| Project/Area Number |
10650771
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | The University of Tokushima |
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Principal Investigator |
HAYASHI Hiromu University of Tokushima, Faculty of Engineering, Professor, 工学部, 教授 (00035627)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1999: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1998: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Keywords | Dimethyl carbonate / Ethylene carbonate / Methanol / Transesterification / Ethylene glycol / Oxidative carbonlylation / Cuprous chloride / Redox catalysi / レドックス触媒体 / 炭酸エレチン / トランス・エチエル化 / 炭酸カリ / リン酸カリ / イオン交換樹脂 |
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| Research Abstract |
To develop a new process for the synthesis of dimethyl carbonate, base-catalyzed transesterification of ethylene carbonate-methanol system has been studied. The route is of interest, as ethylene carbonate could be obtained in a low cost through reaction of ethylene oxide with carbon dioxide. Basic catalysts such as magnesia and hydrotalcites are effective for transesterification, but a trace of moisture may cause to decompose carbonate to carbon dioxide, which unfortunately deactivates the catalyst. In the present work, potassium salts of various acids such as carbonate, dihydrogenphosphate and acetate were examined. The treaction could be carried out without catalyst degeneration.
Recycling use of ethylene glycol which accumulates in the transesterification of ethylene carbonate-alcohol system is an important problem for practical applications. Thus oxidative carbonylation of ethylene glycol to ethylene carbonate has been studied in the present work. Cuprous chloride dissolves into ethylene glycol by absorption of molecular oxygen to give a green solution of cupric glycoxide chloride. The copper(II) complex was resuced by carbon monoxide under pressure of 10 atm at 50-80℃ to afford ethylene carbonate in high yield. The concentration of ethylene carbonate in liquid phase increased linearly with time by continuous absorptions of mixed gas of OィイD22ィエD2/CO=1/2 under pressure of 15 kg/cmィイD12ィエD1. The yield of ethylene carbonate of 739% based on CuCl charged was obtained at 50℃ for 4h, signifying the oxidative carbonylation catalysis through redox cycle of copper-glycoxide chloride.
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