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褐煤煤焦“一步法”制天然气双功能催化剂Fe-Ni/ATP性能研究

汪合龙 刘永卓 郭庆杰

汪合龙, 刘永卓, 郭庆杰. 褐煤煤焦“一步法”制天然气双功能催化剂Fe-Ni/ATP性能研究[J]. 燃料化学学报, 2016, 44(6): 654-660.
引用本文: 汪合龙, 刘永卓, 郭庆杰. 褐煤煤焦“一步法”制天然气双功能催化剂Fe-Ni/ATP性能研究[J]. 燃料化学学报, 2016, 44(6): 654-660.
WANG He-long, LIU Yong-zhuo, GUO Qing-jie. Catalytic performance of Fe-Ni/ATP bifunctional catalyst for natural gas making by one-step lignite char gasification[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 654-660.
Citation: WANG He-long, LIU Yong-zhuo, GUO Qing-jie. Catalytic performance of Fe-Ni/ATP bifunctional catalyst for natural gas making by one-step lignite char gasification[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 654-660.

褐煤煤焦“一步法”制天然气双功能催化剂Fe-Ni/ATP性能研究

基金项目: 

国家自然科学基金 21276129

山东省自然科学基金重点项目 ZR2015QZ02

和山东省自然科学基金 ZR2015BL028

详细信息
  • 中图分类号: TQ546

Catalytic performance of Fe-Ni/ATP bifunctional catalyst for natural gas making by one-step lignite char gasification

More Information
    Corresponding author: Tel: 0532-84022757, Fax: 0532-84022757, E-mail: qj_guo@yahoo.com
  • 摘要: 以Fe-Ni/ATP为催化剂, 在小型固定床反应器上考察其在褐煤煤焦"一步法"制天然气过程中的催化性能。结果表明, 在2MPa、650℃反应条件下, Fe4Ni2/ATP4具有较好的催化气化和甲烷化性能, 甲烷选择性为24.75%, 较Fe4/ATP6的选择性提高了58.76%;且在五次循环实验过程中, 碳转化率和CH4时空产率保持稳定, 具有较高的稳定性。载体ATP中的CaO具有明显的气化催化效果; Fe与水蒸气反应生成的H2可快速提高反应器内H2分压, 促进煤焦直接加氢甲烷化和CO甲烷化; Ni降低了催化剂的还原温度并形成铁镍合金活性组分, 提高了催化剂的甲烷化催化性能。
  • 图  1  实验流程示意图

    Figure  1  Schematic diagram of the laboratory setup

    图  2  Fe/ATP和Fe4Ni2/ATP4催化剂反应前后XRD谱图

    1: SiO2; 2: ATP; 3: CaO; 4: Fe; 5: Fe3O4; 6: Ni

    Figure  2  XRD patterns of the Fe/ATP and Fe4Ni2/ATP4 before and after reaction

    图  3  催化剂的H2-TPR谱图

    Figure  3  H2-TPR patterns of the catalyst

    图  4  不同催化剂作用下碳转化速率随反应时间的变化

    Figure  4  Effect of different catalysts on carbon conversion rate as a function of time

    图  5  不同催化剂作用下氢气产出速率的变化

    Figure  5  Effect of different catalysts on the hydric production rate

    图  6  残焦的FT-IR谱图

    Figure  6  FT-IR spectra of the chars with different hydrogenation degrees

    图  7  Fe含量对碳转化率和氢气含量的影响

    Figure  7  Effect of ferrum content on carbon conversion and hydrogen content

    图  8  Ni含量对甲烷选择性和碳转化率的影响

    Figure  8  Effect of Ni content on methane selectivity and carbon conversion

    图  9  Fe4Ni2/ATP4不同反应时间的XRD谱图

    Figure  9  XRD patterns of Fe4Ni2/ATP4 in different reaction time

    图  10  碳转化速率随循环次数的变化

    Figure  10  Effect of cycle numbers on carbon conversion rate

    图  11  CH4时空产率随循环次数的变化

    Figure  11  Effect of cycle numbers on CH4 space time yield

    表  1  鄂尔多斯褐煤煤焦的工业分析与元素分析

    Table  1  Proximate and ultimate analysis of Ordos lignite char

    Proximate analysis wad/% Ultimate analysis wdaf/%
    M V A CHO+NS
    0.82.3610.26 95.321.632.540.51
    下载: 导出CSV

    表  2  ATP的化学组成

    Table  2  Chemical composition of attapulgite used

    Composition w/%
    SiO2Al2O3Fe2O3MgOCaOK2ONa2OH2O
    57.987.054.579.108.520.560.1111.89
    下载: 导出CSV

    表  3  催化剂组成及其各组分的质量比

    Table  3  Mass ratio and compositions of the prepared hydrogen donor

    SampleComponentMass ratio
    ATPATP0:10
    Fe2/ATP8Fe, ATP2:8
    Fe4/ATP6Fe, ATP4:6
    Fe6/ATP4Fe, ATP6:4
    Fe8/ATP2Fe, ATP8:2
    Fe4Ni1/ATP5Fe, Ni, ATP4:1:5
    Fe4Ni2/ATP4Fe, Ni, ATP4:2:4
    Fe4Ni3/ATP3Fe, Ni, ATP4:3:3
    下载: 导出CSV

    表  4  实验条件

    Table  4  Experimental conditions

    Experimental parameterMass of catalyst m/gMass of char m/gCatalyst diameter d /meshChar diameter d /mesh
    Value5.005.00120-16080-120
    Operating conditions
    Gasifying mediumH2OPressure p/MPa2
    Volume flow rate ρ/(mL·min-1)0.5Nitrogen volume flow rate ρ/(mL·min-1)80
    Vaporizer temperature t/℃230Operating temperature t/℃650
    Inert gasN2Cycle numbers5
    下载: 导出CSV

    表  5  半焦中各官能团的FT-IR吸收峰归属

    Table  5  Infrared spectra of the functional groups

    Wavenumber σ/cm-1Functional groupCharacteristic absorption
    3432O-H -OH stretching vibration
    2921,2852C-H -CH3,-CH2 stretching vibration
    1620C=O -COOH,-C=O stretching vibration
    1450C-H -CH3,-CH2 deformation vibration
    550~850C-Hsubstituting aromatic ring C-H deformation vibration
    下载: 导出CSV
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出版历程
  • 收稿日期:  2016-01-12
  • 修回日期:  2016-03-10
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-06-10

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