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Selective Partial Oxidation of Hydrocarbons by the Cell Reaction System

细胞反应系统选择性部分氧化碳氢化合物

基本信息

批准号：
09555246
负责人：
OTSUKA Kiyoshi
金额：
$ 8.06万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

New oxidation methods for the partial oxidtion od alenes at low temperature (<373K) using gaseous alkene-OィイD22ィエD2 fuel cell systems and for the hydroxykation of alkanes and aromatics applying HィイD22ィエD2-OィイD22ィエD2 fuel cell reactions were studied. Catalytic oxidation systems can be converted into electrochemical cells which control the reaction rate and selectivity by a variable resister or potentiostat in the outer circuit, as shown for the Wacker type and π-allyl type oxidations.Direct oxygenation of aromatics to phenols, C6 alkanes and light alkanes to alcohols and aldehydes are realized at the cathode during HィイD22ィエD2-OィイD22ィエD2 fuel cell reactions at room temperature. The topics are the ω-oxidation of n-hexane with (FeClィイD23ィエD2 + α-cyclodextrin) /graphite cathode, the synergism of Pd-black and iron compounds for the formation of phenol on (Pd-black+FeィイD23ィエD2OィイD24ィエD2)/Carbon-Whisker (CW) cathode, cogeneration of phenol and electricity by using CuSOィイD24ィエD2/CW cathode, the synergism of different carbon materials in the cathode for the product selectivity in the oxidation of toluene on (CW + Active Carbon) cathodes, and the oxidation of propane over (Pal-black +VO(acac)ィイD22ィエD2)/Carbon-Fiber cathodes in the gas phase. Reductive activation of oxygen on the cathode is essential for these oxygenations. For most of the electrocatalytic systems used in this work, the oxygenations of alkanes and aromatics can be explained on the basis of Fenton Chemistry assuming HO・ as the active oxygen species, except for the SmClィイD23ィエD2/graphite cathode.

本文研究了低温（<373 K）下气态烯烃-O_（22）O催化氧化系统可以转化为电化学电池，其通过外回路中的可变电阻器或恒电位仪控制反应速率和选择性，如Wacker型和π-烯丙基型氧化所示。C6烷烃和低碳烷烃到醇和醛的反应在室温下在H_（22）O_（22）燃料电池反应期间在阴极实现。本文研究了正己烷的ω-氧化反应（FeCl_（23）Cl_（Pd-黑+Fe_（23）O_（24不同碳材料在（CW +活性炭）阴极上对甲苯氧化产物选择性的协同作用，以及在（Pal-black +VO（acac）Al_2O_3 D_2）/Carbon-Fiber阴极上对丙烷气相氧化产物选择性的协同作用。氧在阴极上的还原活化对于这些氧化是必不可少的。对于本工作中使用的大多数电催化体系，烷烃和芳烃的氧化反应可以基于假定HO·为活性氧物种的芬顿化学来解释，除了SmCl-D23-D2/石墨阴极。