介孔过渡金属氧化物催化剂合成及其在苯甲醇氧化反应中的应用研究
发布时间：2018-10-14 14:45
【摘要】：在现代化学工业中苯甲醇的催化氧化是一类重要的反应,因为所制备的产物苯甲醛是精细化学品和药物合成不可或缺的中间体。传统生产苯甲醛的工业方法通常使用氯化水解法,不仅工艺复杂,产物分离困难,制备的苯甲醛含有痕量的氯,限制其在香料和制药工业生产无氯苯甲醛的实际使用性。在过去十年中,苯甲醛的市场需求量一直在增加,应用纯氧或空气作为氧化剂的苯甲醇氧化反应对环境友好,成为获得“绿色”产物的主要方式之一。目前文献报道的许多均相金属催化剂用于该反应并具有优越的催化性能,然而均相催化剂有很多的缺点,例如催化剂分离困难,在反应中使用一些对环境不友好的氧化剂。随着催化剂制备和分离技术的迅速发展,均相催化剂多相化是解决均相催化剂缺陷的常用方法。因此,开发能够与环境友好的氧化剂一起操作的多相催化系统已经是未来绿色催化的必然趋势。本论文主要研究内容如下:1、高分散性负载型Ni-Co双金属催化剂的制备及其催化氧化苯甲醇性能的研究本论文将采用简单的水热合成法,合成负载型双金属镍钴纳米氧化物催化剂。经XRD、FT-IR、TEM、SEM、N2吸附-脱附、XPS和ICP等表征手段,证实双金属氧化物已经成功的负载到载体FDU-15上,介孔碳材料FDU-15的结构在负载过程中并没有受到破坏。此外,将负载型双金属纳米氧化物材料用于苯甲醇的氧化反应中,在120 ℃的反应温度下,溶剂为DMF、氧化剂为空气,反应7 h,催化剂Ni-Co_3/FDU-15-N的催化效果最佳,催化剂重复使用4次后活性几乎没有损失。2、三维有序介孔氧化钴在苯甲醇的选择性氧化反应中的性能研究以三维有序介孔硅基材料KIT-6为模板,硝酸钴为前驱体,得到具有立方Ia-3d的介孔3D-Co_3O_4催化剂。通过XRD、N2吸附-脱附、TEM、SEM、XPS等表征手段对新制备的介孔催化剂3D-Co_3O_4进行了表征。XRD、N2吸附-脱附等表征结果都说明催化剂3D-Co_3O_4在制备过程已完全除去模板既形成与模板KIT-6结构反向的三维介孔结构。合成的多相催化剂3D-Co_3O_4用于苯甲醇的需氧氧化反应中,与均相商业氧化钴相比,催化效果更优异。使用ICP-AES表征证明合成的催化剂重复使用3次后几乎没有金属损失,有较好的重复利用率。因为催化反应中使用的是空气作氧化剂,完全符合绿色化学的宗旨。
[Abstract]:The catalytic oxidation of benzyl alcohol is an important reaction in modern chemical industry because benzaldehyde is an indispensable intermediate in the synthesis of fine chemicals and drugs. Chlorination hydrolysis is usually used in the traditional industrial production of benzaldehyde. It is not only complicated in process and difficult to separate the products, but also contains trace chlorine in the prepared benzaldehyde, which limits its practical use in producing chlorobenzaldehyde in the perfume and pharmaceutical industries. In the past ten years, the market demand for benzaldehyde has been increasing. The oxidation of benzyl alcohol using pure oxygen or air as oxidant is environmentally friendly and becomes one of the main ways to obtain "green" products. At present, many homogeneous metal catalysts have been reported for the reaction and have excellent catalytic performance. However, homogeneous catalysts have many disadvantages, such as the difficulty of separation of catalysts, and the use of some environmentally friendly oxidants in the reactions. With the rapid development of catalyst preparation and separation technology, homogeneous heterogeneous catalyst is a common method to solve the defects of homogeneous catalyst. Therefore, it is an inevitable trend of green catalysis in the future to develop a heterogeneous catalytic system that can operate with environmentally friendly oxidants. The main contents of this thesis are as follows: 1. Preparation of highly dispersible supported Ni-Co bimetallic catalysts and their catalytic oxidation of benzyl alcohol. By means of XRD,FT-IR,TEM,SEM,N2 adsorption-desorption, XPS and ICP, it was proved that the bimetallic oxides have been successfully loaded on the support FDU-15, and the structure of the mesoporous carbon material FDU-15 has not been destroyed during the loading process. In addition, the supported bimetallic nano-oxide material was used in the oxidation of benzyl alcohol. At 120 鈩，
本文编号：2270785
[Abstract]:The catalytic oxidation of benzyl alcohol is an important reaction in modern chemical industry because benzaldehyde is an indispensable intermediate in the synthesis of fine chemicals and drugs. Chlorination hydrolysis is usually used in the traditional industrial production of benzaldehyde. It is not only complicated in process and difficult to separate the products, but also contains trace chlorine in the prepared benzaldehyde, which limits its practical use in producing chlorobenzaldehyde in the perfume and pharmaceutical industries. In the past ten years, the market demand for benzaldehyde has been increasing. The oxidation of benzyl alcohol using pure oxygen or air as oxidant is environmentally friendly and becomes one of the main ways to obtain "green" products. At present, many homogeneous metal catalysts have been reported for the reaction and have excellent catalytic performance. However, homogeneous catalysts have many disadvantages, such as the difficulty of separation of catalysts, and the use of some environmentally friendly oxidants in the reactions. With the rapid development of catalyst preparation and separation technology, homogeneous heterogeneous catalyst is a common method to solve the defects of homogeneous catalyst. Therefore, it is an inevitable trend of green catalysis in the future to develop a heterogeneous catalytic system that can operate with environmentally friendly oxidants. The main contents of this thesis are as follows: 1. Preparation of highly dispersible supported Ni-Co bimetallic catalysts and their catalytic oxidation of benzyl alcohol. By means of XRD,FT-IR,TEM,SEM,N2 adsorption-desorption, XPS and ICP, it was proved that the bimetallic oxides have been successfully loaded on the support FDU-15, and the structure of the mesoporous carbon material FDU-15 has not been destroyed during the loading process. In addition, the supported bimetallic nano-oxide material was used in the oxidation of benzyl alcohol. At 120 鈩，
本文编号：2270785
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