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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://dx.doi.org/10.1007/s12613-024-2851-6
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://dx.doi.org/10.1007/s12613-024-2851-6
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FeV2O4和FeCr2O4的非等温氧化动力学与反应机理研究

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

 

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

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.

 

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