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催化剂制备方法对Ni-Ag/SiO2催化草酸二甲酯加氢制乙醇酸甲酯性能的影响

方笛 罗祖伟 曹约强 周静红 李伟

方笛, 罗祖伟, 曹约强, 周静红, 李伟. 催化剂制备方法对Ni-Ag/SiO2催化草酸二甲酯加氢制乙醇酸甲酯性能的影响[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024020
引用本文: 方笛, 罗祖伟, 曹约强, 周静红, 李伟. 催化剂制备方法对Ni-Ag/SiO2催化草酸二甲酯加氢制乙醇酸甲酯性能的影响[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024020
FANG Di, LUO Zuwei, CAO Yueqiang, ZHOU Jinghong, LI Wei. Influence of Ni-Ag/SiO2 catalyst preparation method on its performance in hydrogenation of dimethyl oxalate to methyl glycolate[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024020
Citation: FANG Di, LUO Zuwei, CAO Yueqiang, ZHOU Jinghong, LI Wei. Influence of Ni-Ag/SiO2 catalyst preparation method on its performance in hydrogenation of dimethyl oxalate to methyl glycolate[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024020

催化剂制备方法对Ni-Ag/SiO2催化草酸二甲酯加氢制乙醇酸甲酯性能的影响

doi: 10.19906/j.cnki.JFCT.2024020
基金项目: 国家自然科学基金(22178102)资助
详细信息
    通讯作者:

    Tel: 021-64252169, E-mail: jhzhou@ecust.edu.cn

  • 中图分类号: TQ032.4

Influence of Ni-Ag/SiO2 catalyst preparation method on its performance in hydrogenation of dimethyl oxalate to methyl glycolate

Funds: National Natural Science Foundation of China(22178102).
  • 摘要: 本研究采用均匀沉淀-浸渍和浸渍-浸渍两种分步法分别制备了Ni-Ag/SiO2-p和Ni-Ag/SiO2-i两种Ni-Ag双金属催化剂,用于催化草酸二甲酯(DMO)选择性加氢制乙醇酸甲酯(MG)。利用X射线衍射、红外光谱、透射电镜、N2物理吸附、程序升温脱附实验和X射线光电子能谱表征技术对两种催化剂进行了系统的表征和结构解析,发现催化剂的制备方法对双金属催化剂的结构和性能有着重要影响,Ni-Ag/SiO2-p催化剂中由于层状硅酸镍结构的存在,Ag、Ni活性物种的金属分散度相比于Ni-Ag/SiO2-i催化剂更高,这促进了反应物H2和DMO的吸附与活化;催化剂性能评价结果表明,均匀沉淀-浸渍法制备的Ag负载量仅为0.48%的Ni-Ag/SiO2-p催化剂显著提升了DMO加氢活性,在220 ℃、2.0 MPa、液时空速0.5 h-1、氢酯比50的条件下,DMO转化率和MG选择性达到了99.1%和87.6%。研究结果可为设计和优化DMO加氢制MG催化剂提供一定借鉴。
  • 图  1  Ni-Ag/SiO2和Ni/SiO2前驱体的H2-TPR谱图

    Figure  1  H2-TPR profiles of Ni-Ag/SiO2 and Ni/SiO2 precursors

    图  2  SiO2和Ni-Ag/SiO2催化剂的(a)N2物理吸附-脱附等温线及(b)孔径分布图

    Figure  2  (a) N2 physisorption isotherms and (b) corresponding pore size distributions of SiO2 and Ni-Ag/SiO2 catalysts

    图  3  Ni-Ag/SiO2催化剂的(a)XRD谱图和(b)FT-IR谱图

    Figure  3  (a) XRD patterns and (b) FT-IR spectra of Ni-Ag/SiO2 catalysts

    图  4  (a)Ni-Ag/SiO2-p和(b)Ni-Ag/SiO2-i催化剂的TEM图像和金属粒径分布

    Figure  4  TEM images and histograms of metal particle size distribution of (a) Ni-Ag/SiO2-p and (b) Ni-Ag/SiO2-i catalysts

    图  5  还原后Ni-Ag/SiO2催化剂的(a)Ni 2p和(b)Ag 3d XPS谱图

    Figure  5  (a) Ni 2p and (b) Ag 3d XPS spectra of reduced Ni-Ag/SiO2 catalysts

    图  6  Ni-Ag/SiO2催化剂性能

    Figure  6  Catalytic performances of Ni-Ag/SiO2 catalysts Reaction conditions: (a)−(c) 0.5 h−1, 220 ℃, 2.0 MPa; (d)−(f) 0.5 h−1, 220 ℃, 2.0 MPa, H2/DMO = 50 mol/mol.

    图  7  催化剂的(a)H2-TPD 和(b)DMO-TPD谱图

    Figure  7  (a) H2-TPD and (b) DMO-TPD profiles of catalysts

    图  8  Ni-Ag/SiO2催化剂的(a)MG-TPD和(b)CO-TPD谱图

    Figure  8  (a) MG-TPD and (b) CO-TPD profiles of Ni-Ag/SiO2 catalysts

    表  1  SiO2和Ni-Ag/SiO2催化剂的理化特征

    Table  1  Physicochemical properties of SiO2 and Ni-Ag/SiO2 catalysts

    Sample Loadinga w/% SBETb/
    (m2·g−1)
    vporec/
    (cm3·g−1)
    dBJHc/
    nm
    dmetald/
    nm
    QCOe/
    (mmol·g−1)
    $Q_{\Delta {\mathrm{H}}_2} $f/
    (mmol·g−1)
    Ni Ag
    SiO2 248 0.27 3.72
    Ni-Ag/SiO2-p 8.9 0.48 267 0.58 7.86 3.4 0.0041 0.077
    Ni-Ag/SiO2-i 9.3 0.51 173 0.20 3.96 7.6 0.0017 0.026
    a: Ni content and Ag content determined by ICP; b: Specific surface area calculated by BET method; c: Pore volume and pore size calculated by BJH method; d: Average size of metal particles determined by TEM; e: CO adsorption amount was determined by CO-chem; f: H2 consumption of Ag was determined by the difference between the H2 consumption for H2-TPR test after the oxidation by N2O and the CO adsorption amount for CO-Chem.
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  • 收稿日期:  2024-03-10
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