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.
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.
出处
《催化学报》
SCIE
CAS
CSCD
北大核心
2007年第5期423-428,共6页
基金
中国石油天然气集团公司石油科技中青年创新基金(04E7024).
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
2
6-二叔丁基-4-甲基苯酚
LIU Yinong , XU Zhiming , SUN Xuewen , ZHAO Suoqi , WANG Renan , LONG Jun (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 )supercritical propane
radical
catalytic oxidation
β-hexa-heptabromo-tetrakis (pentafluorophenyl) porphyrinato iron
2,6-ditertbutyl-4-methylphenol