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钙钛矿催化木质素水热液化

娄静 廖玮婷 王智玉 李璐 李雁 解新安

娄静, 廖玮婷, 王智玉, 李璐, 李雁, 解新安. 钙钛矿催化木质素水热液化[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60004-5
引用本文: 娄静, 廖玮婷, 王智玉, 李璐, 李雁, 解新安. 钙钛矿催化木质素水热液化[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60004-5
LOU Jing, LIAO Wei-ting, WANG Zhi-yu, LI Lu, LI Yan, XIE Xin-an. Hydrothermal liquefaction of lignin to aromatics over the perovskite catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60004-5
Citation: LOU Jing, LIAO Wei-ting, WANG Zhi-yu, LI Lu, LI Yan, XIE Xin-an. Hydrothermal liquefaction of lignin to aromatics over the perovskite catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60004-5

钙钛矿催化木质素水热液化

doi: 10.1016/S1872-5813(22)60004-5
基金项目: 国家自然科学基金(21576107)资助
详细信息
    通讯作者:

    E-mail: xinanxie@scau.edu.cn

  • 中图分类号: TK6

Hydrothermal liquefaction of lignin to aromatics over the perovskite catalysts

Funds: The project was supported by the National Natural Science Foundation of China (21576107)
  • 摘要: 以碱木质素为原料,采用GC-MS、FT-IR、元素分析等实验表征手段并结合DFT计算,对LaBO3钙钛矿(LaCoO3、LaFeO3和LaNiO3)催化液化木质素的性能进行了研究,考察了反应时间、温度、催化剂用量和B位阳离子对木质素转化率、生物油收率及生物油化合物分布的影响。结果表明,三种钙钛矿都能促进木质素的裂解生成芳香族化合物,但LaCoO3木质素液化催化性最好,其次为LaNiO3和LaFeO3。LaCoO3添加量为5%、180 °C下反应60 min时,生物油产率最高达67.20%,单芳香族化合物的相对含量最高达89.59%。LaBO3晶体表面的氧原子通过吸附木质素中的氧原子降低了木质素分子内键的解离能(LaCoO3的吸附能最大),同时其疏松多孔的形貌和适中的氧化还原能力,能够有效促进木质素分子内的C−C和CAr−OCH3的断裂,实现大分子解聚和脱甲氧基反应,生成苯酚等高附加值化合物。
  • 图  1  三种钙钛矿催化剂的表征

    Figure  1  FT-IR spectra (a), XRD patterns (b) and SEM images (c) of three LaBO3 perovskites

    (a): FT-IR; (b): XRD; (c): SEM

    图  2  催化剂用量对LaCoO3上木质素HTL和生物油组分分布的影响

    Figure  2  Effect of catalyst dosage on the lignin conversion, bio-oil yield, and product distribution for the HTL of lignin over LaCoO3

    Reaction conditions: 2.000 g AL + 150 mL methanol, reaction at 180 °C for 60 min

    图  3  反应温度对LaBO3上木质素的液化及生物油化合物分布的影响

    Figure  3  Effect of reaction temperature on the HTL of lignin over three LaBO3 perovskites

    (a): LaCoO3; (b): LaFeO3; (c): LaNiO3 Reaction conditions: 2.000 g AL + 150 mL methanol; reaction time, 60 min; catalyst dose, 5.0%

    图  4  反应时间对LaCoO3催化木质素液化和生物油组分分布的影响

    Figure  4  Effect of reaction time on HTL of lignin over LaCoO3

    Reaction condition: 2.000 g AL + 150 mL methanol, 180 °C, catalyst dose: 5.0%

    图  5  木质素原料及液化木质素产生残渣的FT-IR谱图

    Figure  5  FT-IR spectra of raw lignin and residue produced from lignin HTL over various LaBO3 perovskite catalysts

    Reaction conditions: 2.000 g AL + 150 mL methanol, reaction time, 60 min; catalyst dose, 5.0%

    图  6  模型分子在LaBO3表面的吸附模型及吸附能

    a:吸附能, b:吸附模型 (C:黑色,H:白色,O:红色,La:蓝色,Co:紫色,Fe:黄色,Ni:绿色)

    Figure  6  Adsorption energy (a) and views of adsorption model (b) of m-methoxy-phenol on LaBO3

    (a): Calculated energies for molecular adsorption, (b): Views of the adsorption model(C: black, H: white, O: red, La: blue, Co: purple, Fe: yellow, Ni: green)

    图  7  模型分子(GGE)与LaCoO3表面的吸附模型及吸附前后分子结构

    Figure  7  Adsorption energy (a) and views of adsorption model (b) of guaiac-based glycerol ether (GGE) on LaBO3

    (a): Views of the adsorption model; (b): Molecular structure before and after adsorption of GGE(C: black, H: white, O: red, La: blue, Co: purple)

    表  1  木质素原料及液化木质素产生残渣的元素分析

    Table  1  Elemental composition (%) of the raw lignin and residue produced under non-catalytic and catalytic HTL

    SampleUltimate analysis w /%
    CHNO
    Lignin 40.72 4.13 0.51 53.07
    Non-catalyst 38.29 3.95 0.50 54.26
    LaCoO3 32.25 5.28 0.62 57.62
    LaFeO3 33.43 5.57 0.59 56.63
    LaNiO3 32.18 5.24 0.67 56.59
    下载: 导出CSV

    表  2  愈创木酚在LaBO3上吸附后的主要含氧键长

    Table  2  Major oxygen-contained bond length of guaiacol over three LaBO3 perovskite catalysts

    CatalystOxygen-contained bond typeBio-oil yield under
    optimal conditions w/%
    CAr–OCH3CArO–CH3
    Bond lengtha 1.387 1.433 43.73
    LaCoO3 Bond lengthb 1.389 1.431 67.20
    c 0.002 − 0.002
    LaFeO3 Bond lengthb 1.393 1.434 56.69
    c 0.006 0.001
    LaNiO3 Bond lengthb 1.390 1.432 59.74
    c 0.003 − 0.001
    a: Bond length in molecular alone; b: Bond lengths of molecular adsorbed by different perovskite catalysts; c: Difference between the bond length in molecular alone and in adsorbed molecular
    下载: 导出CSV
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  • 收稿日期:  2022-01-04
  • 修回日期:  2022-02-12
  • 网络出版日期:  2022-05-19

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