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非化學計量對鐵氧化物還原熱力學平衡的影響

Effect of nonstoichiometry on the thermodynamic equilibrium of iron oxide reduction processes

  • 摘要: 鐵氧化物是具有非化學計量比的化合物,非化學計量對鐵氧化物的還原過程帶來一系列影響.本文采用Dieckmann缺陷模型和Weiss的浮氏體理想固溶體模型分別對非化學計量比的磁鐵礦和浮氏體進行了熱力學計算.同時根據電荷守恒和物質守恒,對鐵氧化物固溶體的綜合缺陷度δ與還原失重率和亞鐵含量的關系進行了分析,以期對實驗終產物的判定提供依據.通過理論分析與計算,最終明確了不同化學計量比的磁鐵礦和浮氏體在不同溫度下的平衡還原勢PCO(H2),即相應的優勢區圖.在給定還原勢的純赤鐵礦等溫還原過程(未有金屬Fe生成時),當失重率小于6%時,還原產物屬于Fe3+占優勢的磁鐵礦區域;當失重率高于6%時,反應進入Fe2+占優勢的浮氏體區域.

     

    Abstract: Iron oxides were nonstoichiometric chemical compounds. Their reduction processes were remarkably influenced by nonstoichiometries. Dieckmann's defect model of magnetite and Weiss's ideal solid solution model of wustite were adopted to analyze the thermodynamic influences on the reduction processes. The dependences of deficiency degree δ on weight loss and Fe2+ mole ratio were analyzed by using the charge conservation and mass conservation principles. These relationships were recommended to judge the final product of the reduction processes. According to theoretical analyses and calculations,the predominance area diagrams including different nonstoichiometries of magnetite and wustite were determined in equilibrium with the reduction potentials PCO(H2) at different temperatures. It comes to a conclusion that when the reduction weight loss ratio is less than 6%(without metallic Fe),magnetite is predominant in the pure hematite reduction at a certain temperature and reduction potential; but when the reduction weight loss ratio is higher than 6%,the process then enters the zone of wustite.

     

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