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不同镁铝比LDHs对苯甲醚合成反应催化效果的研究

张海永 张璐 刘志攀 刘思琪 崔豫泓

张海永, 张璐, 刘志攀, 刘思琪, 崔豫泓. 不同镁铝比LDHs对苯甲醚合成反应催化效果的研究[J]. 矿业科学学报, 2021, 6(6): 755-763. doi: 10.19606/j.cnki.jmst.2021.06.015
引用本文: 张海永, 张璐, 刘志攀, 刘思琪, 崔豫泓. 不同镁铝比LDHs对苯甲醚合成反应催化效果的研究[J]. 矿业科学学报, 2021, 6(6): 755-763. doi: 10.19606/j.cnki.jmst.2021.06.015
Zhang Haiyong, Zhang Lu, Liu Zhipan, Liu Siqi, Cui Yuhong. Catalytic synthesis of anisole over LDHs with different Mg/Al ratios[J]. Journal of Mining Science and Technology, 2021, 6(6): 755-763. doi: 10.19606/j.cnki.jmst.2021.06.015
Citation: Zhang Haiyong, Zhang Lu, Liu Zhipan, Liu Siqi, Cui Yuhong. Catalytic synthesis of anisole over LDHs with different Mg/Al ratios[J]. Journal of Mining Science and Technology, 2021, 6(6): 755-763. doi: 10.19606/j.cnki.jmst.2021.06.015

不同镁铝比LDHs对苯甲醚合成反应催化效果的研究

doi: 10.19606/j.cnki.jmst.2021.06.015
基金项目: 

国家自然科学基金 21506251

中央高校基本科研业务费专项资金 2020YQHH04

中国矿业大学(北京)大学生创新训练项目 C201903706

详细信息
    作者简介:

    张海永(1983—),男,河北保定人,博士,副教授,主要从事煤焦油提质加工方面的研究工作。Tel:13240916719,E-mail:zhanghy@cumtb.edu.cn

  • 中图分类号: TQ522.6

Catalytic synthesis of anisole over LDHs with different Mg/Al ratios

  • 摘要: 采用共沉淀法合成了一系列不同镁铝比的类水滑型层状金属氢氧化物(LDHs),通过XRD、SEM、FT-IR、NH3-TPD、CO2-TPD、TG和ICP-OES方法对MgAl-LDHs和焙烧产物进行表征,并用于催化苯酚与碳酸二甲酯(DMC)气相合成苯甲醚。结果表明,共沉淀法合成的MgAl-LDHs在Mg/Al比为2~4时具有良好的类水滑石结构,主要以球形层片聚集体的形态存在,其层间距、平均孔径和碱酸比在Mg/Al比为2~4之间逐渐增加;所制备的MgAl-LDHs样品均显示出良好的反应活性,并发现苯甲醚的选择性随催化剂酸碱比先增加后减小,当镁铝比为4时,其酸碱比为0.32,此时苯甲醚选择性最高为88.93 %。此外,还考察了反应温度和质量空速对苯甲醚催化效果的影响。
  • 图  1  不同镁铝比水滑石XRD图谱

    Figure  1.  XRD profiles of hydrotalcite with different Mg/Al ratios

    图  2  不同镁铝比焙烧水滑石N2吸附脱附曲线

    Figure  2.  Adsorption-desorption profiles of calcined hydrotalcite with different Mg/Al ratios

    图  3  不同镁铝比焙烧水滑石的孔径分布

    Figure  3.  Pore size distribution of calcined hydrotalcite with different Mg/Al ratios

    图  4  不同镁铝比焙烧水滑石的CO2-TPD

    Figure  4.  CO2-TPD of calcined hydrotalcite with different Mg/Al ratios

    图  5  不同镁铝比焙烧水滑石的NH3-TPD

    Figure  5.  NH3-TPD of calcined hydrotalcite with different Mg/Al ratios

    图  6  不同镁铝比焙烧水滑石的扫描电镜

    Figure  6.  SEM images of hydrotalcite with different Mg/Al ratios

    图  7  不同镁铝比的MgAl-LDHs样品的FT-IR谱图

    Figure  7.  FT-IR spectra of hydrotalcite with different Mg/Al ratios

    图  8  不同镁铝比水滑石的TG曲线

    Figure  8.  TG analysis of hydrotalcite with different Mg/Al ratios

    图  9  碱酸比对苯甲醚选择性的影响

    Figure  9.  Effect of Mg/Al ratio on selectivity of anisole

    图  10  反应温度对苯甲醚合成反应催化性能的影响

    反应条件:催化剂0.1 g,苯酚、DMC摩尔比为1∶3,时间150 min,质量空速2 h-1,常压

    Figure  10.  Effect of temperature on the catalytic performance of anisole synthesis

    图  11  WHSV对苯甲醚合成反应催化性能的影响

    反应条件:催化剂0.1 g,苯酚、DMC摩尔比为1∶3,温度380 ℃,时间150 min,常压

    Figure  11.  Effect of WHSV on the catalytic performance of anisole synthesis

    表  1  不同镁铝比焙烧水滑石的元素组成

    Table  1.   Elementary composition of calcined hydrotalcite with different Mg/Al ratios

    样品 mMg/(mol·kg-1) mAl/(mol·kg-1) nMg/nAl
    Mg2Al-LDO 0.364 0.195 1.87
    Mg3Al-LDO 0.289 0.130 2.22
    Mg4Al-LDO 0.307 0.084 3.65
    Mg5Al-LDO 0.306 0.067 4.57
    Mg10Al-LDO 0.344 0.038 9.05
    下载: 导出CSV

    表  2  MgAl-LDHs的XRD分析结果

    Table  2.   XRD analysis of MgAl-LDHs

    晶面 参数 Mg2Al-LDH Mg3Al-LDH Mg4Al-LDH
    003 2θ/(°) 11.82 11.42 11.30
    d/nm 0.748 1 0.774 2 0.782 4
    FWHM 0.826 0.814 0.775
    006 2θ/(°) 23.52 22.92 22.66
    d/nm 0.377 9 0.387 7 0.392 1
    FWHM 0.942 0.936 0.852
    009 2θ/(°) 34.96 34.62 34.54
    d/nm 0.256 4 0.258 9 0.259 5
    FWHM 0.897 0.922 0.766
    110 2θ/(°) 61.12 60.50 60.32
    d/nm 0.151 5 0.152 9 0.153 3
    FWHM 0.617 0.691 0.723
    下载: 导出CSV

    表  3  不同镁铝比焙烧水滑石的孔结构参数

    Table  3.   Pore structure of calcined hydrotalcite with different Mg/Al ratios

    样品 比表面积/(m2·g-1) 孔容/(cm3·g-1) 平均孔径/nm
    Mg2Al-LDO 268.00 0.77 13.94
    Mg3Al-LDO 202.73 0.68 16.86
    Mg4Al-LDO 230.66 0.95 19.70
    Mg5Al-LDO 252.05 0.85 17.51
    Mg10Al-LDO 169.47 0.96 27.31
    下载: 导出CSV

    表  4  不同镁铝比焙烧水滑石的酸碱量

    Table  4.   Acid and base amount of calcined hydrotalcite with different Mg/Al ratios

    样品 总碱/(mol·kg-1) 总酸(mol·kg-1) 总酸/总碱
    Mg2Al-LDO 0.491 0.218 0.44
    Mg3Al-LDO 0.500 0.184 0.37
    Mg4Al-LDO 0.549 0.176 0.32
    Mg5Al-LDO 0.549 0.145 0.26
    Mg10Al-LDO 0.397 0.201 0.51
    下载: 导出CSV

    表  5  不同镁铝比水滑石对苯甲醚合成反应的性能

    Table  5.   Performance of MgAl-LDOs with different Mg/Al ratios for anisole synthesis

    转化率/% 选择性/% 收率/%
    Mg2Al-LDO 99.25 88.04 87.38
    Mg3Al-LDO 97.63 87.71 85.63
    Mg4Al-LDO 98.87 88.93 87.92
    Mg5Al-LDO 99.67 80.51 80.24
    Mg10Al-LDO 99.75 85.78 85.57
    反应条件:催化剂0.1 g,苯酚、DMC摩尔比为1∶3,进料量0.2 mL/h,时间150 min,温度380 ℃,常压。
    下载: 导出CSV
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  • 收稿日期:  2021-02-04
  • 修回日期:  2021-04-07
  • 刊出日期:  2021-12-01

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