【摘要】：在現(xiàn)代化學(xué)工業(yè)中苯甲醇的催化氧化是一類重要的反應(yīng),因為所制備的產(chǎn)物苯甲醛是精細(xì)化學(xué)品和藥物合成不可或缺的中間體。傳統(tǒng)生產(chǎn)苯甲醛的工業(yè)方法通常使用氯化水解法,不僅工藝復(fù)雜,產(chǎn)物分離困難,制備的苯甲醛含有痕量的氯,限制其在香料和制藥工業(yè)生產(chǎn)無氯苯甲醛的實際使用性。在過去十年中,苯甲醛的市場需求量一直在增加,應(yīng)用純氧或空氣作為氧化劑的苯甲醇氧化反應(yīng)對環(huán)境友好,成為獲得“綠色”產(chǎn)物的主要方式之一。目前文獻(xiàn)報道的許多均相金屬催化劑用于該反應(yīng)并具有優(yōu)越的催化性能,然而均相催化劑有很多的缺點,例如催化劑分離困難,在反應(yīng)中使用一些對環(huán)境不友好的氧化劑。隨著催化劑制備和分離技術(shù)的迅速發(fā)展,均相催化劑多相化是解決均相催化劑缺陷的常用方法。因此,開發(fā)能夠與環(huán)境友好的氧化劑一起操作的多相催化系統(tǒng)已經(jīng)是未來綠色催化的必然趨勢。本論文主要研究內(nèi)容如下:1、高分散性負(fù)載型Ni-Co雙金屬催化劑的制備及其催化氧化苯甲醇性能的研究本論文將采用簡單的水熱合成法,合成負(fù)載型雙金屬鎳鈷納米氧化物催化劑。經(jīng)XRD、FT-IR、TEM、SEM、N2吸附-脫附、XPS和ICP等表征手段,證實雙金屬氧化物已經(jīng)成功的負(fù)載到載體FDU-15上,介孔碳材料FDU-15的結(jié)構(gòu)在負(fù)載過程中并沒有受到破壞。此外,將負(fù)載型雙金屬納米氧化物材料用于苯甲醇的氧化反應(yīng)中,在120 ℃的反應(yīng)溫度下,溶劑為DMF、氧化劑為空氣,反應(yīng)7 h,催化劑Ni-Co_3/FDU-15-N的催化效果最佳,催化劑重復(fù)使用4次后活性幾乎沒有損失。2、三維有序介孔氧化鈷在苯甲醇的選擇性氧化反應(yīng)中的性能研究以三維有序介孔硅基材料KIT-6為模板,硝酸鈷為前驅(qū)體,得到具有立方Ia-3d的介孔3D-Co_3O_4催化劑。通過XRD、N2吸附-脫附、TEM、SEM、XPS等表征手段對新制備的介孔催化劑3D-Co_3O_4進(jìn)行了表征。XRD、N2吸附-脫附等表征結(jié)果都說明催化劑3D-Co_3O_4在制備過程已完全除去模板既形成與模板KIT-6結(jié)構(gòu)反向的三維介孔結(jié)構(gòu)。合成的多相催化劑3D-Co_3O_4用于苯甲醇的需氧氧化反應(yīng)中,與均相商業(yè)氧化鈷相比,催化效果更優(yōu)異。使用ICP-AES表征證明合成的催化劑重復(fù)使用3次后幾乎沒有金屬損失,有較好的重復(fù)利用率。因為催化反應(yīng)中使用的是空氣作氧化劑,完全符合綠色化學(xué)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，

本文編號：2270785