高钒含量修饰介孔分子筛作为重要芳烃直接氧化反应催化剂研究

项目名称： 高钒含量修饰介孔分子筛作为重要芳烃直接氧化反应催化剂研究

项目编号： No.20876077

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 孔岩

作者单位： 南京工业大学

项目金额： 36万元

中文摘要： 合成了不同结构高钒含量介孔材料。如在氨性条件下合成的 V-MCM41，V/Si 物质的量比达0.14。建立了通过稀溶液浸渍表面钒物种、浓硫酸溶解骨架内钒物种，采用化学分析方法结合多种光谱手段确定含钒介孔材料骨架内外不同价态钒含量的方法；该方法可用于分析其它金属掺杂分子筛。考察了不同结构催化剂室温下苯过氧化氢直接羟基化制备苯酚反应中的催化性能，结果表明含钒介孔材料具有较好的催化性能，尤其苯酚选择性几乎均为100%；介孔结构对催化性能影响较大，相同钒含量下催化活性为V-SBA-15> V-HMS> V-MCM41。合成了含钒中空球、球形V-MCM-48、纳米颗粒V-MCM-41等并研究其在苯乙烯氧化反应中催化性能。球形V-MCM-48在室温即表现出良好的催化性能，且通过调节反应液的PH可改变反应产物苯甲醛及环氧苯乙烷的收率比；纳米颗粒V-MCM-41催化性能随粒径的降低而增加。同时合成了铁、钛、钴、铜等掺杂的介孔分子筛及其催化性能。如含铁介孔分子筛用于水为溶剂、室温苯酚氧化制备苯二酚反应，中试结果表明具有苯二酚收率高；三废少；安全性能高、节能等特点，且重复使用效果良好。

中文关键词： 介孔材料；芳烃；选择氧化；钒；催化性能

英文摘要： We have synthesized a variety of different structures of mesoporous molecular sieves with the high vanadium content that the molar ratio of V/Si of V-MCM41 synthesized in the ammonia is up to 0.14. These mesoporous molecular sieves also were characterized by XRD, N2 adsorption-desorption, and HRTEM. A method to calculate the content of different valences of vanadium inside and outside of the skeleton is created, which is achieved by impregnation of vanadium species in the surface with dilute solution, dissolution of vanadium species inside of the skeleton with sulfuric acid and means for chemical analysis combined with spectroscopy. Meanwhile, change of solution can be used for the analysis of other metal-doped molecular sieves. The results of hydroxylation of phenol at room temperature with benzene and hydrogen peroxide show that mesoporous molecular sieves with vanadium have better catalytic properties, in particular, the selectivity of phenol selectivity are almost 100%. Mesoporous structures has a greater impact on the catalytic properties, the catalytic activity of the same vanadium content is V-SBA-15＞V-HMS＞V-MCM41. At the same time, we also have synthesized V-MCM-41 nanoparticles and hollow spherical and spherical V-MCM-48, and make a research on their catalytic properties in oxidation of styrene. The catalytic properties of V-MCM-41 nanoparticles are increasing with decreasing of particle size. Spherical V-MCM-48 at room temperature show good catalytic properties, and yield of benzaldehyde and styrene oxide can be changed by adjusting PH of the reaction solution. In addition, the iron-, titanium-, cobalt-, and copper-doped mesoporous molecular sieves have been synthesized and their catalytic properties in the selective oxidation of aromatic hydrocarbon could be explored. Compared with other catalysts in the oxidation of phenol to hydroquinone with water as solvent at room temperature, iron-doped mesoporous molecular sieves show high hydroquinone yield, safety, low pollution, low energy consumption and good regeneration.

英文关键词： Mesoporous Materials;aromatics;selective oxidation;vanadium;catalytic activity