铜基甲醛乙炔化催化剂活性铜物种的形成及炔化性能研究

发布时间：2018-05-25 19:02

  本文选题：甲醛乙炔化 + 活性铜物种　； 参考：《山西大学》2014年硕士论文

【摘要】：1,4-丁炔二醇是一种重要的有机化工原料,向下游延伸可得到1,4-丁二醇等一系列高附加值的重要化学品。工业上,合成1,4-丁炔二醇采用以CuO-Bi2O3为催化剂的甲醛乙炔化工艺。目前我国已建成了多套1,4-丁炔二醇装置,但核心技术炔化催化剂一直被国外所垄断,亟待研究开发具有我国自主知识产权的炔化催化剂。本工作采用共沉淀法制备了CuO-Bi2O3/SiO2-MgO炔化催化剂,对比研究了不同活化过程对CuO-Bi2O3/SiO2-MgO催化剂活性铜物种形成及炔化性能的影响；在此基础上,进一步考察了CuO晶粒尺寸及CUO-Bi2O3间相互作用对无载体CuO-Bi2O3炔化催化剂在活化过程中活性铜物种形成及炔化性能的影响,探讨了CuO存在形式及Bi203的助剂作用与催化剂炔化性能间的内在关联。主要研究结果如下：1、采用共沉淀法制备了CuO-Bi2O3/SiO2-MgO炔化催化剂,对比研究了催化剂先甲醛还原获得Cu20,后在乙炔存在下活化(过程Ⅰ)和甲醛/乙炔同时存在下活化(过程Ⅱ)两个过程中CuO物种的转变规律。结果表明,经过程Ⅱ活化的催化剂表现出高的炔化反应性能,而经过程Ⅰ活化后,催化剂炔化反应性能较差。通过对过程Ⅰ中间物种Cu20存在形式的表征发现,造成这一结果的原因可能是过程Ⅰ的甲醛还原导致Cu20晶粒尺寸长大,从而使炔化亚铜活性中心数量减少。2、除铜物种晶粒尺寸外,CuO与Bi2O3间相互作用也可能是影响催化剂炔化性能的重要因素。借鉴第一部分的研究结果与方法,以无载体的CuO-Bi2O3炔化催化剂为研究对象,通过研究具有不同CuO晶粒尺寸及CuO-Bi2O3间相互作用的CuO-Bi2O3催化剂在甲醛乙炔化活化过程中活性铜物种形成以及由此引起的催化剂炔化性能的变化规律,探讨了CuO晶粒尺寸及CuO-Bi2O3间相互作用对催化剂炔化性能的影响。结果表明,除CuO晶粒尺寸外,CuO与Bi203间相互作用也是影响催化剂炔化性能的重要因素。CuO晶粒尺寸低于36 nm,CuO-Bi2O3b间具有适宜相互作用时,在甲醛乙炔活化过程中CuO被有效转变为炔化亚铜活性物种,表现出较高的炔化反应性能。当CuO晶粒尺寸进一步增大,CuO-Bi2O3间表现出强相互作用,形成CuBi2O4固溶体时,阻碍了铜物种向铜炔化活性物种的转变,导致催化剂炔化性能降低。
[Abstract]:1-butynediol is an important organic chemical raw material, and a series of important chemicals with high added value can be obtained by extending downstream. In the industrial synthesis of 1,4-butynediol, formaldehyde acetylene was synthesized by using CuO-Bi2O3 as catalyst. At present, many sets of 1 / 4-butynediol units have been built in China, but the core technology of acetylene catalyst has been monopolized by foreign countries, so it is urgent to research and develop acetylene catalyst with our own intellectual property rights. In this work, CuO-Bi2O3/SiO2-MgO catalyst was prepared by coprecipitation method, and the effects of different activation processes on the formation of active copper species and acetylene properties of CuO-Bi2O3/SiO2-MgO catalyst were studied. The effects of CuO grain size and CUO-Bi2O3 interaction on the formation of active copper species and the acetylene properties of unsupported CuO-Bi2O3 catalyst during activation were investigated. The relationship between the form of CuO and the auxiliaries of Bi203 and the catalytic activity of the catalyst was discussed. The main results are as follows: 1. CuO-Bi2O3/SiO2-MgO acetylene catalyst was prepared by coprecipitation method. The transformation of CuO species in the presence of acetylene (process I) and formaldehyde / acetylene (process II) in the presence of acetylene was studied. The results showed that the catalyst activated by Cheng 鈪，

本文编号：1934315