双环戊二烯氢甲酰化固载化催化剂的改性方法研究
尹铎
学位类型硕士
导师高志贤
2015-05-22
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料物理与化学
关键词双环戊二烯 三环癸烷不饱和单醛 三环癸烷二甲醛 铑基催化剂
摘要

双环戊二烯主要来源于石油裂解制乙烯和煤焦化轻苯副产C5 馏分,通过氢甲酰化反应可以合成一系列的高附加值有机中间体,如三环癸烷不饱和单醛、三环癸烷二甲醛等。其进一步催化加氢可得三环癸烷单甲醇、三环癸烷二甲醇。本文综述了烯烃氢甲酰化反应催化剂及其反应工艺,当前烯烃氢甲酰化研究现状及研究热点,以及双环戊二烯氢甲酰化反应的研究进展及现实意义。由此确定了双环戊二烯氢甲酰化反应固载化催化剂的改性方法的研究方向,即催化剂的载体效应和第二组份引入对固载化铑基催化剂的影响研究方向主要内容和结论如下:1. 根据双环戊二烯氢甲酰化反应当前研究现状以及烯烃氢甲酰化催化剂的发展历程,确定了主要研究方向,以无机氧化物为载体,开展铑基催化剂的固载化在以及双环戊二烯氢甲酰化反应中的系统研究。2. 采用浸渍法制备了5 种不同载体即粉体SiO2、颗粒SiO2,粉体Al2O3,颗粒Al2O3,MCM-41 担载的0.1%Rh 催化剂,并将其应用到双环戊二烯氢甲酰化合成三环癸烷不饱和单醛的研究中,研究表明:反应存在一定的诱导期,其中颗粒SiO2 和粉体Al2O3 担载的催化剂具有最短的诱导期,仅有3 min;以粉体SiO2和粉体Al2O3 担载的0.1% Rh 为催化剂,三环癸烷不饱和单醛的选择性高达98.5%。3. 采用浸渍法制备了5 种不同载体即粉体SiO2、颗粒SiO2,粉体Al2O3,颗粒Al2O3,MCM-41 担载的2%Rh 催化剂,并将其应用到合成三环癸烷二甲醛的反应中,结果表明:双环戊二烯的转化率都达到了99%以上,其中以粉体二氧化硅和粉体氧化铝担载的2%Rh 为催化剂催化活性最高,三环癸烷二甲醛的选择性都达到了70%以上;而MCM-41 担载的2%Rh 催化剂,仅得到了8.7%的三环癸烷二甲醛的选择性。4. 采用浸渍法制备了钴改性的粉体SiO2、颗粒SiO2,粉体Al2O3,颗粒Al2O3固载的铑催化剂,并将其应用到双环戊二烯氢甲酰化合成三环癸烷二甲醛的反应中;结果表明:钴的引入不仅可以加快三环癸烷二甲醛的生成速率,而且可以大幅度的提高产物三环癸烷二甲醛的选择性;与铑催化剂相比,引入钴之后,三环癸烷二甲醛的选择性可以提高20%以上,三环癸烷二甲醛的选择性最高可达88.7%。5. 以MCM-41 为载体,三氯化铑为铑源,氯化钴为钴源,采用浸渍法制备了五种MCM-41 担载的铑基催化剂。以双环戊二烯氢甲酰化合成三环癸烷二甲醛为探针反应研究了这五种MCM-41 担载的铑基催化剂的催化性能,以Rh/MCM-41 为催化剂,仅获得了8.7%的三环癸烷二甲醛,而引入钴,即使钴的量只有铑的1/4,三环癸烷二甲醛的选择性可大幅度的提高至76.2%。对催化剂进行了XRD, XPS, TPR, TPD 和 TEM 等方面的表征。结合实验数据和表征数据可得出以下结论:钴的引入,可使得(1)Rh/MCM-41 催化剂的催化活性大大提高,三环癸烷二甲醛的选择性可提高65%以上;(2)催化剂表面的铑含量降低;(3)应当形成了活性远远高于铑的新物种。

其他摘要

Dicyclopentadiene (DCPD) mostly comes from both the C5 fraction by-product of ethylene cracking process and light benzene fraction of the coal-coking process. A series of value-added fine chemicals such as tricyclodecanedimethylol, tricyclodecanedicarboxylic acid and their polyester derivatives will be synthesized with DCPD as the main feed. In this thesis, the practical significance and the recent development of the DCPD hydroformylation, the development of the catalyst and the reaction process of the olefin hydroformylation are reviewed briefly, from which the research ideas of the present work, e.g. the modification of supported catalysts for hydroformylation of DCPD, i.e, the effect of support and the second component on the heterogeneous rhodium based catalysts, are derived. The main contents and conclusions are listed as follows: 1. According to the current research and the development of olefin hydroformylation catalysts. The main research on the catalyst for the hydroformylation is determined. The heterogeneous catalysts were prepared with inorganic oxides as the supports, Rh or Co as the active component. 2. The comparative studies for monoformyltricyclodecenes (MFTD) synthesis by the hydroformylation of DCPD were carried out over 0.1% Rh catalysts supported on five different supports: the powder SiO2, the particle SiO2, the powder Al2O3, the particle Al2O3 and MCM-41, respectively. The results showed that the induction time was found for all the reactions, and the shortest induction time which was found over the catalysts supported on the powder SiO2 and the powder Al2O3, was about 3 minutes. More than 98.5% MFTD selectivity were achieved over the catalysts supported on the powder SiO2 and the powder Al2O3 3. The comparative studies for diformyltricyclodecanes (DFTD) synthesis by the hydroformylation of DCPD were also carried out over the 2%Rh catalysts supported on five different supports: the powder SiO2, the particle SiO2, the powder Al2O3, the particle Al2O3 and MCM-41, respectively. More than 99% DCPD conversion could be reached for the catalysts used. The 2%Rh catalysts supported on the powder SiO2 and the powder Al2O3 had the highest catalytic activities. Up to 70% DFTD selectivity could be obtained over the catalysts supported on the the powder SiO2 and the powder Al2O3, but the selectivity of DFTD was only 8.7% for MCM41. 4. The effect of Co on properties of Rh based catalysts supported on the inorganic oxides were investigated with the synthesis of DFTD by the hydroformylation of DCPD. The data showed that not only the selectivity of DFTD but also the formation rate of DFTD were significantly improved due to the addition of Co. Compared with Rh catalysts, more than 20% DFTD selectivity could be improved, up to 88.7% DFTD selectivity could be reached. 5. Five different Rh catalysts were prepared by the impregnation with MCM41 as the support, rhodium trichloride as the source of rhodium, cobalt chloride as the source of cobalt. These catalysts were evaluated based on their performance for the hydroformylation of DCPD to produce DFTD. While a selectivity of DFTD was only 8.7 % using monometallic Rh/MCM-41 as the catalyst, the selectivity was enhanced to 76.2% at a similar DCPD conversion using bimetallic Co-Rh/MCM-41 catalyst, even when the Co loading was very low(25 mol% relative to Rh). Extensive catalyst characterization including TPR, TPD, XRD, XPS, BET and TEM was performed to study the nature of metal modification on Rh/MCM-41. It was found that modification on the Rh/MCM-41 by Co addition could 1) substantially enhance the selectivity towards DFTD; 2) A lower content of Rh on the surface of MCM-41 was observed; 3) this improvement was likely attributed to the formation of a more reactive Rh species on the catalyst surface. Key words: dicyclopentadiene; monoformyltricyclodecanes; diformyltricyclodecanes rhodium based catalyst; cobalt

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4256
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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尹铎. 双环戊二烯氢甲酰化固载化催化剂的改性方法研究[D]. 北京. 中国科学院大学,2015.
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