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Zn-Al共掺杂La2O3催化剂在甲烷氧化偶联中的性能

黎营涛 牛鹏宇 王强 贾丽涛 林明桂 李德宝

黎营涛, 牛鹏宇, 王强, 贾丽涛, 林明桂, 李德宝. Zn-Al共掺杂La2O3催化剂在甲烷氧化偶联中的性能[J]. 燃料化学学报(中英文), 2021, 49(10): 1458-1467. doi: 10.1016/S1872-5813(21)60100-7
引用本文: 黎营涛, 牛鹏宇, 王强, 贾丽涛, 林明桂, 李德宝. Zn-Al共掺杂La2O3催化剂在甲烷氧化偶联中的性能[J]. 燃料化学学报(中英文), 2021, 49(10): 1458-1467. doi: 10.1016/S1872-5813(21)60100-7
LI Ying-tao, NIU Peng-yu, WANG Qiang, JIA Li-tao, LIN Ming-gui, LI De-bao. Performance of Zn-Al co-doped La2O3 catalysts in the oxidative coupling of methane[J]. Journal of Fuel Chemistry and Technology, 2021, 49(10): 1458-1467. doi: 10.1016/S1872-5813(21)60100-7
Citation: LI Ying-tao, NIU Peng-yu, WANG Qiang, JIA Li-tao, LIN Ming-gui, LI De-bao. Performance of Zn-Al co-doped La2O3 catalysts in the oxidative coupling of methane[J]. Journal of Fuel Chemistry and Technology, 2021, 49(10): 1458-1467. doi: 10.1016/S1872-5813(21)60100-7

Zn-Al共掺杂La2O3催化剂在甲烷氧化偶联中的性能

doi: 10.1016/S1872-5813(21)60100-7
基金项目: 山西省科技计划揭榜招标项目(20191101012)和煤转化国家重点实验室自主研究课题(2020BWZ003)资助
详细信息
    作者简介:

    黎营涛:18361223156@163.com

    通讯作者:

    Tel: +86-0351-4040428, E-mail: niupy@sxicc.ac.cn

    linmg@sxicc.ac.cn

  • 中图分类号: O643

Performance of Zn-Al co-doped La2O3 catalysts in the oxidative coupling of methane

Funds: The project was supported by Shanxi Science and Technology Department Bidding Project (20191101012) and the Autonomous Research Project of SKLCC (2020BWZ003)
  • 摘要: 采用柠檬酸溶胶凝胶法制备了Zn掺杂和Zn-Al共掺杂的La2O3催化剂,运用原位表征技术研究了该催化剂在甲烷氧化偶联(OCM)反应中的构效关系。原位XRD表征结果发现,La2O3晶体在高温下沿c轴发生热膨胀。H2-TPR结果显示,La2O3基催化剂中含有两种类型的氧物种,即强结合氧和弱结合氧;XPS结果表明,强结合氧归属于为O。Zn掺杂的La2O3催化剂在高温下形成更多的氧空位,能活化氧气产生更多的强结合氧,因而在OCM反应中表现出较好的催化性能。Al的共掺杂能促进Zn在La2O3中的分散,进一步增加强结合氧数量,提升OCM反应C2+烃的选择性。
  • FIG. 965.  FIG. 965.

    FIG. 965.  FIG. 965.

    图  1  La2O3基催化剂的XRD谱图

    Figure  1  XRD patterns of various La2O3-based catalysts

    图  2  La2O3基催化剂的吸附等温线

    Figure  2  N2 adsorption/desorption curves of various La2O3-based catalysts

    图  3  La2O3基催化剂的XPS谱图

    Figure  3  XPS spectra of various La2O3-based catalysts (a): La 3d5/2: (b): Zn 2p

    图  4  催化剂TEM-Mapping照片

    Figure  4  TEM-Mapping images of (1) LZ10 and (2) 1.0Al-LZ10

    图  5  La2O3基催化剂的原位XRD谱图

    Figure  5  In situ XRD patterns of various catalysts at 25 and 750 °C

    (a): L; (b): LZ100; (c):LZ50; (d): LZ10; (e): 1.0Al-LZ10

    图  6  催化剂的H2-TPR谱图

    Figure  6  H2-TPR profiles of various catalysts

    (a): L catalyst pretreated at 100 and 750 °C; (b): La2O3-based catalysts pretreated at 750 °C

    图  7  La2O3基催化剂的XPS O 1s谱图

    Figure  7  O 1 s XPS spectra of various La2O3-based catalysts

    图  8  La2O3基催化剂上的OCM反应性能

    Figure  8  Performance of various La2O3-based catalysts in OCM (a): CH4 conversion; (b): O2 conversion; (c): selectivity to C2+ hydrocarbons; (d): yield of C2+ hydrocarbons

    图  9  800 ℃时C2+选择性与Oβ/Oα的关联性

    Figure  9  Relation between the selectivity to C2+ hydrocarbons and the ratio of Oβ/Oα for OCM over various La2O3-based catalysts at 800 ℃

    表  1  通过XRD计算的La2O3基催化剂晶格参数

    Table  1  Crystalline phase properties of the La2O3-based catalysts measured by XRD

    CatalystLattice parameterα = β /(°)γ /(°)
    a = bc
    L3.93946.139590120
    LZ1003.93836.139290120
    LZ503.93806.135990120
    LZ103.93686.135390120
    下载: 导出CSV

    表  2  催化剂的比表面积和元素分析

    Table  2  Elemental analysis and BET surface area of various La2O3-based catalysts

    CatalystLa/Zn molar ratioSBET/(m2·g−1)
    Bulk, from ICPSurface, from XPS
    L3.4
    LZ100104.0107.72.6
    LZ5051.844.12.7
    LZ1010.17.72.6
    1.0Al-LZ1010.011.13.0
    LA105.0
    下载: 导出CSV

    表  3  La2O3基催化剂原位XRD精修结果

    Table  3  In situ XRD refinement results of the La2O3-based catalysts

    CatalystLattice parameterExpansion rate
    25 ℃750 ℃
    a = bca = bca = b /%c /%
    L3.93946.13953.94016.14700.020.12
    LZ1003.93836.13923.93896.15610.040.28
    LZ503.93806.13593.94046.15890.060.38
    LZ103.93686.13533.93776.16220.020.44
    1.0Al-LZ103.93816.13823.94016.15820.050.33
    下载: 导出CSV

    表  4  催化剂上H2-TPR定量分析

    Table  4  H2-TPR analysis results of various catalysts

    CatalystH2 consumption/(mmol·g−1)Oβ/Oα
    OαOβOβ + Oα
    L-100 ℃0.0160.0030.0190.202
    L-750 ℃0.0640.0640.1280.992
    LZ10-750 °C0.0650.0860.1511.322
    LZ50-750 °C0.0570.1110.1681.947
    LZ100-750 °C0.0560.1160.1722.052
    1.0Al-LZ10-750 °C0.0660.1500.2162.268
    LA10-750 °C0.0780.0860.1641.093
    a:before H2-TPR, the catalyst samples were pretreated under 50% O2-50% N2 (40 mL·min−1) at 750 ℃ or at 100 ℃, as denoted after the catalyst label
    下载: 导出CSV

    表  5  样品的XPS O 1s拟合结果

    Table  5  Contents of various oxygen species in the La2O3-based catalysts derived from O 1 s XPS spectra

    CatalystO2−O$ {\rm{CO}}^{2-}_{3} $$ {\rm{O}}^{-}_{2} $O/$ {\rm{O}}^{-}_{2} $
    BE/eVx/%BE/eVx/%BE/eVx/%BE/eVx/%
    L528.720.78 530.816.86 531.753.61 533.08.75 1.9
    LZ10528.825.31530.820.63531.744.33533.09.732.1
    LZ50528.826.69530.813.15531.756.86532.93.304.0
    LZ100528.827.56530.812.31531.757.29532.72.844.3
    1.0Al-LZ10529.028.98 530.812.75 531.755.61 533.02.66 4.8
    下载: 导出CSV

    表  6  800 ℃下的OCM催化性能

    Table  6  Performance of various La2O3-based catalysts in OCM at 800 °C

    CatalystCH4 Conversion /%O2 Conversion /%Selectivity /%C2H4 /C2H6
    C2+COCO2
    L 25.4 99.9 49.8 11.2 39.0 1.4
    LZ10 25.2 99.9 51.3 11.0 37.7 1.3
    LZ50 25.0 100.0 53.6 10.5 35.9 1.5
    LZ100 26.0 99.9 53.8 10.4 35.8 1.5
    1.0Al-LZ10 25.3 99.9 55.0 7.5 37.5 1.4
    LA10 24.5 99.7 50.7 11.2 38.1 1.5
    ZnO 12.0 80.1 29.5 8.7 61.8 0.5
    下载: 导出CSV
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  • 收稿日期:  2021-04-12
  • 修回日期:  2021-04-21
  • 网络出版日期:  2021-05-28
  • 刊出日期:  2021-10-30

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