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基于Ru/HZSM-5的生物油在线催化提质耐久性研究

熊永莲 卢东升 樊永胜 侯光喜 陈玉炜

熊永莲, 卢东升, 樊永胜, 侯光喜, 陈玉炜. 基于Ru/HZSM-5的生物油在线催化提质耐久性研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60114-7
引用本文: 熊永莲, 卢东升, 樊永胜, 侯光喜, 陈玉炜. 基于Ru/HZSM-5的生物油在线催化提质耐久性研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60114-7
XIONG Yong-lian, LU Dong-sheng, FAN Yong-sheng, HOU Guang-xi, CHEN Yu-wei. Study on Durability of Online Catalytic Upgrading of Bio-oil Based on Ru/HZSM-5[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60114-7
Citation: XIONG Yong-lian, LU Dong-sheng, FAN Yong-sheng, HOU Guang-xi, CHEN Yu-wei. Study on Durability of Online Catalytic Upgrading of Bio-oil Based on Ru/HZSM-5[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60114-7

基于Ru/HZSM-5的生物油在线催化提质耐久性研究

doi: 10.1016/S1872-5813(21)60114-7
基金项目: 国家自然科学基金项目(51806186)和盐城工学院引进人才校级科研基金项目(XJ201708)
详细信息
    作者简介:

    熊永莲(1977-),女,博士,副教授,主要从事动力机械新能源开发与利用研究,E-mail:serena77@126.com

    通讯作者:

    樊永胜(1988-),男,博士,副教授,主要从事动力机械新能源开发与利用研究,E-mail:yongsheng_fan@163.com

  • 中图分类号: TK6; TQ35

Study on Durability of Online Catalytic Upgrading of Bio-oil Based on Ru/HZSM-5

Funds: National Natural Science Foundation of China (51806186) and the Scientific Research Project for the Introduction Talent of Yancheng Institute of Technology (XJ201708)
  • 摘要: 采用Ru/HZSM-5在线催化提质生物油,通过综合品质指数(TQI),分析生物油产率和理化特性变化,并对生物油化学组成及催化剂结焦情况进行分析。结果表明,使用新鲜催化剂所得生物油产率和理化特性均较高,TQI从0.15升至6.45;随着使用次数的增加,TQI先小幅升高至6.68,而后快速下降至1.25,第4次使用后TQI仅为0.27。初期少量结焦反应使强酸位点部分钝化,提升了芳构化性能,当催化剂使用2次时,生物油中烃类相对含量达53.79%,其中,轻质脂肪烃相对含量为16.87%,单环芳香烃相对含量为32.65%;当使用4次时,烃类相对含量仅为9.32%,催化层丧失提质作用,并对热解气产生二次裂解或聚合等不利影响。前两次使用,催化剂焦炭主要是附着在表面的低温热解焦炭;当使用3次时,低温热解焦炭和高温催化焦炭均显著增多,催化剂活性急剧下降;继续使用使焦炭小幅增加,且以热解焦炭增加为主。
  • 图  1  生物油在线催化提质实验系统

    1: temperature controller; 2: catalytic reactor; 3: filter; 4: globe valve A; 5: globe valve B; 6: globe valve C; 7: gas collector; 8: vacuum pump; 9: pressure stabilizing tube; 10: cooling tower; 11: bio-oil collector; 12: cold trap; 13: pyrolysis reactor

    Figure  1  Experimental system for online catalytic upgrading of bio-oil

    图  2  催化剂XRD衍射谱

    Figure  2  XRD patterns of catalysts

    图  3  生物油的化学组成

    Figure  3  Chemical compositions of bio-oils

    图  4  结焦催化剂的TG和DTG曲线

    Figure  4  TG and DTG curves of coked catalysts

    图  5  不同使用时间后催化剂的电镜扫描和透射照片

    Figure  5  SEM and TEM photos of the catalysts after different usage time

    表  1  催化剂酸性和纹理性质

    Table  1  Acidity and texture properties of catalysts

    CatalystB acid/
    (μmol·g-1)
    L acid/
    (μmol·g-1)
    SDFT/
    (m2·g-1)
    VDFT/
    (cm3·g-1)
    Smicro/
    (m2·g-1)
    Vmicro/
    (cm3·g-1)
    Average pore width/nm
    HZSM-5141.7833.55437.150.23324.180.120.98
    Ru/HZSM-5172.4617.10305.000.19230.490.081.02
    下载: 导出CSV

    表  2  生物油产率、理化特性和TQI的变化

    Table  2  The change of bio-oil yield, physicochemical properties and TQI

    Bio-oilYield/%VyieldpH valueVpHHHV
    /(MJ·kg-1)
    VHHVCarbon residue/%wCOxygen content/%wOTQI
    BO-043.251.132.220.5118.080.6916.721.8450.861.460.15
    BO-132.080.846.201.4232.811.263.350.3722.090.636.45
    BO-235.470.936.121.4032.901.263.550.3921.980.636.68
    BO-338.841.024.441.0226.261.017.890.8733.930.971.25
    BO-441.691.092.870.6620.080.7714.021.5445.671.310.27
    下载: 导出CSV

    表  3  BO-0与BO-4中相同化合物含量对比

    Table  3  Comparison of the contents of the same compounds in BO-0 and BO-4

    No.Compound nameStructureFormulaBO-0/%BO-4/%
    12-Cyclopenten-1-one, 2-methyl-C6H8O1.701.87
    2Ethanone, 1-(2-furanyl)-C6H6O21.321.20
    32-Cyclopenten-1-one, 3,4-dimethyl-C7H10O3.282.03
    41,2-Cyclopentanedione, 3-methyl-C6H8O27.946.51
    5Phenol, 2-methoxy-C7H8O211.948.90
    62-Cyclopenten-1-one, 3-ethyl-2-hydroxy-C7H10O23.303.19
    7Phenol, 2-methoxy-4-methyl-C8H10O21.443.03
    8Phenol, 4-ethyl-2-methoxy-C9H12O21.580.91
    9Phenol, 2,6-dimethoxy-C8H10O322.4121.46
    10Homovanillyl alcoholC9H12O32.774.07
    下载: 导出CSV

    表  4  不同使用时间后催化剂的结焦量

    Table  4  Coke contents of the catalysts after different usage time

    CatalystFitting
    / ℃
    Peak temperature/ ℃Peak area/%Coefficient R2
    MainAcromionMainAcromionTotal
    SC-1384~6744946041.270.271.540.9660
    SC-2383~6744946031.730.372.100.9661
    SC-3352~7685226647.311.969.270.9975
    SC-4308~7074836138.132.1810.310.9935
    下载: 导出CSV
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  • 收稿日期:  2021-04-19
  • 修回日期:  2021-05-11
  • 网络出版日期:  2021-06-12

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