Hydroformylation of 1-Octene over Nanotubular TiO2-supported Amorphous Co-B Catalysts  

作　　者：SHI Yukun HU Xiaojing ZHU Baolin ZHANG Shoumin HUANG Weiping 

机构地区：[1]Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, The Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Tianjin Key Lab of Metal and Molecule-based Material Chemistry, Nankai University, Tianjin 300071, P. R. China

出　　处：《Chemical Research in Chinese Universities》2015年第5期851-857,共7页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（Nos.21373120, 21301098, 21071086, 21271110）, the National ＂111＂ Project of China＇s Higher Education（No.B 12015）, the Applied Basic Research Programs of Science and Technology Commission Foundation ofTianjin, China（Nos.13JCQNJC02000, 12JCYBJC13100）.

摘　　要：TiO2 nanotubes supported amorphous Co-B（Co-B/TNTs） catalyst was prepared via impregnation- chemical reduction procedure. The catalyst was characterized with transmission electron microscopy（TEM）, ammonia temperature-programmed desorption（NH3-TPD）, thermogravimetry-differential thermal analysis（TG-DTA）, Fourier transform infrared spectroscopy（FTIR） and Raman spectroscopy. The effects of temperature and ratio of CO to HE on the hydroformylation of 1-octene were studied. At an optimized reaction temperature（150 ℃） and volume ratio of CO to H2（2：1）, the conversion of 1-octene can reach 97.4% with a selectivity of 23.1% for total aldehydes and n/i-aldehyde molar ratio of 40：60. To obtain higher selectivity for linear aldehydes, Co-B/TNTs modified with triphenylphosphine for the hydroformylation of 1-octene were investigated. When molar ratio of P/Co was 4, the yield of total aldehydes was the highest（31.6%） with a good selectivity for linear product（n/i-aldehyde molar ratio was 70：30）. In recycle use, the Co-B/TNTs catalyst modified with triphenylphosphine could be reused five times without reducing the activity and selectivity obviously. For a comparative study, all the Co-B/TNTs to catalyze the hydroformylation of other olefins exhibited high conversion under the optimized conditions.TiO2 nanotubes supported amorphous Co-B（Co-B/TNTs） catalyst was prepared via impregnation- chemical reduction procedure. The catalyst was characterized with transmission electron microscopy（TEM）, ammonia temperature-programmed desorption（NH3-TPD）, thermogravimetry-differential thermal analysis（TG-DTA）, Fourier transform infrared spectroscopy（FTIR） and Raman spectroscopy. The effects of temperature and ratio of CO to HE on the hydroformylation of 1-octene were studied. At an optimized reaction temperature（150 ℃） and volume ratio of CO to H2（2：1）, the conversion of 1-octene can reach 97.4% with a selectivity of 23.1% for total aldehydes and n/i-aldehyde molar ratio of 40：60. To obtain higher selectivity for linear aldehydes, Co-B/TNTs modified with triphenylphosphine for the hydroformylation of 1-octene were investigated. When molar ratio of P/Co was 4, the yield of total aldehydes was the highest（31.6%） with a good selectivity for linear product（n/i-aldehyde molar ratio was 70：30）. In recycle use, the Co-B/TNTs catalyst modified with triphenylphosphine could be reused five times without reducing the activity and selectivity obviously. For a comparative study, all the Co-B/TNTs to catalyze the hydroformylation of other olefins exhibited high conversion under the optimized conditions.

关 键 词：HYDROFORMYLATION TiO2 nanotubes Amorphous Co-B 1-OCTENE 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业] O623.12[理学—有机化学]