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Fe/Zr-SBA-15的制备及其催化氧化脱硫性能

王好 孔黎明 曾勇平

王好, 孔黎明, 曾勇平. Fe/Zr-SBA-15的制备及其催化氧化脱硫性能[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022088
引用本文: 王好, 孔黎明, 曾勇平. Fe/Zr-SBA-15的制备及其催化氧化脱硫性能[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022088
WANG Hao, KONG Li-ming, ZENG Yong-ping. Preparation of Fe/Zr-SBA-15 catalyst and its oxidative desulfurization performance[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022088
Citation: WANG Hao, KONG Li-ming, ZENG Yong-ping. Preparation of Fe/Zr-SBA-15 catalyst and its oxidative desulfurization performance[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022088

Fe/Zr-SBA-15的制备及其催化氧化脱硫性能

doi: 10.19906/j.cnki.JFCT.2022088
基金项目: 国家自然科学基金项目(21676231)资助
详细信息
    通讯作者:

    E-mail: lmkong@yzu.edu.cn

  • 中图分类号: TE624

Preparation of Fe/Zr-SBA-15 catalyst and its oxidative desulfurization performance

Funds: The project was supported by National Natural Science Foundation of China (21676231).
  • 摘要: 为进一步提高氧化脱硫效果,采用直接水热法合成了不同Fe/Zr摩尔比改性的SBA-15分子筛(Fe/Zr-SBA-15),采用XRD、N2吸附-脱附、TEM和UV-Vis等对其进行了表征。Fe/Zr-SBA-15中Zr取代Si进入了分子筛骨架,大部分Fe物种分散良好,存在少量的聚集态铁的氧化物。以Fe/Zr-SBA-15-1.0为催化剂、H2O2为氧化剂、乙腈为萃取剂,分别考察了反应温度、O/S摩尔比和催化剂用量对模拟油中二苯并噻吩(DBT)的氧化效果。在反应温度50 ℃,O/S摩尔比为4,催化剂用量6 g/L的条件下,DBT的脱除率达到97.1%,这是由于催化剂中的Fe3 + 提供氧化活性中心和Zr4 + 提供的吸附中心的双重作用,且催化剂回收利用4次后,DBT的脱除率仍可达到91.3%。
  • 图  1  样品的小角XRD图

    Figure  1  Small-angle XRD patterns of samples

    图  2  样品的广角XRD图

    Figure  2  Wide-angle XRD patterns of samples

    图  3  样品的N2吸附-脱附曲线(A)和孔径分布图(B)

    Figure  3  N2 adsorption-desorption isotherm (A) and pore size distribution (B) of materials

    图  4  不同材料的UV-Vis谱图(A)和Fe/Zr-SBA-15-1.0的UV-Vis分峰谱图(B)

    Figure  4  UV-Vis spectra of different materials (A) and UV-Vis peak spectra of Fe/Zr-SBA-15-1.0 (B) A:SBA-15 (a)、Zr-SBA-15 (b)、Fe/Zr-SBA-15-0.5 (c)、Fe/Zr-SBA-15-1.0 (d) Fe/Zr-SBA-15-1.5 (e)、Fe-SBA-15 (f)

    图  5  样品的TEM图

    Figure  5  TEM diagram of the samples SBA-15 (A)、Fe-SBA-15 (B)、Zr-SBA-15 (C)、 Fe/Zr-SBA-15-0.5 (D)、Fe/Zr-SBA-15-1.0 (E)、Fe/Zr-SBA-15-1.5 (F)

    图  6  Fe/Zr-SBA-15-1.0的元素分布图

    Figure  6  Elemental distribution of Fe/Zr-SBA-15-1.0

    图  7  不同反应温度对脱硫率的影响

    Figure  7  Effect of different reaction temperatures on desulfurization rate reaction conditions: O/S (mol ratio) =2.0, 10 g/L Fe/Zr-SBA-15-1.0, t=60 min

    图  8  O/S物质量的比对脱硫率的影响

    Figure  8  Effect of O/S mol ratio on desulfurization rate reaction conditions: T=50 ℃, 10 g/L Fe/Zr-SBA-15-1.0, t=60 min

    图  9  催化剂加入量对脱硫率的影响

    Figure  9  Effect of catalyst dosage on desulfurization rate reaction conditions: T=50 ℃, O/S (mol ratio) =4.0, t=60 min

    图  10  Fe/Zr-SBA-15-1.0循环使用性能

    Figure  10  Recycling performance of Fe/Zr-SBA-15-1.0 reaction conditions: T=50 ℃, O/S (mol ratio) =4.0, 6 g/L Fe/Zr-SBA-15-1.0, t=60 min

    图  11  反应前(A)和反应后(B)的Fe/Zr-SBA-15-1.0的FT-IR谱图

    Figure  11  FT-IR spectra of Fe/Zr-SBA-15-1.0 catalyst before (A) and after ODS reaction (B)

    图  12  Fe/Zr-SBA-15氧化脱硫机理示意图

    Figure  12  Oxidative desulfurization mechanism over Fe/Zr-SBA-15 catalyst

    表  1  样品的主要结构参数

    Table  1  The structure characteristics of samples

    SampleFe
    (wt%)
    Zr
    (wt%)
    SBET
    (m2·g−1)
    Vp
    (cm3·g−1)
    dp
    (nm)
    SBA-1500907.711.235.43
    Fe-SBA-153.480954.161.395.84
    Zr-SBA-1508.75975.421.526.22
    Fe/Zr-SBA-15-0.53.177.381023.241.516.02
    Fe/Zr-SBA-15-1.03.487.011001.981.576.13
    Fe/Zr-SBA-15-1.53.816.161152.831.846.47
    注:Fe、Zr含量由ICP分析
    下载: 导出CSV

    表  2  不同催化剂的脱硫性能

    Table  2  Performance of different catalysts on oxidation desulfurization

    CatalystAmount of acetonitrile
    (mg·L−1)
    O/SAmount of catalyst
    (g·L−1)
    Desulfurization rate
    (%)
    SBA-15521056.3
    Fe-SBA-15521073.4
    Fe-SBA-15//102.75
    Zr-SBA-15521070.9
    Zr-SBA-15//1010.4
    Fe/Zr-SBA-15-0.5521085.2
    Fe/Zr-SBA-15-1.0521092.7
    Fe/Zr-SBA-15-1.5521084.2
    Fe/Zr-SBA-15-1.0//1015.3
    Fe/Zr-SBA-15-1.02.521077.7
    下载: 导出CSV

    表  3  不同催化剂对DBT的脱硫活性对比

    Table  3  Comparison of desulfurization activities of different catalysts for DBT

    CatalystInitial sulfur
    (mg·L−1)
    OxidantAmount of catalyst
    (g·L−1)
    O/STemperature
    (℃)
    Time
    (h)
    Desulfurization
    rate (%)
    Refs.
    Sn-KIT-6100H2O2104602.599.7[31]
    C9H10O2-0.5ZnCl2/Al2O3500H2O240860399.2[32]
    UiO-66(Zr)-NO2320H2O26.671260297[33]
    Mo-Al2O3-1-1320H2O26.67460193.99[34]
    W/Fe@Si-500500H2O23.25845198.7[35]
    Mo/g-C3N4500H2O24580299[36]
    Fe/Zr-SBA-15-1.0500H2O26450197.1This work
    下载: 导出CSV
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  • 收稿日期:  2022-10-10
  • 录用日期:  2022-11-18
  • 修回日期:  2022-11-17
  • 网络出版日期:  2022-12-13

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