Oxidation behavior of ferrovanadium spinel particles in air:Isothermal kinetic and reaction mechanism  

钒铁尖晶石的高温氧化行为研究:等温动力学与反应机理

作　　者：LU Xi BAI Lu-wei RAO Hong-ru XIANG Jun-yi LUO Ming-shuai YU Jing HUANG Qing-yun SHEN Biao ZHONG Da-peng PEI Gui-shang LYU Xue-wei 陆曦;白路伟;饶鸿儒;向俊一;罗明帅;余菁;黄青云;申彪;钟大鹏;裴贵尚;吕学伟(School of Metallurgy and Materials Engineering,Chongqing University of Science and Technology,Chongqing 401331,China;Pangang Group Research Institute Co.,Ltd.,Panzhihua 617000,China;College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China C Central South University 2024)

机构地区：[1]School of Metallurgy and Materials Engineering,Chongqing University of Science and Technology,Chongqing 401331,China [2]Pangang Group Research Institute Co.,Ltd.,Panzhihua 617000,China [3]College of Materials Science and Engineering,Chongqing University,Chongqing 400044,China C Central South University 2024

出　　处：《Journal of Central South University》2024年第9期3090-3102,共13页中南大学学报（英文版）

基　　金：Project(cstb2022nscq-msx0801)supported by the Natural Science Foundation of Chongqing,China;Project(52004044)supported by the National Natural Science Foundation of China;Project(ckrc2022030)supported by the Foundation of Chongqing University of Science and Technology,China;Project(YKJCX2220216)supported by the Graduate Research Innovation Project of Chongqing University of Science and Technology,China;Project(202311551007)supported by the National Undergraduate Training Program for Innovation and Entrepreneurship,China。

摘　　要：The oxidation behavior of ferrovanadium spinel(FeV_(2)O_(4)),synthesized via high-temperature solid-state reaction,was investigated using thermogravimetry,X-ray diffractometry,and X-ray photoelectron spectroscopy over the temperature range of 450–700℃.The results revealed that the oxidation process of FeV_(2)O_(4)can be divided into three stages with the second stage being responsible for maximum weight gain due to oxidation.Three classical methods were employed to analyze the reaction mechanisms and model functions for distinct oxidation stages.The random nucleation and subsequent growth(A_(3))kinetic model was found to be applicable to both initial and secondary stage.The third stage of oxidation was consistent with the three-dimensional diffusion,spherical symmetry(D_(3))kinetic mode.Both the model-function method and the model-free method were utilized to investigate the apparent activation energy of the oxidation reaction at each stage.It was found that the intermediates including Fe_(3)O_(4),VO_(2),V_(2)O_(3),and Fe_(2.5)V_(7.11)O_(16),played significant roles in the oxidation process prior to the final formation of FeVO_(4)and V_(2)O_(5)through oxidation of FeV_(2)O_(4).钒铁尖晶石(FeV_(2)O_(4))是重要的电池和电子器件材料,也是钒渣中的主要含钒物相,其高温氧化行为对提高钒渣焙烧提钒效率具有重要意义。本文采用热重、X射线衍射以及X射线光电子能谱等方法,研究了FeV_(2)O_(4)在450~700℃范围内的氧化行为。研究结果表明,FeV_(2)O_(4)的氧化过程可分为三个阶段,其中第二阶段的氧化增重最为明显。采用ln-ln、Sharp和模型拟合等三种经典方法分析了FeV_(2)O_(4)在不同氧化阶段的反应机理,结果表明其高温氧化在第一和第二阶段符合随机成核与随后生长控制模型(A_(3))动力学模型,在第三阶段符合三维扩散控制模型(D_(3))。采用模型函数法和无模型法对各阶段氧化反应的表观活化能进行了分析。通过XPS和XRD分析发现FeV_(2)O_(4)在不同氧化温度下生成了Fe_(3)O_(4)、VO_(2)、V_(2)O_(3)以及Fe_(2.5)V_(7.11)O_(16)等大量中间产物,而最终氧化产物为FeVO_(4)和V_(2)O_(5)。

关 键 词：FeV_(2)O_(4) oxidation isothermal kinetic oxidation mechanism 

分 类 号：TF841.3[冶金工程—有色金属冶金]