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钙改性HZSM-5分子筛对油页岩热解特性的影响研究

杨天华 刘家兴 李秉硕 翟英媚 王建 佟勃霖

杨天华, 刘家兴, 李秉硕, 翟英媚, 王建, 佟勃霖. 钙改性HZSM-5分子筛对油页岩热解特性的影响研究[J]. 燃料化学学报, 2021, 49(2): 137-144. doi: 10.19906/j.cnki.JFCT.2021033
引用本文: 杨天华, 刘家兴, 李秉硕, 翟英媚, 王建, 佟勃霖. 钙改性HZSM-5分子筛对油页岩热解特性的影响研究[J]. 燃料化学学报, 2021, 49(2): 137-144. doi: 10.19906/j.cnki.JFCT.2021033
YANG Tian-hua, LIU Jia-xing, LI Bing-shuo, ZHAI Ying-mei, WANG Jian, TONG Bo-lin. Effect of Ca modified HZSM-5 zeolites on catalytic pyrolysis of oil shale[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 137-144. doi: 10.19906/j.cnki.JFCT.2021033
Citation: YANG Tian-hua, LIU Jia-xing, LI Bing-shuo, ZHAI Ying-mei, WANG Jian, TONG Bo-lin. Effect of Ca modified HZSM-5 zeolites on catalytic pyrolysis of oil shale[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 137-144. doi: 10.19906/j.cnki.JFCT.2021033

钙改性HZSM-5分子筛对油页岩热解特性的影响研究

doi: 10.19906/j.cnki.JFCT.2021033
详细信息
    通讯作者:

    E-mail: thyang@sau.edu.cn; Tel & Fax: 024-89724558

  • 中图分类号: TK16

Effect of Ca modified HZSM-5 zeolites on catalytic pyrolysis of oil shale

  • 摘要: 采用热重质谱红外光谱(TG-MS-FTIR)联用技术和管式热解炉,探究了Ca改性前后HZSM-5分子筛对油页岩热解的催化行为,并采取BET、NH3-TPD、TG手段对分子筛进行表征。结果表明,改性前后的HZSM-5均可以显著提高C1−4脂肪烃类产物的产量,降低其析出温度。Ca改性后的HZSM-5可以降低CO2的产量。对页岩油的分析表明,改性后的HZSM-5可以提高页岩油产量,并且有效降低页岩油中脂肪链长度。但是对芳构化促进作用更强。分子筛中Brönsted酸位点对脂肪烃催化效果明显,Lewis酸位点有利于芳构化反应的发生。
  • 图  1  催化剂的N2吸附-脱附曲线

    Figure  1.  N2 adsorption-desorption curves of catalysts

    图  2  Ca改性前后HZSM-5分子筛的热失重曲线

    Figure  2.  TG curves of catalysts before and after modification

    图  3  四种样品热解的TG(a)和DTG(b)曲线

    Figure  3.  TG (a) and DTG (b) curves for pyrolysis of four samples

    图  4  CH4轻质脂肪烃的析出曲线

    Figure  4.  Evolution curves of CH4 light aliphatic hydrocarbons

    图  5  C2−4轻质脂肪烃的析出曲线

    Figure  5.  Evolution curves of C2−4 light aliphatic hydrocarbons

    图  6  H2、CO2和CO的析出曲线

    Figure  6.  Evolution curves of H2, CO2 and CO

    图  7  热解的三项产物分布

    Figure  7.  Distribution of three-phase product during pyrolysis

    图  8  不同催化剂催化热解制得页岩油中含氧组分

    Figure  8.  Oxygen-containing components in shale oil from catalytic pyrolysis of different catalysts

    表  1  抚顺油页岩的基本性质

    Table  1.   Basic properties of Fushun oil shale

    Proximate analysis wad/% Ultimate analysis wad/% Fischer assay retort w/%
    MVAFCaCHObNSoilmoisturechargas
    2.4018.1077.362.149.891.806.160.820.578.104.3084.103.20
    a: calculated,b: by difference
    下载: 导出CSV

    表  2  Ca改性前后HZSM-5分子筛的物理化学性质

    Table  2.   Physicochemical properties of HZSM-5 and Ca/HZSM-5

    CatalystPorosity characteristicsAcidic propertiesCf /%d
    surface areaa
    A/(m2·g−1)
    Pore sizeb/
    nm
    Micropore volumec
    v/(cm3·g−1)
    Brönsted acidity/
    (mmol·g−1)
    Lewis acidity/
    (mmol·g−1)
    HZSM-5186.2 5.90.042.530.953.3
    3%Ca/HZSM-5138.56.690.030.822.196.7
    9%Ca/HZSM-5104.0 9.60.012.716.0
    a: from BET method; b: from BJH analysis; c: from t-plot analysis; d: the mass loss of catalysts
    下载: 导出CSV

    表  3  页岩油中烃类成分

    Table  3.   Hydrocarbons distribution in shale oil

    HydrocarbonsContent [area/%]
    RSHSCa3%MHSCa9%MHS
    Aliphatic hydrocarbons
    Alkane < C10 0.42
    C10−2026.8524.5936.6444.57
    > C2026.8817.5812.9713.64
    Alkene < C10 6.30 3.35
    C10−2016.2917.17 5.81 8.78
    > C2017.6314.14 0.54
    Aromatic hydrocarbons
    Benzene derivatives 1.12 2.22 4.92
    PAHs 1.59 7.3111.67 7.79
    下载: 导出CSV
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出版历程
  • 收稿日期:  2019-12-11
  • 修回日期:  2020-11-17
  • 刊出日期:  2021-02-08

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