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高等学校化学研究 ›› 2015, Vol. 31 ›› Issue (5): 851-857.doi: 10.1007/s40242-015-5002-9

• Articles • 上一篇    下一篇

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

SHI Yukun, HU Xiaojing, ZHU Baolin, ZHANG Shoumin, HUANG Weiping   

  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
  • 收稿日期:2015-01-04 修回日期:2015-04-03 出版日期:2015-10-01 发布日期:2015-05-18
  • 通讯作者: HUANG Weiping, E-mail: hwp914@nankai.edu.cn E-mail:hwp914@nankai.edu.cn
  • 基金资助:

    Supported by the National Natural Science Foundation of China(Nos.21373120, 21301098, 21071086, 21271110), the National "111" Project of China's Higher Education(No.B12015), the Applied Basic Research Programs of Science and Technology Commission Foundation of Tianjin, China(Nos.13JCQNJC02000, 12JCYBJC13100).

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

SHI Yukun, HU Xiaojing, ZHU Baolin, ZHANG Shoumin, HUANG Weiping   

  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
  • Received:2015-01-04 Revised:2015-04-03 Online:2015-10-01 Published:2015-05-18
  • Contact: HUANG Weiping, E-mail: hwp914@nankai.edu.cn E-mail:hwp914@nankai.edu.cn
  • Supported by:

    Supported by the National Natural Science Foundation of China(Nos.21373120, 21301098, 21071086, 21271110), the National "111" Project of China's Higher Education(No.B12015), the Applied Basic Research Programs of Science and Technology Commission Foundation of Tianjin, China(Nos.13JCQNJC02000, 12JCYBJC13100).

摘要:

TiO2 nanotubes supported amorphous Co-B(Co-B/TNTs) catalyst was prepared via impregnationchemical 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 H2 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

Abstract:

TiO2 nanotubes supported amorphous Co-B(Co-B/TNTs) catalyst was prepared via impregnationchemical 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 H2 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.

Key words: Hydroformylation, TiO2 nanotubes, Amorphous Co-B, 1-Octene