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多级孔ZSM-5分子筛对低阶煤流化床快速热解产物分布的影响

张壮壮 刘楠 安重鑫 孙鸣 徐龙 马晓迅 甄延忠 付峰

张壮壮, 刘楠, 安重鑫, 孙鸣, 徐龙, 马晓迅, 甄延忠, 付峰. 多级孔ZSM-5分子筛对低阶煤流化床快速热解产物分布的影响[J]. 燃料化学学报, 2021, 49(4): 407-414. doi: 10.1016/S1872-5813(21)60042-7
引用本文: 张壮壮, 刘楠, 安重鑫, 孙鸣, 徐龙, 马晓迅, 甄延忠, 付峰. 多级孔ZSM-5分子筛对低阶煤流化床快速热解产物分布的影响[J]. 燃料化学学报, 2021, 49(4): 407-414. doi: 10.1016/S1872-5813(21)60042-7
ZHANG Zhuang-zhuang, LIU Nan, AN Chong-xin, SUN Ming, XU Long, MA Xiao-xun, ZHEN Yan-zhong, FU Feng. Effect of hierarchical ZSM-5 zeolites on product distribution of low rank coal fast pyrolysis in a fluidized bed[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 407-414. doi: 10.1016/S1872-5813(21)60042-7
Citation: ZHANG Zhuang-zhuang, LIU Nan, AN Chong-xin, SUN Ming, XU Long, MA Xiao-xun, ZHEN Yan-zhong, FU Feng. Effect of hierarchical ZSM-5 zeolites on product distribution of low rank coal fast pyrolysis in a fluidized bed[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 407-414. doi: 10.1016/S1872-5813(21)60042-7

多级孔ZSM-5分子筛对低阶煤流化床快速热解产物分布的影响

doi: 10.1016/S1872-5813(21)60042-7
基金项目: 国家自然科学基金(21536009),陕西省重点研发计划(2020ZDLGY11-02,2018TSCXL-NY-02-01),陕西省自然科学基础研究计划(2020JQ-791),陕西省教育厅专项科研计划项目(20JK0989)和陕西省大学生创新创业训练计划项目(S202010719075)资助
详细信息
    通讯作者:

    Tel: 13772424852, E-mail: 13772424852@163.com

  • 中图分类号: TQ530.2

Effect of hierarchical ZSM-5 zeolites on product distribution of low rank coal fast pyrolysis in a fluidized bed

Funds: The project was supported by the National Natural Science Foundation of China (21536009), the Key R & D Plan Projects of Shaanxi Province (2020ZDLGY11-02, 2018TSCXL-NY-02-01), the Natural Science Basic Research Program of Shaanxi Province (2020JQ-791), the Special Scientific Research Project of Shaanxi Province Education Department (20JK0989) and the College Student Innovation and Entrepreneurship Training Program of Shaanxi Province (S202010719075)
  • 摘要: 采用晶种诱导法和碱处理法制备了不同介-微孔复合结构的多级孔ZSM-5分子筛,利用XRD、TEM、NH3-TPD、氮气物理吸附等手段对其结构性质进行了表征,并考察了其对低阶煤流化床快速热解产物分布的影响。结果表明,碱处理后不同程度上增加了分子筛催化剂的比表面积、介孔孔容和平均孔径。多级孔ZSM-5分子筛促进了热解挥发分中脂肪烃的裂解环化和酚池的解离,提高了焦油中轻质芳烃的收率。在碱浓度为0.3 mol/L时轻质芳烃收率达到最大,其中,单环芳烃和萘/甲基萘较微孔分子筛分别增加了2.7倍和0.9倍。在碱浓度达到0.4 mol/L时,由于过度脱硅造成表面塌陷,分子筛催化剂性能下降。
  • FIG. 603.  FIG. 603.

    FIG. 603..  FIG. 603.

    图  1  流化床快速热解反应装置示意图

    Figure  1.  Schematic diagram of the fluidized bed reactor

    图  2  碱处理前后ZSM-5分子筛的XRD谱图

    Figure  2.  XRD patterns of ZSM-5 zeolites before and after alkali-treatment

    图  3  碱处理前后ZSM-5分子筛的TEM照片

    Figure  3.  TEM images of ZSM-5 zeolites before and after alkali-treatment

    图  4  碱处理前后ZSM-5分子筛的氮气物理吸附-脱附曲线(a)和孔径分布图(b)

    Figure  4.  N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of ZSM-5 zeolites before and after alkali-treatment

    图  5  碱处理前后ZSM-5分子筛的NH3-TPD谱图

    Figure  5.  NH3-TPD profiles of ZSM-5 zeolites before and after alkali-treatment

    图  6  热解三相产物的分布

    Figure  6.  Distribution of pyrolysis three-phase products

    图  7  热解气体产物的组成

    Figure  7.  Gas composition of coal pyrolysis

    图  8  多级孔ZSM-5分子筛的热解焦油化学组成

    Figure  8.  Chemical composition of tar upgraded by hierarchical ZSM-5 zeolites

    图  9  多级孔ZSM-5分子筛的苯酚与甲基酚收率

    Figure  9.  Product yields of phenol and methy-P when upgrading by hierarchical ZSM-5 zeolites

    图  10  多级孔ZSM-5分子筛的轻质芳烃收率

    Figure  10.  Product yields of light aromatic hydrocarbons when upgrading by hierarchical ZSM-5 zeolites

    表  1  神东煤的工业分析与元素分析

    Table  1.   Proximate and ultimate analyses of the SD coal

    Proximate analysis w/%Ultimate analysis wdaf/%
    MadAdVdafFCdaf*CHO*NS
    15.329.5335.6164.3977.844.4716.261.040.39
    * by difference
    下载: 导出CSV

    表  2  碱处理前后ZSM-5分子筛的相对结晶度、硅铝比和收率变化

    Table  2.   Relative crystallinity, Si/Al ratio and yields of ZSM-5 before and after alkali-treatment

    SampleRelative crystallinity/%n(Si)/n(Al)Recovery w/%
    Z5010056100
    Z50-0.1M994874
    Z50-0.2M964465
    Z50-0.3M714157
    Z50-0.4M543840
    下载: 导出CSV

    表  3  碱处理前后ZSM-5分子筛的孔结构参数

    Table  3.   Porosity properties of ZSM-5 zeolites before and after alkali-treatment

    SampleSBET/(m2·g−1)Smeso/(m2·g−1)Smicro/(m2·g−1)vtotal/(cm3·g−1)vmicro/(cm3·g−1)vmeso/(cm3·g−1)daver/nmvmicro/vmeso
    Z50422283940.200.170.031.55.7
    Z50-0.1M445364090.250.160.072.72.6
    Z50-0.2M462773850.290.160.125.31.4
    Z50-0.3M4751343410.350.150.209.60.8
    Z50-0.4M5162053110.490.130.3611.40.4
    下载: 导出CSV

    表  4  碱处理前后ZSM-5分子筛的NH3-TPD计算

    Table  4.   NH3-TPD computed results of ZSM-5 samples before and after alkali-treatment

    SampleWeak acid peakStrong acid peakTotal acid content/ (mmol·g−1)
    desorption peak temperature/℃acid content/ (mmol·g−1)desorption peak temperature/℃acid content/ (mmol·g−1)
    Z502110.1944370.2130.407
    Z50-0.1M2120.1894050.2390.428
    Z50-0.2M2150.2114100.2630.474
    Z50-0.3M2170.2614030.2640.525
    Z50-0.4M2210.3284050.3310.659
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-12-03
  • 修回日期:  2020-12-28
  • 网络出版日期:  2021-03-12
  • 刊出日期:  2021-04-10

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