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超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡

郭栋 李姗姗 王虎 郑青榕

郭栋, 李姗姗, 王虎, 郑青榕. 超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡[J]. 燃料化学学报(中英文), 2023, 51(12): 1879-1888. doi: 10.1016/S1872-5813(23)60364-0
引用本文: 郭栋, 李姗姗, 王虎, 郑青榕. 超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡[J]. 燃料化学学报(中英文), 2023, 51(12): 1879-1888. doi: 10.1016/S1872-5813(23)60364-0
GUO Dong, LI Shan-shan, WANG Hu, ZHENG Qing-rong. Adsorption equilibrium of methane on activated carbon and typical metal organic frameworks[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1879-1888. doi: 10.1016/S1872-5813(23)60364-0
Citation: GUO Dong, LI Shan-shan, WANG Hu, ZHENG Qing-rong. Adsorption equilibrium of methane on activated carbon and typical metal organic frameworks[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1879-1888. doi: 10.1016/S1872-5813(23)60364-0

超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡

doi: 10.1016/S1872-5813(23)60364-0
基金项目: 国家自然科学基金(51979121),福建省自然科学基金重点项目(2020J02041)和厦门市科技计划项目(3502Z20226011)资助
详细信息
    作者简介:

    郭栋(1999—),硕士研究生,研究方向:从事燃气(氢气、甲烷)吸附储存技术研究。E-mail:guod1201@163.com

    通讯作者:

    E-mail: qrzheng816@sina.com, zhengqr@jmu.edu.cn

  • 中图分类号: O647.32

Adsorption equilibrium of methane on activated carbon and typical metal organic frameworks

Funds: The project was supported by National Natural Science Foundation of China (51979121), Natural Science Foundation of Fujian Province (2020J02041) and Xiamen Municipal Bureau of Sciences & Technology (3502Z20226011)
  • 摘要: 针对吸附天然气(ANG)应用的吸附剂研发,试制了SAC-02活性炭、HKUST-1和MIL-101(Cr),通过微观形貌观察、氮气物理吸附和293.15–313.15 K、0–4 MPa条件下甲烷吸附等温线测定,采用Toth、D-A和Ono-Kondo等方程对实验数据进行关联预测比较,由等量吸附热和吸附相密度分析这些吸附剂样品对甲烷的吸附性能。结果表明,在测试范围内,Toth方程预测的吸附平衡数据精度最高,可用于ANG系统的吸附平衡分析;甲烷在MIL-101(Cr)上的平均等量吸附热最大,吸附相密度比液态甲烷的密度小但随压力的增高而增大,比活性炭和HKUST-1更适合于甲烷吸附。
  • FIG. 2814.  FIG. 2814.

    FIG. 2814.  FIG. 2814.

    图  1  实验装置示意图

    Figure  1  Schematic design of the experimental setup for measuring methane adsorption equilibrium

    图  2  HKUST-1 的 XRD谱图(a)和晶体颗粒的 SEM 照片(b)

    Figure  2  XRD pattern (a) and SEM image (b) of the HKUST-1 sample

    图  3  MIL-101(Cr)的 XRD谱图(a)和晶体颗粒的 SEM照片(b)

    Figure  3  XRD pattern (a) and SEM image (b) of the MIL-101(Cr) sample

    图  4  77.15 K时氮在样品上的吸附等温线(a)及其孔径分布(b)

    Figure  4  Isotherms of nitrogen adsorption at 77.15 K (a) and the pore size distribution curves of three samples (b)

    图  5  甲烷在 SAC-02 活性炭 (a)、HKUST-1(b)和 MIL-101(Cr) (c)上的低压吸附等温线

    Figure  5  Adsorption isotherms of methane at a low pressure on activated carbon SAC-02 (a), HKUST-1 (b) and MIL-101(Cr) (c)

    图  6  甲烷在 SAC-02 活性炭(a)、HKUST-1(b)和 MIL-101 (Cr) (c)上的高压吸附等温线

    Figure  6  Adsorption isotherms of methane at a high pressure on activated carbon SAC-02 (a), HKUST-1 (b) and MIL-101(Cr) (c)

    图  7  模型预测甲烷在 SAC-02 活性炭(a)、HKUST-1(b) 和 MIL-101 (Cr)(c) 上吸附平衡数据的相对误差

    Figure  7  Relative errors of adsorption equilibrium data predicted by different models on the activated carbon SAC-02 (a), HKUST-1 (b) and MIL-101(Cr) (c)

    图  8  甲烷在吸附剂上的等量吸附热

    Figure  8  Isosteric heats of methane adsorption on the samples

    图  9  303.15 K时甲烷在吸附剂上的吸附相密度

    Figure  9  Densities of the adsorbed methane phase on different samples at 303.15 K

    表  1  吸附剂的结构参数

    Table  1  Textural properties of the samples

    SampleSpecific surface area /
    (m2·g−1)
    Average pore size /
    nm
    Micropore volume / (cm3·g−1)
    SAC-0214841.20.58
    HKUST-118500.700.77
    MIL-101(Cr)31411.861.09
    下载: 导出CSV

    表  2  甲烷在吸附剂上吸附的热力学参数

    Table  2  Thermodynamic parameters of methane adsorption on the samples

    AdsorbentT /
    K
    Hp /(mmol·Pa−1·g−1)qst0 /(kJ·mol−1)Isosteric adsorption heat /(kJ·mol−1)
    SAC-02293.150.0095823.95224.035
    303.150.0078624.035
    313.150.0054424.118
    HKUST-1293.150.0107726.60126.685
    303.150.0082426.685
    323.150.0057126.768
    MIL-101(Cr)293.150.0060829.41829.501
    303.150.0042229.501
    313.150.0035829.584
    下载: 导出CSV

    表  3  甲烷在吸附剂上吸附平衡的Toth方程拟合参数

    Table  3  Parameters fitted with the Toth equation for methane adsorption on the samples

    SampleT /
    K
    b /
    MPa−1
    tnm /(mmol∙g−1)va /(cm3·g−1)
    SAC-02293.152.7620.242648.010.7241
    303.152.1030.284342.000.8526
    313.150.8310.316135.850.8253
    HKUST-1293.150.8370.294036.890.2164
    303.150.2500.536726.861.6300
    313.150.5460.66606.510.4563
    MIL-101(Cr)293.150.1110.4549141.501.9700
    303.150.1200.615587.852.5360
    313.150.1590.739050.631.3440
    下载: 导出CSV

    表  4  甲烷在吸附剂上吸附平衡的D-A方程拟合参数

    Table  4  Parameters fitted with the D-A equation for methane adsorption on three samples

    SampleT /
    K
    n0 /(mmol∙g−1)E /(J∙mol−1)q
    SAC-02293.156.81685801.816
    303.156.68685081.662
    313.156.10485011.931
    HKUST-1293.154.86079821.645
    303.154.64077691.329
    313.154.40184201.707
    MIL-101(Cr)293.1521.21054851.468
    303.1518.66057421.585
    313.1518.99061121.614
    下载: 导出CSV

    表  5  甲烷在吸附剂上吸附平衡的Ono-Kondo方程参数

    Table  5  Parameters of the Ono-Kondo equation for methane adsorption on different samples

    SampleT /
    K
    $ C $ /(mmol·g−1)$ {-(\varepsilon }_{{\rm{A}}}/k) $/
    K
    $ {\rho }_{{\rm{mc}}} $ /(mol·L−1)
    SAC-02293.153.995893.2421.03
    303.153.670916.7520.51
    313.153.769900.7019.99
    HKUST-1293.153.0881222.0622.52
    303.153.0301206.6521.96
    313.152.8821225.5721.40
    MIL-101(Cr)293.1529.481242.2424.77
    303.1513.561289.0724.15
    313.1513.761260.7323.54
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-02-18
  • 修回日期:  2023-04-08
  • 录用日期:  2023-04-11
  • 网络出版日期:  2023-05-06
  • 刊出日期:  2023-12-05

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