| Project/Area Number |
59850139
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | University of Tokyo |
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Principal Investigator |
TOMINAGA Hiro-o University of Tokyo, 工学部, 教授 (00010760)
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| Co-Investigator(Kenkyū-buntansha) |
此木 恵三 東洋エンジニアリング技術研究所, 所長
OMATA Kohji University of Tokyo, 工学部, 助手 (70185669)
SHIKADA Tsutomu University of Tokyo, 工学部, 助手 (40134499)
FUJIMOTO Kaoru University of Tokyo, 工学部, 助教授 (30011026)
KONOKI Keizou Toyo Engineering Corporation
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| Project Period (FY) |
1984 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥20,500,000 (Direct Cost: ¥20,500,000)
Fiscal Year 1986: ¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 1985: ¥5,800,000 (Direct Cost: ¥5,800,000)
Fiscal Year 1984: ¥9,900,000 (Direct Cost: ¥9,900,000)
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| Keywords | Metanol / Carbon monoxide / Carbonylation / Acetic acid / Vapor phase / Fluidized bed / Nickel catalyst / 非ロジウム系触媒 / 酢酸合成 / 流動床 / CVD法 / 活性炭 / 触媒寿命 / 触媒再生 |
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| Research Abstract |
It was found that a nickel on active carbon (Ni/A.C.) catalyst exhibited a high activity and selectivity for the vapor phase carbonylation of methanol to acetic acid under moderately pressurized (5-30 atm) and heated (200-300 ゜C) conditions. The 2.5% Ni/A.C. catalyst gave ; 100% methanol conversion and 97% acetic acid yield, in the presence of methyl iodide promoter and excess carbon monoxide. The reaction path was clarified as follows: The yield of each product as a function of time factor was well simulated by calculating numerically the rate of each unit reaction. The Ni/A.C. catalyst was stable during the reaction, which exhibited a half life time of 50 days. The decrease in the catalytic activity was not attributed to the vaporization of nickel from the catalyst but to the deposition of tarry material on the catalyst, which caused the plugging of micro-pores in the catalyst.
A fluidized bed reactor, which was able to be operated under pressurized conditions with a gas-recycle, was built and subjected to the methanol carbonylation. A remarkable flat temperature profile was attained in the catalyst bed during the reaction, which gave a result of more than 1 Kg-acetic acid/Kg-cat.h with a selectivity of 99% carbonylated products. The level is even superior to that of a fixed bed reaction and is sufficient for industrialization.
It was also found that hydrogen in the feed gas, which commonly exist in CO, remarkably promotes the reaction with little change in the product selectivity. The hydrogen did not promote any particular reaction but promoted all reactions in the reaction network. However, little hydrogen in the gas phase was not incorporated in the product, suggesting that the promotional effect being not in the direct way but in the indirect way.
The feasibility study of the present process suggests that it is competitive to a presently operating process which uses rhodium catalyst.
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