吴文军 ,韩 召,张福元 ,刘鹏飞 ,李 杰
(安徽工业大学冶金工程学院 ,安徽马鞍山 243032)
引用格式 :
吴文军 ,韩召 ,张福元 ,等.高纯纳米氧化铁的制备 [J].中国粉体技术 , 2024, 30(1): 56-65.
WU W J, HAN Z, ZHANG F Y, et al. Preparation of high-purity nano iron oxide[J]. China Powder Science and Technology, 2024, 30(1): 56-65.
DOI:10.13732 / j.issn.1008-5548.2024.01.006
收稿日期 : 2023-07-07,修回日期 :2023-11-16,上线日期 :2023-11-28。
基金项目 :国家自然科学基金项目 ,编号:52074003。
第一作者简介 :吴文军 (1999—) ,男,硕士生 ,研究方向为粉体制备技术。 E-mail: w543150801@163.com。
通信作者简介 :韩召 (1976—),男,副教授 ,博士 ,硕士生导师 ,研究方向为粉体制备及应用技术。 E-mail: authan@163.com。
摘要:【目的】改进纳米氧化铁的制备工艺流程 ,制备高纯纳米氧化铁。【方法】首先 ,采用重结晶法去除硫酸亚铁中 Ca2+、 Mg2+、 Mn2+等杂质离子 ,采用氟化铵沉淀进一步去除硫酸亚铁中的 Ca2+、 Mg2+杂质离子 ,然后使用过氧化氢氧化法、氨水沉淀法对硫酸亚铁进行沉淀制得羟基氧化铁 ,接着采用调浆法和超声法洗涤羟基氧化铁制得前驱体 ,最后焙烧前驱体制得高纯纳米氧化铁 ;使用仪器和设备分析高纯纳米氧化铁的颗粒形貌、粒径分布和杂质离子的质量浓度。【结果】改进后的制备高纯纳米氧化铁的工艺流程为 :将温度为 60 ℃时的饱和硫酸亚铁溶液进行降温 ,在温度至 10 ℃时实现 2次重结晶 ,将重结晶后的硫酸亚铁配置为 pH为 6的溶液 ;在水浴温度为 30 ℃时,氟化铵过量系数设为 5以使 Ca2+、 Mg2+沉淀 ,制得纯净硫酸亚铁溶液 ;利用过氧化氢氧化、氨水沉淀硫酸亚铁溶液制得羟基氧化铁 ;重复利用调浆洗涤、超声洗涤羟基氧化铁去除铵根离子和硫酸根离子 ;将沉淀物在温度为 600 ℃时焙烧 1h,制得高纯纳米氧化铁。【结论】由改进的制备方法制得的高纯纳米氧化铁球形颗粒形貌均匀 ,中位粒径为 300 nm,高纯纳米氧化铁中 α-Fe2O3的质量分数大于 99. 95%。
关键词 :高纯纳米氧化铁 ;重结晶法 ;氟化铵沉淀 ;调浆 -超声洗涤法 ;氨水沉淀法 ;物相分析
Abstract
Objective Various application areas put forward demanding requirements for high-purity iron oxide nanoparticles with high purity,small particle size and narrow particle size distribution. Currently, studies on prepared iron oxide nanoparticles pay less attentionto the purity, mainly because of the failure to purify the iron source used in the experiments. It is difficult to completely removethe remaining ammonium ion and sulfate ion in the iron oxide by hydrothermal method of preparation, so there is a need to find anoperationally simple and effective method for the preparation of high-purity iron oxide nanoparticles. To prepare high-purity ironoxide nanoparticles, the preparation method of iron oxide nanoparticles needs to be further improve, followed by detailed phaseanalysis.
Methods Firstly, the recrystallization method was used to purify ferrous sulfate at one time. The saturated ferrous sulfate solution was put into a low-temperature circulating thermostat for crystallization, and the ferrous sulfate crystals were prepared after removing impurities. The crystallization processes above were repeated until the purity reached the requirements. Secondly, the second purification of ferrous sulfate was carried out by ammonium fluoride precipitation method. The ferrous sulfate crystals afterthe initial purification were first configured as a solution, and then ammonium fluoride and ammonia were added to the ferroussulfate solution. After precipitation and removing the impurities, a pure ferrous sulfate solution was obtained. Finally, hydrogen peroxide was added to the pure ferrous sulfate solution for oxidation. The hydroxyl iron oxide was precipitated by adding ammonia.After further removing impurities by the slurry mixing method and ultrasonic washing method, the iron oxide precursor was prepared and calcined to obtain high-purity nano iron oxide. Subsequently, atomic absorption spectroscopy and inductively coupled plasma atomic emission spectrometry were used to analyze the ionic mass concentration in ferrous sulfate solution and high-purity nano iron oxide. An X-ray diffractometer was used to analyze the phase composition, field emission scanning electron microscopywas used to analyze the particle morphology and a nanolaser particle size analyzer was used to analyze the particle size distributionof the final product of high-purity nano iron oxide.
Results and Discussion When the ferrous sulfate solution is purified by recrystallization method, the crystallization temperature ofthe saturated ferrous sulfate solution is selected as 10 ℃, and the mass concentrations of impurities Ca2+, Mg2+ and Mn2+ in ferrous sulfate decrease from 161, 128 and 91 mg / L to 20, 16 and 6 mg / L respectively. With the increase of ferrous sulfate solution pH, the mass concentration of Ca2+, Mg2+ impurities decreases, Ca2+, Mg2+ impurities form CaF2, MgF2 precipitates. When the pH is 6, the mass concentration of Ca2+, Mg2+ in the ferrous sulfate solution is 11.5, 7.0 mg /L, and when the pH is more than 7, more FeOOH precipitates are generated in the solution. When the solution pH is 4, there is a minimum point in the removal of Ca2+ and Mg2+ because [MFn ] 2-n coordination ions (M is impurity ions such as Ca2+ and Mg2+) are formed when the solution pH is from 3. 5 to 4, and part of the CaF2 and MgF2 precipitates will be re-dissolved, which leads to a slowdown in the trend of decreasing the mass concentration of Ca2+ and Mg2+ in the solution. Therefore, the pH of ferrous sulfate solution is adjusted to 6 with dilute ammonia water when the ferrous sulfate solution is purified by the ammonium fluoride method, the reactiontemperature is set to 30 ℃ , the excess coefficient of ammonium fluoride is set to 5, and the mass concentrations of Ca2+ and Mg2+ in the ferrous sulfate solution are reduced to 10. 4 and 6. 5 mg / L respectively. The concentration of ammonium ion and sulfate ion in the filtrate decreases from 3, 500 mg / L to 18 mg / L after 8 times of slurry washing and 17 mg / L after 3 times of ultrasonic washing, which tends to be stable. The SEM image results show that at the roasting temperature of 600 ℃ , the high-purity ironoxide nanoparticles are all spherical particles with uniform morphology and nanometer size, and there are agglomerates betweenthe particles, which is because high-purity iron oxide nanoparticles have a small diameter, large specific surface area, high surface energy, and easy to produce agglomerates. The results of the particle size distribution show that the median particle size D50 of iron oxide is 300 nm, and the particle size distribution is narrow.
Conclusion The XRD pattern result indicates that the product calcined at from 600 ℃ to 800 ℃ shows better crystallinity. At the calcined temperature of 600 ℃ , the high-purity iron oxide nanoparticles are all spherical particles with uniform morphology andnanometer size, and there are agglomerations between the particles. The prepared high-purity nano iron oxide is sphericalparticles, with uniform morphology, a median particle size of 300 nm, and the mass fraction of α-Fe2O3 in high-purity nano-iron oxide is greater than 99. 95%.
Keywords: high purity nano iron oxide; recrystallization method; ammonium fluoride precipitation; mixing-ultrasonic washing method; ammonia precipitation; phase analysis
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