Ni基催化剂在二甘醇和叔丁胺胺化反应中的研究

发布时间：2018-05-21 17:44

  本文选题：二甘醇 + 叔丁胺　； 参考：《吉林大学》2017年硕士论文

【摘要】：天然气中通常含有CO_2、H_2S和有机硫化合物,这三者又通称为酸性气体。其中H_2S在运输和存储的过程当中会使存储设备和运输管道发生腐蚀,而且H_2S燃烧之后产生的气体会严重污染空气环境。叔丁氨基乙氧基乙醇(TBEE)具有空间位阻的效应,这种效应可以让氨基表现出更高的化学活性,是一种非常有效的选择性脱硫溶剂。被广泛应用在石油、油田伴生气、天然气以及合成气等气体的选择性脱硫。现在有关其合成工艺的报道很少,其合成方法和相应的催化剂体系需进行深入研究。本论文选择通过二甘醇和叔丁胺胺化反应合成TBEE,针对该反应的特点设计制备了一系列Ni基催化剂,在间歇釜式反应体系中考察了催化剂在二甘醇和叔丁胺胺化反应中的催化性能,并优化了反应条件。同时结合反应结果和多种表征手段,研究了催化剂的结构、活性组分以及酸碱性等在催化剂反应体系中所起的作用。还考察了催化剂的制备条件对催化性能的影响。论文的主要工作如下:(1)针对二甘醇和叔丁胺的胺化反应,对催化剂的活性组分进行了筛选,并考察了反应温度、压强、溶剂、转速等反应条件对催化剂催化反应性能的影响。结果表明,以Ni为催化剂的主要组分,反应温度为200℃,转速为400r/min,H_2压强为0.5MPa,原料摩尔比TBA:DEG为2:1,无溶剂时,催化剂有较好的催化性能。(2)采用共沉淀法制备了一系列的Ni-Al_2O_3催化剂,考察了Ni/Al、焙烧温度和还原温度对二甘醇和叔丁胺胺化反应合成TBEE的影响。结果表明,共沉淀法制备的Ni-Al_2O_3催化剂,Ni/Al为1:1,在450℃焙烧和550℃还原时,催化剂表现出较高的活性和选择性。结合相关表征和催化性能结果,金属Ni颗粒(Ni0)是反应的活性中心,并且催化剂的酸-碱中心在提高催化剂的活性和选择性方面发挥着协同作用。(3)对Ni-Al_2O_3催化剂的制备条件(如Ni含量、沉淀剂、合成温度和沉淀方法)进行了进一步优化,并考察了合成条件以及反应时间对催化剂的胺化反应性能的影响。结果表明,催化剂制备条件对催化剂的结构性质及催化反应性能有较大影响。最适宜的制备条件为,Ni含量为20%,以Na2CO3为沉淀剂,合成温度为80℃,在最佳的反应条件下反应6h,催化剂有较好的反应性能。
[Abstract]:Natural gas usually contains CO _ 2H _ 2S and organic sulfur compounds, which are also known as acid gases. In the process of transportation and storage of H2S, the storage equipment and transportation pipeline will be corroded, and the gas produced after the combustion of H2S will pollute the air environment seriously. Tert-butylamino ethoxy ethanol (TBEE) has the effect of steric hindrance which can make amino show higher chemical activity and is a very effective solvent for selective desulfurization. It is widely used in selective desulfurization of petroleum, oil field associated gas, natural gas and syngas. At present, there are few reports about the synthesis process, and the synthesis method and the corresponding catalyst system need to be deeply studied. In this paper, a series of Ni-based catalysts were designed and prepared by the reaction of diethylene glycol and tert-butylamination to synthesize TBEE. in accordance with the characteristics of the reaction, a series of Ni based catalysts were prepared. The catalytic performance of the catalyst in diethylene glycol and tert-butylamination was investigated in the batch reactor system, and the reaction conditions were optimized. At the same time, combined with the reaction results and various characterization methods, the role of catalyst structure, active components, acid and basic in the catalyst reaction system was studied. The effect of preparation conditions on the catalytic performance was also investigated. The main work of this paper is as follows: (1) for the amination of diethylene glycol and tert-butylamine, the active components of the catalyst were screened, and the effects of reaction temperature, pressure, solvent and rotational speed on the catalytic performance of the catalyst were investigated. The results showed that a series of Ni-Al_2O_3 catalysts were prepared by coprecipitation method with Ni as the main component, reaction temperature at 200 鈩，

本文编号：1920158