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Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究

张华伟 陈江艳 赵可 牛庆欣 王力

张华伟, 陈江艳, 赵可, 牛庆欣, 王力. Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究[J]. 燃料化学学报, 2016, 44(4): 394-400.
引用本文: 张华伟, 陈江艳, 赵可, 牛庆欣, 王力. Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究[J]. 燃料化学学报, 2016, 44(4): 394-400.
ZHANG Hua-wei, CHEN Jiang-yan, ZHAO Ke, NIU Qing-xin, WANG Li. Removal of vapor-phase elemental mercury from simulated syngas using semi-coke modified by Mn/Ce doping[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 394-400.
Citation: ZHANG Hua-wei, CHEN Jiang-yan, ZHAO Ke, NIU Qing-xin, WANG Li. Removal of vapor-phase elemental mercury from simulated syngas using semi-coke modified by Mn/Ce doping[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 394-400.

Mn/Ce掺杂改性半焦对模拟煤气中单质汞的脱除性能研究

基金项目: 

国家自然科学基金 51406107

国家自然科学基金 21276146

山东科技大学研究生科技创新基金 YC150110

详细信息
  • 中图分类号: TQ534.9

Removal of vapor-phase elemental mercury from simulated syngas using semi-coke modified by Mn/Ce doping

More Information
  • 摘要: 制备了Mn改性半焦(Mn-SC)及Mn/Ce掺杂改性半焦(Mn/Ce-SC)吸附剂,在小型固定床吸附反应器上考查了改性半焦对模拟煤气中单质汞的吸附特性,并利用BET比表面积测试、X射线衍射、X射线光电子能谱等手段对半焦吸附剂进行了表征。结果表明,Mn改性后半焦的比表面积、总孔容和平均孔径都有所增加,而Mn/Ce掺杂改性半焦的孔隙结构发达程度有一定程度的降低;MnxOy及CexOy均以高分散的无定形态存在于半焦表面;Mn/Ce-SC的脱汞效率明显高于Mn-SC和SC,其脱汞性能随吸附温度的升高会有所下降,但总体保持较高的水平。当煤气中有1%的O2存在时,Mn/Ce-SC表面会发生Ce4+/Ce3+间的氧化还原反应循环,从而将煤气中的气相氧转化为高氧化活性的晶格氧,使Mn/Ce-SC的脱汞效率一直稳定在95%以上,Hg0在Mn/Ce-SC半焦表面的吸附符合Mars-Maessen机制。
  • 图  1  气态汞吸附实验装置示意图

    Figure  1  Schematic diagram of the fixed-bed reactor for removal of gas-phase Hg0

    图  2  SC、Mn-SC与Mn/Ce-SC的XPS谱图

    Figure  2  XPS spectra of SC,Mn-SC and Mn/Ce-SC

    图  3  SC、Mn-SC与Mn/Ce-SC的XRD谱图

    Figure  3  XRD patterns of the SC,Mn-SC and Mn/Ce-SC

    图  4  SC、Mn-SC与Mn/Ce-SC的脱汞效率

    Figure  4  Mercury removal efficiency of SC,Mn-SC and Mn/Ce-SC

    图  5  温度对Mn/Ce-SC脱汞效率的影响

    Figure  5  Effect of temperature on the mercury removal efficiency of Mn/Ce-SC

    图  6  氧气对Mn/Ce-SC脱汞效率的影响

    Figure  6  Effect of O2 on the mercury removal efficiency of Mn/Ce-SC

    图  7  Mn/Ce-SC脱汞反应前后Mn 2p 及Ce 3d的XPS谱图

    Figure  7  Mn 2p and Ce 3d XPS spectra of Mn/Ce-SC before and after Hg0 adsorption experiment

    (a): Mn/Ce-SC; (b): Mn/Ce-SC-Hg; (c): Mn/Ce-SC-Hg(O); (d): Mn/Ce-SC; (e): Mn/Ce-SC-Hg; (f): Mn/Ce-SC-Hg(O)

    表  1  SC、 Mn-SC与Mn/Ce-SC的BET比表面积与孔结构

    Table  1  BET surface area and pore parameters of SC,Mn-SC and Mn/Ce-SC

    SampleBET surface areaA /(m2·g-1)Average poresize d /nmTotal pore volume v /(cm3·g-1)
    SC95.906.700.0373
    Mn-SC132.917.050.0588
    Mn/Ce-SC87.856.290.0456
    下载: 导出CSV

    表  2  Mn/Ce-SC脱汞前后各价态Mn和Ce的相对含量

    Table  2  Relative content of different forms Mn and Ce of Mn/Ce-SC before and after Hg0 adsorption

    SampleRelative content w/%
    Mn2+Mn3+Mn4+Ce3+Ce4+
    Mn/Ce-SC28.4138.4233.1728.9471.06
    Mn/Ce-SC-Hg40.8638.1720.9735.1064.90
    Mn/Ce-SC-Hg(O)32.7443.7123.5533.3766.63
    下载: 导出CSV
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出版历程
  • 收稿日期:  2015-12-15
  • 修回日期:  2016-01-28
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-04-30

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