化工学报 ›› 2016, Vol. 67 ›› Issue (4): 1313-1323.DOI: 10.11949/j.issn.0438-1157.20151221

• 催化、动力学与反应器 • 上一篇    下一篇

载体改性对Cu/B/Al2O3结构及其催化醋酸仲丁酯加氢性能的影响

孙培永1, 贾长斌1,2, 罗学清1, 张胜红1, 姚志龙1   

  1. 1. 北京石油化工学院化学工程学院, 恩泽生物质精细化工北京市重点实验室, 北京 102617;
    2. 北京化工大学化学工程学院, 北京 100029
  • 收稿日期:2015-07-29 修回日期:2015-11-17 出版日期:2016-04-05 发布日期:2016-04-05
  • 通讯作者: 张胜红
  • 基金资助:

    北京市自然科学基金项目(2154048);北京市属高等学校高层次人才引进与培养计划项目(长城学者: CIT&TCD 20150316)。

Effects of support modifications on catalyst structure and catalytic performance for hydrogenation of sec-butyl acetate over Cu/B/Al2O3 catalyst

SUN Peiyong1, JIA Changbin1,2, LUO Xueqing1, ZHANG Shenghong1, YAO Zhilong1   

  1. 1. Beijing Key Laboratory of Enze Biomass Fine Chemicals, College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China;
    2. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2015-07-29 Revised:2015-11-17 Online:2016-04-05 Published:2016-04-05
  • Supported by:

    supported by the Natural Science Foundation of Beijing (2154048) and the Changcheng Scholars Program of Beijing (CIT&TCD 20150316).

摘要:

以γ-Al2O3为载体采用分步浸渍法制备了不同金属氧化物进行载体改性的Cu/B/M/Al2O3(M=Mg,Ca,Ni)催化剂,并测试了其催化醋酸仲丁酯加氢反应的性能。结果表明,以NiO进行载体改性的催化剂导致酯加氢反应中大量酸催化产物及烃类出现;以MgO进行载体改性不利于金属Cu的分散且催化剂的结构稳定性较差;以CaO对γ-Al2O3载体进行改性不仅能够促进金属Cu的分散,提高催化剂的酯加氢活性和产物选择性,而且可以有效减少反应中非活性碳物种在催化剂表面的沉积。

关键词: 催化, 加氢, 载体改性, 铜, 醋酸仲丁酯, 仲丁醇

Abstract:

Cu-based catalysts(Cu/B/M/Al2O3, M = Mg, Ca, Ni)supported on the modified γ-Al2O3 by incorporating MgO, CaO or NiO were prepared by an incipient wetness impregnation method, of which each active component was solely deposited on support. The catalysts were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), NH3 temperature-programmed desorption(NH3-TPD), H2 temperature-programmed reduction(H2-TPR)and X-ray photoelectron spectroscopy(XPS)techniques. It showed that effects of the modifications of γ-Al2O3 support with varied metal oxides on the structure of Cu-based catalysts and the catalytic performances for the hydrogenation of sec-butyl acetate(SBA)were significant. NiO-modified catalysts exhibited dramatic increases in the yields of both ethyl acetate and butane, due to the intrinsic activity of Ni metal for alkene hydrogenation and the acidic support beneficial to transesterification and sec-butanol dehydration, while the modification with MgO resulted in a poor dispersion of Cu metal on support and an inferior catalyst stability for the SBA hydrogenation. For above two catalysts, the modification of NiO or MgO was conducted after loading B2O3 and Cu precursors on support. On the contrary, the modification with CaO was done before loading B2O3 and Cu precursors, which facilitated the Cu dispersion on support and improved both SBA conversions and the selectivity to sec-butanol. Moreover, formation and accumulation of non-reactive carbonaceous species on the surface of CaO-modified catalyst might be effectively minimized.

Key words: catalysis, hydrogenation, support modification, copper, sec-butyl acetate, sec-butanol

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