催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (5): 423-428.

• 研究论文 • 上一篇    下一篇

四(五氟化苯基)-六, 七溴-卟啉氯化铁选择性催化氧化超临界丙烷的反应机理

刘依农1,2,许志明1,孙学文1,赵锁奇1,王仁安1,龙军2   

  1. 1 中国石油大学重质油国家重点实验室, 北京 102249; 2 中国石油化工股份有限公司石油化工科学研究院, 北京 100083
  • 收稿日期:2007-05-25 出版日期:2007-05-25 发布日期:2011-04-28

Reaction Mechanism for Selective Oxidation of Supercritical Propane Catalyzed by β-Hexa-heptabromo-tetrakis (Pentafluorophenyl) Porphyrinato Iron

LIU Yinong1,2, XU Zhiming1*, SUN Xuewen1, ZHAO Suoqi1, WANG Renan1, LONG Jun2   

  1. 1 State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China; 2 Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
  • Received:2007-05-25 Online:2007-05-25 Published:2011-04-28

PDF

842

被引次数

3

摘要： 以2,6-二叔丁基-4-甲基苯酚(BHT)为自由基捕捉剂,研究了四(五氟化苯基)-六,七溴-卟啉氯化铁选择性催化氧化超临界丙烷为丙醇的反应机理. 结果表明,添加少量的BHT能促进反应进行,过量的BHT则抑制反应进行. 反应产物中除有丙基自由基外,还有异丙氧自由基及其他微量反应产物(如异己烷、正己烷、双丙基过氧化物)存在. 超临界丙烷在催化剂的作用下形成更多的丙基自由基,进一步证明金属卟啉催化氧化超临界丙烷是链式自由基自氧化反应机理. 对于其他微量反应产物如乙醇、乙酸和丙酸的存在,不能用链式自由基自氧化反应机理进行解释.

关键词: 超临界丙烷, 自由基, 催化氧化, 四(五氟化苯基)-六, 七溴-卟啉氯化铁, 6-二叔丁基-4-甲基苯酚

Abstract: Using BHT (butylated hydroxyltoluene, i.e.,2,6-ditertbutyl-4-methylphenol) as a radical trap, the reaction mechanism for oxidation of supercritical propane catalyzed by β-hexa-heptabromo-tetrakis(pentafluorophenyl) porphyrinato iron was investigated. A small amount of BHT significantly promoted the reaction, whereas its extra amount restrained the reaction. Besides the propyl radical, the isopropoxy radical and a small quantity of oxidation products such as n-hexane, i-hexane, and di-isopropyl peroxide were detected, being the very important evidence to the reaction mechanism of radical chain autooxidation. The minimum other products such as ethanol, acetic acid, and propionic acid could not be explained upon this reaction mechanism.

Key words: supercritical propane, radical, catalytic oxidation, β-hexa-heptabromo-tetrakis (pentafluorophenyl) porphyrinato iron, 6-ditertbutyl-4-methylphenol