固相还原法制备纳米氧化铁热力学分析及其实验研究
收稿日期: 2024-04-11
网络出版日期: 2025-04-21
基金资助
四川省科技厅重点研发项目(22YFS0461);四川省大学生创新创业项目(S202310641115)
Thermodynamic analysis and experiment research on preparation of α-Fe2O3nanoparticles by solid-phase reduction method
Received date: 2024-04-11
Online published: 2025-04-21
热力学分析是研究化学反应的重要手段，通过对FeS2-FeSO4反应体系进行热力学分析可预测反应体系中可能发生的化学反应及反应条件对化学平衡组成的影响。为了揭示出FeS2还原FeSO4制备纳米氧化铁反应体系的反应机理及工艺参数对平衡组成的影响，用HSC Chemistry软件对FeS2-FeSO4反应体系进行热力学分析，然后通过实验进行验证。根据不同温度下反应过程的∆rG⊖及化学平衡组成，推断出FeS2-FeSO4反应体系在450 ℃时主要按R1~R2反应生成α-Fe2O3和Fe3O4，生成的Fe3O4与FeSO4按R12反应生成α-Fe2O3，但此温度下R1~R2反应不完全。热力学分析表明：R1~R2均为吸热反应，相同温度下R1反应的∆rG⊖ 恒小于R2反应的∆rG⊖，且R1平衡常数大于R2平衡常数，升高温度更有利于R1反应的进行，当温度升高至500 ℃时，此时R1~R2反应可进行较为完全。此外，通过控制n（FeSO4）/n（FeS2）（13∶1）大于反应R1理论配比促使生成的Fe3O4与FeSO4能充分反应生成α-Fe2O3。基于分析结果，控制反应温度为500 ℃、反应时间为60 min，采用固相还原法成功合成纳米α-Fe2O3颗粒，其平均粒径为62 nm。由此可见，FeS2-FeSO4反应体系的热力学分析为α-Fe2O3纳米颗粒制备提供理论依据。
任根宽 , 罗欣 , 朱登磊 , 张敏 . 固相还原法制备纳米氧化铁热力学分析及其实验研究[J]. 无机盐工业, 2025 , 57(4) : 73 -78 . DOI: 10.19964/j.issn.1006-4990.2024-0209
Thermodynamic analysis is an important means of studying chemical reactions.The possible occurrence of chemical reactions in the reaction system and effect of reaction conditions on equilibrium compositions are predicted by conducting thermodynamic analysis.In order to reveal the mechanism of FeS2-FeSO4 reaction system for preparing iron oxide and theoretical basis for the preparation of material，thermodynamic analysis of FeS2-FeSO4 reaction system was performed by HSC Chemistry software.The analysis results according to the ∆rG⊖ and chemical equilibrium composition of the reaction process at different temperatures showed that R1~R2 reaction were undergone to generate α-Fe2O3 and Fe3O4 in the FeS2-FeSO4 reaction system within the temperature of 450 ℃，and the generated Fe3O4 reacted with FeSO4 to form α-Fe2O3 base on R12 reaction.But at this temperature，R1~R2 reaction were incomplete.The thermodynamic analysis showed that R1~R2 were all endothermic reactions，and the ∆rG⊖ of R1 was less than that of R2 and equilibrium constant of R1 was greater than that of R2 at the same temperature，indicating that it was more conducive to the R1 reaction.When the temperature was rised to 500 ℃，R1~R2 reaction could proceed relatively completely.In addition，the produced Fe3O4 could be fully reacted with FeSO4 to form α-Fe2O3 by controlling FeSO4/FeS2 ratio（13∶1），which was greater than the theoretical ratio of reaction R1.Based on thermodynamic analysis，α-Fe2O3 with the mean diameter of 62 nm was successfully synthesized by solid-phase reduction method at 500 ℃ for 60 minutes with the FeSO4/FeS2 ratio of 13∶1.From this，it could be seen that thermodynamic analysis of the FeS2-FeSO4 reaction system provided theoretical basis for the preparation of α-Fe2O3 nanoparticles.
Key words： ferrous sulfate; pyrite; α-Fe2O3; thermodynamic analysis
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