• Korean Journal of Materials Research
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• v.9 no.2
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• pp.117-123
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• 1999

This work was focused on the synthesis and their catalytic performance on microporous materials having various pore types and dimensions in structures, such as the SAPO-34 and the SAPO-44 with CHA type, the SAPO-17 with ERI type of three dimensional structures, and the ZSM-23 with MTT type of one dimensional structure. Synthesized materials exhibited various acidities and the selectivities to olefin in methanol conversion. As a result, the order of their acid strength was as follows; SAPO-44>SAPO-34>SAPO-17>ZSM-5. On the other hand, the CHA type materials, such as SAPO-34 and SAPO-44, had high selectivity to light olefins(ethylene or propylene), and ZSM-23 with MTT typ of one dimensional structure showed high selectivity to paraffins over $\textrm{C}_{5}$~. This result is a proof that the structure in material had strong influence on catalytic performance. In addition, a surprising result is that the catalytic selectivity to ethylene enhanced on Ni-corporated materials compared with the non-corporated.

• Applied Chemistry for Engineering
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• v.32 no.3
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• pp.305-311
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• 2021

Effects of chitosan as a mesopore directing agent of SAPO-34 catalysts were investigated to improve the catalytic lifetime in DTO reaction. The synthesized catalysts were characterized by XRD, SEM, N₂ adsorption-desorption isotherm and NH₃-temperature programmed desorption (TPD). The modified SAPO-34 catalysts prepared by varying the added amount of chitosan showed the same cubic morphology and chabazite structure as the conventional SAPO-34 catalyst. As the added amount of chitosan increased to 3 wt%, the surface area, mesopore volume and concentration of weak acid sites of modified SAPO-34 catalysts increased. The modified SAPO-34 catalysts showed enhanced catalytic lifetime and high selectivity for light olefins in the DTO reaction. In particular, the SAPO-CHI 3 catalyst (3 wt%) exhibited the longest catalytic lifetime than that of the conventional SAPO-34. Therefore, it was confirmed that chitosan was a suitable material as a mesopore directing agent to delay deactivation of the SAPO-34 catalyst.

• Journal of the Korean Chemical Society
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• v.40 no.3
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• pp.202-208
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• 1996

SAPO-11 was synthesized hydrothermally and dealuminated with $H_4$EDTA. The framework structure of SAPO-11 was maintained safely by 24 hours' dealumination, but further dealumination for 48 hours caused SAPO-11 collapsed and to be changed to variscite($AIPO_4{\cdot}2H_2O$) and tridymite($SiO_2$). Dealuminated SAPO-11 showed two structural hydroxyl bands at 3607 $cm^{-1}$ and 3453 $cm^{-1}$ respectively. The intensities of these two bands increased according to the extent of dealumination, and disappeared by the adsorption of methylamine. Dealuminated SAPO-11 showed higher desorption temperatures and greater activation energies in desorption of water and methylamine compared to non-dealuminated SAPO-11. All the phenomena may be due to the stronger interactions of Bronsted acid sites of structural hydroxyl groups generated by dealumination with adsorbed water and methylamine molecules respectively.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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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.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.558-562
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• 2005

Crystallization of SAPO-5 and SAPO-34 molecular sieves with microwave and conventional electric heating of the same gel has been investigated in an alkaline condition using N,N,N’N’tetraethylethylenediamine as a template molecule. SAPO-5 structure can be selectively prepared with microwave heating because of the fast crystallization of the technique. On the other hand, SAPO-34 is the sole product with usual conventional electric heating because SAPO-5 can be gradually transformed into SAPO-34 structure with an increase in crystallization time. This phase selectivity is probably because of the relative stability of the two phases at the reaction conditions (kinetic effect). Crystallization with microwave heating can be suggested as a phase selective synthesis method for relatively unstable materials because of fast crystallization.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1957-1964
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• 2011

Various reaction conditions uding temperature, time and type and concentration of templates have been changed in order to facilely synthesize, especially with microwave (MW) heating, SAPO-34 molecular sieves. SAPO-34 molecular sieve can be synthesized rapidly with microwave irradiation from a gel containing tetraethylammonium hydroxide (TEAOH) as a template. However, other several templating molecules lead to SAPO-5 molecular sieve under microwave irradiation even though SAPO-34 is obtained by conventional electric synthesis from the same reactant gels. Moreover, SAPO-34 can be obtained more easily by increasing the TEAOH or silica concentration or by increasing the reaction temperature. SAPO-34 can be obtained within 5 min in a selected condition (high temperature of 210 $^{\circ}C$) with microwave heating, which may lead to a continuous production of the important material. SAPO-34 synthesized by microwave irradiation is homogeneous and small in size and shows acidity and a stable performance in the dehydration of methanol and 2-butanol to olefins, suggesting potential applications in acid catalysis.

• Applied Chemistry for Engineering
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• v.32 no.1
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• pp.20-27
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• 2021

Effects of the etching treatment of SAPO-34 catalyst were investigated to improve the catalytic lifetime in DTO reaction. The aqueous NH3 solution was a more appropriate treatment agent which could control the degree of etching progress, compared to that of using a strong acid (HCl) or alkali (NaOH) solution. Therefore, the effect on characteristics and lifetime of SAPO-34 catalyst was observed using the treatment concentration and time of aqueous NH3 solution as variables. As the treatment concentration or time of aqueous NH3 solution increased, the growth of erosion was proceeded from the center of SAPO-34 crystal plane, and the acid site concentration and strength gradually decreased. Meanwhile, it was found that external surface area and mesopore volume of SAPO-34 catalyst increased at appropriate treatment conditions. When the treatment concentration and time were 0.05 M and 3 h, respectively, the lifetime of the treated SAPO-34 catalyst was the longest, and was significantly enhanced by ca. 36% (based on DME conversion of > 90%) compared to that of using the untreated catalyst. The model for the etching progress of SAPO-34 catalyst in a mild treatment process using aqueous NH3 solution was also proposed.

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.217-223
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• 2015

Effects of the post-acid treatment of SAPO-34 sample by hydrochloric acid were investigated to enhance the catalytic performance in DTO reaction. Uniformly sized SAPO-34 samples with cubic-like morphology were prepared by hydrothermal method using TEAOH and DEA as the structure directing agents. It was modified in terms of the HCl concentration and treating time. As a result, the total surface area and micropore volume for the well modified samples increased and the total acid site was somewhat decreased along with the erosion of the external surface. Especially, the catalytic lifetime and light olefins selectivity for acid treated SAPO-0.2 M (3 h) samples were considerably enhanced compared with those of untreated SAPO-34 samples. It indicates that the deactivation by coke formation proceeds mainly at the pore entrance on the external surface. Therefore, the acid treatment was confirmed to be a simple method which can significantly improve the catalytic performance by modifying the external surface of SAPO-34 catalyst.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.34-40
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• 2014

Mesoporous SAPO-34 catalyst was successfully synthesized by the hydrothermal method using carbon nanotube (CNT) as a secondary template. The effects of CNT contents (0.5, 1.5, 2.5, and 4.5 mol%) on catalytic performances were investigated. The synthesized catalysts were characterized with XRD, SEM, nitrogen physisorption isotherm and $NH_3$-TPD. Among the synthesized catalysts, SAPO-34 catalyst prepared by the addition of 1.5 mol% CNT (1.5C-SAPO-34) observed not only the largest amounts of mesopore volume but also acid sites. However, the mesopore volume was relatively decreased by further increasing of CNT contents due to the formation of small crystalline. The catalytic lifetime and the selectivity of light olefins ($C_2{\sim}C_4$) were examined for the dimethyl ether to olefins reaction. As a result, the 1.5C-SAPO-34 catalyst showed an improvement of ca. 36% in a catalytic lifetime and a better selectivity to light olefins as compared with the general SAPO-34 catalyst.

• Journal of the Korean Magnetic Resonance Society
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• v.6 no.2
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• pp.118-131
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• 2002

Manganese-doped H-SAPO-34 samples were prepared by an ion-exchanged reaction between H-SAPO-34 and paramagnetic Mn(II) species in methanol media and characterized by ESR and Electron Spin-Echo Modulation(ESEM) studies. In the hydrated (W)MnH-SAPO-34 measured in water, the Mn(II) ion was octahedrally coordinated with four framework oxygens and two water molecules at a displaced site IV of the eight membered ring window in the ellipsoidal cavity, while the Mn(II) ion was octahedrally coordinated to three framework oxygens and three water molecules at a displaced site I' of the six membered ring window in the ellipsoidal cavity in hydrated(M)MnH-SAPO-34 measured in methanol. The similar result was found in the experiments with methanol adsorbents except ethanol.