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酸活化蒙脱土在二甲醚水蒸气重整制氢中的应用

高天宇 赵永华 郑择 张启俭 刘会敏 王欢 冯效迁 孟庆润

高天宇, 赵永华, 郑择, 张启俭, 刘会敏, 王欢, 冯效迁, 孟庆润. 酸活化蒙脱土在二甲醚水蒸气重整制氢中的应用[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60103-2
引用本文: 高天宇, 赵永华, 郑择, 张启俭, 刘会敏, 王欢, 冯效迁, 孟庆润. 酸活化蒙脱土在二甲醚水蒸气重整制氢中的应用[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60103-2
GAO Tian-yu, ZHAO Yong-hua, ZHENG Ze, ZHANG Qi-jian, LIU Hui-min, WANG Huan, FENG Xiao-qian, MENG Qing-run. Acid activation of montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60103-2
Citation: GAO Tian-yu, ZHAO Yong-hua, ZHENG Ze, ZHANG Qi-jian, LIU Hui-min, WANG Huan, FENG Xiao-qian, MENG Qing-run. Acid activation of montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60103-2

酸活化蒙脱土在二甲醚水蒸气重整制氢中的应用

doi: 10.1016/S1872-5813(21)60103-2
基金项目: 国家自然科学基金(22075120),辽宁省自然科学基金(2019-ZD-0699)和辽宁省教育厅重点公关项目(JZL202015405)资助
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    Tel: 0416-4199013, E-mail: lgdzyh@163.com

Acid activation of montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether

Funds: The project was supported by Natural Science Foundation of China (22075120), Liaoning Provincial Natural Science Foundation of China (2019-ZD-0699) and the Key projects of Liaoning Province Education Department of China (JZL202015405)
  • 摘要: 采用硝酸溶液在不同温度和时间下对钠基蒙脱土进行处理,制备了一系列酸活化蒙脱土(Acid-MMT),并以其为固体酸与商品化的Cu/ZnO/Al2O3物理混合组成双功能催化剂用于二甲醚水蒸气重整(SRD)反应。结果表明,与钠基蒙脱土相比,酸活化蒙脱土的结构、织构及酸性均发生了明显的变化,且变化的程度与酸处理条件密切相关。酸活化蒙脱土的结构和酸性明显影响双功能催化剂的SRD反应性能。其中,在80 ℃处理12 h的酸活化蒙脱土(Acid-MMT-80/12)与Cu/ZnO/Al2O3组成双功能催化剂表现出较好的SRD性能,在p = 0.1 MPa,t = 350 ℃,GHSV = 3000 h−1的反应条件下,二甲醚转化率和氢收率分别达到了97%和94%,且在反应10 h内基本保持不变,表现出了较好的稳定性。
  • 图  1  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/4(c),Acid-MMT-80/12(d),Acid-MMT-80/24(e),Acid-MMT-100/12(f)的XRD谱图

    Figure  1  XRD patterns of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/4 (c), Acid-MMT-80/12 (d), Acid-MMT-80/24 (e), Acid-MMT-100/12 (f)

    图  2  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/4(c),Acid-MMT-80/12(d),Acid-MMT-80/24(e), Acid-MMT-100/12(f)的FT-IR谱图

    Figure  2  FT-IR spectra of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/4 (c), Acid-MMT-80/12 (d), Acid-MMT-80/24 (e), Acid-MMT-100/12 (f)

    图  3  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/4(c),Acid-MMT-80/12(d),Acid-MMT-80/24(e),Acid-MMT-100/12(f)的N2吸附-脱附等温线

    Figure  3  N2 adsorption-desorption isotherms of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/4 (c), Acid-MMT-80/12 (d), Acid-MMT-80/24 (e), Acid-MMT-100/12 (f)

    图  4  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/4(c),Acid-MMT-80/12(d),Acid-MMT-80/24(e),Acid-MMT-100/12(f)的孔径分布

    Figure  4  Pore size distribution curves by BJH method using desorption branch data of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/4 (c), Acid-MMT-80/12 (d), Acid-MMT-80/24 (e), Acid-MMT-100/12 (f)

    图  5  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/12(c),Acid-MMT-100/12(d)的SEM照片

    Figure  5  SEM images of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/12 (c), Acid-MMT-100/12 (d)

    图  6  Na-MMT(a),Acid-MMT-60/4(b),Acid-MMT-80/4(c),Acid-MMT-80/12(d),Acid-MMT-80/24(e),Acid-MMT-100/12(f)的NH3-TPD谱图

    Figure  6  NH3-TPD patterns of Na-MMT (a), Acid-MMT-60/4 (b), Acid-MMT-80/4 (c), Acid-MMT-80/12 (d), Acid-MMT-80/24 (e), Acid-MMT-100/12 (f)

    图  7  不同双功能催化剂的DME转化率(a)及H2收率(b)

    Figure  7  DME conversation (a), H2 yield (b) over different bifunctional catalysts under the conditions of p = 0.1 MPa,t = 350 ℃,GHSV = 3000 h−1

    图  8  反应8 h含碳产物选择性

    Figure  8  Selectivity of the carbon-containing products at TOS of 8 h

    表  1  各样品的XRF分析

    Table  1  Summary of the XRF results of different samples

    SampleSiO2/%Al2O3/%Na2O/%MgO/%CaO/%Fe2O3/%
    Na-MMT64.1624.082.953.332.881.54
    Acid-MMT-60/471.6722.522.670.191.38
    Acid-MMT-80/472.5622.062.750.221.33
    Acid-MMT-80/1275.6320.272.540.191.20
    Acid-MMT-80/2478.5716.772.290.161.07
    Acid-MMT-100/1287.549.440.990.110.61
    下载: 导出CSV

    表  2  各样品的织构特征

    Table  2  Summary of the textural properties of different samples

    SampleBET surface area/(m2·g−1)Pore volume/(cm3·g−1)Average pore size/nm
    Na-MMT120.0724.9
    Acid-MMT-60/41390.174.9
    Acid-MMT-80/41830.245.2
    Acid-MMT-80/122820.517.3
    Acid-MMT-80/242620.7110.8
    Acid-MMT-100/122500.8413.4
    下载: 导出CSV
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  • 收稿日期:  2021-03-03
  • 修回日期:  2021-04-16
  • 网络出版日期:  2021-05-28

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