新型仿生催化剂催化氧化环己烷  

Oxidation of Cyclohexane by Oxygen on Novel Biomimetic Catalyst

作　　者：高利柱[1] 赵文军[1] 苏建玲[1] 杨丹红[1] 范晓芸[1] 高林[1] 

机构地区：[1]中国科学院新疆理化技术研究所

出　　处：《石油化工》2007年第8期774-779,共6页Petrochemical Technology

摘　　要：考察了仿生催化剂四苯基金属卟啉-金属Schiff碱-四苯基金属卟啉催化氧化环己烷的反应,探讨了反应温度、氧气压力、反应时间、催化剂用量、不同金属离子配合物催化剂对环己基过氧化氢产量、氧化产物产量、氧化产物酸值、己二酸酸值、氧化产物酯值的影响。研究结果表明,在此催化剂作用下,氧化结果与反应温度、氧气压力、反应时间、催化剂用量及配位的金属离子均有密切的关系。得到了适宜的反应条件:四苯基卟啉锰-Schiff碱锰-四苯基卟啉锰为催化剂,反应温度140℃,氧气压力2.00MPa,反应时间240min,m(催化剂)∶m(环己烷)=8.5×10-5;在此条件下,环己烷转化率36.32%,己二酸收率11.41%,氧化产物选择性达91.65%,催化剂每个活性中心上平均转化环己烷分子数达到17000。Oxidation of cyclohexane to cyclohexyl hydroperoxide, adipic acid and KA oil（ mixture of cyclohexanol and cyclohexanone ） in presence of oxygen with MTPP - MSalen - MTPP （TPP： tetraphenylporphyrin; M： metallic ion）as catalyst was studied. Effects of reaction time, reaction temperature, oxygen pressure, catalyst dosage and coordination metallic ions on yield of cyclohexyl hydroperoxide, total yield of oxidation products, acid value of products, acid value of adipic acid and ester value of products were investigated. The apparent activation energy is significantly lowered by using the novel catalyst in the oxidation. Under same reaction conditions, 29. 5 g oxidation products can be obtained with FeTPP - FeSalen - FeTPP as catalyst but only 9. 0 g with FeTPP. Under appropriate conditions： MnTPP - MnSalen - MnTPP as catalyst, reaction temperature 140 ℃, oxygen pressure 2.00 MPa, reaction time 240 min and re（catalyst） ： m （cyclohexane） 8.5 × 10^-5, the conversion of cyclohexane, yield of adipic acid, and selectivity to the oxidation products are 36. 32%, 11.41% and 91.65%, respectively. On each active center of catalyst, apporox. 17 000 molecules of cyclohexane convert.

关 键 词：环己烷 仿生催化剂 氧化 环己基过氧化氢 

分 类 号：TQ032.4[化学工程]