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铜基载氧体催化电厂烟气脱氧研究

司马皓 王雪峰 邓存宝

司马皓, 王雪峰, 邓存宝. 铜基载氧体催化电厂烟气脱氧研究[J]. 燃料化学学报(中英文), 2024, 52(6): 839-849. doi: 10.1016/S1872-5813(23)60409-8
引用本文: 司马皓, 王雪峰, 邓存宝. 铜基载氧体催化电厂烟气脱氧研究[J]. 燃料化学学报(中英文), 2024, 52(6): 839-849. doi: 10.1016/S1872-5813(23)60409-8
SIMA Hao, WANG Xuefeng, DENG Cunbao. Study on copper-based oxygen carrier catalytic power plant flue gas deoxidation[J]. Journal of Fuel Chemistry and Technology, 2024, 52(6): 839-849. doi: 10.1016/S1872-5813(23)60409-8
Citation: SIMA Hao, WANG Xuefeng, DENG Cunbao. Study on copper-based oxygen carrier catalytic power plant flue gas deoxidation[J]. Journal of Fuel Chemistry and Technology, 2024, 52(6): 839-849. doi: 10.1016/S1872-5813(23)60409-8

铜基载氧体催化电厂烟气脱氧研究

doi: 10.1016/S1872-5813(23)60409-8
基金项目: 国家自然科学基金联合基金 ( U1810206 )资助
详细信息
    通讯作者:

    Tel: 13303433823, E-mail: wangxuefeng01@tyut.edu.cn

  • 中图分类号: X936

Study on copper-based oxygen carrier catalytic power plant flue gas deoxidation

Funds: The project was supported by National Natural Science Foundation Joint fund project of China ( U1810206 ).
  • 摘要: 电厂烟气主要成分为N2、CO2和部分O2,将电厂烟气注入矿井采空区可实现CO2封存,并替代注氮气防治遗煤自燃,但是烟气中的O2是造成遗煤自燃的因素之一。因此,亟待开发一种经济有效的催化剂来脱除电厂烟气中的O2。本研究采用共沉淀法,通过调变载体和负载量可控制备了铜基催化剂和系列xCuO/CeO2催化剂,利用BET、XRD、ICP、TEM、H2-TPR和XPS等手段对催化剂进行了表征,并建立催化剂结构与催化电厂烟气脱氧性能之间的构效关系。结果表明,CeO2的加入提高了CuO的分散性、增加了催化剂的氧空位,提高了催化剂的活性和还原氧化性能,Cu-Ce界面结构的协同效应促进了还原氧化过程,表现出良好的活性和循环稳定性。30CuO/CeO2由于其CuO颗粒尺寸最小、分散性最高、氧空位浓度最高,表现出较优的催化电厂烟气脱氧性能。本研究为开发低成本可循环使用、高活性和高稳定性的脱氧催化剂提供了参考。
  • FIG. 3161.  FIG. 3161.

    FIG. 3161.  FIG. 3161.

    图  1  Cu基催化剂的XRD谱图(a)和xCuO/CeO2催化剂的XRD谱图(b)

    Figure  1  XRD patterns of Cu-based catalysts (a) and XRD patterns of xCuO/CeO2 catalysts (b)

    图  2  40CuO/CeO2催化剂的HRTEM 照片

    Figure  2  HRTEM photograph of 40CuO/CeO2

    图  3  40CuO/CeO2催化剂反应前后的XRD谱图

    Figure  3  XRD patterns of 40CuO/CeO2 catalyst before and after the reaction

    图  4  催化剂的H2-TPR谱图(a)和(b)

    Figure  4  H2-TPR of the catalysts (a) and (b)

    图  5  xCuO/CeO2催化剂的XPS谱图

    Figure  5  XPS spectra of xCuO/CeO2 catalysts (O 1s (a) ; Cu 2p (b) ; Ce 3d (c))

    图  6  40CuO/CeO2、40CuO/MgO、40CuO/Al2O3、40CuO/SiO2催化剂在250 ℃下的还原性能(a)和氧化性能(b)

    Figure  6  Reduction performance (a) and oxidation performance (b) curves of 40CuO/CeO2, 40CuO/MgO, 40CuO/Al2O3 and 40CuO/SiO2 catalysts at 250 ℃

    图  7  40CuO/CeO2催化剂在不同温度下的还原性能(a)和氧化性能(b)

    Figure  7  Reduction performance (a) and oxidation performance (b) curves of 40CuO/CeO2 catalysts at different temperatures

    图  8  xCuO/CeO2催化剂在250 ℃下的还原性能(a)和氧化性能(b)

    Figure  8  Reduction performance (a) and oxidation performance (b) curves of xCuO/CeO2 catalysts at 250 ℃

    图  9  30CuO/CeO2催化剂在不同氧体积分数下的氧化性能

    (反应条件:GHSV=420 mL/(g·h),O2:N2:CO2=x:21:79-x,其中x分别为4、5、7、10)

    Figure  9  Oxidation performance of 30CuO/CeO2 catalyst at different oxygen concentrations

    Reaction conditions: GHSV=420 mL/(g·h), O2∶N2∶CO2=x∶21∶79−x, where x is 4, 5, 7, 10.

    图  10  30CuO/CeO2催化剂在不同气体流量下的氧化性能

    Figure  10  Oxidation performance of 30CuO/CeO2 catalysts at different gas flow rates

    图  11  30CuO/CeO2催化剂CLC循环实验的热重曲线

    (反应条件:H2:N2=10:90,N2,O2:N2:CO2=5:15:80,流速50 mL/min)

    Figure  11  Thermogravimetric curve of 30CuO/CeO2 catalyst for CLC cycling experiments

    Reaction condition: H2∶N2=10∶90, N2, O2∶N2∶CO2=5∶15∶80, flow rate 50 mL/min.

    图  12  30CuO/CeO2、40CuO/Al2O3、40CuO/MgO、40CuO/SiO2催化剂在250 ℃的H2-TPR谱图

    Figure  12  H2-TPR of 30CuO/CeO2, 40CuO/Al2O3, 40CuO/MgO, 40CuO/SiO2 catalysts at 250 ℃

    表  1  催化剂的物理参数

    Table  1  Physical parameters of the catalyst

    Catalyst dCuO/nm Abefore/(m2·g−1 Aafter/(m2·g−1 vbefore/(cm3·g−1 vafter/(cm3·g−1 Cu w/%
    CuO 40 1.929 1.897 0.005 0.005
    40CuO/MgO 23 10.393 10.048 0.047 0.044 40.493
    40CuO/Al2O3 11 21.790 21.304 0.110 0.062 41.508
    40CuO/SiO2 13 18.155 18.096 0.103 0.098 40.464
    40CuO/CeO2 17 15.796 8.477 0.101 0.060 39.112
    30CuO/CeO2 15 21.380 17.451 0.140 0.109 30.412
    20CuO/CeO2 16 19.159 15.374 0.052 0.112 20.019
    10CuO/CeO2 19 18.439 14.877 0.123 0.096 9.984
    下载: 导出CSV

    表  2  xCuO/CeO2的XPS表征

    Table  2  XPS results of xCuO/CeO2 catalyst

    Catalyst Ce3+/(Ce3++Ce4+)/%
    10CuO/CeO2 13.54
    20CuO/CeO2 16.78
    30CuO/CeO2 23.19
    40CuO/CeO2 15.02
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-12-06
  • 修回日期:  2024-01-16
  • 录用日期:  2024-01-17
  • 网络出版日期:  2024-02-28
  • 刊出日期:  2024-06-01

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