氧气氧化环己烷合成环己酮的高效催化体系  

Highly Efficient Catalytic System for Cyclohexanone Synthesis by Cyclohexane Oxidation With Oxygen

作　　者：蒋晓丽[1] 单玉华[1] 巫丽君[1] 鲁墨弘[1] 李明时[1] 

机构地区：[1]常州大学江苏省绿色催化材料与技术重点实验室,江苏常州213164

出　　处：《石油学报（石油加工）》2013年第6期984-990,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：江苏高校优势学科建设工程项目资助

摘　　要：通过筛选一系列催化剂和助催化剂,构建了氧气氧化环己烷合成环己酮的高效催化体系。考察了溶剂和反应条件对环己烷转化率和环己酮选择性的影响。采用气相色谱(GC)对产物进行定量分析,采用色质联用(GC-MS)对反应途径和催化剂失活机理进行探讨。结果表明,以N-羟基邻苯二甲酰亚胺(NHPI)为催化剂,以Co(OAc)2、Cr(OAc)3和AlCl3为助催化剂,以乙腈为溶剂,可以高效地催化氧气氧化环己烷反应。当n(NHPI)∶n(Co(OAc)2)∶n(Cr(OAc)3)∶n(AlCl3)=10∶3∶1∶1,n(NHPI)∶n(CH3CN)∶n(C6H12)=1∶20∶10,氧气压力1.0MPa,于75℃反应6h时,环己烷的转化率为54.4%,环己酮选择性为93.2%,环己醇选择性为4.9%。己二酸为主要的副产物,氧化过程生成的水是造成催化剂失活的主要原因。A highly efficient catalytic system for the synthesis of cyclohexanone from cyclohexane oxidation with oxygen was fabricated by screening a series of catalysts and cocatalysts, and the effects of solvents and reaction conditions on cyclohexane conversion and cyclohexanone selectivity were investigated. The products were quantitatively analyzed by GC and the reaction pathways and catalyst deactivation mechanism were discussed by means of GC-MS. The results showed that with N-hydroxyphthalimide（NHPI） as catalyst, Co（OAc）2, Cr（OAc）3 and AlCl3 as cocatalysts and acetonitrile as solvent, the cyclohexane oxidation by O2 could be efficiently catalyzed. The suitable reaction conditions were n（NHPI）∶n（Co（OAc）2）∶n（Cr（OAc）3）∶n（AlCl3）=10∶3∶1∶1, n（NHPI）∶n（CH3CN）∶n（C6H12）=1∶20∶10, 75℃, 1.0 MPa O2 and 6 h, under which 54.4% conversion of cyclohexane with 93.2% selectivity for cyclohexanone and 4.9% selectivity for cyclohexanol was obtained. Adipic acid was the main by product of the synthesis reaction, and the water formed during the oxidation process was the main cause of the catalyst deactivation.

关 键 词：环己烷 氧化 催化剂 环己酮 N-羟基邻苯二甲酰亚胺(NHPI) 

分 类 号：O643.3[理学—物理化学]