缺碳预还原MoO<sub>3</sub>+氢气深脱氧工艺制备超细钼粉

张勇; 张国华; 周国治

doi:10.19591/j.cnki.cn11-1974/tf.2021010010

缺碳预还原MoO₃+氢气深脱氧工艺制备超细钼粉

doi: 10.19591/j.cnki.cn11-1974/tf.2021010010

北京科技大学钢铁冶金新技术国家重点实验室，北京 100083

详细信息

通讯作者:
E-mail：ghzhang0914@ustb.edu.cn

中图分类号: TF8
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出版历程
- 收稿日期: 2021-01-16
- 刊出日期: 2021-08-28

Preparation of ultrafine Mo powders by MoO₃ pre-reduction with insufficient carbon and hydrogen deep reduction

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: ghzhang0914@ustb.edu.cn

摘要

摘要: 以炭黑为还原剂还原MoO₃制备存在少量MoO₂的预还原Mo粉，然后对预还原Mo粉进行氢气深还原，成功制备出平均粒径为99～190 nm的超细钼粉，研究了碳热还原温度对Mo粉平均粒度和残碳量的影响。结果表明，在同一还原温度下，当C/MoO₃摩尔比从2.0增加到2.1时，产物的粒径变化很小。碳热还原温度对产物粒径和纯度有显著影响。当C/MoO₃摩尔比为2.1时，还原温度从950 ℃增加到1150 ℃，氢还原后钼粉的平均粒径从100 nm增加到190 nm，且残碳量（质量分数）由0.030%降低到0.009%。
- 超细钼粉 /
- 碳热还原 /
- 氢气还原 /
- 形核 /
- 长大
Abstract: The pre-reduction molybdenum powders containing minor amount of MoO₂ were prepared by the carbothermic reduction of MoO₃, using the carbon black as the reducing agent, then the obtained pre-reduction molybdenum powders were deep reduced by hydrogen to finally prepare the ultrafine molybdenum powders with the average particle size of 99 nm to 190 nm. The effects of the carbothermic reduction temperature on the particle size and the residual carbon content by mass of the ultrafine molybdenum powders were studied. In the results, with the increase of C/MoO₃ molar ratio from 2.0 to 2.1, the particle sizes of the ultrafine molybdenum powder products change little at the same reduction temperature. But the carbothermal reduction temperature shows a significant effect on the particle size and purity of products. When the C/MoO₃ molar ratio is 2.1, with the increase of reduction temperature from 950 ℃ to 1150 ℃, the average particle sizes of products increase from 100 nm to 190 nm, and the content of the residual carbon by mass decreases from 0.030% to 0.009% after the hydrogen reduction.
- ultrafine molybdenum powders /
- carbothermic reduction /
- hydrogen reduction /
- nucleation /
- growth

HTML全文

图 1 原料XRD分析和微观形貌：（a）MoO₃XRD分析；（b）MoO₃显微形貌；（c）炭黑显微形貌；（d）MoO₃和炭黑混合物显微形貌

Figure 1. XRD patterns and SEM images of the raw materials: (a) XRD pattern of MoO₃; (b) SEM image of MoO₃; (c) SEM image of carbon black; (d) SEM image of MoO₃ and carbon black mixture

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图 2 实验装置示意图

Figure 2. Schematic diagram of the experimental apparatus

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图 3 碳热还原产物X射线衍射分析

Figure 3. XRD patterns of the carbothermic reduction products

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图 4 不同温度和不同C/MoO₃摩尔比的碳热还原产物显微形貌：（a）950 ℃，2.0；（b）950 ℃，2.1；（c）950 ℃，2.2；（d）1000 ℃，2.0；（e）1000 ℃，2.1；（f）1050 ℃，2.0；（g）1050 ℃，2.1；（h）1100 ℃，2.1；（i）1150 ℃，2.1

Figure 4. SEM images of the carbothermic reduction products at different temperatures and C/MoO₃ ratios by mole: (a) 950 ℃, 2.0; (b) 950 ℃, 2.1; (c) 950 ℃, 2.2; (d) 1000 ℃, 2.0; (e) 1000 ℃, 2.1; (f) 1050 ℃, 2.0; (g) 1050 ℃, 2.1; (h) 1100 ℃, 2.1; (i) 1150 ℃, 2.1

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图 5 不同温度和不同C/MoO₃摩尔比的氢气还原产物X射线衍射分析、平均粒径及显微形貌：（a）X射线衍射分析；（b）平均粒径；（c）950 ℃，C/MoO₃摩尔比2.0产物显微形貌；（d）950 ℃，C/MoO₃摩尔比2.1产物显微形貌；（e）1000 ℃，C/MoO₃摩尔比2.0产物显微形貌；（f）1000 ℃，C/MoO₃摩尔比2.1产物显微形貌；（g）1050 ℃，C/MoO₃摩尔比2.0产物显微形貌；（h）1050 ℃，C/MoO₃摩尔比2.1产物显微形貌；（i）1100 ℃，C/MoO₃摩尔比2.1产物显微形貌；（j）1150 ℃，C/MoO₃摩尔比2.1产物显微形貌；

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图 6 炭黑还原MoO₃机理示意图

Figure 6. Schematic diagram of the MoO₃ reduction by carbon black

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表 1 Mo、MoO₂和MoO₃的基本物理性能参数^[8,17‒18]

Table 1. Physical property parameters of Mo, MoO₂, and MoO₃

物相摩尔质量/(g·mol^‒1) 密度/(g·cm^‒3) 摩尔体积/(cm³·mol^‒1)

Mo 95.94 10.2 9.41
MoO₂ 127.94 6.47 19.77
MoO₃ 143.94 4.692 30.68

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