基于亲水性材料包覆的Ru基催化剂的苯部分加氢制备环己烯

发布时间：2018-02-13 11:57

  本文关键词： 环己烯 亲水性 包覆 苯部分加氢 钌基催化剂　出处：《华东理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：作为一种重要的有机合成中间体,环己烯具有较为活泼的C=C双键,通过传统水合等反应可以制得环己醇、己二酸与己内酰胺等工业原料。苯部分加氢制备环己烯工艺具有操作简便、反应路线简单、原料来源广泛等优点,备受工业界青睐。然而在实际的反应过程中,苯更倾向于发生深度加氢得到环己烷,而不是仅仅停留在中间产物环己烯阶段。催化剂的设计在苯部分加氢过程中由此特别重要,其中催化剂表面的亲水性更是发挥着关键作用。本研究从提高Ru基催化剂的亲水性角度出发,首先通过氢气还原法制备微米尺度的Ru颗粒,并在其表面包覆亲水性材料Si02和Zr02。根据苯部分加氢性能评价发现环己烯的收率较纯Ru颗粒分别最高提高了约25.0和20.0%。在此过程中考察了亲水性前驱体正硅酸乙酯(TEOS)、正丁醇锆(TBOZ)添加量对催化剂部分加氢性能的影响以及苯部分加氢的最优操作条件。实验结果表明,Si02包覆Ru基催化剂的最优反应条件为6MPa、150℃、1000rpm、和225μL的TEOS加入量,而ZrO_2包覆Ru基催化剂最优反应条件为6MPa、160℃、1000rpm、和225 μL的TBOZ加入量。通过实验证实,亲水材料在Ru颗粒表面构建的滞留水膜对于提高环己烯的选择性具有关键作用,其可能作用机理在于抑制了环己烯在滞留水膜中的扩散。对同批及不同批亲水性材料包覆的Ru催化剂的重复性能进行表征发现,催化剂的重复效果良好,具有良好的工业应用前景。
[Abstract]:As an important intermediate of organic synthesis, cyclohexene has a more active C-C bond. Cyclohexanol can be synthesized by traditional hydration reaction. Industrial raw materials such as adipic acid and caprolactam. The process of partial hydrogenation of benzene to cyclohexene has the advantages of simple operation, simple reaction route, wide source of raw materials and so on. Benzene is more inclined to produce cyclohexane by deep hydrogenation than at the intermediate product cyclohexene stage. The design of the catalyst is particularly important in the partial hydrogenation of benzene. In order to improve the hydrophilicity of Ru based catalysts, micron Ru particles were prepared by hydrogen reduction method. The hydrophilic materials Si02 and Zr02.According to the evaluation of partial hydrogenation of benzene, it was found that the yield of cyclohexene was increased by 25.0 and 20.0 than that of pure Ru, respectively. In the process, the hydrophilic precursor tetraethyl orthosilicate (TEOS) was investigated. The effect of the amount of n-butanol zirconium butanol (TBOZ) on the partial hydrogenation performance of the catalyst and the optimum operating conditions for the partial hydrogenation of benzene were investigated. The experimental results showed that the optimum reaction conditions of SiO2 coated Ru based catalyst were as follows: 6MPA 150 鈩，

本文编号：1508105