• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4015-4022
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• 2012

Manganese(III) 5-(4-carboxyphenyl)-10,15,20-triphenyl porphyrin chloride (Mn(TCPP)Cl) was grafted through amide bond on silica zeolite Y (HY), zeolite beta ($H{\beta}$) and hexagonal mesoporous silica (HMS). XRD, ICP-AES, $N_2$ physisorption, SEM, TEM, FTIR and thermal analysis were employed to analyse these novel heterogeneous materials. These silica supported catalysts were shown to be used for epoxidation and good shape selectivity was observed. The effect of support structure on catalytic performance was also discussed. The catalytic activity remained when the catalysts were recycled five times. The energy changes about epoxidation of alkenes by $NaIO_4$ and $H_2O_2$ were also computationally calculated to explain the different catalytic efficiency.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.583-588
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• 1993

Encapsulation capacities $(V_{gas})$ of, $H_2,\;N_2,\;CO,\;CH_4$ and CO, for $Cs_{2.5}Na_{9.5}-A (C_s-A)$ and $Na_{12}$-A (Na-A) zeolites have been measured in order to understand the effect of molecular properties on the $V_{gas}$. With appropriate number of large blocking cations on the main windows of cavities in zeolite A, gas molecules can be encapsulated in both the ${\alpha}$ -and ${\beta}$-cages, resulting in much large $V_{gas}.\;V_{gas}$ is proportional to the encapsulation pressure (Pe) and is also dependent on the molecular properties of encapsulated gases themselves, especially on intermolecular forces originated from the quadrupole moments of molecules in the molecular-dimensioned cavities of zeolite A. At the low range of Pe, molecules with larger $V_{gas}$ and intermolecular forces apparently have smaller increasing tendencies of $V_{gas}$ upon increases in Pe, showing a linear relationship between the tendencies and intermolecular forces rather than their sizes. Interactions between encapsulated molecules of $CH_4$ and framework of Cs-A have been estimated and they seem to depend on the number of encapsulated molecules per unit cell. On the basis of calculated density of $CO_2$, presence of liquid-like phase for the encapsulated molecules in the molecular dimensioned cavities of zeolite A is postulated.

• 공업화학
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• 제18권4호
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• pp.337-343
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• 2007

천연가스의 누출을 감지하기 위해서 첨가되는 유기 황 화합물질인 부취제에 의해 연료전지 내의 스택 전극과 개질기 촉매들이 피독되어 시스템 성능저하의 큰 원인이 되고 있다. 본 연구에서는 실리카, 알루미나, 활성탄, HZSM-5, Ultra-stable Y 제올라이트(USY) 및 베타 제올라이트와 같은 흡착제들을 부취제 제거용 흡착제로 사용하여, tetra-hydrothiophene (THT)와 tert-butylmercaptan (TBM)에 대한 흡착 성능을 연속식 흡착시스템에서 얻은 흡착파과곡선을 비교하여 평가하였다. 제올 라이트의 Si/Al 비, 흡착온도 및 Balance Gas (메탄, 헬륨) 종류의 변화가 흡착성능에 미치는 영향을 조사하고, THT와 TBM의 경쟁적인 흡착특성을 비교하였다. 여러 흡착제 중에서 H형, beta-zeolite (BEA)가 부취제인 TBM과 THT에 대해서 가장 우수한 흡착능력을 나타내었으며, 동일한 흡착제 상에서는 THT가 TBM보다 많은 양으로 흡착제거되었다. Temperature Programmed Desorption (TPD) 및 Infrared 스팩트럼(IR) 분석결과 부취제 황화합물은 제올라이트 표면에서 물리흡착과 더불어 산점에 의한 화학흡착을 이루는 것을 확인하였다.

• 한국광물학회지
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• 제10권2호
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• pp.105-113
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• 1997

Mineral description and mineralogical characterization were made for the wellsite, a barrian zeolite, which found as diagenetic alterations in the Miocene pyroclastic rocks in Gampo area. The wellsite occurs together with clinoptilolite, smectite and apatite as euhedral crystallites (0.2~0.4mm) forming interpenetraion twinning in the vesicles of altered pmice fragments. Compared to other reported wellsites, the wellsite is rather silicic (Si/(Al+Fe): 3.12-3.16) and Ca-rich. Unit cell dimensions and chemical formular determined from XRD, EMPA and TGA data are as follows:a=9.883$\AA$, b=14.204$\AA$, c=8.677$\AA$, $\beta$-124.764$^{\circ}$, (Ba0.57K0.36)(Ca1.18Na0.04)Al3.9Si12.1O32.13.9H2O.The cation composition of the Gampo wellsite, which shows an exchange reaction in the form of Ba2++Ca2+=2(K++Na-), is deviated far from the compositional range of a phillipsite-harmotome series. Due to higher abundance of divalent cations (Ca, Ba) and si in the wellsite, cimpared to those of the phillipsite and harmotome reported in other areas, the zeolite seems to be characteristic of higher water content (18.7 wt%) and higher thermal stability. XRD, chemical and thermo-chemical results of the wellsite reflects that wellsite is rather a Ba- and Ca-rich end member of a phillipsite-harmotome-wellsite series than an intermediate phase of phillipsite-harmotome series or a barrian variety of phillipste.

• 청정기술
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• 제14권1호
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• pp.40-46
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• 2008

MCM 48, USY, beta 등과 같은 제올라이트를 세라믹종이에 실리카와 함께 도포하여 제습소자를 제조하였고, $H_2O$ 흡수 및 재생에 대한 평가를 고정층반응기에서 실시하였다. 제올라이트가 도포된 제습소자의 $H_2O$ 흡수력은 제올라이트가 도포되지 않은 제습소자보다 약 $1.5{\sim}2$배 가량 높은 것을 볼 수 있었다. 특히 콜로이드 실리카와 MCM 48을 도포한 제습소자는 약 42.1g $H_2O/g$ absorbent의 매우 우수한 제습 능력을 보여 주었다. 이러한 결과는 넓은 비표면적과 큰 기공부피를 가지고 있는 제올라이트에 의해 $H_2O$를 흡수할 수 있는 실리카 겔이 함침될 수 있는 공간이 증가하고 이에 따른 $H_2O$의 흡수량도 증가하는 것으로 판단된다. 또한 제올라이트가 도포된 제습소자는 $80^{\circ}C$의 재생 온도에서도 쉽게 $H_2O$가 탈착되고, 이 때 탈착된 $H_2O$의 양은 제습소자가 흡수한 $H_2O$의 양과 동일하였다. 반복순환실험을 통한 $H_2O$의 흡수력 감소는 발견되지 않았고 초기 흡수력이 유지되었다.

• 대한화학회지
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• 제33권2호
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• pp.177-184
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• 1989

ZSM-5 제올라이트 촉매의 고체산 특성을 암모니아 승온 탈착법과 적외선 분광법에 의하여 조사하였다. HZSM-5의 암모니아 승온 탈착 곡선에는 ${\alpha}$,${\beta}$,${\gamma}$의 세가지 상태가 나타나는데, ${\gamma}$-상태의 양은 실리카/알루미나 비가 클수록 그리고 알칼리 금속의 양이온 교환에 의하여 감소됨을 알았다. ZSM-5에 흡착시킨 피리딘의 적외선 흡수스펙트럼과 톨루엔의 알킬화반응으로부터 ${\gamma}$-상태는 Si-OH-Al의 수산기 즉 브뢴스테드산점에 기인하며 산촉매반응의 활성점으로 작용하는 것을 알았다. 또 알칼리양이온 교환시킨 ZSM-5의 암모니아, 피리딘 등의 염기와의 상호작용의 세기는 양이온 크기가 작아질수록 증가함을 알 수 있었다.

• 공업화학
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• 제17권3호
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• pp.235-242
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• 2006

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.