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原位DRIFTS研究分子筛Brönsted酸和Lewis酸催化戊烯转化的作用机理

伊凤娇 陈会民 杨勇 曹景沛

伊凤娇, 陈会民, 杨勇, 曹景沛. 原位DRIFTS研究分子筛Brönsted酸和Lewis酸催化戊烯转化的作用机理[J]. 燃料化学学报(中英文), 2023, 51(5): 625-634. doi: 10.19906/j.cnki.JFCT.2022083
引用本文: 伊凤娇, 陈会民, 杨勇, 曹景沛. 原位DRIFTS研究分子筛Brönsted酸和Lewis酸催化戊烯转化的作用机理[J]. 燃料化学学报(中英文), 2023, 51(5): 625-634. doi: 10.19906/j.cnki.JFCT.2022083
YI Feng-jiao, CHEN Hui-min, YANG Yong, CAO Jing-pei. Mechanisms of Brönsted and Lewis acids of zeolite on pentenes conversion by in situ DRIFTS[J]. Journal of Fuel Chemistry and Technology, 2023, 51(5): 625-634. doi: 10.19906/j.cnki.JFCT.2022083
Citation: YI Feng-jiao, CHEN Hui-min, YANG Yong, CAO Jing-pei. Mechanisms of Brönsted and Lewis acids of zeolite on pentenes conversion by in situ DRIFTS[J]. Journal of Fuel Chemistry and Technology, 2023, 51(5): 625-634. doi: 10.19906/j.cnki.JFCT.2022083

原位DRIFTS研究分子筛Brönsted酸和Lewis酸催化戊烯转化的作用机理

doi: 10.19906/j.cnki.JFCT.2022083
基金项目: 国家自然科学基金(22208370),中国博士后科学基金(2021M703500)和江苏省“卓博计划”(2022ZB514)资助
详细信息
    通讯作者:

    Tel: + 86-0516-83591053, E-mail:caojingpei@cumt.edu.cn

  • 中图分类号: O643.38

Mechanisms of Brönsted and Lewis acids of zeolite on pentenes conversion by in situ DRIFTS

Funds: The project was supported by the National Natural Science Foundation of China (22208370), China Postdoctoral Science Foundation (2021M703500) and Jiangsu Funding Program for Excellent Postdoctoral Talent (2022ZB514).
  • 摘要: 本研究基于原位水热合成和气相浸渍的方法分别合成了含有Brönsted/Lewis酸的Beta分子筛和只含有Lewis酸的AlCl3@Si-Beta样品,并通过原位漫反射红外技术对比研究了Brönsted酸和Lewis酸催化直链和侧链戊烯同分异构体转化作用机理的差异。结果表明,同时含有Brönsted/Lewis酸的Beta分子筛中,Brönsted酸起主要的活化作用,催化戊烯进行异构和叠合反应时均遵循经典的碳正离子机理;而AlCl3@Si-Beta中的Lewis酸不含氢质子或羟基,催化α-戊烯进行双键迁移和2-戊烯的顺反异构反应时遵循AB-AD机理,以类烯丙基物种作为中间体,无法催化戊烯进行骨架异构和叠合反应。
  • FIG. 2292.  FIG. 2292.

    FIG. 2292.  FIG. 2292.

    图  1  不同Beta分子筛的XRD谱图

    Figure  1  XRD patterns of different Beta zeolites

    图  2  不同样品的SEM照片

    Figure  2  SEM images of different samples

    图  3  AlCl3@Si-Beta样品的STEM-EDX 照片

    Figure  3  STEM-EDX mappings of AlCl3@Si-Beta

    图  4  (a)Si-Beta载体的FT-IR谱图,(b)不同样品的NH3-TPD谱图,(c)AlCl3@Si-Beta样品的Py-FTIR谱图和(d)Beta分子筛的Py-FTIR谱图

    Figure  4  (a) FT-IR spectra of Si-Beta support, (b) NH3-TPD spectra of different samples and Py-FTIR spectra of (c) AlCl3@Si-Beta and (d) Beta

    图  5  正丁烯和2-戊烯吸附在不同样品上的原位漫反射红外光谱谱图

    Figure  5  In situ DRIFTS of n-pentene and 2-pentene adsorbed on different samples

    图  6  Brönsted酸催化戊烯的反应路径示意图

    Figure  6  Reaction pathway of pentenes on Brönsted acid

    图  7  Lewis酸催化戊烯的反应路径示意图

    Figure  7  Reaction pathway of pentenes on Lewis acid

    图  8  2-甲基-1-丁烯和2-甲基-2-丁烯吸附在不同样品上的原位漫反射红外光谱谱图

    Figure  8  In-situ DRIFT spectra of 2-methyl-1-butene and 2-methyl-2-butene adsorbed on samples

    图  9  Brönsted和Lewis酸催化侧链戊烯的反应路径示意图

    Figure  9  Reaction pathway of pentenes with side chains on Brönsted and Lewis acids

    表  1  不同样品的织构性质

    Table  1  Textual properties of two samples.

    SampleSurface area/(m2·g−1)Volume b/
    (cm3·g−1)
    SBET aSmic bSext c
    Beta592.1335.1256.90.13
    AlCl3@Si-Beta465.7432.932.80.17
    a: SBET obtained by the BET method, b: Calculated from the t-plot method, c: Calculated from difference value of SBET and Smic
    下载: 导出CSV

    表  2  不同样品的酸性质

    Table  2  Acidic properties of samples

    SampleAcid types/(μmol Py·g−1) a
    Brönsted acid b Lewis acid c
    30 ℃200 ℃350 ℃30 ℃200 ℃350 ℃
    Beta160.4156.182.7 445.8124.9120.1
    AlCl3@Si-Beta0.00.00.0160.932.412.7
    a: Calculated from the band areas of the FT-IR spectra obtained by pyridine desorption at 30, 200, and 350 ℃, b: SBrönsted acid =1.88*A*0.65*0.65/M (A represents peak area at about 1540 cm−1; M represents mass of catalyst), c: SLewis acid = 1.42*A*0.65*0.65/M (A represents peak area at about 1450 cm−1; M represents mass of catalyst)
    下载: 导出CSV

    表  3  不同酸性分子筛催化戊烯反应的产物分布[29]

    Table  3  Product distribution of pentene isomers reactions on two zeolites with different acids[29]

    SampleReactantProduct distribution
    n-pentenecis-2-pentenetrans-2-pentene2-methyl-1-butene2-methyl-2-buteneC6 +
    Betan-pentene×
    cis-2-pentene×
    2-methyl-1-butene×
    2-methyl-2-butene×
    AlCl3@Si-Betan-pentene××××
    cis-2-pentene××××
    2-methyl-1-butene×××××
    2-methyl-2-butene×××××
    Reaction condition: 10% pentenes in helium and reaction temperature 100 ℃, “√” represents a large amount of product, “×” represents none, “−” represents a very small amount of product which can be ignored
    下载: 导出CSV
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  • 收稿日期:  2022-10-09
  • 修回日期:  2022-10-30
  • 录用日期:  2022-11-08
  • 网络出版日期:  2022-11-16
  • 刊出日期:  2023-05-15

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