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Mg修饰锌孔雀石催化甲醇合成的性能研究

袁治国 张凡 杨世礼 徐晓颖 刘晨阳 邱正璞 魏伟

袁治国, 张凡, 杨世礼, 徐晓颖, 刘晨阳, 邱正璞, 魏伟. Mg修饰锌孔雀石催化甲醇合成的性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60455-X
引用本文: 袁治国, 张凡, 杨世礼, 徐晓颖, 刘晨阳, 邱正璞, 魏伟. Mg修饰锌孔雀石催化甲醇合成的性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60455-X
YUAN Zhiguo, ZHANG Fan, YANG Shili, XU Xiaoying, LIU Chenyang, QIU Zhengpu, WEI Wei. Effect of Mg modification on the catalytic performance of zinc malachite for methanol synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60455-X
Citation: YUAN Zhiguo, ZHANG Fan, YANG Shili, XU Xiaoying, LIU Chenyang, QIU Zhengpu, WEI Wei. Effect of Mg modification on the catalytic performance of zinc malachite for methanol synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60455-X

Mg修饰锌孔雀石催化甲醇合成的性能研究

doi: 10.1016/S1872-5813(24)60455-X
基金项目: 国家能源集团科技创新项目(ST930023003N)资助
详细信息
    通讯作者:

    Tel: 010-57337302, E-mail: xiaoying.xu.d@chnenergy.com.cn

  • 中图分类号: O643

Effect of Mg modification on the catalytic performance of zinc malachite for methanol synthesis

Funds: The project was supported by Science and Technology Innovation Project of CHN ENERGY Group (ST930023003N).
  • 摘要: 焦炉煤气制甲醇的复杂工况给铜基甲醇合成催化剂的稳定性和寿命带来挑战。本工作制备了一系列不同镁含量的锌孔雀石样品,采用原位X射线衍射、热重-质谱、N2物理吸附、H2程序升温还原、CO2程序升温脱附等方法对锌孔雀石及焙烧后的样品进行表征,考察镁元素的添加对锌孔雀石结构和甲醇合成催化性能的影响。结果发现,镁元素的添加提高了锌孔雀石结构内部的铜取代程度,促进了焙烧后催化剂内部高温碳酸盐的形成。随着镁含量的增加,焙烧后催化剂的比表面积逐渐增大,还原后的单质铜晶粒尺寸逐渐减小。原位XRD结果表明少量镁元素在催化剂热处理过程中能有效抑制单质铜晶粒尺寸生长。评价显示催化剂的初始活性随着镁元素的添加呈现先升高后降低的趋势,热处理后含镁催化剂活性仍保持在相对较高的水平。镁元素的适量添加有助于提高铜基甲醇合成催化剂初始活性和热稳定性。
  • 图  1  不同镁含量的前驱体样品的XRD结果

    Figure  1  XRD results of precursor samples with different Mg contents

    图  2  催化剂前驱体的热重质谱联用分析结果(10 oC/min, 空气气氛)

    Figure  2  Thermogravimetric mass spectrometry results of catalyst precursors (10 oC/min, air atmosphere)

    图  3  焙烧后(a)和230 ℃还原后(b)催化剂样品的XRD结果

    Figure  3  XRD results of catalyst samples after calcination (a) and reduction at 230 ℃ (b)

    图  4  CuZn和CuZnMg0.25样品的原位XRD结果

    Figure  4  In-situ XRD results of CuZn and CuZnMg0.25 samples

    图  5  CuZn和CuZnMg0.25样品热处理过程中的Cu晶粒尺寸变化

    Figure  5  Variation of Cu grain sizes of CuZn and CuZnMg0.25 samples during heat treatment

    图  6  不同镁含量催化剂样品的H2-TPR结果

    Figure  6  H2-TPR results of catalyst samples with different Mg contents

    图  7  不同镁含量催化剂样品的CO2-TPD结果

    Figure  7  CO2-TPD results of catalyst samples with different Mg contents

    图  8  催化剂样品的初始活性和热稳定性评价结果

    Figure  8  Evaluation results of initial activity and thermal stability of catalyst samples

    表  1  甲醇合成催化剂样品的设计元素组成

    Table  1  Designed atomic ratio of the methanol synthesis catalyst samples

    Sample Cu2+∶Zn2+∶Mg2+
    mole ratio
    CuO∶ZnO∶MgO
    mass ratio
    CuZn 7∶ 3∶ 0 69.5∶30.5∶0
    CuZnMg0.25 7∶ 3∶ 0.25 68.7∶30.1∶1.2
    CuZnMg0.50 7∶ 3∶ 0.50 67.8∶29.7∶2.5
    下载: 导出CSV

    表  2  不同镁含量样品的物化性质表征结果

    Table  2  Physicochemical characterization results of samples with different Mg contents

    Sample Grain sizea/nm Specific surface area /(m2·g−1) Elemental compositionc w/%
    Precursor CuO Cu b CuO ZnO MgO CO2
    CuZn 24.78 9.45 13.2 38.6 68.6 26.9 0.0 4.5
    CuZnMg0.25 18.06 7.85 10.5 46.1 66.6 27.2 0.4 5.8
    CuZnMg0.50 13.91 6.93 7.81 65.7 65.4 26.5 1.0 7.1
    a: Precursors calculated by the $12\bar0 $> reflection, CuO and Cu calculated by the $11\bar1 $ reflection; b: In-situ XRD results at 230 ℃; c: Normalized results of XRF analyses
    下载: 导出CSV

    表  3  不同镁含量样品的CO2-TPD曲线分峰拟合结果

    Table  3  Peak fitting results of CO2-TPD curves of samples with different Mg contents

    SampleAmount of total basic sites /
    (µmol·g−1)
    α peakβ peakγ peak
    T/℃basic sites /
    (µmol·g−1)
    T/℃basic sites /
    (µmol·g−1)
    T/℃basic sites /
    (µmol·g−1)
    CuZn2459334 (13.8%)14357 (23.1%)385155 (63.1%)
    CuZnMg0.253369352 (15.4%)150107 (31.9%)389177 (52.7%)
    CuZnMg0.504099554 (13.1%)157153 (37.4%)391203 (49.5%)
    下载: 导出CSV
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  • 收稿日期:  2024-02-21
  • 修回日期:  2024-04-07
  • 录用日期:  2024-04-07
  • 网络出版日期:  2024-05-13

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