| Project/Area Number |
07555248
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
触媒・化学プロセス
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| Research Institution | TOKYO INSTITUTE OF TECHNOLOGY |
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Principal Investigator |
YASHIMA Tatsuaki Tokyo Institute of Technology, Department of Chemistry, Professor, 理学部, 教授 (60016409)
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| Co-Investigator(Kenkyū-buntansha) |
SHOUJI Hiroshi Maruzen Petrochmical Co.Ltd., Research Center Senior research associate, 研究所, 主任研究員
KOMATSU Takayuki Tokyo Institute of Technology, Department of Chemistry, Resarch associate, 理学部, 助手 (40186797)
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 1997: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1996: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1995: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | Mordenite / Titanosilicate / Catalyst / Atom-planting method / Liquid-phase oxidation / Hydrogen peroxide / Hydroxylation / Ammoximation / 脱アルミニウム / ゼオライト / アトム・プランティング / 触媒作用 / キャラクタリゼーション / アトム-プランティング法 / アンモオキシメーション / フェノール |
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| Research Abstract |
Titanosilicate with mordenite structure was prepared by Atom-planting method using dealuminated mordenite and TiCl_4. A strong absorption at 220 nm in UV spectra indicated tetrahedral coordination of Ti species. An absorption band also appeared at 963 cm^<-1> in IR spectra. Its absorbance was in proportion to the concentration of Ti. This was an evidence of framework incorporation of all the Ti species. A TiCl_4 reacts with a defect site, hydroxyl nest, to form four Ti-O-Si bonds.
Liquid-phase hydroxylation of toluene with hydrogen peroxide was carried out on titanosilicate. Cresol isomers were produced with selectivity higher than 99%. Turnover number (TON) increased with increasing hydrophobisity of catalyst by dealumination. Benzene, ethylbenzene and cumene gave almost the same TON as toluene, while TON in the hydroxylation of t-butylbenzene was much lower. On MFI-type titanosilicate, however, only benzene was reacted with the same TON ; the others showed much less reactivity. It was revealed that titanosilicate with mordenite structure is effective catalyst for the hydroxylation of large aromatic molecules compared with that with MFI structure. The framework Ti species in titanosilicate catalyzes ammoximation of ketones with ammonia and hydrogen peroxide, because absorbance of the 963 cm^<-1> IR band was in proportion to the reaction rate of ammoximation. Dealumination of the parent mordenite caused the increase in oxime selectivity as well as activity through the increase in hydrophobic nature of the catalyst.
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