| Project/Area Number |
09450300
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
触媒・化学プロセス
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| Research Institution | Sophia university |
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Principal Investigator |
SEGAWA Kohichi Sophia university, Faculty of Science and Technology, Department of Chemistry, Professor, 理工学部・化学科, 教授 (60053675)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥14,100,000 (Direct Cost: ¥14,100,000)
Fiscal Year 1998: ¥4,900,000 (Direct Cost: ¥4,900,000)
Fiscal Year 1997: ¥9,200,000 (Direct Cost: ¥9,200,000)
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| Keywords | mordenite / selective synthesis / ethanolamine / ethylenediamine / by-products / dealumination / pyridine adsorption (IR spectra) / Bronsted acid / ブレンステッド酸点 / 形状選択性 / 固体酸触媒 / ゼオライト / 骨格外アルミ / 脱アルミ |
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| Research Abstract |
The synthesis of EDA (ethylenediamine) from EA (ehtanolamine) with NH_3 over acidic types of zeofite catalyst was investigated. Among the zeolites tested in this study, H-EDTA-MOR (H-type mordenite dealuminated with H_4EDTA) was the best catalyst. The reaction proved to be highly selective for EDA over H-EDTA-MOR, with small amounts of ethyleneimine and piperazine derivatives as the side products. The catalytic activity for EDA synthesis rises with increasing partial pressure of NH_3. The initial product of reaction was El, and the formation of EDA followed. The results suggest that the formation of EDA required stronger acidic sites in the mordenite channels with excess amounts of NH_3. The mordenite channels may retard the formation of bulkier piperazine derivatives and other polyamines. The reactions of EA proceed through ammonio-ions by the addition of protons of H-EDTA-MOR ; then intramolecular condensation of ammonioions of EA occurred to produce an El intermediate over the active sites of the catalyst. ethyleneimine is protonated by the stronger acidic sites with excess amounts of NH_3 to produce EDA.Dealuminated mordenites by H_4EDTA and hydrochloric acid of different concentration were investigated with IR (pyridine adsorption), XRD, XRF, MAS NMR.Each catalyst was used to test the catalytic activity and the produsts were analyzed with GO-MS.The amount of adsorbed pyridine (calculated from IR spectra) increased as the dealumination proceeds. It reached its maximum around Si/Al (bulk) =5, and then decreased. The catalytic activity increased as the amount of pyridine increased, and it decreased as the crystallinity and the pyridine amount decreased. That is, the curve of catalytic reaction strongly relates to the acid amount, especially Bronsted acid. It is under investigation the reason the acid amount increased with dealumination.
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