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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(中英文), 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(中英文), 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
  • [1] YOU Y Y, HAN X X, WANG X Y, JIANG X M. Evolution of gas and shale oil during oil shale kerogen pyrolysis based on structural characteristics[J]. J Anal Appl Pyrolsis,2019,138:203−210.
    [2] TARIK S, LIN Q Y, BRANKOB, MARTIN J B. Microstructural imaging and characterization of oil shale before and after pyrolysis[J]. Fuel,2017,197:562−574.
    [3] LIU T L, CAO J P, ZHAO X, WANG J, REN X, FAN X, ZHAO Y, WEI X. In situ upgrading of Shengli lignite pyrolysis vapors over metal-loaded HZSM-5 catalyst[J]. Fuel Process Technol,2017,160:19−26.
    [4] SHI W J, WANG Z, SONG W L, LI S G, LI X Y. Pyrolysis of Huadian oil shale under catalysis of shale ash[J]. J Anal Appl Pyrolsis,2017,123:160−164.
    [5] ZHANG H, LIU J, KANG Z Q, YANG D. Experimental research of the pyrolytic properties and mineral components of Bogda oil shale, China[J]. Oil Shale,2018,35(3):214.
    [6] CHEN H, CHENG H, ZHOU F, CHEN K Q, QIAO K, LU X Y, OUYANG P K, FU J. Catalytic fast pyrolysis of rice straw to aromatic compounds over hierarchical HZSM-5 produced by alkali treatment and metal-modification[J]. J Anal Appl Pyrolsis,2018,131:76−84.
    [7] ZHANG C D, GEUNJAE K, HAEGU P, KIWON J, LEE Y, SEOK C K, SUNGTAK K. Light hydrocarbons to BTEX aromatics over hierarchical HZSM-5: Effects of alkali treatment on catalytic performance[J]. Microporous Mesoporous Mater,2019,276:292−301.
    [8] ZHANG Z Z, CHANG H, GAO T, ZHANG J B, SUN M, XU L, MA X X. Catalytic upgrading of coal pyrolysis volatiles over metal-loaded HZSM-5 catalysts in a fluidized bed reactor[J]. J Anal Appl Pyrolsis,2019,139:31−39.
    [9] DAI M Q, YU Z S, FANG S W, MA X Q. Behaviors, product characteristics and kinetics of catalytic co-pyrolysis spirulina and oil shale[J]. Energ Convers Manage,2019,192:1−10.
    [10] ZHANG B, ZHONG Z P, CHEN P, RUAN R. Microwave-assisted catalytic fast co-pyrolysis of Ageratinaadenophora and kerogen with CaO and ZSM-5[J]. J Anal Appl Pyrolsis,2017,127:246−257.
    [11] GU B, CAO J P, WEI F, ZHAO X Y, REN X Y, ZHU C, GUO Z X, BAI J, SHEN W Z, WEI X Y. Nitrogen migration mechanism and formation of aromatics during catalytic fast pyrolysis of sewage sludge over metal-loaded HZSM-5[J]. Fuel,2019,244:151−158.
    [12] CHEN L, ZENG C, GUO X, MAO Y, ZHANG Y, ZHANG X, LI W H, LONG Y, ZHU H, B EITENEER, VLADIMIR M Z. Gas evolution kinetics of two coal samples during rapid pyrolysis[J]. Fuel Process Technol,2010,91:848−852.
    [13] SHI L, LIU Q Y, ZHOU B, GUO X J, LI Z K, CHENG X J, YANG R, LIU Z Y. Interpretation of methane and hydrogen evolution in coal pyrolysis from the bond cleavage perspective[J]. Energy Fuels,2017,31(1):429−437.
    [14] PORADA S. The reactions of formation of selected gas products during coal pyrolysis[J]. Fuel,2004,83:1191−1196.
    [15] HOU X, NI N, WANG Y, ZHU W J, QIU Y, DIAO Z H, LIU G Z, ZHANG X W. Roles of the free radical and carbenium ion mechanisms in pentane cracking to produce light olefins[J]. J Anal Appl Pyrolsis,2019,138:270−280.
    [16] ILIOPOULOU E F, STEFANIDIS S D, KALOGIANNIS K G, DELIMITIS A, LAPPAS A A, TRIANTAFYLLIDIS K S. Catalytic upgrading of biomass pyrolysis vapors using transition metal-modified ZSM-5 zeolite[J]. Appl Catal B: Environ,2012,127:281−290.
    [17] 马跃, 李术元, 王娟, 方朝合. 水介质条件下油页岩热解机理研究[J]. 燃料化学学报,2011,39(12):881−886. doi: 10.3969/j.issn.0253-2409.2011.12.001

    MA YUE, LI SHU-YUAN, WANG JUAN, FANG CHAO-HE. Mechanism of oil shale pyrolysis under high water[J]. J Fuel Chem Technol,2011,39(12):881−886. doi: 10.3969/j.issn.0253-2409.2011.12.001
    [18] REN X, CAO J, ZHAO X, YANG Z, LIU T, FAN X, ZHAO Y, WEI X. Catalytic upgrading of pyrolysis vapors from lignite over mono/bimetal-loaded mesoporous HZSM-5[J]. Fuel,2018,218:33−40.
    [19] TRIPATHI A K, OJHA D K, VINU R. Selective production of valuable hydrocarbons from waste motorbike engine oils via catalytic fast pyrolysis using zeolites[J]. J Anal Appl pyrolsis,2015,114:281−292.
    [20] JI X, LIU B, MA W, CHEN G, YAN B, CHENG Z. Effect of MgO promoter on Ni-Mg/ZSM-5 catalysts for catalytic pyrolysis of lipid-extracted residue of Tribonema minus[J]. J Anal Appl Pyrolsis,2017,123:278−283.
    [21] YOU Y, HAN X, LIU J, JIANG X. Structural characteristics and pyrolysis behaviors of huadian oil shale kerogens using solid-state 13 C NMR, Py-GCMS and TG[J]. J Therm Anal Calorim,2017,131:1−11.
    [22] LI S, CHEN J, HAO T, LIANG W, LIU X, SUN M, MA X. Pyrolysis of Huang Tu Miao coal over faujasite zeolite and supported transition metal catalysts[J]. J Anal Appl Pyrolsis,2013,102:161−169.
    [23] BILIGETU T, WANG Y, NISHITOBA T, OTOMO R, PARK S, MOCHIZUKI H, KONDO J N, TASTUMI T, YOKOI T. Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols[J]. J Catal,2017,353:1−10.
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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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