Thermodynamic analysis and experimental studies on chemical looping gasification of biomass with CoFe2O4 as oxygen carrier
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摘要: 对基于CoFe2O4载氧体的生物质化学链气化反应进行了热力学分析，研究了载氧体添加量、温度及水蒸气含量对气化反应特性的影响。同时应用热重分析仪对CoFe2O4和生物质的气化反应特性进行了实验研究，并利用XRD对反应前后载氧体的物相组成进行分析。热力学研究表明，CoFe2O4在气化反应中能够提供晶格氧，有效促进生物质气化，提高碳转化率。随着反应温度升高，合成气中H2和CO的含量增加，CO2的含量减少。随着水蒸气含量增加，H2和CO2含量会增加，CO含量减少。添加水蒸气能够提高合成气中H2和CO的比值，改善合成气的品质。热重实验及XRD结果表明，钴优先于铁被还原，钴与铁存在协同作用，钴能够促进铁的进一步还原。随着载氧体添加量的增加，载氧体被还原的程度会降低，载氧体与生物质的最佳质量比为0.8。Abstract: The reactivity of biomass with CoFe2O4 oxygen carrier was investigated through thermodynamic analysis. The effects including amount of oxygen carrier, temperature and steam content on gasification characteristics of biomass were examined. Meanwhile, the reaction was experimentally investigated using thermogravimetric analysis. The phase of fresh and reacted oxygen carrier was characterized by X-ray diffraction (XRD).Thermodynamic analysis results show that CoFe2O4 can provide lattice oxygen and effectively improve gasification of biomass and carbon conversion efficiency. As the temperature goes up, amount of H2 and CO increases, while CO2 decreases. With amount of steam increases, H2 and CO2 yield increases while CO yield decreases. The ratio of H2 to CO increases and high quality syngas can be obtained with the addition of steam. Thermogravimetric analysis and XRD results show that cobalt can be first reduced which can promote the further reduction of iron due to the synergistic effect. With the amount of oxygen carrier increases, reduction degree of oxygen carrier decreases. The optimal mass ratio of oxygen carrier to biomass is 0.8.
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Key words:
- biomass /
- chemical-looping gasification /
- CoFe2O4 /
- thermodynamics analysis /
- thermogravimetric analysis
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图 1 载氧体添加量对松木屑气化反应特性的影响
Figure 1 Effect of CoFe2O4 on the CLG characteristics of pine sawdust
图 4 载氧体与生物质不同质量比气化反应的TG和DTG曲线
Figure 4 TG and DTG curves for gasification of samples with different mass ratio of oxygen carrier to biomass
表 1 松木屑的元素分析和工业分析
Table 1 Ultimate analysis and proximate analysis of pine sawdust
Ultimate analysis wad/% Proximate analysis wad/% C H O* N S V FC A M 48.51 6.43 44.92 0.05 0.09 80.28 16.22 0.19 3.31 *: by difference 
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表 2 热力学计算中考虑的物相组分
Table 2 Species considered in the thermodynamic calculations
Species C(s), C(g), C2(g), C3(g), C4(g), C5(g), CO(g), CO2(g), CH4(g), C2H2(g), C2H4(g), C2H6(g) H(g), H2(g), H2O(g), H2O(l), O(g), O2(g) Fe, FeO, Fe3O4, Fe2O3, FeCO3, Fe3C CoCO3, CoFe2O4, CoO, Co3O4, Co2C, Co
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