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Application of Laser to Selective Partial Oxidation of Hydrocarbons by Dioxygen

激光在分子氧选择性部分氧化碳氢化合物中的应用

基本信息

批准号：
63430017
负责人：
TOMINAGA Hiro-o
金额：
$ 9.34万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1990
项目状态：
已结题

项目摘要

Study of partial oxidation of hydrocarbons, such as ethane, propane, cyclohexane and benzene, initiated by irradiation of ArF or KrF excimer laser on various initiators, has led to the conclusions as follows ;(1) Partial oxidation of paraffins initiated by N_2O or O_3 photolysisReaction is initiated by photochemical decomposition of either N_2O or O_3 by excimer laser light. The singlet oxygen produced by the photolysis of N_2O reacted with hydrocarbons by insertion into C-H bond to produce "hot" alcohols. The product distribution of the reaction in which O_3 is introduced as an initiator shows that use of KrF laser light to generate O(^1D) from ozone was found to have the advantage, over ArF laser and N_2O, of better selectivity for cyclohexanol and cyclohexanone. The advantage essentially results from the fact that KrF laser light does not promote the decarbonylation of cyclohexanone to cyclopentane and carbon monoxide, while ArF laser light does.(2) Partial oxidation of cyclohexane in liquid phaseIn the liquid phase oxidation, selectivity for oxygen-containing compounds is over 85%, and quantum yield is more than 10^3 times larger than that in gas phase reaction, which may be due to higher concentration of cyclohexane. The formation of compounds formed by radical recombination, which was not observed in gas phase reaction at all, can be explained by the cage effect in the liquid phase oxidation.(3) Reactions of aromatics by irradiation of excimer laserIn the photoreactions of aromatics (benzene and toluene), decomposition into C_2 - C_4 olefins occurs and no oxygen-containing compounds are observed, due to the photolysis of the reactant itself by absorbing of either ArF or KrF excimer laser light.

本文研究了ArF或KrF准分子激光在不同引发剂上引发乙烷、丙烷、环己烷和苯等烃类的部分氧化反应，得到如下结论：（1）N_2O或O_3光解引发烷烃的部分氧化反应。N_2O光解产生的单线态氧通过插入碳氢键与碳氢化合物反应生成热醇。以O_3为引发剂的反应产物分布表明，用KrF激光从臭氧中生成O（^1D）的反应比用ArF激光和N_2O的反应具有更好的环己醇和环己酮选择性。该优点主要是由于KrF激光不促进环己酮脱羰成环戊烷和一氧化碳，而ArF激光促进环己酮脱羰成环戊烷和一氧化碳。(2)环己烷的液相部分氧化在液相氧化中，含氧化合物的选择性超过85%，量子产率是气相反应的10^3倍以上，这可能是由于环己烷浓度较高所致。在液相氧化反应中，自由基复合形成化合物，这在气相反应中根本没有观察到，可以用笼效应来解释。(3)芳烃在准分子激光照射下的反应在芳烃（苯和甲苯）的光反应中，由于反应物本身吸收ArF或KrF准分子激光而发生光解，生成C_2 - C_4烯烃，没有观察到含氧化合物。