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活性炭和HY分子筛复合催化促进生物质热解挥发物转化机理研究

徐吉 吴博文 韩震 胡浩权 靳立军

徐吉, 吴博文, 韩震, 胡浩权, 靳立军. 活性炭和HY分子筛复合催化促进生物质热解挥发物转化机理研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60447-0
引用本文: 徐吉, 吴博文, 韩震, 胡浩权, 靳立军. 活性炭和HY分子筛复合催化促进生物质热解挥发物转化机理研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60447-0
XU Ji, WU Bowen, HAN Zhen, HU Haoquan, JIN Lijun. Catalytic conversion of biomass pyrolysis volatiles over composite catalysts of activated carbon and HY zeolite[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60447-0
Citation: XU Ji, WU Bowen, HAN Zhen, HU Haoquan, JIN Lijun. Catalytic conversion of biomass pyrolysis volatiles over composite catalysts of activated carbon and HY zeolite[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60447-0

活性炭和HY分子筛复合催化促进生物质热解挥发物转化机理研究

doi: 10.1016/S1872-5813(24)60447-0
基金项目: 国家自然科学基金(22178051)和中央高校基本科研业务费(DUT21TD103)资助
详细信息
    通讯作者:

    E-mail: ljin@dlut.edu.cn

  • 中图分类号: TK6

Catalytic conversion of biomass pyrolysis volatiles over composite catalysts of activated carbon and HY zeolite

Funds: The project was supported by the National Natural Science Foundation of China (22178051) and the Fundamental Research Funds for the Central Universities (DUT21TD103).
  • 摘要: 生物油组成复杂,含氧量较高,制约其高值化利用。本研究以商业活性炭(AC)和HY分子筛为复合催化剂,通过改变催化区的装填方式研究其对稻草和杨木屑两种典型生物质热解挥发物提质的影响规律。结果表明,AC和HY分子筛装填方式影响生物质热解产物分布和生物油组成。在HY与AC按1∶1比例均匀混合(YACM)作用后,生物油产率最低。但YACM方式有利于生物油的脱氧和芳香烃的生成,稻草和杨木屑热解生物油中的芳烃含量在YACM作用下可分别由提质前的13.8%和8.0%提高至56.4%和53.1%。上层HY分子筛和下层AC(YTACL)的催化方式有利于酚类物质生成。对单环芳烃的选择性遵循YTACL>ACTYL>YACM,而对双环芳烃的选择性为YACM>ACTYL>YTACL。分析认为,AC孔径较HY分子筛小,酸性低于分子筛,其活性中心有助于呋喃化合物重排生成环戊酮、2-环戊烯酮、甲基环戊烯酮,后重排形成苯酚,因此,YTACL的装填方式对苯酚、甲酚、甲苯、乙苯、对二甲苯的生成有较好的促进作用。HY分子筛的酸性强,有利于芳构化反应发生,因此,ACTYL装填方式表现出对萘、甲基萘、蒽、芘的生成较高的选择性。该工作为生物油的组成调控以及芳烃和酚类物质的富集等提供重要指导。
  • 图  1  两段式固定床反应装置图(a)和催化剂的装填方式(b)

    Figure  1  Diagram of two-stage fixed bed reaction device (a) and the loading models of catalysts (b)

    图  2  活性炭和HY分子筛的N2吸附-脱附等温线(a)和孔径分布(b)

    Figure  2  N2 adsorption/desorption isotherms (a) and pore size distributions (b) of AC and HY zeolite catalysts

    图  3  活性炭和HY的NH3-TPD谱图

    Figure  3  NH3-TPD curves of AC and HY catalysts

    图  4  催化剂装填方式对RS(a)和PS(b)热解产物分布的影响

    Figure  4  Effect of loading modes of catalysts on the products distribution of RS (a) and PS (b) pyrolysis

    图  5  催化剂装填方式对RS(a)和PS(b)热解气体产率的影响

    Figure  5  Influence of loading modes of catalyst on the gas yields from RS (a) and PS (b) pyrolysis

    图  6  催化剂装填方式对RS(a)、(c)、(e)和PS(b)、(d)、(f)热解焦油主要组成的影响

    Figure  6  Effect of the loading modes of catalyst on tar composition from pyrolysis of RS (a), (c), (e) and PS (b), (d), (f)

    图  7  活性炭和HY分子筛催化提质反应路径示意图

    Figure  7  Possible reaction pathways for pyrolysis compounds over AC and HY zeolite catalysts

    表  1  生物质样品的工业分析和元素分析

    Table  1  Proximate and ultimate analyses of raw biomasses

    Sample Proximate analysis w/% Ultimate analysis wdaf/%
    Mad Ad Vdaf C H N S O*
    RS 1.24 21.38 83.26 49.77 7.13 1.91 0.08 41.11
    PS 0.08 12.39 85.08 48.33 6.68 0.83 0.13 44.03
    ad: air dry basis; d: dry basis; daf: dry ash-free basis; *: by difference.
    下载: 导出CSV

    表  2  活性炭和HY分子筛的表面性质

    Table  2  Surface properties of AC and HY zeolite catalysts

    Sample S/(m2·g−1) v/(cm3·g−1) Dave/
    nm
    SBET Smic Smeso vt vmic vmeso
    AC 910 405 505 0.69 0.19 0.50 4.1
    HY 522 410 112 0.43 0.20 0.22 6.5
    下载: 导出CSV
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  • 收稿日期:  2024-02-18
  • 修回日期:  2024-03-28
  • 录用日期:  2024-03-28
  • 网络出版日期:  2024-04-29

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