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钛副族金属氧化物催化合成气转化性能的研究

杨世诚 朱万胜 马书启 薛晓晓 张玉龙 孙琦

杨世诚, 朱万胜, 马书启, 薛晓晓, 张玉龙, 孙琦. 钛副族金属氧化物催化合成气转化性能的研究[J]. 燃料化学学报(中英文), 2022, 50(5): 591-600. doi: 10.1016/S1872-5813(21)60180-9
引用本文: 杨世诚, 朱万胜, 马书启, 薛晓晓, 张玉龙, 孙琦. 钛副族金属氧化物催化合成气转化性能的研究[J]. 燃料化学学报(中英文), 2022, 50(5): 591-600. doi: 10.1016/S1872-5813(21)60180-9
YANG Shi-cheng, ZHU Wan-sheng, MA Shu-qi, XUE Xiao-xiao, ZHANG Yu-long, SUN Qi. Catalytic performance of titanium subgroup metal oxides for syngas conversion[J]. Journal of Fuel Chemistry and Technology, 2022, 50(5): 591-600. doi: 10.1016/S1872-5813(21)60180-9
Citation: YANG Shi-cheng, ZHU Wan-sheng, MA Shu-qi, XUE Xiao-xiao, ZHANG Yu-long, SUN Qi. Catalytic performance of titanium subgroup metal oxides for syngas conversion[J]. Journal of Fuel Chemistry and Technology, 2022, 50(5): 591-600. doi: 10.1016/S1872-5813(21)60180-9

钛副族金属氧化物催化合成气转化性能的研究

doi: 10.1016/S1872-5813(21)60180-9
基金项目: 河南省煤炭绿色转化杰出外籍科学家工作室(GZS2020012)资助
详细信息
    通讯作者:

    E-mail: zhangyulong@hpu.edu.cn

    Qisun_L@hotmail.com

  • 中图分类号: O643; TQ241

Catalytic performance of titanium subgroup metal oxides for syngas conversion

Funds: The project was supported by the Distinguished Foreign Scientist Workshop on Coal Green Conversion of Henan Province (GZS2020012)
  • 摘要: 将超临界法制备的钛副族纳米金属氧化物(TiO2、ZrO2、HfO2)分别与ZSM-5分子筛和石英砂混合得到双功能催化剂(Ti/HZ、Zr/HZ、Hf/HZ)和金属氧化物催化剂(Ti/Si、Zr/Si、Hf/Si)。研究了金属氧化物的晶体结构、表面氧空位和合成气吸附性能对金属氧化物催化剂和双功能催化剂催化CO加氢性能的影响。结果表明,双功能催化剂可以直接催化合成气制芳烃。金属氧化物表面氧空位浓度、氧空位电子性质和金属氧化物的H/C比(CO和H2吸附量之比)共同决定着金属氧化物表面中间体产物的种类。ZrO2表面的碳氢氧(CHxO*)中间体产物有利于Zr/HZ获得芳烃高选择性(71.15%),而TiO2和HfO2中的CH3*则导致Ti/HZ和Hf/HZ的催化产物CH4选择性较高。
  • FIG. 1527.  FIG. 1527.

    FIG. 1527.  FIG. 1527.

    图  1  金属氧化物催化剂和双能催化剂的催化性能

    Figure  1  Catalytic performance of metal oxides and bifunctional catalysts

    图  2  金属氧化物的结构特征(a)XRD谱图,(b)N2吸附-脱附等温曲线,(c)和(d)为TiO2的TEM照片,(e)和(f)为ZrO2的TEM照片,(g)和(h)为HfO2的TEM照片

    Figure  2  Structural characteristics of metal oxides, (a) XRD pattern, (b) N2-adsorption and desorption isotherm, (c) and (d) TEM pictures of TiO2, (e) and (f) TEM pictures of ZrO2, (g) and (h) TEM pictures of HfO2

    图  3  金属氧化物的吸附性能

    Figure  3  Desorption performance of metal oxides

    (a): H2-TPD; (b): CO-TPD

    图  4  金属氧化物的O 1s XPS谱图

    Figure  4  O 1s XPS spectra of metal oxides

    图  5  金属氧化物的原位红外光谱谱图

    Figure  5  In-situ infrared spectra of metal oxides in syngas (a) TiO2, (b) ZrO2 and (c) HfO2 at different temperatures, and (d) in-situ infrared spectra of metal oxides at 400 ℃

    表  1  金属氧化物的结构性质

    Table  1  Textural properties of metal oxides

    SampleSBET /(m2·g−1)vtotal /(cm3·g−1)Dave /nmCave /nm
    TiO2740.189.739.9
    ZrO2970.3213.524.2
    HfO21110.3312.063.9
    note: SBET , vtotal , Dave and Cave are the specific surface area, pore volume, pore size and grain size of metal oxides, respectively
    下载: 导出CSV

    表  2  金属氧化物的H2、CO脱附温度及相应的脱附量

    Table  2  H2, CO desorption temperatures and corresponding desorption amounts of metal oxides

    Samplet1 /℃t2 /℃I1 /(μmol·g−1)I2 /(μmol·g−1)H/C (ratio)
    TiO2 H2-TPD 50−220 220−410 60.79 5.17 0.75
    CO-TPD 161−405 87.69
    ZrO2 H2-TPD 201−367 2.49 0.01
    CO-TPD 172−432 233.55
    HfO2 H2-TPD 145−382 46.13 0.66
    CO-TPD 50−139 238−416 53.81 16.56
    下载: 导出CSV

    表  3  金属氧化物中O 1s的结合能及相对氧物种的分数

    Table  3  Binding energy and the corresponding surface atomic concentration of O 1s in metal oxides

    SampleBinding energy /eVI /%
    BE1BE2BE3BE4I1I2I3I4I2+I3
    TiO2 529.28 530.80 531.68 532.68 49.52 22.26 12.82 15.39 35.08
    ZrO2 530.14 532.16 533.18 535.14 46.66 19.65 26.00 7.68 45.65
    HfO2 530.02 531.60 532.80 533.82 55.40 26.41 12.10 6.08 38.51
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-09-26
  • 修回日期:  2021-11-13
  • 录用日期:  2021-11-15
  • 网络出版日期:  2021-11-19
  • 刊出日期:  2022-05-24

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