• Applied Chemistry for Engineering
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• v.8 no.6
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• pp.1048-1053
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• 1997

Modified mordenites by HF treatement, which have different $SiO_2/Al_2O_3$ ratio, and those mixed with $\gamma$-alumina are prepared and used for catalytic cracking of triphenylmethane(TPM) in micro-activity tester(MAT). Dealumination of mordenites decreased the acid content but developed secondary mesopores. The conversion and the selectivity of benzene over modified mordenites with the mesopores were increased. However, for the further dealuminated mordenites, they decreased due to the destruction of pore structure and low acid amount. Accordingly, the maximum cracking activity and the maximum selectivity of benzene were obtained about 17 $SiO_2/Al_2O_3$ ratio of modified mordenites. The modified mordenites mixed with alumina enhanced the cracking activity of TPM compared with the pure mordenites. It can be explained that TPM is cracked at active sites with in large pores of alumina firstly and further cracked into small molecules in zeolite pores as step mechanism of catalytic cracking.

• Clean Technology
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• v.13 no.1 s.36
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• pp.64-71
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• 2007

The selection of a suitable adsorbent for removing organic sulfur compounds tetrahydrothiophene (THT) and t-butylmercaptan (TBM) from natural gas has been carried out. The saturation adsorption capacity for the sulfur compounds were determined by pulse adsorption method for a group of nanoporous materials, including Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-Mordenite, Na,K-Clinoptitolite, Ti/MCM-41, Ti/SBA-15 and amorphous titanosilicates. Among the materials tested, Na-Y and Na,K-ET(A)S-10 zeolites showed high adsorptive capacities for THT and TBM. The saturation capacity for THT on Na,K-ETS-10 was comparable with that on Na-Y zeolite, which is well known as an effective adsorbent. The capacity and adsorptivity for THT and TBM on Na,K-ETAS-10 were improved by an increase in crystallinity of Na,K-ETAS-10. An investigation of the competitive adsorption between THT and TBM from the breakthrough test using a simulated natural gas indicates that Na,K-ETS-10 selectively adsorbs THT. The breakthrough capacity for THT on Na,K-ETS-10 was 1.19 mmol/g. The results show that the high adsorption performance of Na.K-ETS-10 and Na,K-ETAS-10 is due to the highly exchanged cations in the zeolitic structure which exhibit the strong electrostatic interactions with organic sulfur compounds and their wide pore nature.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.3
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• pp.345-353
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• 2022

This study aimed to fundamentally understand changes of cell parameters of cation-exchanged mordenites using high resolution X-ray powder diffraction for studies that immobilization of various heavy metal cation using synthesis mordenite (Na_6.6Al_6.6Si_41.4O₉₆·20.4H₂O, Na-MOR). As a results of measurement by Thermogravimetric analysis (TGA), it was confirmed that 19.4, 20.4 water molecules per unit cell were present in monovalent-cation substituted MOR (Cs-MOR, Na-MOR), and 21, 23.1, 23.2 water molecules per unit cell were present in divalent-cation substituted MOR (Pb-MOR, Sr-MOR, Cd-MOR). The space group of all the samples were identified as Cmcm belonging to the orthorhombic crystal system. Compared to Na-MOR, starting material, relative peak intensity of (110) and (200) is significantly changed after cation substitution whereas peak position is almost similar. Also, (220) peak that was not found in Na-MOR was clearly observed in Pb-, Cd- and Sr-exchanged MOR. Thus, it was estimated that changes of atomic distribution usually occurred on ab-plane while changes of cell parameters were little. Detailed changes in the cell parameters of cation-exchanged mordenites were derived from whole profile fitting method using the GSAS suite program. Changes in the axial lengths and unit cell volume of cation substitution showed different relationship depending on ionic radius and charge number. In case of monovalent-cation substituted MOR, the length of a-axis increases whereas the length of b- and c-axis decrease by absorbed cation radius. In the case of divalent-cation exchanged MOR, the length of a-axis usually decreases while the length of b- and c-axis increases by cation radius. It was confirmed that unit cell volume of monovalent and divalent cation substituted MORs had an independent tendency by cation radius.

• 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.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.4
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• pp.609-617
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• 2000

This study is aimed at investigating an effect of HCl gas on selective reduction of NOx over a CuHM and $V_2O_5-WO_3/TiO_2$ catalyst. SCR process is the most effective method to remove NOx, but catalyst can be deactivated by the acidic gas such as HCl gas which is also included in flue gas from the incinerator. In dry condition of flue gas, the CuHM catalyst treated by HCl gas has shown higher NO removal activity than the fresh catalyst. The activity of the catalyst can be restored by treating at $500^{\circ}C$. On the contrary. $V_2O_5-WO_3/TiO_2$ catalyst is obviously deactivated by HCl and the deactivation increases in proportion to the concentration of HCl gas. The deactivated catalyst is not restored to it's original activity by heat treatment for regeneration. In wet flue gas stream, the CuHM catalyst has shown lower activity than fresh catalyst and $V_2O_5-WO_3/TiO_2$ catalyst was severely deactivated by HCl treatment. The activity loss of catalysts are mainly due to the decrease of Br$\ddot{o}$nsted acid site on the catalyst surface by $NH_3$ TPD. The change of BET surface area of CuHM catalyst after the reaction isn't observed but $V_2O_5-WO_3/TiO_2$ catalyst is observed. The amount of $Cu^{{+}{+}}$ and $V_2O_5$ is decreased after the reaction. From these results, it is expected that CuHM catalyst should be better than $V_2O_5-WO_3/TiO_2$ catalyst for its application to the incineration of flue gas.