不同载体担载的铑催化剂在双环戊二烯氢甲酰化反应中的对比研究  

Comparative study of Rh catalysts supported on various supports for hydroformylation of dicyclopentadiene

作　　者：尹铎[1,2] 马昱博[1] 高志贤[1,3] 李娜娜[1,2] 吾满江·艾力[1] 

机构地区：[1]中国科学院新疆理化技术研究所,精细化工工程中心,新疆乌鲁木齐830026 [2]中国科学院大学,北京100049 [3]中国科学院山西煤炭化学研究所,山西太原030001

出　　处：《天然气化工—C1化学与化工》2014年第5期27-30,共4页Natural Gas Chemical Industry

基　　金：国家基金委-新疆联合基金重点项目(U1139302);中国科学院西部之光项目(XBBS201114);乌鲁木齐市科技局重点项目(Y121120006)

摘　　要：以粉体SiO2、颗粒SiO2、粉体Al2O3、颗粒Al2O3、MCM-41担载的0.1%Rh(以质量分数表示,下同)催化剂对双环戊二烯(DCPD)氢甲酰化合成三环癸烷不饱和单醛(MFTD)进行了对比研究,其中颗粒SiO2和粉体Al2O3具有最短的诱导期,仅有3min;以粉体SiO2和粉体Al2O3担载的0.1%Rh为催化剂,可取得高达98.5%三环癸烷不饱和单醛的选择性;因此,较合适的高效合成三环癸烷不饱和单醛的载体为粉体二氧化硅和粉体氧化铝。以粉体SiO2、颗粒SiO2、粉体Al2O3、颗粒Al2O3、MCM-41担载的2%Rh催化剂对双环戊二烯氢甲酰化合成三环癸烷二甲醛(DFTD)进行了对比研究,双环戊二烯的转化率都达到了100%,其中以粉体SiO2和粉体Al2O3担载的2%Rh为催化剂,三环癸烷二甲醛的选择性达到了70%以上;在2h的反应时间内,所有的催化剂催化合成三环癸烷二甲醛的反应进行的都比较快,但是仅有粉体SiO2担载的2%Rh催化剂在后续的反应时间里,展示了相对强劲的催化活性,在12h的反应时间里,三环癸烷二甲醛的选择性可以达到91%,因此,较合适的高效合成三环癸烷二甲醛的载体为粉体SiO2。A comparative study for synthesis of monoformyltricyclo [5.2.1.02,6]dec-3-ene （MFTD） by hydroformylation of dicyclopentadiene （DCPD） was carried out over the 0.1% Rh catalysts supported on the powder SiO2, the particle SiO2, the powder Al2O3, the particle Al2O3 and MCM-41, respectively. The results indicated that the powder SiO2 and the powder Al2O3 were the appropriate supports for MFTD synthesis, as the catalysts using them as supports had a short induction time of 3 minutes and high MFTD selectivity of up to 98.5% . A comparative study for synthesis of diformyltricyclodecane （DFTD） by hydroformylation of dicyclopentadiene was also carried out over the 2% Rh catalysts supported on the supports as used for above 0.1% Rh catalysts. The results showed that 100% DCPD conversion could be reached for all the catalysts, and DFTD selectivities of above 70% could be obtained for the catalysts supported on the powder SiO2 and the powder Al2O3. A fast reaction rate for DFTD synthesis within 2 hour reaction time were observed for all the catalysts, but only 2% Rh supported on the powder SiO2 showed a sustainable catalytic performance in all the reaction time and a DFTD selectivity of up to 91% could be achieved with it in 12 hour reaction. So, the powder SiO2 was the appropriate support for DFTD synthesis.

关 键 词：双环戊二烯 氢甲酰化 三环癸烷不饱和单醛 三环癸烷二甲醛 催化剂 载体 

分 类 号：TQ426[化学工程] O643[理学—物理化学]