Thesis Advisor文彬
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
Keyword环己烷 Nhpi Schiff碱 超声 Β-环糊精

在烃类化合物的氧化反应中,环己烷氧化制备环己醇和环己酮(两者混合物称为KA油)是工业生产中一类重要的反应。由于此反应工艺转化率和选择性较低,三废污染严重及能耗过大,因此该领域一直是国内外研究的热点和难点。 在现有环己烷催化氧化反应中,仿生催化氧化法和N-羟基邻苯二甲酰亚胺(英文名N-Hydroxyphthalimide,简称NHPI)催化氧化法在环己烷转化率和产物选择性方面显示出较大的优势。本文首次将仿生催化氧化方法中三类催化剂(Schiff碱钴配合物、卟啉钴配合物和尿素钴配合物)与NHPI结合组成新的催化体系,研究其对环己烷的催化氧化效果。在反应过程中,钴配合物既可以自身对环己烷进行氧化,又可以作为助催化剂协助NHPI完成催化氧化过程。三类钴配合物分别和NHPI组成的催化体系中,卟啉钴配合物/NHPI体系体现出较好的催化效果,环己烷转化率最高可达52.6%,Schiff碱钴配合物/NHPI体系次之,尿素钴配合物/NHPI体系较差。 三类钴配合物中Schiff碱钴配合物具有制备简单,产率较高的特点,本文选用Schiff碱钴配合物/NHPI催化体系,研究在不同实验条件下催化氧化性能,条件实验结果表明在反应温度100oC、反应时间8 h,氧气压力为1.0 MPa时环己烷转化率最高。 NHPI常温条件下在水相中溶解度较差,限制了其在水相中的进一步应用,为拓宽NHPI的溶剂使用范围,本文选用β-环糊精作为载体,将NHPI作为客体分子与之形成包合物,经计算得出NHPI-β-环糊精包合物在水相中的包合常数为1412 L•mol-1(25oC),并通过Hildebrand-Benesi计算公式确定包合比为1:1。鉴于超声对β-环糊精的包合行为会产生影响,本文研究了在不同配比和不同超声强度下的包合规律,结果表明,超声可以促进包合过程的进行,并且能够提高包合产率。

Other Abstract

Among the oxidation reactions of hydrocarbon compounds, it is a kind of important reaction that is the preparation of cyclohexanol and cyclohexanone(the mixture of two substances called KA oil) by oxidizing cyclohexane. This reaction has been becoming the research focus because of its bare conversion, bad selectivity, especially its serious pollution and overburdening cost of energy. In these existing reactions on cyclohexane catalytic oxidation, bionic catalytic oxidation and NHPI catalytic oxidation acquired high qualities in the aspect of cyclohexane conversion and target products selectivity. In this paper, three kinds of catalysts in bionic catalytic oxidation were prepared. Each kind of catalysts coupled with NHPI was firstly used in the reaction of cyclohexane catalytic oxidation. Cobalt complexes as a catalyst, which can take part in the process of cyclohexane oxidation, provided assistance for NHPI as an co-catalyst to complete cyclohexane oxidation process. During three new catalyst systems, the porphyrin cobalt-complexes/NHPI system better reflected the catalytic effect of cyclohexane conversion which went up to 52.6%, Schiff base cobalt-complexes/NHPI catalyst system followed, urea cobalt-complexes/NHPI catalyst system were less effective. Schiff base cobalt-complexes in the three cobalt-complexes were prepared simply with high yield, this paper selected Schiff base cobalt-complexes/NHPI catalyst system to oxide cyclohexane under different experimental conditions. The results showed that the conversion of cyclohexane can reach an high level at the reaction temperature 100oC and 1.0 MPa oxygen pressure after 8 reaction hours. The solubility of NHPI at room temperature in the aqueous phase is poor, which limited its further application in the aqueous phase. β-cyclodextrin was chosen as a carrier to enclose NHPI as a guest molecules. The inclusion constant of 1412 L•mol-1 (25oC) was calculated in aqueous phase. The inclusion ratio of 1:1 was determined through the Hildebrand-Benesi formula. In view of ultrasound on β-cyclodextrin inclusion behavior will have an impact, this paper researched the law of inclusion in different proportions under different ultrasonic intensity The results showed that ultrasound can facilitate the process of inclusion and can improve the yield of inclusion rate.

Document Type学位论文
Recommended Citation
GB/T 7714
贺永桓. NHPI与钴配合物协同催化氧化环己烷及NHPI与环糊精包合性质研究[D]. 北京. 中国科学院研究生院,2011.
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