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Ag+改性NaY分子筛的制备及其吸附脱氮性能研究

富添 洪新 田宇 孙潇镝 王聚财 唐克 栾秀阳

富添, 洪新, 田宇, 孙潇镝, 王聚财, 唐克, 栾秀阳. Ag+改性NaY分子筛的制备及其吸附脱氮性能研究[J]. 燃料化学学报(中英文), 2024, 52(3): 384-394. doi: 10.1016/S1872-5813(23)60386-X
引用本文: 富添, 洪新, 田宇, 孙潇镝, 王聚财, 唐克, 栾秀阳. Ag+改性NaY分子筛的制备及其吸附脱氮性能研究[J]. 燃料化学学报(中英文), 2024, 52(3): 384-394. doi: 10.1016/S1872-5813(23)60386-X
FU Tian, HONG Xin, TIAN Yu, SUN Xiaodi, WANG Jucai, TANG Ke, LUAN Xiuyang. Preparation of Ag+ modified NaY molecular sieve and its adsorption and denitrogenation properties[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 384-394. doi: 10.1016/S1872-5813(23)60386-X
Citation: FU Tian, HONG Xin, TIAN Yu, SUN Xiaodi, WANG Jucai, TANG Ke, LUAN Xiuyang. Preparation of Ag+ modified NaY molecular sieve and its adsorption and denitrogenation properties[J]. Journal of Fuel Chemistry and Technology, 2024, 52(3): 384-394. doi: 10.1016/S1872-5813(23)60386-X

Ag+改性NaY分子筛的制备及其吸附脱氮性能研究

doi: 10.1016/S1872-5813(23)60386-X
基金项目: 2023年度省教育厅高等学校基本科研项目(JYTMS20230852)和2023年国家级大学生创新创业训练计划(202310154014)资助
详细信息
    通讯作者:

    Tel:13940616508,E-mail:hongxin12@sohu.com

  • 中图分类号: X511

Preparation of Ag+ modified NaY molecular sieve and its adsorption and denitrogenation properties

Funds: The project was supported by 2023 Provincial Department of Education Basic Research Projects for Higher Education Institutions (JYTMS20230852) and 2023 National College Student Innovation and Entrepreneurship Training Program Project (202310154014)
  • 摘要: 采用Ag+改性NaY分子筛成功制备了AgY分子筛,利用XRD射线衍射、FT-IR、N2吸附-脱附对NaY和AgY分子筛进行了表征,并用于吸附脱除模拟燃料中吡啶、苯胺、喹啉碱性氮化物,AgY分子筛的吸附能力明显优于NaY分子筛。考察了吸附温度、吸附时间对AgY分子筛吸附三种氮化物的影响,实验结果表明,吸附能力均为:苯胺>喹啉>吡啶,为了进一步研究其吸附机理,采用Materials Studio软件建立了AgY分子筛12T团簇模型并在303、323、343 K下模拟三种氮化物分子在AgY分子筛上的吸附,计算了吸附能、活性中心与吡啶、苯胺、喹啉分子的距离、前线轨道、等密度分布、径向分布函数等相关参数,计算结果也表明,AgY分子筛对苯胺的吸附优于喹啉,优于吡啶,与实验结果一致,且吸附以化学吸附为主,AgY分子筛S位和W位为主要吸附位。吸附等温线研究结果表明,AgY分子筛对吡啶的吸附符合Langmuir-Freundlich混合吸附模型,对苯胺、喹啉的吸附符合Freundlich吸附模型。吸附动力学和吸附热力学结果表明,AgY分子筛对吡啶的吸附符合准二级动力学模型,对苯胺、喹啉的吸附符合准一级动力学模型,吸附是自发的熵增过程。
  • FIG. 3017.  FIG. 3017.

    FIG. 3017.  FIG. 3017.

    图  1  AgY分子筛12T团簇模型和优化后的氮化物3D模型结构

    Figure  1  AgY molecular sieve 12T cluster model and optimized nitride 3D model structure

    图  2  AgY和NaY分子筛的XRD谱图

    Figure  2  XRD patterns of AgY and NaY molecular sieves

    图  3  AgY和NaY分子筛的红外光谱谱图

    Figure  3  Infrared spectra of AgY and NaY molecular sieves

    图  4  AgY和NaY分子筛的N2吸附-脱附等温曲线

    Figure  4  N2 adsorption-desorption curves of AgY and NaY molecular sieves

    图  5  吸附温度对AgY分子筛吸附脱除模拟燃料中吡啶、苯胺、喹啉的影响

    Figure  5  Effect of adsorption temperature on the adsorption and removal of pyridine, aniline, and quinoline from model fuels by AgY molecular sieve

    图  6  AgY分子筛12T团簇吸附吡啶、苯胺、喹啉的构型示意图

    Figure  6  Configuration diagram of AgY molecular sieve 12T cluster adsorption for aniline, pyridine, and quinoline

    (Numbers in the figure are the distances between the N atoms in the nitride and the Ag atoms in the AgY molecular sieve; units are nm)

    图  7  吡啶、苯胺、喹啉分子的前线轨道示意图

    Figure  7  Frontline orbitals of pyridine, aniline and quinoline molecules

    图  8  不同温度下AgY分子筛吸附脱吡啶、苯胺、喹啉的等密度分布

    Figure  8  Isodensity distribution diagram of adsorbed adsorption of pyridine, aniline and quinoline on AgY molecular sieve at different temperatures

    图  9  吸附时间对AgY分子筛吸附脱除模拟燃料中吡啶、苯胺、喹啉的影响

    Figure  9  Effect of adsorption time on the adsorption and removal of pyridine, aniline, and quinoline from model fuels by AgY molecular sieve

    图  10  吡啶、苯胺、喹啉与AgY分子筛中Ag原子的径向分布函数

    Figure  10  Radial distribution function between pyridine, aniline, quinoline and Ag atom in AgY molecular sieve

    图  11  AgY分子筛吸附脱除模拟燃料中吡啶、苯胺、喹啉的吸附等温线拟合

    Figure  11  Adsorption isotherms fitting of pyridine, aniline and quinoline in model fuels on AgY molecular sieve

    图  12  AgY分子筛吸附脱除模拟燃料中吡啶、苯胺、喹啉的动力学拟合曲线

    Figure  12  Kinetic fitting curve of adsorption and removal of pyridine, aniline, and quinoline from model fuels using AgY molecular sieve

    表  1  NaY和AgY吸附脱除模拟燃料中吡啶的脱氮性能

    Table  1  Denitrification performance of NaY and AgY molecular sieves for adsorption and removal of pyridine from model fuels

    ProjectNaYAgY
    Adsorption capacity/(mg·g−151.2662.60
    Removal rate/%57.6970.46
    下载: 导出CSV

    表  2  AgY分子筛团簇吸附吡啶、苯胺、喹啉的吸附能

    Table  2  Adsorption energy of AgY molecular sieve clusters for aniline, pyridine and quinoline

    ProjectAdsorption complex
    energy/eV
    Adsorbent energy/eVAdsorbed molecule
    energy/eV
    Adsorption energy/eV
    AgY adsorbed pyridine−172864.913−166114.168−6749.4881.257
    AgY adsorbed aniline−310406.903−302585.559−7818.5462.798
    AgY adsorbed quinoline−177043.348−166113.821−10927.2362.291
    下载: 导出CSV

    表  3  吡啶、苯胺、喹啉与AgY分子筛活性中心的距离d(Ag-N)和前线轨道能量值

    Table  3  Distance d(Ag-N) and frontline orbital energy values of aniline, pyridine, quinoline and AgY molecular sieve active centers

    ProjectHOMO/eVLUMO/eVE/eVd(Ag-N)/nm
    AgY adsorbed pyridine−5.960−2.5753.3853.410
    AgY adsorbed aniline−4.569−1.7102.8592.328
    AgY adsorbed quinoline−7.198−3.1354.0632.777
    下载: 导出CSV

    表  4  三种吸附模型拟合AgY分子筛吸附模吡啶、苯胺、喹啉的相关参数值

    Table  4  Model parameter values of the adsorption for pyridine, aniline, and quinoline on the AgY molecular sieve with three adsorption models

    TemperatureLangmuirFreundlichLangmuir-Freundlich
    qmKL × 105R2nKFR2qmKa × 105nR2
    Pyridine
    303 K142.910.7880.9260.5080.6390.934291.61.7690.6580.986
    323 K185.68.3020.9250.5720.6070.935600.40.5760.6520.980
    343 K171.28.9550.9150.5590.2530.926592.30.4970.6340.982
    Aniline
    293 K650.57.0550.9850.8110.1680.991305241.2760.972
    313 K733.75.9290.9830.8280.1440.989320201.1720.970
    333 K637.56.9370.9830.8110.1440.990320201.1760.974
    Quinoline
    303 K27701.3020.9860.9230.0650.987265261.4410.947
    323 K12233.2800.9890.8850.0920.992250301.5020.956
    343 K10923.7900.9890.8770.0990.99226928.31.4450.965
    下载: 导出CSV

    表  5  热力学模型拟合的相关参数

    Table  5  Relevant parameters for thermodynamic model fitting

    ProjectΔG/(kJ·mol−1)S/(kJ·mol−1·K−1)H/(kJ·mol−1)
    Pyridine
    303 K−28.760.1828.39
    323 K−33.40
    343 K−36.04
    Aniline
    303 K−8.4370.0558.228
    323 K−9.537
    343 K−10.637
    Quinoline
    293 K−3.2730.0202.587
    313 K−3.673
    333 K−4.073
    Note: ΔG is Gibbs free energy; ΔH is enthalpy change; ΔS is entropy change.
    下载: 导出CSV

    表  6  准一级和准二级动力学模型拟合相关参数

    Table  6  Parameters fitted with quasi-first-order and quasi-second-order kinetic models

    ProjectQuasi-first-order kinetic equationQuasi-second-order kinetic equation
    QeK1R2QeK2R2
    Pyridine30.1620.1970.98632.2520.0130.993
    Aniline79.0030.4730.99782.1370.0220.994
    Quinoline63.0122.9360.97564.2340.6270.969
    下载: 导出CSV
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  • 收稿日期:  2023-08-28
  • 修回日期:  2023-09-12
  • 录用日期:  2023-09-14
  • 网络出版日期:  2023-10-12
  • 刊出日期:  2024-03-08

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