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离子液体中异丁烷/2-丁烯烷基化反应机理研究

王丽红 李瑞 刘鹰 胡瑞生

王丽红, 李瑞, 刘鹰, 胡瑞生. 离子液体中异丁烷/2-丁烯烷基化反应机理研究[J]. 燃料化学学报, 2016, 44(6): 738-744.
引用本文: 王丽红, 李瑞, 刘鹰, 胡瑞生. 离子液体中异丁烷/2-丁烯烷基化反应机理研究[J]. 燃料化学学报, 2016, 44(6): 738-744.
WANG Li-hong, LI Rui, LIU Ying, HU Rui-sheng. Reaction mechanism of isoparaffin alkylation in the presence of ionic liquid[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 738-744.
Citation: WANG Li-hong, LI Rui, LIU Ying, HU Rui-sheng. Reaction mechanism of isoparaffin alkylation in the presence of ionic liquid[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 738-744.

离子液体中异丁烷/2-丁烯烷基化反应机理研究

基金项目: 

国家自然科学基金 21266015, 20806036

详细信息
  • 中图分类号: TE624.9

Reaction mechanism of isoparaffin alkylation in the presence of ionic liquid

More Information
  • 摘要: 以复合离子液体[Et3NH]Cl-AlCl3-CuCl为催化剂, 在连续搅拌釜式反应器中进行了异丁烷与2-丁烯烷基化反应; 利用氘代异丁烷同位素示踪法研究了催化反应机理。结果表明, 在离子液体中异丁烷烷基化的反应诱导期较短; 三甲基戊烷产物主要源于异丁烷的自烷基化、丁烷/丁烯的直接烷基化以及C12+中间体的裂化反应, 而大部分二甲基己烷是仲丁基碳正离子与丁烯加成的产物。
  • 图  1  异丁烷/2-丁烯连续烷基化反应装置示意图

    Figure  1  Schematic diagram of the continuous stirred tank reactor for the alkylation of isobutane with 2-butene

    图  2  H2SO4催化异丁烷和2-丁烯反应产物分布随时间的变化

    Figure  2  Product distribution with time on stream for the alkylation of isobutane with 2-butene catalyzed by H2SO4

    图  3  CIL催化异丁烷和2-丁烯反应产物分布随时间的变化

    Figure  3  Product distribution with time on stream for the alkylation of isobutane with 2-butene catalyzed by CIL

    图  4  CIL中的烷基化阶段气相2-丁烯的加入量 (B) 与气相异丁烷的消耗量 (S)

    Figure  4  Consumption of isobutane (S) and amount of 2-butene added (B) during the alkylation of isobutane with 2-butene catalyzed by CIL

    图  5  异丁烷m/z=41.0丰度峰随反应时间的变化

    Figure  5  (a) Mass spectrum of i-C4H10 and i-C4D10; (b) Relative abundance of i-C4D10 at m/z=41.0 with time on stream for the alkylation catalyzed by CIL

    图  6  离子液体催化C4烷基化反应机理

    Figure  6  Proposed reaction mechanism for the alkylation of isobutane with 2-butene catalyzed by CIL

    表  1  异丁烷/2-丁烯烷基化C8产物分布a

    Table  1  Product distribution of isobutane/ 2-butene alkylation a

    ComponentMolecular weightH2SO4 [Et3NH]Cl-AlCl3-CuCl
    Alkane
    TMP (C8H8D10)124 -0.05
    2, 2, 4-TMP (C8H18)1149.1313.63
    TMP (C8H5D13)127 -0.04
    2, 2-DMH (C8H18)114 -0.01
    2, 4-DMH (C8H18)1143.22.71
    2, 5-DMH (C8H18)1144.512.28
    2, 2, 3-TMP (C8H18)1140.921.66
    TMP (C8H9D9)123 -0.12
    TMP (C8H16D2)116 -0.24
    3, 3-DMH (C8H18)114 -0.01
    2, 3, 4-TMP (C8H18)1146.0113.72
    2, 2, 3-TMP (C8H18)1148.1211.43
    TMP (C8D18)132 -0.02
    a the mixture of i-C4D10 (5g), i-C4H10 (50g) was used as the feed and sampling was made after continuous reaction for 30min
    下载: 导出CSV

    表  2  不同催化剂中异丁烷/2-丁烯烷基化副产物的分布

    Table  2  Side-product distribution of isobutane/ 2-butene alkylation

    ComponentMolecular weightH2SO4 [Et3NH]Cl-AlCl3-CuCl
    C4H10595.23
    C4H9D59 0.36
    C5H12722.730.16
    C6H14864.480.30
    C7H161005.211.14
    C6D14100 -0.04
    C8H1611217.361.01
    C12H24D2172 -0.16
    C12H12D14184 -0.08
    C12H18D8178 -0.02
    C12H12D14184 -0.05
    C12H2617011.8423.62
    下载: 导出CSV
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出版历程
  • 收稿日期:  2015-12-30
  • 修回日期:  2016-04-09
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-06-10

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