铁酸钙与生物质焦的化学链气化反应动力学研究

Kinetic analysis of biochar chemical looping gasification with calcium ferrite as oxygen carriers

  • 摘要: 为探究铁酸钙载氧体与生物质焦的化学链气化反应动力学,基于热重实验研究了载氧体和生物质焦种类对反应性的影响,结合XRD、SEM、BET等表征手段对实验现象进行分析,并采用 Škvára-Šesták 方法确定了动力学机制函数。结果表明,载氧体反应速率Ca2Fe2O5>CaFe2O4>Fe2O3,载氧量CaFe2O4>Ca2Fe2O5>Fe2O3,生物质焦能够将载氧体完全还原为Fe和CaO;CaFe2O4与生物质焦反应的活化能为167.44–600.83 kJ/mol,Ca2Fe2O5与生物质焦反应的活化能为413.62–583.51 kJ/mol; 其中,CaFe2O4在还原的过程中生成了中间体CaFe3O5,对晶格氧的扩散有一定的影响;CaFe2O4的还原可分为两阶段,当转化率α小于0.15时,CaFe2O4还原为Ca2Fe2O5,还原过程遵循随机成核和核生长模型,当α大于0.15时,进一步还原为CaO和Fe,还原过程遵循三维扩散机制;Ca2Fe2O5的还原机制与CaFe2O4还原的第二阶段相同。

     

    Abstract: The chemical looping gasification (CLG) kinetics of biochars with calcium ferrite as oxygen carriers and the effects of different kinds of calcium ferrite and biochars were investigated by TGA. The properties of biochars and calcium ferrite were analyzed by XRD, SEM, BET, etc. The Škvára-Šesták method was used to determine the kinetic mechanism function. The results show that the reduction reaction rate and the oxygen carrying capacity of oxygen carriers follow the sequence: Ca2Fe2O5 > CaFe2O4 > Fe2O3, and CaFe2O4 > Ca2Fe2O5 > Fe2O3, respectively. The oxygen carriers can be completely reduced to Fe and CaO by biochar. The activation energy of CaFe2O4 reduction is in the range of 167.44–600.83 kJ/mol; and the activation energy of Ca2Fe2O5 reduction is in the range of 413.62–583.51 kJ/mol. The CaFe3O5 generated during the reduction of CaFe2O4 may have a negative influence on the lattice oxygen diffusion. The reduction of CaFe2O4 can be divided into two stages: when the conversion degree α is less than 0.15, the CaFe2O4 is reduced to Ca2Fe2O5 following the random nucleation and nuclei growth model; when α is greater than 0.15, Ca2Fe2O5 is further reduced to CaO and Fe following the 3-D diffusion mechanism. The mechanism function of the reduction of Ca2Fe2O5 is the same as that of the second stage of CaFe2O4 reduction.

     

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