V-O固溶体氧势及金属钒制备热力学研究

钟大鹏; 于杰; 侯勇; 喻文昊; 吕学伟

doi:10.7513/j.issn.1004-7638.2025.02.002

V-O固溶体氧势及金属钒制备热力学研究

doi: 10.7513/j.issn.1004-7638.2025.02.002

1.
重庆大学材料科学与工程学院, 重庆 400044
2.
重庆科技大学冶金与动力工程学院, 重庆 401331

基金项目: 国家自然科学基金青年基金（52304345）；中央高校基本科研业务费（2024CDJXY003）。

详细信息

作者简介:
钟大鹏，1993年出生，男，重庆奉节人，博士，长期从事冶金物化方面的基础研究工作，E-mail：Zhongdapengcqu@163.com

中图分类号: TF841.3
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- 被引次数: 0
出版历程
- 收稿日期: 2024-09-09
- 刊出日期: 2025-05-06

Thermodynamic evaluation on oxygen potential of V-O solid solution and preparation of metallic vanadium

1.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
2.
School of Metallurgical and Power Engineering, Chongqing University of Science and Technology, Chongqing 401331, China

摘要

摘要: 非金属元素O熔解在V晶格中形成固溶体，固溶体的氧脱除极限取决于氧的活度和温度，但目前对V-O固溶体热力学性质研究较少。以 Sieverts 定律为计算准则，收集V-O体系热力学数据，计算获得了不同氧含量下固溶体VO_y的氧势。同时将热力学模型导入 Factsage 并建立自定义数据库，以辅助计算金属热还原法制备钒的相变及平衡组成，明确Ca、Mg、Al等还原剂的极限脱氧能力。结果表明，合理控制Al加入量和反应温度所制备出的金属钒理论上氧含量可降至约0.1%～0.5%；Mg作为还原剂时，理论上可制备出氧含量0.01%～0.1%的金属钒产品；Ca的还原能力更出色，制备出金属钒产品中氧含量<0.01%；增加C添加量、提升反应温度、降低P_CO 理论上均可制备出氧含量低于0.1%的金属钒产品。
- V-O固溶体 /
- 氧势 /
- 金属热还原 /
- 金属钒 /
- 脱氧极限
Abstract: Non-metallic element O dissolves in the V lattice to form a V-O solid solution. The oxygen removal limit of the solid solution depends on the oxygen activity and temperature, but currently, there are few studies on the thermodynamic properties of the V-O solid solution. In this paper, based on the Sieverts’ law as the calculation criterion, the thermodynamic data of the V-O system was collected, and the oxygen potential of the solid solution VO_y with different oxygen contents was calculated. At the same time, the thermodynamic model was imported into Factsage and a custom database was established to assist in calculating the phase transition and equilibrium composition of vanadium prepared by the metal thermal reduction method, and to clarify the limit deoxidation ability of reducing agents such as Ca, Mg, and Al. The results show that by reasonably controlling the addition amount of Al and the reaction temperature, the oxygen content in the prepared metallic vanadium can theoretically be reduced to approximately 0.1 wt%-0.5 wt%. When Mg is used as the reducing agent, the metallic vanadium product with an oxygen content of 0.01 wt%-0.1 wt% can be theoretically prepared. The reduction ability of Ca is more excellent, and the oxygen content in the prepared metallic vanadium product is < 0.01 wt%. Increasing the addition amount of C, increasing the reaction temperature, and reducing P_CO can theoretically prepare metallic vanadium products with an oxygen content lower than 0.1 wt%.
- V-O solid solution /
- oxygen potential /
- metal thermal reduction /
- metallic vanadium /
- deoxidation limit

HTML全文

图 1 V–O 相图^[30]

氧等压线由压力中的指数k表示p =10^−k atm

Figure 1. Phase diagram of the V–O system^[30]

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图 2 MgO、Al₂O₃、SiO₂、V₂O₅、V₂O₃、VO 以及V-O固溶体在不同温度下的氧势

Figure 2. The oxygen potential of MgO, Al₂O₃, SiO₂, V₂O₅, V₂O₃, VO and V-O solid solution with temperature

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图 3 铝热还原V-O固溶体过程标准吉布斯自由能-温度图

Figure 3. Standard Gibbs free energy change of aluminium reduction of V-O solid solution

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图 4 不同温度和铝添加量下反应产物的平衡相组成

Figure 4. Equilibrium amounts of species in roasted products as a function of temperature and Al addition

(a) 800 ℃；(b) 1200 ℃

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图 5 镁热还原V-O固溶体过程标准吉布斯自由能-温度图

Figure 5. Standard Gibbs free energy change of magnesium reduction of V-O solid solution

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图 6 不同温度和镁添加量下反应产物的平衡相组成

Figure 6. Equilibrium amounts of species in roasted products as a function of temperature and Mg addition

(a) 800 ℃；(b) 1200 ℃

下载: 全尺寸图片幻灯片

图 7 钙热还原V-O固溶体过程标准吉布斯自由能-温度图

Figure 7. Standard Gibbs free energy change of calcium thermal reduction of V-O solid solution

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图 8 不同温度和钙添加量下反应产物的平衡相组成

Figure 8. Equilibrium amounts of species in roasted products as a function of temperature and Ca addition

(a) 800 ℃; (b) 1200 ℃

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图 9 真空碳热还原V-O固溶体过程标准吉布斯自由能变化

Figure 9. Standard Gibbs free energy change of vacuum carbothermal reduction of V-O solid solution

(a) 1 Pa; (b) 0.1 Pa; (c) 1 500 ℃; (d) 1 600 ℃

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图 10 不同条件下反应产物的平衡相组成

(a) C添加量的影响，温度1 500 ℃，CO分压1 Pa；(b) 温度的影响，C添加量3.2 mol，CO分压1 Pa；(c) CO分压的影响，C添加量3.2 mol，温度1 500 ℃

Figure 10. Equilibrium amounts of species in roasted products as a function of C amount, temperature and CO partial pressure

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表 1 基于生成1 mol VO_y的标准生成吉布斯自由能

Table 1. The standard Gibbs free energy of formation of VO_y with temperature (based on formation of 1 mol VO_y)

V-O固溶体	氧含量/%	$ \Delta G{_{\rm{f}}^{{\theta}}} $(VO_y)/(kJ·mol⁻¹)= a + b(T/K) + c(T/K)ln(T/K) + σ/(kJ·mol⁻¹)
V-O固溶体	氧含量/%	A	b	c	σ
V₂O	13.56	−425.0552	0.0160	0.0072	±0.3833
V₄O	7.27	−433.6947	0.0027	0.0070	±0.2209
V₉O	3.37	−466.9019	0.0531	0.0018	±0.5393
V₂₀O	1.50	−518.6935	0.3808	−0.0392	±0.2400
V₃₁O	1.00	−518.6935	0.3771	−0.0392	±0.2836
V₆₂O	0.50	−518.6935	0.3714	−0.0392	±0.2350
V₁₅₇O	0.20	−518.6935	0.3636	−0.0392	±0.2933
V₂₅₅O	0.12	−518.6935	0.3596	−0.0392	±0.2682
V₃₁₃O	0.10	−518.6935	0.3579	−0.0392	±0.1623
V₆₂₇O	0.05	−518.6935	0.3521	−0.0392	±0.1623
V₁₅₆₈O	0.02	−518.6935	0.3445	−0.0392	±0.1623
V₃₁₆₇O	0.01	−518.6935	0.3387	−0.0392	±0.1623

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