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In2O3/SSZ-13催化CO2加氢高选择性合成液化石油气

卢思宇 杨海艳 杨承广 高鹏 孙予罕

卢思宇, 杨海艳, 杨承广, 高鹏, 孙予罕. In2O3/SSZ-13催化CO2加氢高选择性合成液化石油气[J]. 燃料化学学报(中英文), 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9
引用本文: 卢思宇, 杨海艳, 杨承广, 高鹏, 孙予罕. In2O3/SSZ-13催化CO2加氢高选择性合成液化石油气[J]. 燃料化学学报(中英文), 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9
LU Si-yu, YANG Hai-yan, YANG Cheng-guang, GAO Peng, SUN Yu-han. Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9
Citation: LU Si-yu, YANG Hai-yan, YANG Cheng-guang, GAO Peng, SUN Yu-han. Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9

In2O3/SSZ-13催化CO2加氢高选择性合成液化石油气

doi: 10.1016/S1872-5813(21)60057-9
基金项目: 国家自然科学基金(21773286,U1832162),中国科学院青年创新促进会(2018330),中国科学院洁净能源先导科技专项(XDA21090204),上海市青年科技启明星计划(19QA1409900)项目资助
详细信息
    作者简介:

    卢思宇:lusiyu2018@sari.ac.cn

    通讯作者:

    Tel: +86-20350994, +86-21-20325009

    E-mail: gaopeng@sari.ac.cn (P.G.), sunyh@sari.ac.cn (Y.S.)

  • 中图分类号: O643

Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst

Funds: The projected was supported by the National Natural Science Foundation of China (21773286, U1832162), Youth Innovation Promotion Association CAS (2018330), “Transformational Technologies for Clean Energy and Demonstration,” Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21090204), the Shanghai Rising-Star Program, China (19QA1409900)
  • 摘要: 通过In2O3/SSZ-13双功能催化剂实现了二氧化碳(CO2)加氢高选择性合成液化石油气(LPG,${\rm{C}}_3^0 $${\rm{C}}_4^0 $)。利用X射线衍射(XRD)、N2吸附-脱附、扫描电镜(SEM)、透射电镜(TEM)、NH3程序升温脱附(NH3-TPD)等表征手段对双功能催化剂的物化性质进行了表征。在固定床反应器上研究了氧化铟的晶粒尺寸、反应条件对In2O3/SSZ-13催化二氧化碳加氢制液化石油气性能的影响。结果表明,SSZ-13分子筛的八元环结构和强酸性位点有利于丙烷的选择性生成,初始晶粒尺寸为5 nm的氧化铟具有最高的CO2转化率(11.7%)和CO选择性(61.0%),而烃类产物分布受In2O3晶粒尺寸影响较小,其中,烃类产物中LPG的选择性基本维持在90%左右,丙烷选择性约为75%。增加反应压力、降低反应空速均有利于LPG收率的提高,在350 ℃,3 MPa,9000 mL/(gcat·h)的反应条件下,In2O3/SSZ-13双功能催化剂反应100 h未观察到显著失活现象。本研究为CO2加氢高选择合成液化石油气提供了新的探索途径。
  • FIG. 839.  FIG. 839.

    FIG. 839.  FIG. 839.

    图  1  In2O3/SSZ-13双功能催化剂及SSZ-13分子筛的XRD谱图

    Figure  1  XRD patterns of In2O3-x/SSZ-13 composite catalysts and SSZ-13 zeolite

    图  2  SSZ-13的SEM照片及粒径分布(a) SSZ-13分子筛,氧化铟的TEM照片及粒径分布 (b) In2O3-300,(c) In2O3-500,(d) In2O3-700

    Figure  2  SEM images and size distribution (insert) of SSZ-13 zeolite (a) SSZ-13, TEM images and size distribution (insert) of In2O3-x samples (b) In2O3-300,(c) In2O3-500, (d) In2O3-700

    图  3  In2O3-x/SSZ-13及SSZ-13分子筛的N2物理吸附-脱附曲线

    Figure  3  N2 isothermal adsorption-desorption curves of the In2O3/SSZ-13 composite catalyst and SSZ-13 zeolite

    图  4  In2O3-x/SSZ-13及SSZ-13分子筛的NH3-TPD谱图

    Figure  4  NH3-TPD patterns of In2O3-x/SSZ-13 composite catalysts and SSZ-13 zeolite

    图  5  In2O3-300/SSZ-13(In2O3:SSZ-13=1:2)双功能催化剂上CO2加氢制LPG反应性能

    Figure  5  Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 composite catalyst. reaction conditions: 350 ℃,H2/CO2= 3,WHSV = 9000 mL/(gcat·h) mass ratio=1:2

    表  1  In2O3/SSZ-13双功能催化剂的结构性质

    Table  1  Texture properties of the In2O3x/SSZ-13 composite catalysts

    SampleSBET/
    (m2·g–1)
    Smicro/
    (m2·g–1)
    vmeso/
    (cm3·g–1)
    vmicro/
    (cm3·g–1)
    SSZ-134874600.350.23
    In2O3-300/SSZ-134473800.300.19
    In2O3-500/SSZ-134103710.280.18
    In2O3-600/SSZ-133943630.280.17
    In2O3-650/SSZ-133733440.260.17
    In2O3-700/SSZ-133503180.250.16
    下载: 导出CSV

    表  2  双功能催化剂In2O3-x/SSZ-13上的CO2加氢制LPG催化性能

    Table  2  Catalytic performance for CO2 hydrogenation to LPG over bifunctional catalysts containing In2O3 oxides with different crystal sizes and SSZ-13 zeolites

    SampleCO2 conv. /%CO sel. /%Hydrocarbon distribution/%STYLPG/
    (mmol·gcat–1·h–1)
    CH4${\rm{C}}_2^0 $LPG (${\rm{C}}_3^0 $)${\rm{C}}_2^= $– ${\rm{C}}_4^= $C5+
    In2O3-300/SSZ1311.761.03.42.290.6 (76.8)2.31.53.99
    In2O3-500/SSZ1311.357.83.22.489.2 (75.7)3.12.24.10
    In2O3-600/SSZ139.856.73.52.389.9 (76.7)2.12.23.68
    In2O3-650/SSZ139.054.23.52.389.8 (76.4)2.32.13.57
    In2O3-700/SSZ137.653.83.62.488.6 (75.5)3.02.43.00
    standard reaction conditions: In2O3 (0.4 g) + SSZ-13 (0.8 g), 350 ℃, 3.0 MPa, H2/CO2 = 3, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream
    下载: 导出CSV

    表  3  In2O3-300/SSZ-13在不同温度下催化CO2加氢制液化石油气的反应性能

    Table  3  Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction temperatures

    Temperature/℃CO2 conv. /%CO sel. /%Hydrocarbon distribution/%STYLPG/
    (mmol·gcat–1·h–1)
    CH4${\rm{C}}_2^0 $LPG (${\rm{C}}_3^0 $)${\rm{C}}_2^= $– ${\rm{C}}_4^= $C5+
    3105.850.54.22.289.5 (74.3)1.92.22.48
    3309.758.83.52.590.8 (77.0)1.91.33.50
    35011.761.03.42.290.6 (76.8)2.31.53.99
    37022.972.23.93.088.5 (75.8)2.52.15.43
    39029.478.36.13.684.8 (72.7)3.52.05.22
    standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 3 MPa, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream
    下载: 导出CSV

    表  4  In2O3-300/SSZ-13在不同空速下催化CO2加氢制液化石油气的反应性能

    Table  4  Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction space velocity

    Space velocity/
    (mL·gcat–1·h–1)
    CO2 conv. /%CO sel. /%Hydrocarbon distribution/%STYLPG/
    (mmol·gcat–1·h–1)
    CH4${\rm{C}}_2^0 $LPG (${\rm{C}}_3^0 $)${\rm{C}}_2^= $– ${\rm{C}}_4^= $C5+
    300014.967.13.62.490.7 (77.8)1.81.54.29
    600011.962.83.62.391.1 (77.7)2.30.73.89
    900011.761.03.42.290.6 (76.8)2.31.53.99
    1200010.055.43.62.289.1 (75.4)2.92.23.83
    150008.955.03.72.189.0 (75.2)3.41.83.44
    standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 350 ℃, 3 MPa results from 12 h time on stream
    下载: 导出CSV

    表  5  In2O3-300/SSZ-13在不同压力下催化CO2加氢制液化石油气的反应性能

    Table  5  Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction pressure

    Pressure/MPaCO2 conv. /%CO sel. /%Hydrocarbon distribution/%STYLPG/
    (mmol·gcat–1·h–1)
    CH4${\rm{C}}_2^0 $LPG (${\rm{C}}_3^0 $)${\rm{C}}_2^= $– ${\rm{C}}_4^= $C5+
    1.08.170.92.63.381.8 (70.8)11.11.21.86
    2.09.765.33.12.388.1 (75.5)4.52.02.86
    3.011.761.03.42.290.6 (76.8)2.31.53.99
    4.013.457.63.72.489.4 (75.6)2.02.54.90
    5.015.957.13.82.590.2 (75.9)1.42.15.93
    standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 350 ℃, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream
    下载: 导出CSV
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  • 收稿日期:  2021-02-05
  • 修回日期:  2021-02-22
  • 网络出版日期:  2021-03-09
  • 刊出日期:  2021-08-31

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