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Production of renewable aromatics and olefins by catalytic co-cracking of fatty acid methyl esters and methanol

LIU Sen GUO Yu-qian SUN Pei-yong ZHANG Sheng-hong YAO Zhi-long

刘森, 国玉倩, 孙培永, 张胜红, 姚志龙. 脂肪酸甲酯和甲醇催化共裂化制备可再生芳烃和烯烃[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60146-9
引用本文: 刘森, 国玉倩, 孙培永, 张胜红, 姚志龙. 脂肪酸甲酯和甲醇催化共裂化制备可再生芳烃和烯烃[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60146-9
LIU Sen, GUO Yu-qian, SUN Pei-yong, ZHANG Sheng-hong, YAO Zhi-long. Production of renewable aromatics and olefins by catalytic co-cracking of fatty acid methyl esters and methanol[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60146-9
Citation: LIU Sen, GUO Yu-qian, SUN Pei-yong, ZHANG Sheng-hong, YAO Zhi-long. Production of renewable aromatics and olefins by catalytic co-cracking of fatty acid methyl esters and methanol[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60146-9

脂肪酸甲酯和甲醇催化共裂化制备可再生芳烃和烯烃

doi: 10.1016/S1872-5813(21)60146-9
详细信息
  • 中图分类号: O643

Production of renewable aromatics and olefins by catalytic co-cracking of fatty acid methyl esters and methanol

Funds: The project was supported by the National Natural Science Foundation of China (21703012) and the Scientific Research Project of Beijing Municipal Education Commission (KM 201910017010)
More Information
  • 摘要: 甘油三酸酯及其衍生物(如脂肪酸甲酯,FAMEs)催化裂化是制备可再生芳烃和烯烃的潜在途径,但该路径严重受限于HZSM-5分子筛催化剂的积碳失活。为调控FAMEs裂化产物分布并减缓催化剂的失活速率,本工作发展了FAMEs和甲醇催化共裂化的反应策略。结果表明:FAMEs和甲醇催化共裂化能够提高烯体的选择性并降低芳烃的选择性,在原料中甲醇含量为60%时芳烃和烯烃的总选择性高达70.9%。甲醇的引入不仅能够提高烯烃的收率,而且有助于抑制单环芳烃持续脱氢形成多环芳烃,进而减少积碳的生成并延长HZSM-5/Al2O3催化剂的使用寿命。在温度为450 ℃、压力为0.16 MPa、FAMEs空速为4 h−1和反应时长为12 h的条件下,引入等质量的甲醇能够将催化剂的积碳量从17.8%降低为10.1%。此外,FAMEs和甲醇共裂化反应中部分失活的HZSM-5/Al2O3可以通过简单焙烧进行再生,再生催化剂的结构、酸性和反应活性与新鲜催化剂相比无明显改变。
  • Figure  1  Simplified flow diagram of the setup for co-cracking FAMEs and methanol

    Figure  2  SEM images of Al2O3 (a), HZSM-5 (b), and HZSM-5/Al2O3 (c); XRD patterns (d) and N2 adsorption-desorption isotherms (e) of the steam-treated HZSM-5/Al2O3 catalyst.

    Figure  3  Effect of steam treatment on the NH3-TPD profiles (a), 29Si MAS NMR spectra (b), and Py-IR spectra (c,d) of HZSM-5/Al2O3 catalyst recorded at 200 and 350 ℃, respectively.

    Figure  4  Effect of the methanol blending ratios on the co-cracking of FAMEs and CH3OH over HZSM-5/Al2O3 catalysts (reaction conditions: 450 ℃, 0.16 MPa, WHSV (FAMEs) = 1 h−1)

    Figure  5  Effect of the methanol blending ratios on the selectivities of (a) aromatics, (b) olefins, and (c) paraffins in the co-cracking of FAMEs and CH3OH over HZSM-5/Al2O3 catalysts (reaction conditions: 450 ℃, 0.16 MPa, WHSV (FAMEs) = 1 h−1)

    Figure  6  Proposed reaction pathway for the co-cracking of FAMEs and CH3OH over the HZSM-5/Al2O3 catalyst[5-7, 22-26]

    Figure  7  Variation of FAMEs and CH3OH conversions with time-on-stream for the cracking of (a) FAMEs, (b) CH3OH, and (c) the mixture of FAMEs and CH3OH (conditions: 450 ℃, 0.16 MPa, WHSV (FAMEs) = 4 h−1, WHSV (CH3OH) = 4 h−1)

    Figure  8  TG curves of the used HZSM-5/Al2O3 catalysts after reaction for 12 h with different feeds (reaction conditions: 450 ℃, 0.16 MPa, WHSV (FAMEs) = 4 h−1, WHSV (CH3OH) = 4 h−1)

    Figure  9  XRD patterns (a), N2 adsorption-desorption isotherms (b), NH3-TPD profiles (c), and 29Si MAS NMR spectra (d) of the fresh, used, and reactivated HZSM-5/Al2O3 catalysts

    Figure  10  Reusability of the HZSM-5/Al2O3 catalyst for the co-cracking of FAMEs and methanol (conditions: 450 ℃, 0.16 MPa, WHSV (FAMEs) = 4 h−1, WHSV (CH3OH) = 4 h−1)

    Table  1  Physicochemical properties of HZSM-5/Al2O3 catalysts

    HZSM-5/Al2O3
    (Si/Al)f
    Specific surface area (m2·g−1)Pore volume (mL·g−1)
    internalexternaltotalmicroporemesoporetotal
    calcined23303423450.1630.2710.434
    steam-treated31232993310.1190.2820.401
    used32127351620.0600.1800.240
    reactivated322191133320.1110.3120.423
    下载: 导出CSV

    Table  2  Amount of Brønsted (B) and Lewis (L) acid sites determined by Py-IR on HZSM-5/Al2O3 catalysts.

    HZSM-5/Al2O3Total acid (mmol·g−1, 200 ℃)Medium & strong acid (mmol·g−1, 350 ℃)
    BLB+LB/LBLB+LB/L
    fresh0.350.0670.425.30.210.0440.264.8
    steam-treated0.170.0910.261.80.140.0490.192.8
    reactivated 0.200.0470.254.20.160.0410.203.9
    下载: 导出CSV
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  • 收稿日期:  2021-03-26
  • 修回日期:  2021-05-07
  • 网络出版日期:  2021-08-25

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