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ZrO2晶型对CO加氢制异丁烯反应影响的研究

武雪梅 谭明慧 耿海伦 赵生迎 徐冰 谭猗生

武雪梅, 谭明慧, 耿海伦, 赵生迎, 徐冰, 谭猗生. ZrO2晶型对CO加氢制异丁烯反应影响的研究[J]. 燃料化学学报(中英文), 2023, 51(4): 473-481. doi: 10.1016/S1872-5813(22)60050-1
引用本文: 武雪梅, 谭明慧, 耿海伦, 赵生迎, 徐冰, 谭猗生. ZrO2晶型对CO加氢制异丁烯反应影响的研究[J]. 燃料化学学报(中英文), 2023, 51(4): 473-481. doi: 10.1016/S1872-5813(22)60050-1
WU Xue-mei, TAN Ming-hui, GENG Hai-lun, ZHAO Sheng-ying, XU Bing, TAN Yi-sheng. Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 473-481. doi: 10.1016/S1872-5813(22)60050-1
Citation: WU Xue-mei, TAN Ming-hui, GENG Hai-lun, ZHAO Sheng-ying, XU Bing, TAN Yi-sheng. Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 473-481. doi: 10.1016/S1872-5813(22)60050-1

ZrO2晶型对CO加氢制异丁烯反应影响的研究

doi: 10.1016/S1872-5813(22)60050-1
基金项目: 国家自然科学基金(21978312,21908235,22172182)资助
详细信息
    通讯作者:

    Tel/Fax: 0351-4044287,0351-4044287,E-mail: tanmh@sxicc.ac.cn

    tan@sxicc.ac.cn

  • 中图分类号: O643

Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation

Funds: The project was supported by the National Natural Science Foundation of China (21978312, 21908235, 22172182)
  • 摘要:

    不同晶型结构的ZrO2在CO加氢制异丁烯反应中表现出不同的催化性能。尽管单斜相ZrO2在合成气制异丁烯反应中具有最优异的催化性能,但是对于其异构化活性位仍缺乏深入认识。通过研究ZrO2晶型结构对反应性能的影响差异,有利于深入认识ZrO2催化剂上合成气制异丁烯反应的关键影响因素。因此,本研究制备了一系列不同晶型结构的ZrO2催化剂,研究了它们在结构性质及催化CO加氢制异丁烯反应性能方面的差异。相对于四方相和无定型ZrO2,在单斜相ZrO2催化剂表面,有较多的配位不饱和的Zr位点和O位点。配位不饱和的Zr位点是CO吸附活化的位点,有利于CO的转化。而较多的不饱和配位的O位点,为异丁烯的生成提供了更多的碱性位。此外,在单斜相ZrO2催化剂表面,配位不饱和的Zr位点和O位点的存在,抑制了电子向反应中生成的甲酸盐物种转移,因此,甲酸盐物种在催化剂表面吸附较弱,有利于CO加氢生成异丁烯。

  • FIG. 2206.  FIG. 2206.

    FIG. 2206.  FIG. 2206.

    图  1  不同晶型结构ZrO2催化剂的(a)XRD谱图和(b)Raman谱图

    Figure  1  (a) XRD patterns and (b) Raman spectra of ZrO2 catalysts with varied crystal phase

    图  2  不晶型结构ZrO2催化剂的NH3-TPD-MS谱图

    Figure  2  NH3-TPD-MS patterns of ZrO2 catalysts with varied crystal phase

    图  3  不同晶型结构ZrO2催化剂的CO2-TPD-MS谱图

    Figure  3  CO2-TPD-MS patterns of ZrO2 catalysts with varied crystal phase

    图  4  ZrO2催化剂的UV-Vis DRS谱图

    Figure  4  UV-vis DRS spectra of H2-pretreated ZrO2 samples

    图  5  ZrO2催化剂的EPR谱图

    Figure  5  EPR spectra of H2-pretreated ZrO2 samples

    图  6  ZrO2样品(a)O 1s和(b)Zr 3d的XPS谱图

    Figure  6  XPS spectra of (a) O 1s and (b) Zr 3d of the ZrO2 samples

    图  7  不同晶型结构ZrO2样品在400 ℃,0.1 MPa下CO吸附30 min的红外光谱谱图

    Figure  7  In-situ CO DRIFTS analysis of CO adsorption under atmosphere at 400 ℃ for 30 min on ZrO2 catalysts with varied crystal phase: (a) 4000–2500 cm−1; (b) 1800–1100 cm−1

    表  1  不同晶型结构ZrO2催化剂上CO加氢制异丁烯催化性能a

    Table  1  Catalytic performance of CO hydrogenation to isobutene over ZrO2 catalysts with different crystal phase a

    CatalystCO Conv.
    /%b
    Sel. Cmol/% Products distribution in CHn
    CHnbDMECO2C1${\rm{C} }_{{2}}^=$${\rm{C}}_{{3}}^= $${ {n} }{\text{-} }{\rm{C} }_{{4} }^{= \;{\rm{c} } }$${ {i} }{\text{-} }{\rm{C} }_{{4} }^{= \;{\rm{c} } }$C5 +
    m-ZrO231.932.13.964.0 3.38.6 (1.7)3.0 (2.5)3.6 (2.1)d50.225.0
    t-ZrO224.736.16.757.214.95.1 (5.0)2.0 (2.7)6.7 (3.1)38.422.1
    am-ZrO231.135.10.064.932.56.6 (12.4)6.1 (4.7)9.3 (7.9)6.514.0
    a: Reaction conditions: H2/CO=1, 400 ℃, 5.0 MPa, GHSV=430 h−1, catalysts were pretreated in a stream of H2/N2=1∶10 at 400 ℃ for 6 h before reaction;
    b: CHn means the hydrocarbons products except for oxygenated chemicals and CO2;
    c: ${{n}}{\text{-}}{\rm{C}}_{{4}}^{=} $ and ${{i}}{\text{-}}{\rm{C}}_{{4}}^{=} $ stand for the linear butenes and isobutene, respectively;
    d: data in parentheses mean the selectivity of alkane (Cn) in total hydrocarbons
    下载: 导出CSV

    表  2  不同晶型结构ZrO2样品的织构性质参数

    Table  2  Textural properties of the resulting ZrO2 samples

    SampleSBET/(m2∙g−1) avpore/(cm3∙g−1) bdave/nm c
    m-ZrO2125.60.268.2
    t-ZrO285.80.094.3
    am-ZrO2215.00.163.1
    a: BJH desorption cumulative surface area of pores between 1.7 and 300 nm width;
    b: BJH desorption cumulative volume of pores between 1.7 and 300 nm width;
    c: BJH desorption average pore width (4V/A)
    下载: 导出CSV

    表  3  ZrO2样品的XPS拟合

    Table  3  XPS fitting results of ZrO2 samples

    SampleBinding energy /eVArea/%
    Zr 3d5/2Zr 3d3/2OLatticeODefectOOHOLatticeODefectOOHOLattice/
    (ODefect + OOH)
    m-ZrO2181.86184.23529.74531.40532.94 70.825.73.60.41
    t-ZrO2181.99184.38529.84531.46532.9469.126.54.40.45
    am-ZrO2182.23184.60530.16531.79533.0070.026.13.90.43
    下载: 导出CSV
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  • 收稿日期:  2022-06-16
  • 修回日期:  2022-07-08
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  • 网络出版日期:  2022-07-19
  • 刊出日期:  2023-04-15

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