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杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃

蔡伟 黄明 朱亮 郑宇博 蔡博 马中青

蔡伟, 黄明, 朱亮, 郑宇博, 蔡博, 马中青. 杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2023004
引用本文: 蔡伟, 黄明, 朱亮, 郑宇博, 蔡博, 马中青. 杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2023004
CAI Wei, HUANG Ming, ZHU Liang, ZHENG Yu-bo, CAI Bo, MA Zhong-qing. Enhancement of the production of light aromatics from poplar wood by combined approach of wet torrefaction pretreatment and catalytic fast pyrolysis using metal modified hierarchical zeolite[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023004
Citation: CAI Wei, HUANG Ming, ZHU Liang, ZHENG Yu-bo, CAI Bo, MA Zhong-qing. Enhancement of the production of light aromatics from poplar wood by combined approach of wet torrefaction pretreatment and catalytic fast pyrolysis using metal modified hierarchical zeolite[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2023004

杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃

doi: 10.19906/j.cnki.JFCT.2023004
基金项目: “领雁”研发攻关计划项目(2022C03092),浙江省自然科学基金(LY21E060001),浙江省属高校基本科研业务费专项资金资助(2020YQ006),国家林业和草原局科技创新青年拔尖人才项目(2019132617), 浙江大学能源清洁利用国家重点实验室开放基金(ZJU-CEU2020021)
详细信息
    作者简介:

    蔡伟(1999—),男,硕士研究生,caiwei962464@163.com

    通讯作者:

    E-mail: mazq@zafu.edu.cn

  • 中图分类号: TK6

Enhancement of the production of light aromatics from poplar wood by combined approach of wet torrefaction pretreatment and catalytic fast pyrolysis using metal modified hierarchical zeolite

Funds: The project was supported by the Key R & D Program of Zhejiang Province (2022C03092), Natural Science Foundation of Zhejiang Province (LY21E060001), the Fundamental Research Funds for the Provincial Universities of Zhejiang (2020YQ006), the Youth Talent Support Program by National Forestry and Grassland Administration (2019132617), the Open Foundation from the State Key Laboratory of Clean Energy Utilization (ZJU-CEU2020021)
  • 摘要: 轻质芳烃是化工领域重要的基础有机原料,生物质催化热解的技术路线可制取生物基的轻质芳烃化学品。首先,采用湿法烘焙预处理,对杨木进行协同脱氧和脱灰改性提质;其次,采用NaOH脱硅预处理和负载活性金属(Zn、Ga和Fe),对微孔HZSM-5进行修饰改性,构建金属改性多级孔HZSM-5催化剂,并将其用于湿法烘焙杨木催化热解,研究烘焙温度、催化剂改性、催化剂与原料质量比和热解温度等参数对轻质芳烃产率的影响。结果表明,随着湿法烘焙温度的增加,杨木的脱氧率和碱/碱土金属脱除率逐渐增加,其中O元素、K、Mg、Ca和Na的最大脱除率分别为47.96%、90.99%、86.65%、66.09%和36.29%。与HZSM-5相比,采用NaOH脱硅后的多级孔HZSM-5(Hie-H)及金属改性的多级孔HZSM-5(Ga/Hie-H、Zn/Hie-H和Fe/Hie-H),均促进了轻质芳烃的形成,其中Zn/Hie-H对杨木湿法烘焙后固体产物催化热解制取轻质芳烃产率最高;在湿法烘焙温度为220 ℃,Zn/Hie-H与烘焙杨木质量比为3∶1,热解温度为850 ℃时,轻质芳烃的产率达到最大值,为7.83 × 107 p.a./mg。
  • 图  1  湿法烘焙温度对碱和碱土金属含量(a)、结晶度(b)和表面官能团(c)的影响

    Figure  1  Effect of wet torrefaction temperature on the contents of alkali and alkali earth metals, crystallinity, and the surface chemical functional groups

    图  2  金属改性前后多级孔HZSM-5催化剂的 N2吸附-脱附等温曲线(a),孔径分布曲线(b)和NH3-TPD曲线(c)

    Figure  2  N2 adsorption-desorption isotherms (a), pore size distribution curves (b), and NH3-TPD profiles of the parent and metal modified hierarchical HZSM-5

    图  3  湿法烘焙温度对杨木非催化热解生物油组分的影响

    Figure  3  Effect of wet torrefaction temperature on the components in bio-oil derived from non-CFP of PW

    图  4  碱改性处理和金属修饰HZSM-5催化剂对烘焙杨木催化热解生物油组分分布的影响

    Figure  4  Effect of the NaOH and metal modified HZSM-5 on the compound distribution in bio-oil during CFP of torrefied PW

    图  5  催化剂与烘焙杨木的质量比对催化热解生物油组分的影响

    Figure  5  Effect of the mass ratio of catalyst and wet torrefied PW on the compound distribution in bio-oil during CFP of torrefied PW

    图  6  催化热解温度对生物油组分的影响

    Figure  6  Effect of pyrolysis tempearture on the compound distribution in bio-oil during CFP of torrefied PW

    表  1  湿法烘焙温度对杨木基本特性的影响

    Table  1  Effect of wet torrefaction temperature on the yield of torrefied products and the basic properties of torrefied PW

    Temperature (℃)Mass yields of torrefied product (%)Ultimate analysis (%)Proximate analysis (%)Other properties
    GasLiquidSolidCHOAshVolatileFixed carbonHHV (MJ·kg−1)O/C ratioDeoxygenation rate (%)Energy
    yield (%)
    Raw\\\46.696.2047.024.3282.1713.5116.230.76\\
    1802.0727.0270.9449.336.1944.370.0984.0815.8317.620.675.6477.02
    2003.4132.5864.0152.076.0041.710.3481.0618.6018.580.6011.2973.28
    22012.4635.5452.0052.895.9141.162.0872.8625.0618.990.5812.4660.84
    24014.9137.1947.9060.285.7833.922.6062.7034.7022.610.4227.8656.23
    26016.5040.1743.3370.155.3724.473.4057.4839.1227.060.2647.9649.76
    下载: 导出CSV

    表  2  金属改性前后多级孔HZSM-5催化剂的孔结构特征和酸量

    Table  2  Pore structural characteristics and acid amount of the parent and metal modified hierarchical HZSM-5

    CatalystaSBET (m2·g−1)bVTotal (cm3·g−1)cVMicro (cm3·g−1)dVMeso (cm3·g−1)eDPore (nm)Weak acid (mmol·g−1)Strong acid (mmol·g−1)Total acid (mmol·g−1)
    HZSM-5288.4900.2120.1360.0762.3650.4600.6001.060
    Hie-H357.7290.2710.1170.1533.0300.6250.2300.855
    Ga/Hie-H309.8390.2520.1020.1513.2570.7690.1050.874
    Fe/Hie-H296.6130.2310.1050.1253.1130.6800.1390.819
    Zn/Hie-H298.3960.2260.1020.1253.0360.7480.1020.850
    aSBET: Specific surface area. bVTotal: Total pore volume. cVMicro: Micropore volume. dVMeso: Mesopore volume. eDPore: Average pore diameter
    下载: 导出CSV
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  • 收稿日期:  2022-11-17
  • 录用日期:  2022-12-30
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