XJIPC OpenIR  > 资源化学研究室
Thesis Advisor高 林 ; 赵文军
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
Keyword仿生催化剂 环己烷 氧气 氧化 Ka 油 己二酸

环己醇、环己酮和己二酸都是非常重要的化工原料。本工作以氧气氧化环己烷制取KA 油(环己醇和环己酮的混合物)和己二酸为原则,合成了一系列过渡金属卟啉化合物,对金属卟啉、席夫碱金属配合物和四苯基金属卟啉-金属席夫碱-四苯基金属卟啉三种仿生催化剂进行了评价,并对四苯基金属卟啉-金属席夫碱-四苯基金属卟啉催化氧化环己烷进行了系统的研究。本论文共包括以下几个方面的内容:1、绪论部分介绍了本文研究的背景和意义,综述了国内外KA 油和己二酸的工业生产现状和最新研究进展。2、合成一系列四-(取代苯基)卟吩和一系列四-(取代苯基)卟吩的过渡金属配合物,总结了作者在实验过程中的经验和体会。3、建立了催化氧气氧化环己烷制取氧化产物的评价体系。4、以四苯基金属卟啉作为催化剂,用氧气氧化环己烷制取氧化产物。考察了不同反应条件对氧化产物产量和己二酸收率的影响,发现存在环己烷转化率低、产物选择性低以及过氧化物含量高的缺点。5、以席夫碱金属配合物作为催化剂,用氧气氧化环己烷,发现席夫碱金属配合物在环己烷转化之前下发生自聚。6、以四苯基金属卟啉-金属席夫碱-四苯基金属卟啉作为催化剂,用氧气氧化环己烷制取氧化产物,考察了不同反应条件(反应温度、氧气压力、反应时间、催化剂用量和配位金属离子)对氧化产物产量、环己基过氧化氢产量、氧化产物酸值、己二酸酸值以及酯值的影响。结果显示,其催化性能优于金属卟啉。

Other Abstract

Cyclohexanol, cyclohexanone and adipic acid are important chemical materials. Because of the unactivated C-H bond of cyclohexane, traditional cyclohexane oxidation by dioxygen often suffers from relatively harsh conditions and limited conversion and selectivity. So it is of great importance to develop a biomemetic catalyst to oxidize cyclohexane under mild condition. In this work, we synthesized a series of metalloporphyrins and evaluated their biomemetic catalytic performances in cyclohexane oxidation. Meanwhile, the cooperators of the research team provided M-salen and MTPP-MSalen-MTPP. After testing research, we found MTPP-MSalen-MTPP performed excellently in cyclohexane oxidation. The contents of this thesis are presented as follows: 1. In the introduction, we presented the research background and meaning of this thesis, introduced the current industrial production technique of cyclohexanol, cyclohexanone and adipic acid production, summarized the development of cyclohexane oxidation. 2. The synthesis of five kinds of porphines and a series of metalloporphyrins bearing different substituents were presented in the second chapter. In addition, synthesis experience and knowledge had been summarized. 3. The establishment of evaluation system of catalytic performance in cyclohexane oxidation was presented. 4. To oxidize cyclohexane by molecular oxygen using MTPP as catalyst, we studied the effects of reaction conditions on output of the oxidation products and the adipic acid yield. We found that the conversion of cyclohexane and the selective of the products were not satisfied and the reaction conditions were relatively harsh. 5. Taking M-Salen as catalyst in oxidation of cyclohexane, we found that this kind of catalyst could not play their role under the reaction conditions. Because of the lability of imine group, they had been polymerized before conversion of cyclohexane. 6. Oxidation of cyclohexane to cyclohexyl hydroperoxide, KA oils, adipic acid and ester in presence of molecule oxygen catalyzed by MTPP-MSalen-MTPP had been done. Kinetic studies had been performed to study the effect of reaction conditions, such as reaction time, temperature, oxygen pressure, catalyst dosage and the metal ions that complex coordinated. Results showed that the mass of cyclohexyl hydroperoxide and total oxidation products, the value of total acid, adipic acid and ester, all related reaction conditions closely. Through experiments, it was proved that the performance active energy was significantly lower than the oxidation absence of this new catalyst. Catalyzed by MnTPP-MnSalen-MnTPP, when reaction temperature was 140℃, oxygen pressure was 2 MPa, reaction time was 240 min and m(cyclohexane) : m(catalyst) was 1: 8.5×10-5, the conversion of cyclohexane, yield of adipic acid, selectivity, and turn over number can reach 36.32%, 11.41%, 91.65%, 17 000 respectively. Key words:biomemetic catalyst, oxidation, cyclohexane, oxygen, KA oils, adipic acid

Document Type学位论文
Recommended Citation
GB/T 7714
高利柱. 拟生物氧化环己烷的研究[D]. 北京. 中国科学院研究生院,2007.
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