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等离子体催化甲烷干重整实验研究

李嘉卿 徐彬 王文博 谢建军 阴秀丽 吴创之 肖进彬

李嘉卿, 徐彬, 王文博, 谢建军, 阴秀丽, 吴创之, 肖进彬. 等离子体催化甲烷干重整实验研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60070-1
引用本文: 李嘉卿, 徐彬, 王文博, 谢建军, 阴秀丽, 吴创之, 肖进彬. 等离子体催化甲烷干重整实验研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60070-1
LI Jia-qing, XU Bin, WANG Wen-bo, XIE Jian-jun, YIN Xiu-li, WU Chuang-zhi, XIAO Jin-bin. Experimental Study on Dry Reforming of Methane by a Plasma Catalytic Hybrid System[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60070-1
Citation: LI Jia-qing, XU Bin, WANG Wen-bo, XIE Jian-jun, YIN Xiu-li, WU Chuang-zhi, XIAO Jin-bin. Experimental Study on Dry Reforming of Methane by a Plasma Catalytic Hybrid System[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60070-1

等离子体催化甲烷干重整实验研究

doi: 10.1016/S1872-5813(21)60070-1
基金项目: 国家重点研发计划项目(2019YFB1503902),国家自然科学基金项目(51576200),广州市科技计划项目(202002030126)和中国科学院可再生能源重点实验室(中国科学院广州能源研究所)(E0290109)资助
详细信息
    通讯作者:

    Tel: 020-87057757, E-mail: xiejj@ms.giec.ac.cn

  • 中图分类号: TK6

Experimental Study on Dry Reforming of Methane by a Plasma Catalytic Hybrid System

Funds: The project was supported by the National Key R&D Program of China (2019YFB1503902), the National Natural Science Foundation of China (51576200), the Science and Technology Program of Guangzhou (202002030126) and CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion (E0290109)
  • 摘要: 本文中,利用等离子体耦合催化剂的方式进行CH4干重整(Dry Reforming of Methane,DRM),重点考察了反应温度、CO2/CH4摩尔比、合成气主要气体组分浓度(N2、H2、CO、H2O)对CH4转化率及等离子体催化能量效率的影响。结果表明,以La-Ni/γ-Al2O3为催化剂,当反应温度450 ℃,CO2/CH4摩尔比为1.0时,CH4转化率为41.57%;提高CO2/CH4摩尔比可提高CH4转化率,当CO2/CH4摩尔比为5.0时,等离子体催化CH4干重整过程的CH4转化率可达92.82%。温度和CO2/CH4摩尔比对CH4转化率有着显著影响,气体组分的变化改变了体系中的激发态粒子,不仅直接影响到CH4转化率,还影响着催化剂表面积碳情况。向反应体系中添加N2、H2O可提高CH4转化率,并抑制积碳;而添加H2、CO后CH4转化率显著降低。研究结果可望为生物质气化合成化工品的工艺开发提供基础数据和参考依据。
  • 图  1  实验装置示意图

    Figure  1.  Schematic diagram of experimental device

    图  2  不同催化剂H2-TPR谱图

    Figure  2.  H2-TPR spectra of different catalysts

    图  3  Ni/γ-Al2O3和La-Ni/γ-Al2O3催化剂Ni 2p3/2区域的XPS光谱

    Figure  3.  XPS spectra of Ni 2p3/2 region of the Ni/γ-Al2O3 and La-Ni/γ-Al2O3 catalyst

    图  4  γ-Al2O3、Ni/γ-Al2O3及La-Ni/γ-Al2O3催化剂的XRD谱图

    Figure  4.  XRD spectra of γ-Al2O3, Ni/γ-Al2O3 and La-Ni/γ-Al2O3 catalysts

    图  5  催化剂对CH4干重整的影响:(a)CH4和CO2转化率、H2和CO收率,(b)H2、CO、C2H6、C3H8选择性

    Figure  5.  Effect of catalyst on (a) the conversion rate of CH4, CO2 and the yield of H2 and CO (b) the selectivity of H2, CO, C2H6 and C3H8

    图  6  温度对CH4干重整的影响:(a)CH4、CO2转化率(b)H2、CO收率(c)能量效率

    Figure  6.  Influence of temperature on (a) the conversion rate of CH4 and CO2, (b) the yield of H2 and CO, (c) energy efficiency

    图  7  CO2/CH4对CH4干重整的影响:(a)CH4、CO2转化率(b)H2、CO、C2H6选择性(c)能量效率

    Figure  7.  Effect of CO2/CH4 molar ratio on (a) the conversion rate of CH4 and CO2 (b) the selectivity H2, CO and C2H6 (c) the energy efficiency

    图  8  入口气体中N2、H2、CO浓度变化对CH4、CO2转化率的影响(a)CH4(b)CO2

    Figure  8.  Influence of the concentration of N2, H2 and CO in the inlet gas on the conversion rate of (a) CH4 (b) CO2

    图  9  入口气体中N2、H2、CO浓度变化对H2、CO选择性及能量效率的影响:(a)H2(b)CO(c)SEC

    Figure  9.  Influence of the concentration of N2、H2 and CO in the inlet gas on the selectivity of H2, CO and energy efficiency: (a) H2 (b) CO (c) SEC

    图  10  不同CO添加量工况下反应后催化剂的TG曲线

    Figure  10.  TG curves of the catalyst after the reaction under different CO addition conditions

    图  11  不同气氛条件下催化剂的拉曼光谱

    Figure  11.  Raman spectra of catalysts in different atmosphere conditions

    图  12  H2O含量对CH4干重整的影响:(a)CH4、CO2转化率(b)H2、CO收率和选择性(c)C2H6选择性(d)能量效率

    Figure  12.  Influence of the concentration of H2O in the inlet gas on (a) the conversion rate CH4 and CO2 (b) the yield and selectivity of H2, CO, (c) the selectivity of C2H6, and (d) the energy efficiency

    表  1  生物质富氧-水蒸气气化的产气组成

    Table  1.   Gas composition of biomass oxygen-steam gasification

    Gasification agentMaterialTemperature/℃Gas composition /vol.%literature
    H2COCO2CH4C2HmN2
    Enriched oxygen + water vaporGasification agent825~88723~2929~3729~354~62~33~4[3]
    Water vaporPine Sawdust700~95023~4522~3312~1510~173~7/[4]
    Water vaporStraw750~90038~4732~3811~155~11//[5]
    下载: 导出CSV

    表  2  介质阻挡放电甲烷干重整研究进展

    Table  2.   Research progress of dry reforming of methane by dielectric barrier discharge

    Experimental conditionsConversion rates /%Yield /%Energy efficiency SEC/mmol·kJ−1Literature
    Power /WMolar ratio/ CO2:CH4CatalystCH4CO2H2CO
    451:1Pt/Al2O332.522.1//0.205[15]
    1401:1Al2O3797121320.084[16]
    1003:1Ni/La2O3-MgAl2O478.868.130.4370.125[17]
    2001:1Ni/ZrO252.860.852.163.5/[18]
    1001:1Ni/La2O3-MgAl2O486.084.542400.26[19]
    下载: 导出CSV

    表  3  Ni/γ-Al2O3和La-Ni/γ-Al2O3催化剂XPS光谱Ni 2p3/2区峰面积表

    Table  3.   Peak areas of Ni 2p3/2region in XPS spectra of Ni/γ- Al2O3 and La Ni/γ- Al2O3 catalysts

    CatalystPeak area /%
    851.4 eV856.5 eV862.4 eV
    Ni/γ-Al2O310.765.723.6
    La-Ni/γ-Al2O327.553.828.7
    下载: 导出CSV

    表  4  不同催化剂比表面积和孔容积

    Table  4.   Specific surface area and pore volume of different catalysts

    Packing
    materials
    Specific surface
    area/cm2·g−1
    Pore
    volume/cm3·g−1
    γ-Al2O3110.310.281
    Ni/γ-Al2O3112.760.259
    La-Ni/γ-Al2O397.990.243
    下载: 导出CSV

    表  5  不同气氛下反应20 min后催化剂的积碳量

    Table  5.   Carbon deposition on catalyst after 20 min reaction under different atmosphere

    ProcessCarbon deposition(wt.%)
    No addition1.65
    30 vol.% N2 addition1.67
    30 vol.% H2 addition1.30
    30 vol.% CO addition7.69
    20 vol.% CO addition4.62
    15 vol.% H2O addition1.20
    下载: 导出CSV
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