueous 0.1 M $LiNO_3$ at 293 (crystal 1) and 333 K(crystal 2), followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. Their structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd{\overline{3}}$ at 100(1) K. Their structures were refined using all intensities to the final error indices (using the 1281 and 883 reflections for which ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2$ = 0.075/0.244 and 0.074/0.223 for crystals 1 and 2, respectively. Their compositions are seen to be ${\mid}Li_{86}Na_6{\mid}[Si_{100}Al_{92}O_{384}]$-FAU and ${\mid}Li_{87}Na_5{\mid}[Si_{100}Al_{92}O_{384}]$-FAU, respectively. In crystal 1, 17 $Li^+$ ions per unit cell are at site I', 15 another site I', 30 at site II, and the remaining 16 at site III; 2 $Na^+$ ions are at site II and the remaining 4 at site III'. In crystal 2, 32 and 30 $Li^+$ ions per unit cell fill sites I' and II, respectively, and the remaining 25 at site III'; 2 and 3 $Na^+$ ions are found at sites II and III', respectively. The extent of $Li^+$ exchange increases slightly with increasing ion exchange temperature from 93% to 95%.

• Korean Chemical Engineering Research
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• 제56권4호
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• pp.600-606
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• 2018

다양한 Si/Al 몰비를 지닌 MTT 제올라이트를 합성하여 methanol-to-olefin(MTO) 반응에서 촉매의 산성도가 미치는 영향을 조사하였다. Si/Al 몰비를 조절하기 위해 N,N,N',N'-테트라메틸-1,3-디아미노프로판을 구조유도물질(SDA)로 사용하였으며, 알루민산나트륨의 함량을 달리하여 $20SiO_2$ : 30SDA : x (=0.25~1.25)$NaAlO_2$ : 2NaOH : $624H_2O$ 조성으로 모액을 제조한 후 433 K에서 4일 동안 수열 합성하였다. 알루민산나트륨의 함량이 감소함에 따라 MTT 제올라이트의 입자 크기가 증가하였으며 또한 산점의 양도 감소하였다. 제조한 MTT 제올라이트의 촉매 활성을 평가하기 위해 673 K에서 공간속도(WHSV)가 $1.2h^{-1}$인 조건으로 MTO 반응을 수행한 결과, Si/Al 몰비가 24인 H-MTT (1.00Al) 촉매가 900분까지 90% 이상의 전환율을 유지함을 확인하였다.

• Korean Chemical Engineering Research
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• 제43권5호
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• pp.560-565
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• 2005

1-methylnaphthalene(1-MN)과 2-methylnaphthalene(2-MN) 사이에서의 트랜스메틸화 반응을 제올라이트, H-mordenite(HM), H-Beta$(H{\beta})$, H-USY(HUSY) 촉매를 이용한 고정층 반응기에서 수행하였다. $H{\beta}_{25}(SiO_2/Al_2O_3=25)$ 촉매는 다음과 같은 조건, 반응온도 $350^{\circ}C$, 반응압력 1.5 Mpa, 전체 액상 반응물의 WHSV $2.7g_{feed}/g_{cat}{\cdot}h$, 반응물 1-MN과 2-MN의 몰비 1:1, 반응 1시간에서 2-MN/1-MN 비=2.3와 2,6-DMN/2,7-DMN 비=1.3을 보이면서 다른 촉매보다 높은 전환율과 안정성을 나타내었다. 촉매의 세공구조, 산성도와 관련하여 촉매성능을 해석하였다.

• 한국환경과학회지
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• 제20권6호
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• pp.729-736
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• 2011

This work is to compare the experiment results by a continuous fixed-bed adsorption of water vapor, acetone vapor, and toluene vapor on zeolite 13X (SAU) and silica-alumina (SAK). SAU and SAK have very different pore structure but similar composition as inorganic adsorbent. The relationship between the equilibrium adsorption capacity and specific pore size range were studied. Adsorption of water vapor was more suitable on SAU than SAK because SAU has relatively more developed pores around $5\;\AA$ than SAK in the pore range of $10\sim100\;\AA$. Adsorption of acetone vapor was more suitable on SAK than SAU because SAK has relatively more developed pores around $5\sim10\;\AA$ than SAK in the pore range of less than $10\;\AA$. Adsorption of toluene vapor was more suitable on SAK than SAU because SAK has relatively more developed pores in the pore range of $10\sim100\;\AA$ than SAK. Adsorption capacity of the adsorbent was closely related to the surface area generated in the specific pore size region. But it was difficult to distinguish the relationships between adsorption capacity and micro area, and the external surface area of adsorbent.

• 한국토양비료학회지
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• 제46권4호
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• pp.260-269
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• 2013

Two single-crystals of fully dehydrated, partially $Li^+$-exchanged zeolites X (Si/Al = 1.09, crystal 1) and Y (Si/Al = 1.56, crystal 2), were prepared by flow method using 0.1 M $LiNO_3$ at 393 K for 48 h, respectively, followed by vacuum dehydration at 673 K and $1{\times}10^{-6}$ Torr. Their structures were determined by single-crystal X-ray diffraction techniques in the cubic space group $Fd\bar{3}$ and $Fd\bar{3}m$ at 100(1) K for crystals 1 and 2, respectively. They were refined to the final error indices $R_1/wR_2$ = 0.065/0.211 and 0.043/0.169 for crystals 1 and 2, respectively. In crystal 1, about 53 $Li^+$ ions per unit cell are found at three distinct positions; 9 at site I', 19 at another site I', and the remaining 25 at site II. The residual 25 $Na^+$ ions occupy three equipoints; 2 are at site I, 7 at site II, and 16 at site III'. In crystal 2, about 31 $Li^+$ ions per unit cell occupy sites I' and II with occupancies at 22 and 9, respectively; 3, 4, 23, and 3 $Na^+$ ions are found at sites I, I', II, and III', respectively. The extent of $Li^+$ ion exchange into zeolite X (crystal 1) is higher than that of zeolite Y (crystal 2), ca. 73% and 56% in crystals 1 and 2, respectively.

• 한국광물학회지
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• 제4권2호
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• pp.99-107
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• 1991

Three fully dehydrated fully Rb+-exchanged zeolite A single crystals have been prepared by the reduction of all Na+ ions in dehydrated Na12-A by rubidium vapor at various experimental conditions (220 $\leq$ T $\leq$ 33$0^{\circ}C$, 2 $\leq$ t $\leq$24 hours, and 0.1 $\leq$ PRb $\leq$ 1.1 Torr). Their structures were determined by single-crystal X-ray diffraction methods in the space group {{{{ RHO }}m3m (a=12.245(3) A) at 22(1)$^{\circ}C$. In these structures 12.6(2) to 13.5(2) Rb species are found per unit cell, more than the 12 Rb+ ions needed to balance the anionic charge of the zeolite framework, indication that the sorption of Rb0 has occurred. In each structure, three Rb+ ions per unit cell are located at the centers of 8-rings. Beyond that, the fractional occupancies observed are simply explained by two unit cell arrangments. In one, two Rb+ ions are in the sodalite unit near opposite 6-rings, six are in the large cavity near 6-ring, and one is in the large cavity near a 4-ring. In the other, three Rb species in the sodalite cavity (forming a triangle 3.7 A on an edge) each bond (3.4 A) through a 6-ring to an Rb species in the large cavity to give an (Rb6)4+ cluster of symmetry 3m (C3V). Five additional Rb+ ions fill the remaining large-cavity 6-ring sites.

• 분석과학
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• 제15권6호
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• pp.540-549
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• 2002

The arrangement of encapsulated Ar atoms in the molecular-dimensioned cavities of fully dehydrated zeolite A of unit-cell composition $Cs_3Na_8HSi_{12}Al_{12}O_{48}$ ($Cs_3$-A) has been studied crystallographically to probe the confinement effect of guest species in microporous environment. Atoms of Ar were encapsulated in the cavities of $Cs_3$-A by treatment with 410 atm of Ar at $400^{\circ}C$ for two days, followed by cooling at room temperature. The crystal structure of $Cs_3Na_8H$-A(4Ar) ($P_e$ = 410 atm, $a=12.245(2){\AA}$, $R_1=0.0543$, and $R_2=0.0552$) has been determined by single crystal X-ray diffraction technique in the cubic space group $Pm\bar{3}m$ at 21 (1) $^{\circ}C$ and 1 atm. Encapsulated Ar atoms are distributed in three crystallographic distinct positions: 1.5 Ar atoms per unit cell opposite 6-rings, 1.5 opposite four-rings in the large cavity, and finally 1.0 in the sodalite-unit. The possible structures of argon clusters, such as $Ar_2$, $Ar_3$, and $Ar_4$, are proposed.

• Bulletin of the Korean Chemical Society
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• 제15권5호
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• pp.341-346
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• 1994

The frameworks of $(Cu(NH_3)_3OH^+)_x(NH_4^+)_{12-x}-A{\cdot} zH_2O$ which were prepared by the ion-exchange of zeolite A with ammoniac cupric nitrate solution are more stable than those of $Cu_xNa_{12-2x} -A$ obtained by the ion exchange with aqueous cupric nitrate solution are more stable than those of $Cu_xNa_{12-2x} -A$ obtained by the ion exchange with aqueous cupric nitrate solution. An energetic calculation was made on the relatively stable $(CuOH^+)_2(NH_4^+)_{10}-A{\cdot} 2H_2O$ prepared by the partial evacuation of $(Cu(NH_3)_3OH^+)_2(NH_4^+)_{10}-A{\cdot} zH_2O$. The mean stabilization energies of water, OH-, and $NH_4^+$ ions are -30.23 kcal/mol, -60.24 kcal/mol, and -16.65 kcal/mol, respectively. The results of calculation were discussed in terms of framework stability. The $(Cu(NH_3)_3OH^+)_2(NH_4^+)_{10}-A{\cdot} zH_2O$ zeolite shows two step deammoniation reactions. The first deammoniation around 210 $^{\circ}$C (third DSC peak) was attributed to the decomposition of $[Cu(NH_3)_3OH^+]$ ion and the second one around 380 $^{\circ}$C (fourth DSC peak) was ascribed to the decomposition of $NH_4^+$ ion. The activation energies of the first and second deammoniation reactions were 99.75 kJ/mol and 176.57 kJ/mol, respectively.

• 한국결정학회지
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• 제15권2호
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• pp.59-68
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• 2004

부분적으로 $Co^{2+}$ 이온으로 치환된 제올라이트 A를 진공 탈수한 후 $300^{\circ}C$에서 12시간, 6시간, 2시간 동안 각각 0.6 torr의 K증기로 반응시킨 3개의 구조$(a=12.181(1)\;{\AA},\; a=12.184(1)\;{\AA},\; a=12.215(1)\;{\AA})$를 $21^{\circ}C$에서 입방공간군 Pm3m를 사용하여 단결정 X-선 회절법으로 해석하고 정밀화한다. K 증기로 반응시킨 3개의 구조는 Full-matrix 최소자승법 정밀화 계산에서 $1>\sigma(I)$인 70, 82, 80개의 독립반사를 각각 사용하여 최종오차인자를 R (weight) = 0.090, 0.091, 0.090까지 각각 정밀화한다. 3개의 구조에서 4개의$Co^{2+}$이온과 4개의 $Na^+$이온모두 K증기에 의해서 환원되어 $Co^{2+}$ 이온과 $Na^+$ 이온은 제올라이트 내에 더 이상 생성되지 않는다. K종류는 5개의 다른 결정학적 자리에 위치하는데 3개의 $K^+$이온은 8-링의 평면에 완전히 채워져 위치하고 약 11.5개의 $K^+$ 이온은 3회 회전축상의 6-링에 위치하고 약 4개는 큰 동공, 4개는 소다라이트 동공, 0.5개는 큰 공동의 4-링과 마주보는 위치에 위치하고 3개의 $K^0$원자는 3회 회전축상의 큰 동공 깊숙이 위치한다. 이들 구조는 제올라이트 A의 소다라이트 동공에서 사면체 $K_4$ (혹은 삼각형 $K_3$) 클라스터를 이루고 있으며 $K_4$ 혹은 $K_3$ 클라스터는 6-링의 3개의 산소와 삼면체로 결합한다. 이들 클라스터의 부분적으로 환원된 이온은 제올라이트 골조 산소와 우선적으로 결합한다. 이들 구조에서 제올라이트 골조의 음전하를 상쇄시키는데 필요한 12개의 $K^+$ 이온보다 많은 단위세포당 14.5개의 K종류가 존재하는데 이들 결과로 $K^0$원자가 흡착되었음을 알 수 있다. 큰 동공 깊숙이 위치한 3개의 $K^0$ 원자는 4개의 큰 동공에 위치한 $K^+$ 이온 중 3개와 결합하여 $K_7^{4+}$클라스터를 형성하며$K_7^{4+}$ 클라스터는 골조산소와 우선적으로 결합한다.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2379-2382
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• 2010