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不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响

王德亮 陈兆辉 余剑 高士秋

王德亮, 陈兆辉, 余剑, 高士秋. 不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60030-0
引用本文: 王德亮, 陈兆辉, 余剑, 高士秋. 不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60030-0
WANG De-liang, CHEN Zhao-hui, YU Jian, GAO Shi-qiu. Effect of Si/Al ratio of HZSM-5 zeolites on catalytic upgrading of coal pyrolysis volatiles[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60030-0
Citation: WANG De-liang, CHEN Zhao-hui, YU Jian, GAO Shi-qiu. Effect of Si/Al ratio of HZSM-5 zeolites on catalytic upgrading of coal pyrolysis volatiles[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60030-0

不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响

doi: 10.1016/S1872-5813(21)60030-0
基金项目: 国家重点研发计划(2016YFB0600304)和国家自然科学基金(21878310)资助
详细信息
    作者简介:

    王德亮:wangdl2007@126.com

    通讯作者:

    E-mail: sqgao@ipe.ac.cn

  • 中图分类号: TQ 643.1

Effect of Si/Al ratio of HZSM-5 zeolites on catalytic upgrading of coal pyrolysis volatiles

Funds: The project was supported by the National Key Research and Development Program of China (2016YFB0600304) and the National Natural Science Foundation of China (21878310)
  • 摘要: 采用不同硅铝比的HZSM-5作为煤热解挥发物提质催化剂,研究了催化剂酸性特征对挥发物提质后的焦油品质、催化剂积炭的影响。结果表明,随着硅铝比的增加,HZSM-5的强酸和弱酸量均降低;硅铝比从23增大到310时,催化剂积炭量从120.1 mg/g-catalyst降到23.9 mg/g-catalyst。并且,HZSM-5中强酸与弱酸位点的比值越高,焦油中轻质组分的含量越高。随硅铝比的降低,HZSM-5酸性增强,所得焦油中芳烃组分含量逐渐提高,这表明,HZSM-5在催化煤热解过程中促进了挥发物的氢转移、环化、芳构化反应,从而生成了更多的芳烃组分。
  • 图  1  实验装置示意图

    Figure  1.  Schematic diagram of the experimental apparatus

    1: mass flow meter; 2,3,5,15: valve; 4: feeder; 6,10: thermocouple; 7,9: quartz sieve plate; 8: electric furnace; 11: condenser; 12: acetone trap; 13: NaHCO3 (aq) trap; 14: dry silica gel bottle; 16: volumetric flowmeter

    图  2  不同硅铝比HZSM-5的XRD谱图

    Figure  2.  XRD patterns of HZSM-5 with different SiO2/Al2O3 ratio

    图  3  不同硅铝比HZSM-5的NH3-TPD谱图

    Figure  3.  NH3-TPD profiles of HZSM-5 with different SiO2/Al2O3 ratio

    图  4  不同硅铝比HZSM-5催化煤热解挥发物热解产物

    Figure  4.  Product distribution (a), tar quality and (b) pyrolysis gas component yield (c) over HZSM-5 with different SiO2/Al2O3 ratio (tpy = 600 ℃, tcr = 500 ℃, catalyst: 10% of the tested coal)

    图  5  不同硅铝比HZSM-5酸性特征与焦油品质的关系

    Figure  5.  The relationship between tar quality and the acidity of HZSM-5 with different SiO2/Al2O3 ratio

    表  1  淖毛湖煤的工业分析和元素分析

    Table  1.   Proximate and ultimate analyses of Naomaohu coal

    Proximate analysis
    (dry base) w/%
    Ultimate analysis
    (dry and ash-free base) w/%
    AVFCCHSNOa
    7.1647.7845.0674.775.670.270.9318.36
    a: by difference
    下载: 导出CSV

    表  2  不同硅铝比的HZSM-5的酸性位点数量特征对比

    Table  2.   Acidity of HZSM-5 with different SiO2/Al2O3 ratio

    CatalystWeak acid Strong acidRatio of quantity of strong
    and weak acidic sites
    temperature at
    maximum/℃
    quantity
    /(μmol∙g−1)
    temperature at
    maximum/℃
    quantity
    /(μmol∙g−1)
    HZ23139.72285 387.7602.40.264
    HZ50124.31438384.7313.20.218
    HZ80118.5891.3378.8268.30.301
    HZ280115.6415.5357.0191.90.462
    HZ310141.4396.4356.5171.80.433
    下载: 导出CSV

    表  3  不同硅铝比HZSM-5的结构特征

    Table  3.   Structural characters of HZSM-5 with different SiO2/Al2O3 ratio

    CatalystSpecific surface area A/(m2∙g−1)Pore volume
    v/(cm3∙g−1)
    SBETaSmicrobSmesoc
    HZ23422.3308.1114.20.089
    HZ50414.6243.2171.40.136
    HZ80489.8264.4225.40.174
    HZ280407.9224.6183.30.153
    HZ310588.6435.0153.60.243
    a: BET method; b: t-plot method; c: Smeso = SBETSmirco
    下载: 导出CSV

    表  4  不同硅铝比HZSM-5上的积炭量

    Table  4.   Carbon deposition over HZSM-5 with different SiO2/Al2O3 ratio

    CatalystHZ23HZ50HZ80HZ280HZ310
    Specific C
    deposition/(mg·g−1) *
    120.199.073.826.523.9
    *: specific C deposition refers to the deposited carbon in mg on per gram HZSM-5
    下载: 导出CSV

    表  5  不同硅铝比HZSM-5积炭的丙酮可溶物GC-MS表征

    Table  5.   The acetone-soluble matter of coke over HZSM-5 with different SiO2/Al2O3 ratio

    NameFormulaContent w/%
    HZ23HZ50HZ80HZ280HZ310
    4-methyl-3-penten-2-oneC6H10O42.9184.2434.7612.3720.23
    4-methyl-4-penten-2-oneC6H10O3.793.383.912.463.32
    Tetramethyl-oxiraneC6H12O53.269.2861.1585.1476.4
    TolueneC7H80.030.150.020.020.03
    2,3,4-trimethyl-pentaneC8H180.010.070.010.02
    Others2.880.16
    下载: 导出CSV

    表  6  HZSM-5催化煤热解所得焦油的元素分析

    Table  6.   Ultimate analysis of tars obtained over HZSM-5 with different SiO2/Al2O3 ratio

    CatalystUitimate analysis w/%H/C
    (mol ratio)
    CHO aNS
    Without
    catalyst
    78.318.99111.390.8810.4281.378
    HZ2382.028.6488.4540.6860.1921.265
    HZ5080.378.26310.400.7280.2391.234
    HZ8078.228.16312.570.8350.2131.252
    HZ28080.538.6129.840.8140.2141.283
    HZ31079.978.60510.420.8190.1861.291
    a: by difference
    下载: 导出CSV

    表  7  HZSM-5催化煤热解所得焦油中组分分布

    Table  7.   The component distribution of tars obtained over HZSM-5 with different SiO2/Al2O3 ratio

    CatalystContent w/%
    SAHsUSHsAHsHCHs
    Without catalyst38.110.613.138.2
    HZ2311.40.556.431.7
    HZ5010.60.458.430.6
    HZ8013.752.733.6
    HZ28021.946.631.5
    HZ31016.335.847.9
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-12-22
  • 修回日期:  2021-01-14
  • 网络出版日期:  2021-03-30

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