FeV2O4和FeCr2O4的非等温氧化动力学与反应机理研究

向俊一; 陆曦; 白路伟; 饶鸿儒; 刘胜; 黄青云; 张生芹; 裴贵尚; 吕学伟

doi:10.1007/s12613-024-2851-6

Volume 31 Issue 8

Aug. 2024

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文章导航 > 矿物冶金与材料学报（英文） > 2024 > 31(8): 1839-1848

Junyi Xiang, Xi Lu, Luwei Bai, Hongru Rao, Sheng Liu, Qingyun Huang, Shengqin Zhang, Guishang Pei, and Xuewei Lü, Oxidation behavior of FeV₂O₄ and FeCr₂O₄ particles in the air: Nonisothermal kinetic and reaction mechanism, Int. J. Miner. Metall. Mater., 31(2024), No. 8, pp. 1839-1848. https://doi.org/10.1007/s12613-024-2851-6

Cite this article as:

Junyi Xiang, Xi Lu, Luwei Bai, Hongru Rao, Sheng Liu, Qingyun Huang, Shengqin Zhang, Guishang Pei, and Xuewei Lü, Oxidation behavior of FeV2O4 and FeCr2O4 particles in the air: Nonisothermal kinetic and reaction mechanism, Int. J. Miner. Metall. Mater., 31(2024), No. 8, pp. 1839-1848. https://doi.org/10.1007/s12613-024-2851-6

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研究论文

FeV₂O₄和FeCr₂O₄的非等温氧化动力学与反应机理研究

1)
重庆科技大学冶金与科学工程学院, 重庆 401331 , 中国
2)
首尔大学材料科学与工程系, 首尔 08826, 韩国
3)
重庆大学材料科学与工程学院, 重庆 400044, 中国

通讯作者:
向俊一 E-mail: xiangjunyi126@126.com

裴贵尚 E-mail: peiguishang@snu.ac.kr

文章亮点

(1) 采用热分析技术研究了钒铁尖晶石（FeV₂O₄）和铬铁尖晶石（FeCr₂O₄）的非等温氧化行为。

(2) 借助KAS方法获得了FeV₂O₄和FeCr₂O₄非等温氧化的表观活化能，同时利用Malek法对其氧化机理函数进行了分析，进而比较并分析了两者的氧化动力学差异。

(3) 采用高温原位XRD技术对FeV₂O₄和FeCr₂O₄在氧化过程的物相转变规律进行了系统研究，并在此基础上推导了两者的氧化机理。

中文摘要

钒铁尖晶石（FeV₂O₄）和铬铁尖晶石（FeCr₂O₄）的高温氧化行为对尖晶石类新能源材料在高温环境下的服役性能具有显著影响，同时对钒渣及高铬钒渣中钒铬的清洁提取研究也具有重大意义。因此，本文通过高温固相反应方法合成了FeV₂O₄和FeCr₂O₄材料，并利用热重分析法和高温原位X射线衍射技术（XRD）研究了两种材料在空气气氛下的非等温氧化行为。通过Kissinger-Akahira-Sunose (KAS)法和Malek法分别计算了两种材料氧化反应的表观活化能和机理函数。结果表明，FeV₂O₄和FeCr₂O₄的氧化表观活化能均随转化率的提升逐渐增大，且FeV₂O₄的表观活化能显著高于FeCr₂O₄。两者在氧化机理上均呈现出复杂性，氧化过程均可细分为四个反应阶段。其中FeV₂O₄的整个氧化过程符合化学反应模型，而FeCr₂O₄的氧化过程则逐渐从三维扩散模型过渡到化学反应模型。高温原位XRD结果进一步表明，FeV₂O₄和FeCr₂O₄在氧化过程中均生成了大量中间产物。对于FeV₂O₄，其最终氧化产物为FeVO₄和V₂O₅；而对于FeCr₂O₄，其最终氧化产物为Fe₂O₃和Cr₂O₃。

关键词:

Research Article

Oxidation behavior of FeV₂O₄ and FeCr₂O₄ particles in the air: Nonisothermal kinetic and reaction mechanism

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Abstract

Abstract

High-temperature oxidation behavior of ferrovanadium (FeV₂O₄) and ferrochrome (FeCr₂O₄) spinels is crucial for the application of spinel as an energy material, as well as for the clean usage of high-chromium vanadium slag. Herein, the nonisothermal oxidation behavior of FeV₂O₄ and FeCr₂O₄ prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction (XRD) at heating rates of 5, 10, and 15 K/min. The apparent activation energy was determined by the Kissinger–Akahira–Sunose (KAS) method, whereas the mechanism function was elucidated by the Malek method. Moreover, in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV₂O₄ and FeCr₂O₄. The results reveal a gradual increase in the overall apparent activation energies for FeV₂O₄ and FeCr₂O₄ during oxidation. Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound. The oxidation mechanisms of FeV₂O₄ and FeCr₂O₄ are complex and have distinct mechanisms. In particular, the chemical reaction controls the entire oxidation process for FeV₂O₄, whereas that for FeCr₂O₄ transitions from a three-dimensional diffusion model to a chemical reaction model. According to the in-situ XRD results, numerous intermediate products are observed during the oxidation process of both compounds, eventually resulting in the final products FeVO₄ and V₂O₅ for FeV₂O₄ and Fe₂O₃ and Cr₂O₃ for FeCr₂O₄, respectively.
- FeV₂O₄;
- FeCr₂O₄;
- oxidation;
- nonisothermal kinetics;
- mechanism

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