Rational oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid with air over metalloporphyrin and cobalt salt
Rational oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid with air over metalloporphyrin and cobalt salt
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DOI：
10.1142/s1088424608000054
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发表时间：
2008
影响因子：
1.5
通讯作者：
Bo Hu;Yong Yuan;Jiang Xiao;C. Guo;Qiang Liu;Ze Tan;Qing-Hong Li
中科院分区：
文献类型：
--
作者：
Bo Hu;Yong Yuan;Jiang Xiao;C. Guo;Qiang Liu;Ze Tan;Qing-Hong Li
以异辛酸钴、金属卟啉p-ClTPPCo和[p-ClTPPFe]2O为催化剂，系统地研究了催化剂对环己烷好氧氧化反应的影响。结果表明，金属卟啉催化体系在环己醇和环己酮(KA油)的反应转化率和选择性方面均优于传统的钴盐(异辛酸钴)。更重要的是，我们发现，传统上被认为对碳氢化合物氧化没有活性或不太活性的双硅卟啉配合物在155℃时表现优异，对KA油实现了高选择性(80%)和良好的反应转化率(13.8%)。这一结果与其他人早先的结果形成了鲜明对比。同时，己二酸的产量也得到了提高，副产物中己二酸的选择性也很好。我们的研究表明，除KA油外，[p-ClTPPFe]2O催化的好氧氧化也可用于生产己二酸。根据[p-ClTPPFe]2O催化剂独特的结构和化学性质，提出了其优异性能的一些机理解释。
A systematic study on the effect of a catalyst on the aerobic oxidation of cyclohexane was carried out using cobalt isooctanoate, metalloporphyrin p-ClTPPCo and [p-ClTPPFe]2O as catalysts. The results showed that the metalloporphyrin-catalyzed system performed better than the traditional cobalt salt (Co isooctanoate) in terms of both the reaction conversion and the selectivity of cyclohexanol and cyclohexanone (KA oil). More importantly, we discovered that bisironporphyrin complex, which was traditionally considered to be either non-active or not-so-active for hydrocarbon oxidation, excelled at 155°C, achieving high selectivity for KA oil (80%) and good reaction conversion (13.8%). This result is in sharp contrast to earlier results by others. Meanwhile, the production of adipic acid was also increased and good selectivity of adipic acid among the by-products was also obtained. Our study suggested that [p-ClTPPFe]2O catalyzed aerobic oxidation could be used to produce adipic acid in addition to KA oil. Some mechanistic rationales were proposed to explain the superior performance of the [p-ClTPPFe]2O catalyst based on its unique structural and chemical properties.