化工学报 ›› 2023, Vol. 74 ›› Issue (3): 1082-1091.DOI: 10.11949/0438-1157.20221517

• 催化、动力学与反应器 • 上一篇    下一篇

乙醇制高级醇有序介孔氧化铝负载铜基催化剂研究

何金峰1(), 李秀珍2, 寇建耀1, 陶庭杰1, 余灿1, 刘欢1, 陈永元1, 赵豪健1, 江大好1(), 李小年1   

  1. 1.浙江工业大学工业催化研究所,浙江 杭州 310014
    2.福建润华化工有限公司,福建 南平 354003
  • 收稿日期:2022-11-22 修回日期:2023-02-15 出版日期:2023-03-05 发布日期:2023-04-19
  • 通讯作者: 江大好
  • 作者简介:何金峰(1997—),男,硕士研究生,944458893@qq.com
  • 基金资助:
    浙江省自然科学基金项目(LY19B030007)

Ethanol upgrading to higher alcohols over ordered mesoporous alumina supported Cu-based catalysts

Jinfeng HE1(), Xiuzhen LI2, Jianyao KOU1, Tingjie TAO1, Can YU1, Huan LIU1, Yongyuan CHEN1, Haojian ZHAO1, Dahao JIANG1(), Xiaonian LI1   

  1. 1.Institute of Industrial Catalysis, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
    2.Fujian Runhua Chemical Co. , Ltd. , Nanping 354003, Fujian, China
  • Received:2022-11-22 Revised:2023-02-15 Online:2023-03-05 Published:2023-04-19
  • Contact: Dahao JIANG

摘要:

为了实现乙醇向高级醇的高效转化,以蒸发诱导自组装法合成的有序介孔氧化铝(ordered mesoporous alumina,OMA)为载体制备了系列Cu-La2O3/OMA催化剂,并深入研究了其在乙醇制高级醇反应中的构效关系。在533 K、3 MPa、LHSV=2 ml/(g cat·h)、V(N2)/V(EtOH)=250∶1的反应条件下,最佳的Cu-La2O3/OMA(973)催化剂表现出高达55.5%的乙醇转化率和40.1%的高级醇收率,并且在200 h的连续反应中展现出优异的稳定性。OMA载体表面高度分散的Cu和La2O3活性组分协同OMA载体提供了大量的金属和酸碱中心,同时其较大的介孔孔径有利于降低反应物及产物分子在催化剂孔道中的扩散阻力,从而使得Cu-La2O3/OMA催化剂表现出较高的活性及高级醇选择性。此外,OMA载体表面五配位Al3+通过Cu-O-Al键对Cu活性物种的锚定作用是催化剂具有良好稳定性的重要原因。

关键词: 有序介孔氧化铝, Cu基催化剂, 乙醇, 高级醇

Abstract:

In order to realize highly efficient conversion of ethanol to higher alcohols, a series of Cu-La2O3/OMA catalysts were prepared on the basis of ordered mesoporous alumina (OMA) synthesized by evaporation-induced self-assembly method, and their structure-activity relationships in higher alcohol synthesis reaction were studied in depth. The optimal Cu-La2O3/OMA (973) catalyst exhibited up to 55.5% ethanol conversion and 40.1% yield of higher alcohols under the reaction conditions of 533 K, 3 MPa, LHSV=2 ml/(g cat·h) and V(N2)/V(EtOH)=250∶1. Moreover, it showed excellent stability in 200 h on-stream evaluation. The highly dispersed Cu and La2O3 active components and OMA support afforded large amounts of metal and acid-base sites while OMA support also provided mesoporous channels with larger pore size to reduce the diffusion resistance of the reactants and products, thus resulting in higher ethanol conversion and selectivity to higher alcohols. Additionally, the penta-coordinated Al3+ on the surface of OMA anchored the Cu active species by formation of Cu-O-Al bonds, thus enhancing the stability of the Cu-based catalysts.

Key words: ordered mesoporous alumina, Cu-based catalysts, ethanol, higher alcohols

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