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Impact of B-site cations of MgX2O4 (X=Cr, Fe, Mn) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene

LIANG Xiaocen WANG Xuemei XING Zifan MAO Min SONG Da LI Yang LONG Tao ZHOU Yuchao CHEN Peili HE Fang

梁晓岑, 王雪梅, 幸子凡, 毛敏, 宋达, 李杨, 龙涛, 周宇超, 陈佩丽, 何方. MgX2O4 (X=Cr、Fe、Mn) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响[J]. 燃料化学学报(中英文), 2024, 52(7): 1006-1019. doi: 10.1016/S1872-5813(24)60434-2
引用本文: 梁晓岑, 王雪梅, 幸子凡, 毛敏, 宋达, 李杨, 龙涛, 周宇超, 陈佩丽, 何方. MgX2O4 (X=Cr、Fe、Mn) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响[J]. 燃料化学学报(中英文), 2024, 52(7): 1006-1019. doi: 10.1016/S1872-5813(24)60434-2
LIANG Xiaocen, WANG Xuemei, XING Zifan, MAO Min, SONG Da, LI Yang, LONG Tao, ZHOU Yuchao, CHEN Peili, HE Fang. Impact of B-site cations of MgX2O4 (X=Cr, Fe, Mn) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 1006-1019. doi: 10.1016/S1872-5813(24)60434-2
Citation: LIANG Xiaocen, WANG Xuemei, XING Zifan, MAO Min, SONG Da, LI Yang, LONG Tao, ZHOU Yuchao, CHEN Peili, HE Fang. Impact of B-site cations of MgX2O4 (X=Cr, Fe, Mn) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 1006-1019. doi: 10.1016/S1872-5813(24)60434-2

MgX2O4 (X=Cr、Fe、Mn) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响

doi: 10.1016/S1872-5813(24)60434-2
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  • 中图分类号: O643.36

Impact of B-site cations of MgX2O4 (X=Cr, Fe, Mn) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene

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    Corresponding author: E-mail: hefang@glut.edu.cnE-mail: hefang@glut.edu.cn
  • 摘要: 化学链循环氧化脱氢技术(CL-ODH)是一个多功能的平台,它可以利用载氧体中晶格氧的选择性氧化这一特性,实现乙烷向乙烯的高值化转化。本研究探讨了MgX2O4(X=Cr、Fe或Mn)型尖晶石载氧体中B位元素对乙烷CL-ODH性能的影响。采用固定床和H2-TPR、O2-TPD、TG、原位拉曼、SEM、TEM等方法对MgX2O4尖晶石进行了性能测试和表征。结果表明,MgCr2O4仅释放微量表面吸附氧,更倾向于催化乙烷转化为焦炭和氢气。MgFe2O4通过提供更多的表面晶格氧,促进乙烷深度氧化成CO2。MgMn2O4载氧体在乙烷CL-ODH反应中能够释放出大量的体相晶格氧,它可以选择性燃烧氢气以推进反应正向进行,增加乙烯的选择性,实现了73.72%的乙烷转化率和81.46%的乙烯选择性。此外,MgMn2O4催化剂在乙烷CL-ODH反应中进行了30次的氧化还原循环实验,表现出稳定的反应性能,在整个循环测试中乙烯收率大约为62.00%。MgX2O4尖晶石氧化物中B位元素影响了其晶格氧的供应能力,从而影响了其在乙烷CL-ODH反应中的性能。
  • Figure  1  Process diagram of ethane CL-ODH reaction

    Figure  2  XRD patterns of the fresh oxygen carriers

    Figure  3  Scanning electron microscopy of fresh oxygen carriers MCO (a), MFO (b), and MMO (c)

    Figure  4  Transmission electron microscope and lattice fringe calculation of fresh oxygen carriers MCO (a), MFO (b), and MMO (c)

    Figure  5  Ethylene yield of MCO (a), MFO (b), MMO (c), hydrogen conversion (d), total yield (e) and C balance (f)

    Figure  6  XRD patterns of fresh and reduced oxygen carriers

    Figure  7  Scanning electron microscopy of reduced oxygen carriers MCO (a), MFO (b), and MMO (c)

    Figure  8  XPS of oxygen carrier before and after reaction (O 1s (a)−(c), Cr 2p (d), Fe 2p (e) and Mn 2p (f))

    Figure  9  CO2-TPD (a), H2-TPR (b), O2-TPD (c) and TG (d) of fresh oxygen carriers

    Figure  10  In-situ Raman results for MCO (a) and MMO (b) at 775 °C

    Figure  11  Ethylene yield (a) and XRD patterns (b) of MMO before and after the 30 consecutive redox cycles at 775 °C

    Table  1  Specific surface areas of fresh oxygen carriers of MCO, MFO and MMO

    SBET/(m2·g−1) vpore/(cm3·g−1) Average pore diameter d/nm
    MgCr2O4 21.002 0.142 27.071
    MgFe2O4 14.638 0.057 15.464
    MgMn2O4 7.716 0.035 18.248
    下载: 导出CSV

    Table  2  Content changes of O 1s and B-position elements before and after reaction

    O O O O(Ⅱ+Ⅲ)/ O Change of valence state of B-site ions
    fresh reduced fresh reduced fresh reduced fresh reduced fresh reduced
    MgCr2O4 59.26 54.61 25.78 39.38 14.96 6.01 0.69 0.83 Cr6+/Cr3+ 0.70 0.57
    MgFe2O4 57.50 39.17 36.03 40.05 6.46 20.78 0.74 1.55 Fe3+/Fe2+ 1.07 0.76
    MgMn2O4 50.71 30.81 34.12 63.00 15.16 6.19 0.97 2.24 Mn4+/(Mn3++Mn2+) 0.55 0.37
    下载: 导出CSV
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  • 收稿日期:  2023-12-04
  • 修回日期:  2024-01-31
  • 录用日期:  2024-01-31
  • 网络出版日期:  2024-03-30
  • 刊出日期:  2024-07-01

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