| Project/Area Number |
14350427
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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 | Ehime University |
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Principal Investigator |
TSUTOMU Yamaguchi Ehime University, Faculty of Engineering, Professor, 工学部, 教授 (10000861)
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| Co-Investigator(Kenkyū-buntansha) |
OOKAWA Masashi Ehime University, Faculty of Engineering, Instructor, 工学部, 助手 (00274340)
宮崎 隆文 愛媛大学, 工学部, 助教授 (70260156)
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| Project Period (FY) |
2002 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥12,700,000 (Direct Cost: ¥12,700,000)
Fiscal Year 2004: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2003: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2002: ¥9,300,000 (Direct Cost: ¥9,300,000)
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| Keywords | solid base / alkali metal salts / olefin isomerization / green chemistry / アルドール縮合 |
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| Research Abstract |
1.A highly basic solid catalyst was obtained by dispersing metal salts of Group 1 and 2 elements over supports at the surface density of 10-15 cations nm^<-2> and activating them at proper temperature in an inert atmosphere. Effective supports were alumina and zirconia ; silica and titania were ineffective.
2.The catalyst exhibited high activity in the isomerizations of cis-but-2-ene, 3-methyl-but-1-ene, propa-1,2-diene and α-pinene, and the isomerization/dehydrogenation of cyclohexadiene to benzene, cyclohexene and hydrogen, and of limonene to p-cymene.
3.In case of the isomerization of cis but-2-ene, the highest reaction rate of 10 mol g^<-1> h^<-1> was obtained on the catalyst derived from CsNO_3/alumina. The order of effectiveness of metal nitrates on alumina for this reaction was found to be in the order of group 1 elements > group 2 elements and the elements in the lower rows in the periodic table gave higher activity.
4.From TPD and IR/Raman spectroscopy, it was found that mounted metal salts existed as both an agglomerated phase when the surface density was high and an ion-separated phase when the surface density was low. The former decomposes at the temperature close to its own decomposition temperature, while the latter decomposes far below the decomposition temperature and was attributed to the anion decomposition that may be free from its counter cation.
5.The generation of the basic property closely relates to the anion decomposition. NO_3^-decomposes to NO_2+O^- and CO_3^<2-> decomposes to CO_2+O^<2->. It is suspected that the liberated oxygen anion(s) constitutes basic centers.
6.Thus developed novel solid base catalysts have a high applicability to environmentally benign heterogenous systems by replacing undesirable homogeneous systems using strongly basic media such as aqueous solutions of KOH,NaOH etc.
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