Catalytic performance of Fe-Ni/ATP bifunctional catalyst for natural gas making by one-step lignite char gasification
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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。Abstract: The performance of Fe-Ni/ATP for catalytic lignite char gasification was investigated by one-step method in a small fixed-bed reactor. The catalyst Fe4Ni2/ATP4 shows an excellent catalysis for coal gasification and methanation at 650℃ and 2MPa with the methane selectivity of 24.75%, increasing by 58.76% compared to Fe4/ATP6. After five cycles, the catalyst still has a high stability with stable carbon conversion and space-time yield (STY) of CH4 production rate. The CaO that exists in the attapulgite carrier could enhance the gasification reaction. The Fe can react with water vapor to produce hydrogen significantly, which can promote coal char hydrogenation and CO methanation. When the active component Ni is introduced into the system, the reduction temperature of catalyst is reduced due to the formation of iron-nickel alloy, and the methanation activity of the prepared catalyst is increased further.
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Key words:
- coal chemical industry /
- one-step method /
- bifunctional catalyst /
- synthetic natural gas
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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 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
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 C H O+N S 0.8 2.36 10.26 95.32 1.63 2.54 0.51 
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表 2 ATP的化学组成
Table 2 Chemical composition of attapulgite used
Composition w/% SiO2 Al2O3 Fe2O3 MgO CaO K2O Na2O H2O 57.98 7.05 4.57 9.10 8.52 0.56 0.11 11.89
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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
Sample Component Mass ratio ATP ATP 0:10 Fe2/ATP8 Fe, ATP 2:8 Fe4/ATP6 Fe, ATP 4:6 Fe6/ATP4 Fe, ATP 6:4 Fe8/ATP2 Fe, ATP 8:2 Fe4Ni1/ATP5 Fe, Ni, ATP 4:1:5 Fe4Ni2/ATP4 Fe, Ni, ATP 4:2:4 Fe4Ni3/ATP3 Fe, Ni, ATP 4:3:3
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表 4 实验条件
Table 4 Experimental conditions
Experimental parameter Mass of catalyst m/g Mass of char m/g Catalyst diameter d /mesh Char diameter d /mesh Value 5.00 5.00 120-160 80-120 Operating conditions Gasifying medium H2O Pressure p/MPa 2 Volume flow rate ρ/(mL·min-1) 0.5 Nitrogen volume flow rate ρ/(mL·min-1) 80 Vaporizer temperature t/℃ 230 Operating temperature t/℃ 650 Inert gas N2 Cycle numbers 5
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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-1 Functional group Characteristic absorption 3432 O-H -OH stretching vibration 2921，2852 C-H -CH3，-CH2 stretching vibration 1620 C=O -COOH，-C=O stretching vibration 1450 C-H -CH3，-CH2 deformation vibration 550~850 C-H substituting aromatic ring C-H deformation vibration
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