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Fe原位改性小晶粒Silicalite-1分子筛催化醛氨缩合性能研究

陶金泉 贾亦静 白天瑜 黄文斌 崔岩 周亚松 魏强

陶金泉, 贾亦静, 白天瑜, 黄文斌, 崔岩, 周亚松, 魏强. Fe原位改性小晶粒Silicalite-1分子筛催化醛氨缩合性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60443-3
引用本文: 陶金泉, 贾亦静, 白天瑜, 黄文斌, 崔岩, 周亚松, 魏强. Fe原位改性小晶粒Silicalite-1分子筛催化醛氨缩合性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60443-3
TAO Jinquan, JIA Yijing, BAI Tianyu, HUANG Wenbin, CUI Yan, ZHOU Yasong, WEI Qiang. Study on the catalytic performance of Fe in-situ modified small crystallite Silicalite-1 zeolite in Chichibabin condensation reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60443-3
Citation: TAO Jinquan, JIA Yijing, BAI Tianyu, HUANG Wenbin, CUI Yan, ZHOU Yasong, WEI Qiang. Study on the catalytic performance of Fe in-situ modified small crystallite Silicalite-1 zeolite in Chichibabin condensation reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60443-3

Fe原位改性小晶粒Silicalite-1分子筛催化醛氨缩合性能研究

doi: 10.1016/S1872-5813(24)60443-3
详细信息
    通讯作者:

    E-mail: qwei@cup.edu.cn

  • 中图分类号: O643.36

Study on the catalytic performance of Fe in-situ modified small crystallite Silicalite-1 zeolite in Chichibabin condensation reaction

  • 摘要: 吡啶及其衍生物统称为吡啶碱,其广泛应用于农药、医药等领域。Chichibabin醛氨缩合反应是目前工业制取吡啶碱最广泛的路线。目前,使用最广泛的ZSM-5分子筛受制于硅铝骨架结构的不稳定性,高活性反应周期较短(5 h),针对这一问题,本研究选用热稳定性、水热稳定性优异的Silicalite-1分子筛,使用聚乙烯吡咯烷酮(PVP)作为胶体分散剂,在水热合成分子筛的过程中向骨架中引入Fe,结合XRD、SEM、TG、BET、NH3-TPD、Py-FTIR等表征方法探究了晶化条件对Silicalite-1分子筛结晶度、孔结构和酸性质的影响。实验结果表明,在晶种投入量15%、PVP添加量3.75%时产品相对结晶度达到最高(103%),粒径约为200 nm。改性后的Silicalite-1具有更丰富的酸位点,醛氨缩合反应的初始活性由66%增加至85%,在反应进行15 h后,原料转化率和吡啶碱收率分别保持在66%和40%以上。研究提出的原位改性Silicalite-1分子筛策略极大扩宽了纯硅沸石在酸催化领域的应用,具有显著的科研价值和工业化潜力。
  • 图  1  Silicalite-1晶种的XRD谱图和SEM图像

    Figure  1  XRD spectrum and SEM photographs of Silicalite-1 SEED

    图  2  不同晶种加入量合成Fe-S-1分子筛XRD谱图

    Figure  2  XRD patterns of Fe-S-1 zeolites synthesized with different seed addition amounts

    图  3  不同晶种加入量合成Fe-S-1分子筛SEM图像

    Figure  3  SEM photographs of Silicalite-1 zeolites synthesized with different seed addition amounts(x% SEED, x=0 (a), x=5 (b), x=10 (c), x=15 (d))

    图  4  不同TPAOH加入量合成Fe-S-1分子筛XRD谱图

    Figure  4  XRD patterns of Fe-S-1 zeolites synthesized with different TPAOH addition amounts

    图  5  Fe-S-1分子筛的合成过程示意图

    Figure  5  Schematic diagram of the synthesis process of Fe-S-1 zeolite

    图  6  不同PVP添加量合成Fe-S-1分子筛XRD谱图

    Figure  6  XRD spectrum of Fe-S-1 zeolites synthesized under different PVP addition amounts conditions

    图  7  不同PVP添加量合成Fe-S-1分子筛SEM图像

    Figure  7  SEM photographs of Fe-S-1 zeolites synthesized under different PVP addition amounts conditions

    (a): 0 PVP; (b): 2.5% PVP; (c): 3.75% PVP; (d): EDS for 3.75%PVP sample (c+).

    图  8  PVP添加量3.75%时合成Fe-S-1分子筛的TEM图像

    Figure  8  TEM photographs of Fe-S-1 zeolites synthesized with 3.75% PVP

    图  9  TS-S-1分子筛(a)和Fe-S-1分子筛(b)的TG/DTG曲线

    Figure  9  TG/DTG spectrum of TS-S-1 zeolite (a) and Fe-S-1 zeolite (b)

    图  10  Fe-S-1分子筛的酸性表征与分析

    Figure  10  (a) Py-FTIR spectrum, (b) NH3-TPD spectrum, (c) XPS spectrum and (d) FT-IR spectrum of Fe-S-1 zeolite

    图  11  TS-S-1和T-S-1催化剂的总碳转化率(a),吡啶碱收率(b)和吡啶碱选择性(c)Fe-S-1、TS-S-1与HZSM-5催化剂的总碳转化率(d),吡啶碱收率(e)和吡啶碱选择性(f)

    Figure  11  Total carbon conversion rate (a), pyridine bases yield (b), and pyridine bases selectivity (c) of TS-S-1 and T-S-1 catalysts,Total carbon conversion rate (d), pyridine bases yield (e), and pyridine bases selectivity(f) of Fe-S-1, TS-S-1, and HZSM-5 catalysts

    图  12  新鲜催化剂(a)与反应后催化剂(b)的XRD谱图

    Figure  12  XRD spectrum of the fresh catalyst (a) and the catalyst after reaction (b)

    表  1  Silicalite-1分子筛的孔结构

    Table  1  Pore structure properties of Silicalite-1 zeolites

    Sample PVP/% SBET/(m2·g−1) SMicro/(m2·g−1) vTotal/(cm3·g−1) vMicro/(cm3·g−1) vMeso/(cm3·g−1)
    Fe-S-1 3.75 348 215 0.18 0.10 0.08
    TS-S-1 3.75 341 211 0.18 0.11 0.07
    TS-S-1 357 231 0.18 0.11 0.07
    T-S-1 3.75 302 235 0.19 0.11 0.08
    T-S-1 311 247 0.18 0.11 0.07
    下载: 导出CSV

    表  2  Fe-S-1分子筛样品元素分析与酸性

    Table  2  Elemental composition analysis and acidity of Fe-S-1 zeolite sample

    Sample PVP addition
    amount/%
    Fe/% Si/% Fe/Si Acidityc/(μmol·g−1)
    balka surfaceb balka surfaceb balka surfaceb 200 ℃ 300 ℃
    BASd LASe BASd LASe
    Fe-S-1 3.75 2.39 2.21 23.24 22.12 0.10 0.10 7.2 19.9 5.8 7.9
    Fe-S-1 2.5 1.91 1.59 20.31 19.41 0.09 0.08 6.3 16.3 4.9 8.1
    TS-S-1 0 24.12 22.60 1.3 6.7 0.8 3.0
    a: ICP test result; b: XPS test result; c: Py-FTIR test result; d: Brønsted acid site; e: Lewis acid site.
    下载: 导出CSV

    表  3  反应前后催化剂的孔结构和酸性质对比

    Table  3  Comparison of the pore structure and acidity properties of the catalyst before and after the reaction

    Sample Before reaction After reaction Acid loss/% SBET loss/% R.C. lossa/%
    total acid/(μmol·g−1) SBET/(m2·g−1) total acid/(μmol·g−1) SBET/(m2·g−1)
    200HZ-5 594 351 210 195 64.5 44.4 67
    130HZ-5 1791 345 415 206 77.6 40.2 71
    70HZ-5 2166 383 598 163 72.4 57.4 77
    TS-S-1 47 357 16 233 65.9 34.7 29
    Fe-S-1 227 348 127 261 44.8 26.8 33
    Note: (a) the difference in relative crystallinity (R.C.) between fresh catalyst and waste catalyst before and after the reaction.
    下载: 导出CSV
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  • 收稿日期:  2024-02-27
  • 修回日期:  2024-03-20
  • 录用日期:  2024-03-20
  • 网络出版日期:  2024-04-10

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