物理化学学报 >> 2017, Vol. 33 >> Issue (11): 2301-2309.doi: 10.3866/PKU.WHXB201705261

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无额外供氢体下负载型MoFeOx催化剂催化甘油制丙烯醇

兰海1,2,肖熙1,2,袁善良1,2,张彪1,周桂林3,蒋毅1,*()   

  1. 1 中国科学院成都有机化学研究所,成都610041
    2 中国科学院大学,北京100049
    3 重庆工商大学,环境与资源学院,材料科学与工程系,催化与功能有机分子重庆市重点实验室,重庆400067
  • 收稿日期:2017-04-19 发布日期:2017-08-25
  • 通讯作者: 蒋毅 E-mail:yjiang@cioc.ac.cn
  • 基金资助:
    中国科学院“西部之光”项目

MoFeOx-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors

Hai LAN1,2,Xi XIAO1,2,Shan-Liang YUAN1,2,Biao ZHANG1,Gui-Lin ZHOU3,Yi JIANG1,*()   

  1. 1 Chengdu Institute of Organic Chemistry, Chinese Academy of Science, Chengdu 610041, P. R. China
    2 University of Chinese Academy of Science, Beijing 100049, P. R. China
    3 Chongqing Key Laboratory of Catalysis & Environmental New Materials, Department of Materials Science and Engineering, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, P. R. China
  • Received:2017-04-19 Published:2017-08-25
  • Contact: Yi JIANG E-mail:yjiang@cioc.ac.cn
  • Supported by:
    CAS "light of West China" Program 2015

摘要:

采用浸渍法制备MoFe/XX=SnO2,ZrO2,CeO2,TiO2,CNTs,MgO)以及MoFe氧化物催化剂用于甘油气-固相催化转化制丙烯醇。通过XRD、BET、XPS、H2-TPR和NH3-TPD表征,MoFe主要由晶相Fe2O3和Fe2(MoO43组成而MoFe/X主要为高分散态的Fe、Mo氧化物(Fe3+、Mo6+),其表面均只存在弱酸中心;所采用载体由于自身性质(比表面积和酸碱性)差异与Mo、Fe氧化物之间存在不同的相互作用,进而有效地调控了MoFe/X的表面弱酸强度、酸浓度和可还原性能。所制备催化剂对甘油制丙烯醇的催化性能(收率)依次为:MoFe/TiO2 > MoFe/CeO2 > MoFe/ZrO2 > MoFe/CNTs >> MoFe/SnO2 > MoFe >> MoFe/MgO。340℃时,MoFe/TiO2上甘油的转化率达到83.4%,丙烯醇的选择性和收率分别达到26.7%和22.3%;同时其展现出优于MoFe/CeO2、MoFe/ZrO2和MoFe/CNTs的稳定性。甘油转化率与催化剂表面弱酸中心浓度呈正相关性,而丙烯醇的生成则与氧化中心(非酸中心)密切相关。甘油转化率和丙烯醇选择性在MoFe/X上随反应温度变化而呈现相悖的变化趋势。

关键词: Fe-Mo氧化物催化剂, TiO2, 气固多相催化, 甘油, 丙烯醇

Abstract:

Supported MoFe/X (X=SnO2, ZrO2, CeO2, TiO2, CNTs (Carbon nano-tubes)), MgO and MoFe oxide catalysts were prepared for use in the catalytic conversion of glycerol to allyl alcohol. The prepared catalysts were characterized by XRD, BET, XPS, H2-TPR, and NH3-TPD. The results showed that Fe and Mo oxides with high chemical value (Fe3+ and Mo6+) predominated in MoFe/X MoFe oxide catalysts, which exhibited only weakly acidic properties. The applied supports with different physicochemical characteristics showed distinct interactions with Mo and Fe oxides, modifying the concentration of surface weak acid site, acid strength, and reducibility of MoFe/X oxide catalysts. The catalysts, based on their catalytic performance for glycerol conversion to allyl alcohol, can be ranked in terms of allyl alcohol yield as MoFe/TiO2 > MoFe/CeO2 > MoFe/ZrO2 > MoFe/CNTs >> MoFe/SnO2 > MoFe >> MoFe/MgO. Over the MoFe/TiO2, a maximum allyl alcohol yield of 22.3% was from glycerol conversion of 83.4%, which had a selectivity of 26.7%. The MoFe/TiO2 also showed higher catalytic stability than the MoFe/CeO2, MoFe/ZrO2, and MoFe/CNTs oxide catalysts. The glycerol conversion showed positive relationship with the surface weak acid concentration of MoFe and MoFe/X catalysts, while the allyl alcohol was produced over the redox sites (non-acid sites) of catalysts. With increasing reaction temperature, the glycerol conversion increased, while the allyl alcohol selectivity decreased, over the MoFe/X oxide catalysts.

Key words: Fe-Mo oxide catalysts, TiO2, Gas-solid heterogeneous catalysis, Glycerol, Allyl alcohol

MSC2000: 

  • O643