|Place of Conferral||北京|
|Keyword||环己烷 Schiff 碱 N-羟基邻苯二甲酰亚胺 离子液体 超声波|
饱和烷烃的选择氧化具有十分重要的科学意义和应用价值。由于 C-H 键的键能大，极性小，所以活化困难，反应活性低。并且反应产物比原料更活泼，很容易发生深度氧化，生成二氧化碳和水等副产物。因此，寻找有效的烷烃选择氧化的方法，是一个非常有意义和具有挑战性的难题。本文旨在液相条件下，以分子氧为氧化剂，寻找对环己烷氧化高选择性催化剂。合成一系列Schiff 碱、Al2O3 固载型Schiff 碱和双醛淀粉Schiff 碱锰配合物催化剂，研究它们在环己烷氧化反应中的催化活性。通过对比实验，双醛淀粉-Schiff 碱锰配合物具有较好的催化活性，确定了该催化剂催化下环己烷氧化反应的最佳工艺条件。对Ishii 催化体系进行改进。一、通过浸渍法将Ishii 体系中金属离子固载到分子筛ZSM-5 上，研究了M/ZSM-5 ( M= Co2+、Mn2+、Fe3+、Zn2+、Ni2+) 在NHPI 催化氧化环己烷反应中的助催化作用。研究发现，负载后的金属离子能有效地起到助催化作用。二、将NHPI 桥联到高分子载体聚苯乙烯马来酸酐共聚物(SMA)上制得SMA-NHPI，与Co/ZSM-5 共同催化环己烷的非均相氧化反应。结果表明，SMA-NHPI与NHPI 几乎具有相同的催化活性，两种非均相催化剂可以通过简单的过滤与产物进行分离，简化反应后处理的同时，催化剂还可以重复使用。对比所有催化剂，以活性最高的催化剂考察离子液体、超声作用下环己烷的催化氧化反应。实验发现，使用离子液体为溶剂可使环己烷的转化率略有提高，环己烷氧化产物可通过倾析与离子液体分离，离子液体除水后可重复使用；超声对环己烷的非均相氧化反应有促进作用，环己烷的转化率随超声强度的增加而增加。
Selective oxidation of saturated hydrocarbons is of great importance from a fundamental and applied point of view. Because of the high strength and weak polarity of C-H bonds, the C-H bond activation is difficult and alkanes are relatively inert. Moreover, due to the products (oxygen-containing compounds) is more active than the raw material, the deep oxidation to carbon dioxide and water easily occurs. The controlled oxyfunctionalization of alkanes is still one of the major challenges of modern catalysis. In this paper, studies on key factors to improve the efficiency of oxidation of cyclohexane to KA oil and development efficient catalyst for the process using molecular oxygen as oxidant in liquid phase were carried out. A series of N,N'-bis(salicylaldehyde) diamine Schiff base、alumina-supported Schiff base and dialdehyde starch-Schiff base manganese complexes were synthesized and applied to oxidation of cyclohexane. The dialdehyde starch-Schiff base manganese complex was found to be effective by contrastive reactions, and was employed as catalyst for oxidation of cyclohexane to obtain the optimized conditions. Ishii catalytic system was improved. First, M/ZSM-5 was prepared by the method of impregnation, and their co-catalytic actions were investigated in oxidation of cyclohexane catalyzed by N-hydroxyphthalimide. The studies revealed that M/ZSM-5 was the effective co-catalyst. Second, N-Hydroxyphthalimide was anchored onto styrene-maleic anhydride copolymer (SMA) to give SMA-NHPI, and then heterogeneous oxidation of cyclohexane catalyzed by the catalytic system consisting of SMA-NHPI and Co/ZSM-5 was reviewed. The results showed that the catalytic activity of SMA-NHPI was parallel to that of NHPI and led to simplification of reaction work-up, and the anchored species were easily separated from the reaction mass by filtration, moreover, the catalysts could be reused. Compared all catalysts synthesized, the catalyst with the best catalytic activity was used to catalyze oxidation of cyclohexane in ionic liquid or ultrasound irradiation. The results revealed that conversions of cyclohexane were slightly improved in ionic liquid. The products could be extracted and decanted out from ionic liquid, and ionic liquid could be reused after removal of water under vacuum; Ultrasonic irradiation could facilitate the heterogeneous oxidation of cyclohexane, and the conversion of cyclohexane increased with the increase of ultrasound power.
|杨丹红. 环己烷的催化氧化反应研究[D]. 北京. 中国科学院研究生院,2008.|
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