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铌元素改性V2O5-WO3/TiO2催化剂降低脱硝过程 SO2 的氧化率

王博 边瑶 封硕 王少奇 沈伯雄

王博, 边瑶, 封硕, 王少奇, 沈伯雄. 铌元素改性V2O5-WO3/TiO2催化剂降低脱硝过程 SO2 的氧化率[J]. 燃料化学学报(中英文), 2022, 50(4): 503-512. doi: 10.1016/S1872-5813(21)60177-9
引用本文: 王博, 边瑶, 封硕, 王少奇, 沈伯雄. 铌元素改性V2O5-WO3/TiO2催化剂降低脱硝过程 SO2 的氧化率[J]. 燃料化学学报(中英文), 2022, 50(4): 503-512. doi: 10.1016/S1872-5813(21)60177-9
WANG Bo, BIAN Yao, FENG Shuo, WANG Shao-qi, SHEN Bo-xiong. Modification of the V2O5-WO3/TiO2 catalyst with Nb to reduce its activity for SO2 oxidation during the selective catalytic reduction of NOx[J]. Journal of Fuel Chemistry and Technology, 2022, 50(4): 503-512. doi: 10.1016/S1872-5813(21)60177-9
Citation: WANG Bo, BIAN Yao, FENG Shuo, WANG Shao-qi, SHEN Bo-xiong. Modification of the V2O5-WO3/TiO2 catalyst with Nb to reduce its activity for SO2 oxidation during the selective catalytic reduction of NOx[J]. Journal of Fuel Chemistry and Technology, 2022, 50(4): 503-512. doi: 10.1016/S1872-5813(21)60177-9

铌元素改性V2O5-WO3/TiO2催化剂降低脱硝过程 SO2 的氧化率

doi: 10.1016/S1872-5813(21)60177-9
基金项目: 国家自然科学基金(U20A20302), 天津市重点研发项目(19ZXZSN00050,19ZXSZSN00070), 河北省重点研发项目(20373701D)和河北省重大科技攻关项目(21283701Z)资助
详细信息
    通讯作者:

    E-mail: shenbx@hebut.edu.cn

  • 中图分类号: X51;TQ42

Modification of the V2O5-WO3/TiO2 catalyst with Nb to reduce its activity for SO2 oxidation during the selective catalytic reduction of NOx

Funds: The project was supported by Joint Funds of the National Natural Science Foundation of China (U20A20302), Key R & D Projects in Tianjin (19ZXSZSN00050, 19ZXSZSN00070), Key R & D projects in Hebei Province (20373701D), and Project of Great Transformation of Scientific and Technical Research in Hebei Province (21283701Z).
  • 摘要: 本文采用浸渍法制备了Nb改性的V2O5-WO3/TiO2催化剂,研究了脱硝反应中Nb负载量对催化剂SO2氧化活性的影响。结果表明,在350 °C下,Nb2O5负载量为2%的Nb2O5-V2O5-WO3/TiO2催化剂上的SO2氧化率最低(0.6%),而同时NOx 的转化率仍能达到95%。采用TGA、氮吸附、XRD、H2-TPR、CO2-TPD、XPS和in- situ DRIFTS等对催化剂进行了表征分析,结果显示,Nb改性后V2O5-WO3/TiO2催化剂的晶体结构没有发生明显改变,但是其比表面积小幅度下降,有助于减少对SO2的吸附;同时,改性后催化剂表面的吸附氧含量下降,氧化还原性能也稍微减弱,这有利于降低其对SO2的氧化活性。in-situ DRIFTS结果表明,Nb改性后的Nb-V2O5-WO3/TiO2催化剂反应过程中表面中间产物VOSO4的含量明显下降,从而减少了SO3的生成量。
  • FIG. 1472.  FIG. 1472.

    FIG. 1472.  FIG. 1472.

    图  1  催化剂测试系统示意图

    Figure  1  Catalyst testing system

    1: gas; 2: pressure reducing valve; 3: mass flowmeter; 4: gas mixer; 5: imported flue gas sampler; 6:reactor; 7: temperature control instrument; 8: condenser tube; 9: peristaltic pump; 10: water bath; 11: gas treatment units

    图  2  不同Nb负载量催化剂对SO2氧化率的影响

    Figure  2  Effect of Nb loading on SO2 conversion upon oxidation over the Nb-modified catalysts

    图  3  不同Nb负载量催化剂对NH3-SCR活性的影响

    Figure  3  Effect of Nb loading on the NO conversion in NH3-SCR deNOx over the Nb-modified catalysts

    图  4  催化剂脱硝和SO2氧化效率

    Figure  4  Catalytic performance of various catalysts in the simultaneous denitration and SO2 oxidation

    图  5  催化剂的N2吸附-脱附等温曲线

    Figure  5  Nitrogen desorption and desorption isotherms of various catalysts

    图  6  催化剂的孔径分布

    Figure  6  Pore size distribution curves of various catalysts

    图  7  催化剂的XRD谱图

    Figure  7  XRD patterns of various catalysts

    图  8  催化剂的热重分析

    Figure  8  Thermogravimetric curves of various catalysts

    图  9  催化剂的H2-TPR谱图

    Figure  9  H2-TPR profiles of various catalyst

    图  10  催化剂的CO2-TPD谱图

    Figure  10  CO2-TPD profiles of various catalysts

    图  11  催化剂的XPS光谱谱图

    Figure  11  XPS spectra of various catalysts

    图  12  350 ℃下催化剂的原位红外光谱谱图

    Figure  12  In-situ DRIFTS spectra of various catalysts for SO2 oxidation at 350 °C

    表  1  实验所用标准气体

    Table  1  The standard gas for the experiment

    GasPurityProducer
    N299.99%Sizhi Gas Co. LTD, Tianjin
    O299.99%Sizhi Gas Co. LTD, Tianjin
    NO5%Sizhi Gas Co. LTD, Tianjin
    NH35%Sizhi Gas Co. LTD, Tianjin
    SO25%Haipu Gas Co. LTD, Beijing
    下载: 导出CSV

    表  2  样品的孔结构分析

    Table  2  Textural properties of various catalysts

    CatalystSurface area
    A/(m2·g−1)
    Pore volume
    v/(cm3·g−1)
    Pore size
    d/nm
    V2W5/TiO2129.20.49415.31
    V2W5Nb1/TiO2100.680.3817.39
    V2W5Nb2/TiO2111.40.41714.97
    V2W5Nb3/TiO2111.90.44115.72
    下载: 导出CSV

    表  3  催化剂表面组成分析

    Table  3  Surface composition of various catalyst determined by XPS

    CatalystSurface atomic concentration / % Surface atomic ratio / %
    OVTiWNb V5+/(V5++V4+O
    OßOα
    V2W5/TiO2 67.25 0.81 29.24 2.70 0 81.93 76.68 23.32
    V2W5Nb2/TiO2 67.18 0.64 28.69 2.40 1.09 57.12 83.68 16.32
    下载: 导出CSV
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  • 收稿日期:  2021-09-16
  • 修回日期:  2021-10-20
  • 录用日期:  2021-10-20
  • 网络出版日期:  2021-11-15
  • 刊出日期:  2022-04-26

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