以金属钴粉为原料制备四氧化三钴的新工艺研究
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摘要
四氧化三钴粉体的制备大多采用前驱体草酸钴热分解的方法,而制备前驱体草酸钴的常规工艺是可溶性钴盐和草酸或草酸铵的液相沉淀反应。前驱体草酸钻的粒度及其形貌直接影响到最终产品四氧化三钴的性能。本文在分析探讨金属钴粉与酸发生反应的标准自由能及其影响因素的基础上,提出了利用金属钴粉为原料制备前驱体草酸钴的新方法,发展出了金属钴粉与草酸反应合成前驱体草酸钴,再通过前驱体的热分解制备四氧化三钻的新工艺。
对新工艺获得的草酸钴前驱体及四氧化三钴粉体采用X射线衍射、扫描电镜、激光粒度仪、热重-差热分析仪等检测手段进行了表征并探讨了粉末的形成过程及其影响因素。
研究结果表明,利用金属钴粉和草酸的固液反应可以获得针状的草酸钴粉体,且草酸钻粉末的直径和长径比可以通过外部条件的改变得到调控。用粒径不变的缩芯模型来描述钴粉在固液反应中的传质,传质过程由化学反应控制,其活化能Ea=26.335KJ/mol。对金属钻粉与草酸反应获得针状草酸钴的制备工艺参数进行考察时发现,草酸钴的长径比与反应温度、钴粉的浓度、搅拌速度等参数、以及硝酸、盐酸等无机强酸的添加与否密切相关,其中添加硝酸可使针状草酸钴晶体长径比增大,添加盐酸则长径比减小。在反应温度为50℃,草酸与钴粉的计量比(物质的量比)为2.5：1,硝酸添加量为0.05 mol/L的条件下,针状草酸钴粉体的长径比达46。
当温度高于287℃时,热分解草酸钴粉体可以得到四氧化三钴粉末。煅烧温度和保温时间对四氧化三钴粉末的形成有较大的影响,在温度处于400℃或600℃,煅烧时间为1h或3h时,得到的四氧化三钴粉体可以继承前驱体的形貌,温度高于600℃或保温时间超过3h将导致最终产物四氧化三钴粉末产生严重的烧结现象。
The cobalt oxide powder is usually prepared by thermal decomposing of cobalt oxalate precursors, and conventional process to product cobalt oxalate precursor is the liquid phase precipitation raction between solubled cobalt salts and oxalic acid or ammonium oxalate. The final performance of cobalt oxide is directly affected by the particle size and morphology of cobalt oxalate precursor. This paper proposes a new method which employs metal cobalt powder as materixal to prepare cobalt oxalate precursor. This method is based on the analysis of the standard free energy and influencing factors of the reaction. Cobalt oxide is finally prepared by thermal decomposition of the cobalt oxalate precursor.
The powders prepared by the new method were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser particle size analyzer, thermogravimetrie-differential thermal analysis (TG/DTA).
The results show that the needle-like cobalt powder was obtained by the solid-liquid reaction between metal cobalt powder and oxalic acid, and the diameter and length to diameter ratio of the needle-like cobalt oxalate powder can be controlled by changing reaction condition. The mass transfer of cobalt powder in the solid-liquid reaction can be described by the size unchanged shrinking core model, which find that the mass transfer process is controlled by chemical reaction, the activation energy is:Ea=26.335KJ/mol. The process parameters of needle-like cobalt oxalate prepared by cobalt powder and oxalic acid were studied. The results indicate that the length to diameter ratio of cobalt oxalate was closely related to reaction temperature, concentration of cobalt powder, stirring speed and so on. And the particle size and morphology of the product were also effected by whether adding nitric acid, hydrochloric acid and other inorganic acid or not. The length to diameter ratio of cobalt oxalate crystals will increase by adding a certain amount of nitric acid, and decrease by adding a certain amount of hydrochloric acid. Needle-like cobalt oxalate powder with an average diameter of 0.170μm and a length to diameter ratio of 46 was obtained under processing parameters followed:reaction temperature=50℃, n(H2C2O4):n(Co)=2.5:1, and the nitric acid concentration of 0.05 mol/L
CO3O4 powder can be received by thermal decomposing of cobalt oxalate at a temperature higher than 287℃. Calcination temperature and holding time have a greatly effection on the formation of Co3O4 powder. When the temperature is 400℃or 600℃, calcination time is lh or 3h, the powder's morphology can be extended the cobalt oxalate precursor's. When the temperature is higher than 600℃or the holding time lasts more than 3h, the Co3O4 powder occurred serious sintering phenomenon.
对新工艺获得的草酸钴前驱体及四氧化三钴粉体采用X射线衍射、扫描电镜、激光粒度仪、热重-差热分析仪等检测手段进行了表征并探讨了粉末的形成过程及其影响因素。
研究结果表明,利用金属钴粉和草酸的固液反应可以获得针状的草酸钴粉体,且草酸钻粉末的直径和长径比可以通过外部条件的改变得到调控。用粒径不变的缩芯模型来描述钴粉在固液反应中的传质,传质过程由化学反应控制,其活化能Ea=26.335KJ/mol。对金属钻粉与草酸反应获得针状草酸钴的制备工艺参数进行考察时发现,草酸钴的长径比与反应温度、钴粉的浓度、搅拌速度等参数、以及硝酸、盐酸等无机强酸的添加与否密切相关,其中添加硝酸可使针状草酸钴晶体长径比增大,添加盐酸则长径比减小。在反应温度为50℃,草酸与钴粉的计量比(物质的量比)为2.5：1,硝酸添加量为0.05 mol/L的条件下,针状草酸钴粉体的长径比达46。
当温度高于287℃时,热分解草酸钴粉体可以得到四氧化三钴粉末。煅烧温度和保温时间对四氧化三钴粉末的形成有较大的影响,在温度处于400℃或600℃,煅烧时间为1h或3h时,得到的四氧化三钴粉体可以继承前驱体的形貌,温度高于600℃或保温时间超过3h将导致最终产物四氧化三钴粉末产生严重的烧结现象。
The cobalt oxide powder is usually prepared by thermal decomposing of cobalt oxalate precursors, and conventional process to product cobalt oxalate precursor is the liquid phase precipitation raction between solubled cobalt salts and oxalic acid or ammonium oxalate. The final performance of cobalt oxide is directly affected by the particle size and morphology of cobalt oxalate precursor. This paper proposes a new method which employs metal cobalt powder as materixal to prepare cobalt oxalate precursor. This method is based on the analysis of the standard free energy and influencing factors of the reaction. Cobalt oxide is finally prepared by thermal decomposition of the cobalt oxalate precursor.
The powders prepared by the new method were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser particle size analyzer, thermogravimetrie-differential thermal analysis (TG/DTA).
The results show that the needle-like cobalt powder was obtained by the solid-liquid reaction between metal cobalt powder and oxalic acid, and the diameter and length to diameter ratio of the needle-like cobalt oxalate powder can be controlled by changing reaction condition. The mass transfer of cobalt powder in the solid-liquid reaction can be described by the size unchanged shrinking core model, which find that the mass transfer process is controlled by chemical reaction, the activation energy is:Ea=26.335KJ/mol. The process parameters of needle-like cobalt oxalate prepared by cobalt powder and oxalic acid were studied. The results indicate that the length to diameter ratio of cobalt oxalate was closely related to reaction temperature, concentration of cobalt powder, stirring speed and so on. And the particle size and morphology of the product were also effected by whether adding nitric acid, hydrochloric acid and other inorganic acid or not. The length to diameter ratio of cobalt oxalate crystals will increase by adding a certain amount of nitric acid, and decrease by adding a certain amount of hydrochloric acid. Needle-like cobalt oxalate powder with an average diameter of 0.170μm and a length to diameter ratio of 46 was obtained under processing parameters followed:reaction temperature=50℃, n(H2C2O4):n(Co)=2.5:1, and the nitric acid concentration of 0.05 mol/L
CO3O4 powder can be received by thermal decomposing of cobalt oxalate at a temperature higher than 287℃. Calcination temperature and holding time have a greatly effection on the formation of Co3O4 powder. When the temperature is 400℃or 600℃, calcination time is lh or 3h, the powder's morphology can be extended the cobalt oxalate precursor's. When the temperature is higher than 600℃or the holding time lasts more than 3h, the Co3O4 powder occurred serious sintering phenomenon.
引文
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