• 제목/요약/키워드: zeolites

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Diffusion Controlled Alkylation of Aromatic Compounds in Cation-Exchanged ZSM-5 Zeolites

  • Chon, Hak-Ze;Lee, Kyung-Yul;Park, Dong-Ho;Ahn, Byoung-Joon
    • Bulletin of the Korean Chemical Society
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    • 제12권6호
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    • pp.625-628
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    • 1991
  • Using uniform flat plate-like samples of ZSM-5 zeolites, diffusion coefficients were measured volumetrically for the diffusion of xylene, ethyltoluene and diethylbenzene by direct measurement of sorption rate. Toluene disproportionation over H(100)-, K(72)-and Cs(82)-ZSM-5 at 773 K and toluene methylation, toluene ethylation and ethylbenzene ethylation over Cs(75)-ZSM-5 at 623 K were carried out. The selective formation of para xylene during the toluene disproportionation, presumably due to the increased tortuosity over Cs-ZSM-5, could be explained by smaller diffusion coefficient in Cs-ZSM-5 than in K-and H-ZSM-5. The para selectivity increased in the order; toluene methylation < toluene ethylation < ethylbenzene ethylation. As the chain length of the alkyl substituent in dialkylbenzenes is increased, the para selectivity of the products was improved. It may be attributed to the differences in the ratios of diffusion coefficient of para products to that of ortho ones. Diffusion coefficient of m-xylene was about 1 order of magnitude smaller than that of o-xylene.

금속이온교환 제올라이트 촉매상에서 메탄을 이용한 산소과잉 배출가스중의 NO 제거 (Catalytic Removal of Nitric Oxide in Oxygen-Rich Exhaust with Methane over Metal Ion-Exchanged Zeolites)

  • 김상환;박정규
    • 한국자동차공학회논문집
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    • 제10권1호
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    • pp.32-44
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    • 2002
  • Selective catalytic reduction of nitric oxide by methane in the presence of excess oxygen was investigated over copper and cobalt ion-exchanged ZSM-5 zeolites. Copper ion-exchanged ZSM-5(Cu-ZSM-5) has the limitations for commercial applications to lean-bum gasoline and diesel engines due to low thermal stability and resistance to water vapor and sulfur dioxide. But cobalt ion-exchanged ESM-5(Co-ZSM-5) is more active at high temperatures and also stable to water vapor and sulfur dioxide for catalytic reduction of nitric oxide by methane. The catalytic activity of Cu-ZSM-5 for NO reduction increases with increasing temperatures, reaches the maximum conversion of 23.0% at 350\"C. and then decreases with higher temperatures. In the meantime catalytic activities of Co-ZSM-5 show the maximum conversion of 25.8% at $500^{\circ}C$ Therefore Co-ZSM-5 catalysts have higher thermal stability at high temperatures. Catalytic activities of both zeolites were remarkably enhanced with the existence of oxygen in the exhaust. It is noted that the catalytic activity of Cu-ZSM-5 decreases with the increasing concentration of methane while the catalytic activity of Co-ZSM-5 decreases with increasing contents of methane in the exhaust. This may imply the existence of different paths of NO reduction by methane in the presence of excess oxygen fur Cu-ZSM-5 and Co-ZSM-5 catalysts. For binary metal ionexchanged ZSM-5, the primary ion-exchanged metal may be masked by secondary ion-exchanged component, which plays the important role for catalytic activities of binary metal ion-exchanged ZSM-5, Therefore CuCo-ZSM-5 catalysts show the similar volcano-shaped curves to Cu-ZSM-5 catalysts between the activity and temperature. It Is interesting that the activities of CoCu-ZSM-5 catalysts indicate almost no dependence on the concentration of methane in the exhaust.aust.

제올라이트: 압력순환형 흡착제로서의 특성과 CO2 흡착성능 (Zeolites: Their Features as Pressure Swing Adsorbents and CO2 Adsorption Capacity)

  • 김문현;조일흠;최상옥;추수태
    • 한국환경과학회지
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    • 제23권5호
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    • pp.943-962
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    • 2014
  • Industrial gas drying, dilute gas mixtures purification, air fractionation, hydrogen production from steam reformers and petroleum refinery off-gases, etc are conducted by using adsorptive separation technology. The pressure swing adsorption (PSA) has certain advantages over the other methods, such as absorption and membrane, that are a low energy requirement and cost-effectiveness. A key component of PSA systems is adsorbents that should be highly selective to a gas being separated from its mixture streams and have isotherms suitable for the operation principle. The six standard types of isotherms have been examined in this review, and among them the best behavior in the adsorption of $CO_2$ as a function of pressure was proposed in aspects of maximizing a working capacity upon excursion between adsorption and desorption cycles. Zeolites and molecular sieves are historically typical adsorbents for such PSA applications in gas and related industries, and their physicochemical features, e.g., framework, channel structure, pore size, Si-to-Al ratio (SAR), and specific surface area, are strongly associated with the extent of $CO_2$ adsorption at given conditions and those points have been extensively described with literature data. A great body of data of $CO_2$ adsorption on the nanoporous zeolitic materials have been collected according to pressure ranges adsorbed, and these isotherms have been discussed to get an insight into a better $CO_2$ adsorbent for PSA processes.

산성도가 다른 제올라이트 촉매에서 전이에스터화 반응에 의한 폐식용유로부터 바이오디젤 제조 (Production of Biodiesel from Waste Frying Oil by Transesterification on Zeolite Catalysts with Different Acidity)

  • 고태석;정경환
    • 공업화학
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    • 제19권2호
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    • pp.214-221
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    • 2008
  • 산성도와 세공구조가 다른 제올라이트 촉매에서 폐식용유의 전이에스터화 반응에 의해 바이오디젤을 제조하였다. $H^+$ 이온 교환한 MOR, MFI, BEA, FAU 제올라이트와 산점이 거의 없는 실리카라이트 촉매의 반응 수율을 조사하였다. 산세기가 가장 강하고 산점이 많은 $H^+$ 이온 교환한 MOR(10) 제올라이트에서 메틸에스터 수율이 약 95%로 가장 높았다. 제올라이트 골격에서 알루미늄을 제거하면 산점의 수가 줄어들고 산세기도 약해지면서 메틸에스터 수율도 감소하였다. 폐식용유의 전이에스터화 반응에서 메틸에스터의 수율은 제올라이트 촉매의 산세기와 산량에 따라 비례하는 것으로 나타났다. 메틸에스터의 수율은 제올라이트의 세공구조에는 영향을 받지 않는 것으로 조사되었다.

큰 기공 제올라이트에서 에탄올의 아민화반응 (Amination of Ethanol over Large Pore Zeolites)

  • 전희영;전성희;이천재;신채호
    • 청정기술
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    • 제14권2호
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    • pp.87-94
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    • 2008
  • 12-고리를 갖는 큰 기공 제올라이트인 H-모더나이트, H-베타, H-Y상에서 에탄올 아민화반응에 의한 디에틸아민합성반응을 수행하였다. 사용된 큰 기공 제올라이트의 Si/Al 비 증가는 강산점의 감소를 가져왔으며 이 강산점의 세기는 아민으로의 생성 증가와 관련지을 수 있었다. 다차원 채널 형태를 갖는 H-베타, H-Y 제올라이트는 큰 둥지 부피와 낮은 산점세기로 인해 에탄올의 이량화반응에 의한 디에틸에테르의 생성을 촉진하였다. 직선 기공 채널 형태를 갖고 있는 H-모더나이트 제올라이트는 정밀화학 중간체로 널리 쓰이는 모노, 디에틸아민 합성에 적합하였다.

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규질 이암으로부터 제올라이트의 수열 합성에 관한 연구 (Hydrothermal Synthetic Study of Zeolites from Siliceous Mudstone)

  • 노진환
    • 한국광물학회지
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    • 제13권4호
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    • pp.171-185
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    • 2000
  • Siliceous mudstones are embedded on a large scale in the Tertiary formations of Pohang area. Some useful zeolites such as NsP, (Na, TMA)P, analcime and hydroxysodalite were synthesized from the siliceous mudstones by treating with the variety of solution, i.e ., NaOH, NaOH+NaCl, NaOH, NaOH+$NaAlO_2$and NaOH+TMAOH at the low-temperature hydrothermal system ranging 60~12$0^{\circ}C$. Major precursor of zeolites is found as opal-CT in the zeolite-forming reaction. Smectite, which is included in considerable amounts in the mudstone, appears to play a major role of Al-source in the zeolite synthesis. In comparison, chalcedonic quartz and mica are rather insoluble in alkaline solution, and thus, these are observed as major impurities in the reaction products. An addition of $NaAlO_2$to NaOH solution is effective for eliminating these impurities in the reaction procedure, through these are partly dissolved when elevating the reaction temperature, concentration, and time. Phase change from NaP to hydroxysodalite takes place at the NaOH concentrations of 3.0~4.0 M, and the reaction is not sensitive to the temperature shift. NaP is more stable at lower NaOH concentration and higher activity of $Na_{+}$ whereas analcime is sensitive to the temperature change and stable at higher than $100^{\circ}C$ and 2.0~4.0 M in NaOH concentration. For the pure NaP synthesis without any other products, the treatment of mudstones with 1:1 solution of NaOH and $NaAlO _2$ turns out to be quite effective. NaP was successfully synthesized together with analcime at $100^{\circ}C$ as well as lower concentrations of NaOH+NaCl solution. In addition, the organic type, (Na, TMA)P was formed together with smectite in the 1:1 solution of NaOH and TMAOH.

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Dealumination에 의한 NaY zeolite의 개질과 VOCs 흡착특성에 관한 연구 (A Study on Dealumination of NaY Zeolite and its VOCs Adsorption Properties)

  • 강신춘;이화열;박융호
    • Korean Chemical Engineering Research
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    • 제53권3호
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    • pp.339-349
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    • 2015
  • 본 연구에서는 활성탄을 대체하는 소재로서 재생이 용이하고 열적 안정성이 높은 DAY (Dealuminated Y-type) 제올라이트를 제조하였다. 원료물질로는 NaY 제올라이트를 이용하였으며, 이온교환, 소성, 수증기처리, 산처리의 단계를 거쳐 DAY 제올라이트를 제조하였다. 이때 결정성을 유지하면서 높은 Si/Al ratio를 얻기 위하여 소성 온도, 시간 및 수증기 처리 시간에 변화를 주었다. 또한 제조한 DAY 제올라이트, 원료 물질인 NaY 제올라이트 및 상용 제올라이트인 HISIV 1000에 대하여 상대습도 50%의 공기 흐름 중에서 VOCs 들에 대한 흡착 실험을 하였다. $520^{\circ}C$에서 4시간 소성 및 7시간의 수증기처리를 통해 제조한 DAY 제올라이트는 결정성이 유지되었고, Si/Al ratio는 80.4이였다. 수분흡착특성은 NaY 제올라이트의 10% 정도로 소수성을 나타내었다. 상용 DAY 제올라이트인 HISIV 1000과 비교한 결과 극성이 강한 MEK에 대해서는 0.8배 정도의 흡착용량을 보였으나, 무극성이거나 극성이 약한 toluene과 EA에 대해서 각각 1.6배, 1.3배 정도 높은 흡착 용량을 보였다.