• 대한화학회지
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• 제40권3호
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• pp.202-208
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• 1996

수열법으로 합성한 SAPO-11 분자체를 $H_4$EDTA로써 골격내의 알루미늄을 부분적으로 탈알루미늄화시킬때 24시간 탈알루미늄화까지는 골격이 안전하였으나 48시간 탈알루미늄화에 의해서는 구조가 붕괴되어 variscite($AIPO_4{\cdot}2H_2O$)와 tridymite($SiO_2$)로 변하였다. SAPO-11의 탈알루미늄화로 인하여 3607$cm^{-1}$과 3453$cm^{-1}$에서 하이드록실기에 의한 IR 흡수띠가 각각 관측되었다. 이들 하이드록실기 피크들의 세기는 탈알루미늄화의 정도에 비례하여 증가하였으며 메틸아민의 흡착에 의하여 피크가 사라지는 것으로 보아 이들은 Bronsted 산 자리임을 알 수 있었다. TPD(Temperature-Programmed Desorption) 및 DSC(Differential Scanning Calorimetry) 실험결과 탈알루미늄화된 SAPO-11에 흡착된 메틸아민과 물 분자는 탈알루미늄화가 되지않은 SAPO-11보다 높은 온도에서 그 피크들이 관측되었으며 메틸아민과 물 분자의 탈착 및 탈수 활성화 에너지는 탈알루미늄화의 정도에 비례하여 증가하였다. 이와 같은 현상은 제올라이트 분자체에 있어서와 유사하게 탈알루미늄으로 인하여 SAPO-11 분자체 내에 생성된 구조 하이드록실(srtuctural hydroxyl)기의 Bronsted 산 자리와 흡착 분자간의 보다 강한 상호작용에 기인되는 것으로 생각되었다.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3829-3834
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• 2013

$H{\beta}$ (core)/SAPO-11 (shell) composite molecular sieve was synthesized by the hydrothermal method in order to combine the advantages of $H{\beta}$ and SAPO-11 for the methylation of naphthalene with methanol. For comparison, the mechanical mixture was prepared through the blending of $H{\beta}$ and SAPO-11. The physicochemical properties of $H{\beta}$, SAPO-11, the composite and the mechanical mixture were characterized by various characterization methods. The characterization results indicated that $H{\beta}$/SAPO-11 composite molecular sieve exhibited a core-shell structure, with the $H{\beta}$ phase as the core and the SAPO-11 phase as the shell. The pore diameter of the composite was between that of $H{\beta}$ and SAPO-11. The composite had fewer acid sites than $H{\beta}$ and mechanical mixture while more acid sites than SAPO-11. The experimental results indicated that the composite exhibited high catalytic performances for the methylation of naphthalene with methanol.

• 한국자기공명학회논문지
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• 제9권1호
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• pp.1-20
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• 2005

Vanadium-incorporated aluminophophate molecular sieve VH-SAPO-11 has been studied by electron spin resonanace (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium locatin and interaction with various adsorbate molecules. As-synthsized VH-SAPO-11 contains only vanady1 species with distored octahral coordination. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is suggested as a VO$(H_2O)_2^{2+$} complex coordinate to three framwork oxygen bonded to aluminum. When calcined, hydrate VH-SAPO-11 is dehydrated at elevated temperature, species A loses it water ligands and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$at high temperature, thus suggesting oxidation of $v^{4+}$to $v^{5+}$. When dehydrated VH-SAPO-11 contacts with $D_2O$ at room temperature, the ESR signal of species A is observed. This species assumed as a $VO(O_f)_3(D_2O)_2$, by considering 3 framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-11 results in another new vanadium species D, which is identified as a $VO(CD_{3}OH)$ complex. When deuterated ethanol is adsorbed on dehydrated VH-SAPO-11, another new vanadium species E identified as a $VO(C_{2}H_{5}OD)^{2+}$, is observed. When deuterated propanol is adsorbed on dehydrated VH-SAPO-11, a new vanadium species F identified as a $VO(C_{3}H_{7}OD)$, is observed. Possible coordination geometries of these various complexes are discussed.

• 폴리머
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• 제37권3호
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• pp.379-386
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• 2013

SAPO-11을 억새와 random polypropylene(random PP)의 촉매 열분해에 최초로 적용하였다. 열중량 분석 결과 SAPO-11은 억새의 탈수 반응을 촉진시키고, char의 생성을 억제하는 것으로 나타났다. Random PP의 열분해 결과, random PP의 분해온도와 활성화에너지는 촉매를 사용함에 따라 크게 감소하였다. 억새의 무촉매 열분해 반응에 의해 생성되는 oxygenate 생성물들 중에서 levoglucosan이 주 생성물이었다. SAPO-11 촉매 열분해 결과, 상당 부분의 levoglucosan이 furans, phenolics, aromatics 등의 부가가치가 큰 화합물로 전환하였다. 반면, random PP는 가솔린, 디젤 범위의 탄화수소를 생성하였다.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2399-2402
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• 2013

The catalytic pyrolysis of cellulose was carried out over SAPO-11 for the first time. Pyrolyzer-gas chromatography/mass spectroscopy was used for the in-situ analysis of the pyrolysis products. The acid sites of SAPO-11 converted most levoglucosan produced from the non-catalytic pyrolysis of cellulose to furans. In particular, the selectivity toward light furans, such as furfural, furan and 2-methyl furan, was high. When the catalyst/cellulose ratio was increased from 1/1 to 3/1 and 5/1, the increase in the quantity of acid sites led to the promotion of deoxygenation and the resultant increase of the contents of light furan compounds. Because furans can be used as basic feedstock materials, the augmentation of the economical value of bio-oil through the catalytic upgrading over SAPO-11 is considerable.

• 한국자기공명학회논문지
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• 제11권2호
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• pp.95-109
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• 2007

Vanadium-incorporated aluminophosphate microporous molecular sieve VH-SAPO-42 has been studied by electron spin resonance(ESR) and electron spin-echo modulation (ESEM) spectroscopies to determine the vanadium location and interaction with various adsorbate molecules. The results are interpreted in terms of V(IV) ion location and coordination geometry. Assynthesized VH-SAPO-42 contains only vanadyl species with distorted octahedral or trigonal bipyramidal coordination. Vanadium incorporated into H-SAPO-42 occupied extra-framework site. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is identified as a $VO(H_2O)_2^{2+}$ complex coordinated to three framework oxygen atoms bonded to aluminum. When hydrated VH-SAPO-42 is dehydrated at elevated temperature by calcination, species A loses its water ligand and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$ at high temperature, thus suggesting oxidation of $V^{4+}$ to $V^{5+}$. When dehydrated VH-SAPO-42 makes contact with $D_2O$ at room temperature, the ESR signal of species A is regained. The species is assumed as a $VO(O_f)_3(D_2O)_2$ by considering three framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-42 results in another new vanadium species D, which is identified as a $VO(CD_3OH)_2$ complex. When deuterated ethylene is adsorbed on dehydrated VH-SAPO-42, another new vanadium species E identified as a $VO(C_2D_4)^{2+}$, is observed. Possible coordination geometries of these various complexes are discussed.