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ZSM-5酸改性对甲醇芳构化性能的影响

李君华 王丽娜 张丹 钱建华 刘琳 邢锦娟

李君华, 王丽娜, 张丹, 钱建华, 刘琳, 邢锦娟. ZSM-5酸改性对甲醇芳构化性能的影响[J]. 燃料化学学报(中英文), 2019, 47(8): 957-963.
引用本文: 李君华, 王丽娜, 张丹, 钱建华, 刘琳, 邢锦娟. ZSM-5酸改性对甲醇芳构化性能的影响[J]. 燃料化学学报(中英文), 2019, 47(8): 957-963.
LI Jun-hua, WANG Li-na, ZHANG Dan, QIAN Jian-hua, LIU Lin, XING Jin-juan. Effect of ZSM-5 acid modification on aromatization performance of methanol[J]. Journal of Fuel Chemistry and Technology, 2019, 47(8): 957-963.
Citation: LI Jun-hua, WANG Li-na, ZHANG Dan, QIAN Jian-hua, LIU Lin, XING Jin-juan. Effect of ZSM-5 acid modification on aromatization performance of methanol[J]. Journal of Fuel Chemistry and Technology, 2019, 47(8): 957-963.

ZSM-5酸改性对甲醇芳构化性能的影响

基金项目: 

国家自然科学基金 21606117

辽宁省自然科学基金 2015020623

辽宁省自然科学基金 201602380

辽宁省创新团队项目 2018-479-14

辽宁省创新团队项目 LT2015001

渤海大学博士启动基金 0518bs016

渤海大学博士启动基金 0518bs019

详细信息
  • 中图分类号: O643;TQ246

Effect of ZSM-5 acid modification on aromatization performance of methanol

Funds: 

National Natural Science Foundation of China 21606117

Liaoning Natural Science Foundation 2015020623

Liaoning Natural Science Foundation 201602380

Liaoning Innovation Team Project 2018-479-14

Liaoning Innovation Team Project LT2015001

Bohai University Doctoral Start-up Fund 0518bs016

Bohai University Doctoral Start-up Fund 0518bs019

More Information
  • 摘要: 利用硝酸、草酸和酒石酸溶液对ZSM-5分子筛进行改性,并采用XRD、SEM、NH3-TPD、XRF、27Al MAS NMR、吡啶吸附红外光谱和N2吸附-脱附对ZSM-5分子筛结构、酸量、比表面积及孔体积等物化性质进行表征分析。在反应温度为422℃,甲醇质量空速为4.74 h-1的条件下,考察了ZSM-5分子筛的催化活性。结果表明,采用不同酸改性ZSM-5分子筛,影响了分子筛的比表面积、酸性及孔体积,从而改变了催化剂的催化性能。在甲醇芳构化(MTA)反应中,酸改性后的分子筛表现出良好的催化活性,且草酸改性后的催化剂表现出较高的催化活性及选择性,反应8 h时,芳烃及BTX收率分别达到57.40%和39.40%。
  • 图  1  ZSM-5分子筛样品的XRD谱图

    Figure  1  XRD spectra of ZSM-5 zeolite samples

    图  2  ZSM-5分子筛样品的扫描电镜照片

    Figure  2  SEM images of ZSM-5 zeolite samples

    (a): ZSM-5; (b): T-ZSM-5; (c): O-ZSM-5; (d): N-ZSM-5

    图  3  ZSM-5分子筛样品的N2吸附-脱附曲线(a)和孔分布曲线(b)

    Figure  3  (a) N2 adsorption-desorption curve and (b)pore distribution curve of ZSM-5 zeolite samples

    图  4  ZSM-5分子筛样品的27Al MAS NMR谱图

    Figure  4  27Al MAS NMR spectra of ZSM-5 zeolite sample

    图  5  ZSM-5分子筛样品的NH3-TPD谱图

    Figure  5  NH3-TPD spectra of ZSM-5 zeolite sample

    图  6  ZSM-5分子筛样品的Py-FTIR谱图

    Figure  6  Py-FTIR spectra of ZSM-5 zeolite samples

    图  7  ZSM-5分子筛样品的芳烃收率和转化率

    Figure  7  Aromatic hydrocarbon yield of ZSM-5 zeolite samples

    表  1  ZSM-5分子筛样品的结构性质参数及n(SiO2)/n(Al2O3)

    Table  1  Structural properties of ZSM-5 zeolite samples

    Catalyst n(SiO2)/
    n(Al2O3)
    ABET/
    (m2·g-1)
    Aexter/
    (m2·g-1)
    Ainter/
    (m2·g-1)
    vtotal/
    (cm3·g-1)
    vmicro/
    (cm3·g-1)
    vmecro/
    (cm3·g-1)
    N-ZSM-5 129 381 57 324 0.27 0.14 0.13
    O-ZSM-5 117 376 53 323 0.26 0.14 0.12
    T-ZSM-5 86 394 65 329 0.27 0.14 0.13
    ZSM-5 46 306 45 261 0.21 0.11 0.10
    下载: 导出CSV

    表  2  ZSM-5分子筛样品的酸性和酸量分布

    Table  2  Acid and acidity distribution of ZSM-5 zeolite samples

    Catalyst Relative acid amounta Acid amounts/
    (mmol·g-1)b
    B/L
    strong
    acidity
    weak
    acidity
    L B
    N-ZSM-5 0.61 0.43 0.65 1.27 1.95
    O-ZSM-5 0.98 0.82 0.71 1.98 2.77
    T-ZSM-5 0.70 0.72 0.67 1.44 2.14
    ZSM-5 1.00 1.00 1.13 2.02 1.78
    note:a: the relative acid amount was obtained from the NH3-TPD curve; b: the acid amount data was obtained from a Py-FTIR spectrum at 350 ℃
    下载: 导出CSV

    表  3  ZSM-5分子筛样品催化MTA反应的产物分布

    Table  3  Catalytic performance of catalytic MTA reaction

    Catalyst Conversion of
    methanol x/%
    Yield w/%
    benzene toluene m-, p-xylene o-xylene BTX aromatics
    N-ZSM-5 100 0.41 4.62 7.85 1.88 14.76 30.46
    O-ZSM-5 100 0.29 8.31 24.36 6.44 39.40 57.40
    T-ZSM-5 100 1.21 13.00 11.90 3.77 29.88 37.30
    ZSM-5 100 0.53 6.56 10.51 2.00 19.60 24.64
    note: the MTA reaction conditions were p=0.1 MPa, T=695 K, WHSV=4.74 h-1; the data was obtained at 8 h
    下载: 导出CSV
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出版历程
  • 收稿日期:  2019-03-20
  • 修回日期:  2019-06-18
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2019-08-10

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