• 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.

• Journal of the Korean Institute of Gas
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• v.9 no.4 s.29
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• pp.17-25
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• 2005

The dealuminated and alkali/alkaline-earth metal exchanged Y-zeolites were prepared as a catalyst. Elemental compositions and structures of the prepared catalysts were analyzed by the various spectroscopic techniques such as inductively coupled plasma-atomic emission spectroscopy(ICP-AES), X-ray fluorescence(XRF) and X-ray diffraction(XRD), and the desorption behaviors of adsorbed species on the catalyst surfaces were investigated via NO-TPD experiment. Comparing with the composition of the starting material of NaY zeolite, the magnitudes of Si/Al ratio in catalytic materials were increased after dealumination. The Si/Al ratio of catalytic materials after dealumination followed by Cs and Ba cation exchange were additionally decreased. Dealumination to catalysts induced a destruction of basic frame due to a detachment of aluminum, which results in reducing framework structure, while increasing non-framework structure. This phenomenon becomes more serious with increasing time of steam treatment and even more significant for the cation exchanged catalysts. In NO-TPD experiments, the desorption peaks of NO which indicates an activity point of catalysts shifted to the low temperature region after dealumination and cation exchange. The desorption peaks of the NO-TPD profiles taken after steam treatment also shifted to the low temperature region as the steam treatment time increased. In dealuminated and cation exchanged Y-zeolites, the catalytic activities were more influenced by exchanged cation and the formation of non-framework structure.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.390-391
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• 1989

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.339-349
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• 2015

In this work, DAY (Dealuminated Y-type) zeolites were prepared to be used as easily regenerable and thermally stable adsorbent substituting activated carbon. NaY zeolites were transformed into DAY zeolites through ion exchange, calcination, steaming, and acid leaching. Calcination temperature and time, and steaming time were changed to increase the Si/Al ratio and maintain crystallinity. Adsorption of VOCs were done for prepared DAY, commercial NaY and Hisiv 1000 in air with relative humidity of 50%. The DAY zeolite prepared by calcination at $520^{\circ}C$ for 4 hrs and steaming for 7 hrs had a same structure and a Si/Al ratio of 80.4. Its adsorption capacity for water vapor was 10% of NaY, indicating its hydrophobicity. Its adsorption capacity for MEK was 0.8 times of Hisiv 1000, that for toluene 1.6 times, and that for EA 1.3 times.

• Applied Chemistry for Engineering
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• v.16 no.6
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• pp.857-864
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• 2005

Dealuminated and alkali/alkaline-earth metal exchanged Y-type and ZSM-5 zeolites were prepared as catalytic materials. Comparing with the composition of starting material, the magnitude of Si/Al ratio was increased after dealumination and cation exchange process. The ratio of Si/Al on surface was appeared to be larger than that in bulk. The destruction of basic frame in catalysts observed was understood to be due to a detachment of aluminum, which results in reducing framework while increasing non-framework. This phenomenon becomes more serious with increasing time of steam treatment and even more significant for the cation exchanged catalysts. The desorption peaks of the NO-TPD profiles taken after dealumination and cation exchanged Y-type and ZSM-5 zeolites shifted to the low temperature region. It was also found that the longer the steam treatment time, the degree of shift toward low temperature region was increased. The catalytic activities are dependent on the nature of cation exchanged, the ratio of Si/Al and the ratio of framework/non-framework by a change in basic frame.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.291-300
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• 2008

Catalytic cracking of n-octane was carried out over H-ZSM-5 zeolite catalysts after calcination with air and steaming with 100% steam in the temperature range of $550-750^{\circ}C$ for 24 h and compared with the results of thermal cracking. The increase of calcination and steaming temperature resulted in the decrease of surface area, pore volume, and strong acid sites, which was mainly caused by the dealumination of H-ZSM-5 framework. It was found by $^{27}Al$ and $^{29}Si$ MAS NMR that the dealumination was proceeded through the transformation process of tetrahedral framework Al${\rightarrow}$penta-cordinated Al ${\rightarrow}$ octahedral framework Al and the phenomena was much more severe in steaming conditions than that of calcination. In the catalytic cracking of n-octane, as the temperatures of calcination and steaming were increased, the conversion of n-octane, the selectivity of light olefins and ethylene to propylene ratio were decreased due to the dealumination of framework aluminum resulting the loss of acidic strengths. The conversion, selectivity of light olefins and ethylene to propylene ratio reached almost to the level of thermal cracking after steaming at $750^{\circ}C$ for 24 h.

• Proceedings of the Korean Nuclear Society Conference
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• 2005.05a
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• pp.517-518
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• 2005

• Journal of the Korean Magnetic Resonance Society
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• v.9 no.1
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• pp.67-73
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• 2005

$^{27}AI$ triple quantum magic angle spinning (3QMAS) NMR spectra of several mordenite (MOR) sample were simulated with the point charge model method and compared with experimental 3QMAS spectra. Signal positions from different tetrahedral (T) sites in 3QMAS spectra are mainly governed by local structures of T sites such as T-O-T angles and T-O bond lengths. When preparation methods, cations in addition to Si/Al rations vary, the local structures of T sites in MOR change enough to alter signal patterns in 3QMAS of MOR. This inhibits to study the of Al distribution variation over 4 different T sites in mordenite during process such as dealumination by 3QMAS spectra.

• Proceedings of the KAIS Fall Conference
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• 2000.10a
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• pp.36-38
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• 2000

NaY형 Zeoilte는 현재 그들의 촉매적 특성과 흡착성 그리고 이온 교환성들을 이용하여 산업에 중요하게 사용되어지고 있다 본 실험은 고온 스팀을 이용한 방법과 산처리에 의한 방법으로 탈알루미나의 효과를 확인하는 실험을 하였다 먼저 SiO₂/Al₂O₃ 몰비가 4-6인 합성 NaY zeolite를 분위기 소성로에 넣고 증기발생 장치를 이용하여 500℃에서 고온 스팀을 분위기 소성로에서 일정하게 주입하였다. 에에 따른 결과는 탈알루미나 처리 후의 XRF와 BET의 결과로 탈알루미나 처리에 따라서 SiO₂/Al₂O₃의 몰비가 20.6에서 21까지 증가한 것을 알 수 있으며 또한 BET의 결과에서 탈알루미나 처리에 의해서 비표면적이 증가한 것을 확인할 수 있으며 특히 meso pore area의 증가는 탈알루미나에 의해서 zeolite의 골격구조가 일부 파괴되었음을 알 수 있다.

• Applied Chemistry for Engineering
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• v.17 no.3
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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.