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山梨醇快速热解特性与反应机理研究

胡斌 郭学文 李洋 程安帅 刘吉 陆强

胡斌, 郭学文, 李洋, 程安帅, 刘吉, 陆强. 山梨醇快速热解特性与反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60150-0
引用本文: 胡斌, 郭学文, 李洋, 程安帅, 刘吉, 陆强. 山梨醇快速热解特性与反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60150-0
HU Bin, GUO Xue-wen, LI Yang, CHENG An-shuai, LIU Ji, LU Qiang. Reaction characteristics and mechanisms of sorbitol fast pyrolysis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60150-0
Citation: HU Bin, GUO Xue-wen, LI Yang, CHENG An-shuai, LIU Ji, LU Qiang. Reaction characteristics and mechanisms of sorbitol fast pyrolysis[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60150-0

山梨醇快速热解特性与反应机理研究

doi: 10.1016/S1872-5813(21)60150-0
基金项目: 国家自然科学基金(52006069, 51922040),中国博士后科学基金(2021T140202)和新能源电力系统国家重点实验室自主课题(LAPS202111)资助
详细信息
    作者简介:

    胡斌:binhu92@126.com

    通讯作者:

    Tel: 01061771335,E-mail: qianglu@mail.ustc.edu.cn,qlu@ncepu.edu.cn

  • 中图分类号: TK6

Reaction characteristics and mechanisms of sorbitol fast pyrolysis

Funds: The project was supported by the National Natural Science Foundation of China (52006069, 51922040), China Postdoctoral Science Foundation (2021T140202) and State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources (LAPS202111)
  • 摘要: 山梨醇是一种重要的生物质资源,但其热解特性和反应机理还鲜有研究。本文结合快速热解实验和密度泛函理论(DFT)计算,深入探究了山梨醇快速热解主要产物的生成机理与竞争关系。结果表明,山梨醇快速热解产物主要包括:小分子产物羟基乙醛(HAA)、羟基丙酮(HA)等,呋喃类产物糠醛(FF)、1-(2-呋喃基)-乙酮(2-FE)等和脱水糖产物异山梨醇(IS)。小分子产物HA和HAA生成路径的反应能垒较低,因此产率最高,且HA生成过程中伴随着HAA的生成。呋喃类产物2-FE和FF生成能垒相对较高,其能量最优路径与小分子产物生成路径具有相同中间体,但竞争性较弱,因而产率低于小分子产物。脱水糖产物IS生成路径较为简单,不与其他产物共享相同中间体,但反应能垒很高,导致产率很低。本研究为山梨醇选择性热解的机理研究和技术开发奠定了一定的理论基础。
  • 图  1  优化的山梨醇3D结构

    Figure  1  Optimized 3D geometry of sorbitol

    图  2  山梨醇500 ℃快速热解产物的离子总图(a)与主要产物绝对峰面积(b)

    Figure  2  Total ion chromatogram of the sorbitol fast pyrolysis at 500 ℃ (a) and the absolute peak areas of the main products (b)

    图  3  山梨醇快速热解初始反应(单位:kJ/mol)

    Figure  3  Categories of initial reaction pathways for the fast pyrolysis of sorbitol (unit: kJ/mol)

    图  4  HA生成的可能路径(A类路径)

    Figure  4  Possible pathways for HA generation (Type A pathways)

    图  5  HAA生成的可能路径(B类路径)

    Figure  5  Possible pathways for HAA generation (Type B pathways)

    图  6  小分子产物生成的优势路径势能图(a)及过渡态的3D结构(b)

    Figure  6  The energy diagrams (a) and 3D geometries of transition states (b) for the favorable formation pathways of low molecular weight compounds

    图  7  2-FE生成的可能路径(C类路径)

    Figure  7  Possible pathways for 2-FE generation (Type C pathways)

    图  8  FF生成的可能路径(D类路径)

    Figure  8  Possible pathways for FF generation (Type D pathways)

    图  9  呋喃类产物生成的优势路径势能图(a)及过渡态的3D结构(b)

    Figure  9  The energy diagrams (a) and 3D geometries of transition states (b) for the favorable formation pathways of furan products

    图  10  IS生成的可能路径(E类路径,单位:kJ/mol)

    Figure  10  Possible pathways for IS generation (Type E pathways, unit: kJ/mol)

    图  11  各类型反应路径竞争关系

    Figure  11  Competitive relationship of various types of pathways

    表  1  山梨醇快速热解产物

    Table  1  Products in sorbitol fast pyrolysis

    Time (min)Name
    2.1643-hydroxy-butanal
    2.3022,3-butanedione
    2.357hydroxyacetaldehyde (HAA)
    2.528propylene glycol
    2.704benzene
    3.112hydroxyacetone (HA)
    4.1691-hydroxy-2-butanone
    4.902unknown
    5.1172-furanmethanol
    5.166furfural (FF)
    5.3102-methyl-furan
    5.6902-butanone
    6.0421-(2-furanyl)-ethanone (2-FE)
    6.2901,2-cyclopentanedione
    6.555phenol
    6.7645-methyl-2-furancarboxaldehyde
    7.4363-methyl-(1,2-cyclopentanedione)
    10.581isosorbitol (IS)
    下载: 导出CSV

    表  2  小分子产物生成路径决速步及能垒

    Table  2  Rate-determining steps and energy barriers of formation pathways for low molecular weight compounds

    Type A pathwaysrate-determining stepenergy barrier△G(kJ/mol)Type B pathwaysrate-determining stepenergy barrier△G(kJ/mol)
    A1Sorbitol→A1-i1305.8B1Sorbitol→B1-i1267.2
    A2Sorbitol→A2-i1281.7B2Sorbitol→B2-i1275.6
    A3Sorbitol→A3-i1314.7B3EG→B3-i3275.2
    A4Sorbitol→A4-i1276.1B4Sorbitol→B4-i1296.3
    A5Sorbitol→A5-i1305.7B5Sorbitol→B5-i1285.5
    A6Sorbitol→A6-i1303.5B6Sorbitol→B6-i1305.9
    A7Sorbitol→A7-i1314.7B7Sorbitol→B7-i1306.2
    A8Sorbitol→A8-i1292.2B8Sorbitol→B8-i1296.2
    B9Sorbitol→B9-i1304.4
    B10Sorbitol→B10-i1303.5
    下载: 导出CSV

    表  3  呋喃类产物生成路径决速步及能垒表

    Table  3  Rate-determining steps and energy barriers of formation pathways for furan products

    Type C pathwaysrate-determining stepenergy barrier
    G(kJ/mol)
    Type D pathwaysrate-determining stepenergy barrier
    G(kJ/mol)
    C1Sorbitol→C1-i1305.7D1D1-i3→D1-i4366.0
    C2Sorbitol→C2-i1305.7D2D2-i1→D2-i2382.0
    C3Sorbitol→C3-i1292.3D3D3-i3→D3-i4392.6
    C4Sorbitol→C4-i1305.9D4D4-i1→D4-i2374.1
    C5Sorbitol→C5-i1305.9D5Sorbitol→D5-i1369.8
    C6C6-i4→C6-i5325.4D6Sorbitol→D6-i1381.3
    下载: 导出CSV

    表  4  呋喃类产物优势路径与具有相同中间体的竞争路径比较

    Table  4  Comparison of the favorable formation pathways for furan products and the competitive pathways with the same intermediates

    Competitive pathwaysSame intermediateEnergy barriers in subsequent reactions
    A8, C3, D2A8-i1A8 (A8-i2→A8-i3, 219.4)
    C3 (A8-i1→C3-i2, 262.4)
    D2 (A8-i1→D3-i2, 382.4)
    B10, D1B10-i1B10 (B10-i3→B10-i4, 232.4)
    D1 (D1-i2→D1-i3, 366.0)
    下载: 导出CSV
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  • 收稿日期:  2021-06-30
  • 修回日期:  2021-07-29
  • 网络出版日期:  2021-09-03

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