• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.18-23
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• 1992

Three solid acid catalysts developed recently are reviewed. Cloverite is a gallophosphate molecular sieve with very large pore, titanium silicate has a specific structure compared with conventional molecular sieves, and Envirocat is prepared for the replacement of aluminium chloride catalyst.

• 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.

• Applied Chemistry for Engineering
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• v.29 no.1
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• pp.122-126
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• 2018

Mesoporous molecular sieves were prepared by the reaction of $Na_2SiO_3$ and $H_2SiF_6$ using nonionic micelle templates in an aqueous solution. Well-crystalline mesoporous molecular sieves were obtained after several seconds at atmospheric conditions. Powder samples exhibited d-spacing of 3.8-5.1 nm with the sharpness of the d00l peak, showing well-crystalline mesoporous molecular sieves, pore size distributions of 2.5-3.1 nm and large specific surface areas of $290-1,018m^2/g$, depending on types of surfactants. SEM images of samples showed well-divided spherical particles with an uniform size of ${\sim}0.5{\mu}m$ and TEM images demonstrated uniform pores with a worm hole shape.

• Proceedings of the KAIS Fall Conference
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• 2011.05a
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• pp.141-143
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• 2011

Al-SBA-1(Si/Al = 40, 80 and 120) and Al,Mg-SBA-1 (Si/(Al+Mg) = 40 and 80) molecular sieves were synthesized and characterized. Acetalization of n-heptanal with methanol was studied under autogenous pressure between 80 and $150^{\circ}C$. Since protonation of n-heptanal was fast, addition of methanol to the same to formed hemiacetal slowly whereas conversion of hemiacetal to acetal was fast. The catalysts exhibited nearly similar conversion irrespective of their difference in acidity, and all of them showed more than 80 % conversion either at 80 or $100^{\circ}C$. Hence it is evident that the difference in acidity is not so important in differentiating the activity of the catalysts. The large pore size and hydrophilic and hydrophobic properties are suggested to be the main factors that control acetalization.