基于固体氧化剂的铁水间接氧化提钒技术

张宁豫; 谢绍贤; 向俊一; 陈炼; 吕学伟

doi:10.7513/j.issn.1004-7638.2026.01.001

基于固体氧化剂的铁水间接氧化提钒技术

doi: 10.7513/j.issn.1004-7638.2026.01.001

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
3.
攀钢集团攀枝花钢铁研究院有限公司, 钒钛资源综合利用国家重点实验室, 四川攀枝花 617000

详细信息

作者简介:
张宁豫，1995年出生，男，汉族，甘肃靖远人，博士，研究方向：含钒铁水提钒，E-mail：zhangningyu023@163.com

通讯作者:
向俊一，1989年出生，湖北宜昌人，博士，副研究员，研究方向为钒冶金及新材料制备，E-mail: xiangjunyi126@126.com

中图分类号: TF03+1,TF111
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出版历程
- 收稿日期: 2025-06-19
- 录用日期: 2025-08-27
- 修回日期: 2025-08-18
- 网络出版日期: 2026-02-28
- 刊出日期: 2026-02-28

Vanadium extraction from hot metal via indirect oxidation using solid oxidizing agents

1.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
2.
School of Metallurgy and Power Engineering, Chongqing University of Science & Technology, Chongqing 401331, China
3.
State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, Pangang Group Research Institute Co., Ltd., Panzhihua617000, Sichuan, China

摘要

摘要: 针对传统铁水提钒工艺因喷吹O₂所引起的熔池控温难、铁损失和冷却剂使用造成钒渣品位降低等问题，利用间接氧化反应温和、过程可控的特点，提出采用铁氧化物进行铁水提钒的新技术。基于热力学计算，采用具有热力学优势的Fe₂O₃作为氧化剂，明确添加量为1.5%～6.0%；在此基础之上，通过系统考察Fe₂O₃的添加量、粒级以及反应温度对间接氧化提钒的影响规律，揭示了降低粒级与提升温度对钒氧化行为的强化机制；提出“CaO-Fe₂O₃”的氧化剂构建体系，通过降低体系熔化温度进一步提高反应效率；经工艺参数优化，在反应温度1350 ℃，添加4.5%的0.074～0.5 mm粒级Fe₂O₃，并按照n(CaO):n(Fe₂O₃)=0.75配入CaO时，反应2 min达到平衡状态，终点钒含量为0.016%，钒氧化率为95.12%，钒渣中V含量为7.15%，P含量为1.93%。该技术通过“CaO-Fe₂O₃”体系实现了铁水中钒的高效提取，为铁水提钒工艺的发展提供了新的思路。
- 含钒铁水 /
- 提钒 /
- 间接氧化 /
- 钒渣
Abstract: Aiming at solving the problems of temperature control in molten bath, iron loss, and grade reduction of vanadium slag caused by O₂ injection in the traditional process of vanadium extraction from hot metal, a new technology using iron oxides (Fe₂O₃) for vanadium extraction from hot metal was proposed in this study, taking advantage of the characteristics of mild indirect oxidation reaction and controllable process. Thermodynamic calculations identified Fe₂O₃ as the optimal oxidizer with recommended addition ranges of 1.5%–6.0%. A systematic investigation was conducted on the effects of Fe₂O₃ addition ratio, particle size, and bath temperature, revealing the enhancement mechanisms of particle size reduction and temperature elevation on vanadium oxidation. The study further developed a “CaO-Fe₂O₃” oxidizer system that improves reaction efficiency by lowering the melting temperature. Through process parameter optimization, the optimal conditions were determined as: reaction temperature 1350 °C, 4.5% of 0.074–0.5 mm Fe₂O₃ with n(CaO): n(Fe₂O₃) = 0.75. Under these conditions, the reaction reached equilibrium within 2 min, achieving a final V content in the hot metal of 0.016%, oxidation rate of 95.12%, with vanadium slag containing 7.15% V and 1.93% P. This “CaO-Fe₂O₃” system demonstrates efficient vanadium extraction from hot metal and provides new insights for the development of vanadium extraction technologies.
- V-bearing hot metal /
- vanadium extraction /
- indirect oxidation /
- vanadium slag

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图 1 试验设备示意

Figure 1. Schematic diagram of experimental equipment

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图 2 铁氧化物种类对钒氧化率影响的计算结果

Figure 2. Calculations of the effect of iron oxide species on vanadium oxidation rate

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图 3 反应温度对钒氧化率影响的计算结果

Figure 3. Calculations of the effect of reaction temperature on vanadium oxidation rate

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图 4 钒渣的物相组成计算结果

Figure 4. Calculations of the phase composition of vanadium slag

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图 5 Fe₂O₃添加量与铁水中元素氧化率的关系

Figure 5. Relationship between Fe₂O₃ addition ratio and oxidation rate of elements in hot metal

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图 6 Fe₂O₃粒级与铁水中钒元素氧化率的关系

Figure 6. Relationship between Fe₂O₃ particle size and the oxidation rate of vanadium in hot metal

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图 7 反应温度与铁水中钒元素氧化率的关系

Figure 7. Relationship between reaction temperature and the oxidation rate of vanadium in hot metal

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图 8 不同反应条件与铁水中钒元素氧化率的关系

Figure 8. Relationship between different reaction conditions and the oxidation rate of vanadium in hot metal

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图 9 “CaO-Fe₂O₃”二元相图（p(O₂)= 2.13×10⁴ Pa）

Figure 9. CaO–Fe₂O₃ phase diagram (p(O₂)= 2.13×10⁴ Pa)

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图 10 氧化钙添加量与铁水中钒元素氧化率的关系

Figure 10. Relationship between the addition of CaO and the oxidation rate of vanadium in hot metal

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图 11 样品的熔化性检测

Figure 11. Sample melting test

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图 12 钒渣的XRD图谱

Figure 12. XRD pattern of vanadium slag

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图 13 不同n(CaO):n(Fe₂O₃)时钒渣的SEM图像及EDS面扫结果

Figure 13. SEM images and EDS mapping of vanadium slag at different n(CaO):n(Fe₂O₃)

(a) 0；(b) 0.25；(c) 0.50；(d) 0.75；(e)1.00

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表 1 含钒铁水成分

Table 1. Composition of hot metal %

C	Si	V	P	Ti	Mn	S	Cr
4.36	0.19	0.33	0.07	0.24	0.25	0.07	0.11

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表 2 氧化剂的成分及添加量

Table 2. The compositions and addition ratio of the oxidant

Oxidant	w(CaO)/%	w(Fe₂O₃)/%	Addition ratio/%
n(CaO):n(Fe₂O₃)=0.25	8.05	91.95	4.89
n(CaO):n(Fe₂O₃)=0.50	14.89	85.11	5.29
n(CaO):n(Fe₂O₃)=0.75	20.79	79.21	5.68
n(CaO):n(Fe₂O₃)=1.00	25.93	74.07	6.08

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表 3 钒渣的化学成分分析

Table 3. Chemical compositions of vanadium slag %

Sample	TFe	FeO	V	Ca	Si	Ti	Mn	Cr	P
A	38.10	46.47	12.01	0.16	4.51	4.40	5.37	3.58	0.05
B	42.74	53.65	6.34	4.40	4.00	6.38	4.53	1.81	0.33
C	28.08	34.49	6.84	13.38	5.36	5.22	4.37	1.71	1.28
D	21.58	23.64	7.15	19.95	4.58	3.02	3.80	1.53	1.92
E	19.99	24.10	7.49	21.64	4.26	3.45	3.62	1.77	1.93

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表 4 EDS点扫描结果

Table 4. EDS points analysis results %

Point	Fe	Mn	Cr	V	Ti	Ca	P	Si	O
a-1	23.32	4.65	7.68	22.94	2.88	0.02	0.00	0.12	38.39
a-2	11.22	6.73	0.14	0.59	0.52	0.57	0.00	23.71	56.23
b-1	27.51	4.59	3.07	13.84	8.89	0.18	0.00	0.04	41.87
b-2	18.46	6.16	0.06	0.57	0.39	7.20	0.00	16.43	50.73
b-3	7.66	3.02	0.04	0.41	0.93	11.90	0.00	21.85	54.21
c-1	25.68	4.58	4.87	20.33	4.70	0.17	0.00	0.19	39.49
c-2	22.07	7.64	0.19	0.70	0.37	2.63	0.00	16.11	50.30
c-3	8.37	6.40	0.11	0.46	0.19	7.95	0.00	22.44	54.08
d-1	18.59	10.32	7.46	20.10	1.29	2.12	0.00	0.30	39.82
d-2	2.32	0.19	0.28	6.47	15.54	25.98	0.00	1.35	47.87
d-3	0.45	0.18	0.07	3.41	0.11	30.65	8.93	5.95	50.27
d-4	54.29	3.73	0.20	0.96	0.32	0.74	0.00	0.00	39.76
e-1	17.62	11.38	5.87	19.30	4.37	1.50	0.00	0.07	39.90
e-2	0.27	0.52	0.00	2.08	0.13	28.87	9.93	5.93	52.27
e-3	43.05	15.47	0.21	1.42	0.22	0.80	0.00	0.00	38.84
e-4	93.89	0.33	0.22	1.18	0.19	0.97	0.00	0.01	3.22
e-5	1.08	0.39	0.30	9.74	14.44	24.98	0.00	1.03	48.04

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参考文献(16)

[1]	WANG J, YU W, XIANG J, et al. Toward high-purity vanadium-based materials: Fundamentals, purifications, and perspectives[J]. Journal of Cleaner Production, 2024, 476: 143721. doi: 10.1016/j.jclepro.2024.143721
[2]	IBRAHIM M, DU Q, HOVIG E W, et al. Gas-atomized nickel silicide powders alloyed with molybdenum, cobalt, titanium, boron, and vanadium for additive manufacturing[J]. Metals, 2023, 13(9): 1591. doi: 10.3390/met13091591
[3]	MA D, HAN C, LIU B, et al. Vanadium oxide-based electrode materials for advanced supercapacitors: a review[J]. Energy & Fuels, 2024, 38(12): 10494-10516. doi: 10.1021/acs.energyfuels.4c00725
[4]	HAAK M R, INDRARATNE S P. Soil amendments for vanadium remediation: a review of remediation of vanadium in soil through chemical stabilization and bioremediation[J]. Environmental Geochemistry and Health, 2023, 45(7): 4107-4125. doi: 10.1007/s10653-023-01498-8
[5]	TAYLOR P R, SHUEY S A, VIDAL E E, et al. Extractive metallurgy of vanadium-containing titaniferous magnetite ores: a review[J]. Mining, Metallurgy & Exploration, 2006, 23(2): 80-86.
[6]	PENG H, GUO J, LI B, et al. Vanadium properties, toxicity, mineral sources and extraction methods: a review[J]. Environmental Chemistry Letters, 2022, 20(2): 1249-1263. doi: 10.1007/s10311-021-01380-y
[7]	QIN J. Recovery of vanadium from vanadium-bearing molten iron in ladles in a pilot plant[J]. Iron Steel Vanadium Titanium, 2013, 34(1): 13-17. (秦洁. 含钒铁水钢包提钒生产实践[J]. 钢铁钒钛, 2013, 34(1): 13-17. QIN J. Recovery of vanadium from vanadium-bearing molten iron in ladles in a pilot plant[J]. Iron Steel Vanadium Titanium, 2013, 34（1）: 13-17.
[8]	WAN C M, YI B L, ZHONG Z H. Technology of vanadium extraction from low vanadium molten iron[J]. Sichuan Metallurgy, 2010, 32(1): 4-7. (万朝明, 易邦伦, 钟正华. 低钒铁水提钒炼钢工艺分析[J]. 四川冶金, 2010, 32(1): 4-7. WAN C M, YI B L, ZHONG Z H. Technology of vanadium extraction from low vanadium molten iron[J]. Sichuan Metallurgy, 2010, 32（1）: 4-7.
[9]	XIE Y Z. Research on improvement measures of vanadium extraction cooling system in converter of Panzhihua Iron and Steel Group[J]. Sichuan Metallurgy, 2003(4): 12-14. (谢永中. 攀钢铁水转炉提钒冷却制度改进措施研究[J]. 四川冶金, 2003(4): 12-14. doi: 10.3969/j.issn.1001-5108.2003.04.005 XIE Y Z. Research on improvement measures of vanadium extraction cooling system in converter of Panzhihua Iron and Steel Group[J]. Sichuan Metallurgy, 2003（4）: 12-14. doi: 10.3969/j.issn.1001-5108.2003.04.005
[10]	HUANG X H. Principles of ferrous metallurgy[M]. Beijing: Metallurgical Industry Press, 2013: 474-475. (黄希祜. 钢铁冶金原理[M]. 北京: 冶金工业出版社, 2013: 474-475. HUANG X H. Principles of ferrous metallurgy[M]. Beijing: Metallurgical Industry Press, 2013: 474-475.
[11]	DU W T, WANG Y, LIANG X P. System assessment of carbon dioxide used as gas oxidant and coolant in vanadium-extraction converter[J]. JOM, 2017, 69(10): 1785-1789. doi: 10.1007/s11837-017-2463-y
[12]	CHEN L, XIE B, GE W S, et al. Reducing carbon loss during vanadium-extraction process in converter[J]. Journal of Iron and Steel Research, 2020, 32(7): 654-660. (陈炼, 谢兵, 戈文荪, 等. 减少转炉提钒过程碳烧损[J]. 钢铁研究学报, 2020, 32(7): 654-660. doi: 10.13228/j.boyuan.issn1001-0963.20200098 CHEN L, XIE B, GE W S, et al. Reducing carbon loss during vanadium-extraction process in converter[J]. Journal of Iron and Steel Research, 2020, 32（7）: 654-660. doi: 10.13228/j.boyuan.issn1001-0963.20200098
[13]	KANG Y. Desiliconisation and dephosphorisation behaviours of various oxygen sources in hot metal pre-treatment[J]. Metals, 2019, 9(2): 251. doi: 10.3390/met9020251
[14]	PAN F F. Study on the reaction behavior between CaO-Fe₂O₃ based slag and the hot metal[D]. Chongqing: Chongqing University, 2020. (潘飞飞. CaO-Fe₂O₃基渣系与铁水反应行为研究[D]. 重庆: 重庆大学, 2020. PAN F F. Study on the reaction behavior between CaO-Fe₂O₃ based slag and the hot metal[D]. Chongqing: Chongqing University, 2020.
[15]	CHEN G, LI Z D, MOU X H, et al. Research on the conversion temperature of carbon and vanadium during vanadium extraction[J]. Metallurgy and materials, 2020, 40(6): 54-55. (陈刚, 李志丹, 牟小海, 等. 提钒过程中碳钒转换温度研究[J]. 冶金与材料, 2020, 40(6): 54-55. doi: 10.3969/j.issn.1674-5183.2020.06.025 CHEN G, LI Z D, MOU X H, et al. Research on the conversion temperature of carbon and vanadium during vanadium extraction[J]. Metallurgy and materials, 2020, 40（6）: 54-55. doi: 10.3969/j.issn.1674-5183.2020.06.025
[16]	LI Y D, LI G, ZHANG N Y, et al. Metallurgical performance of Ca₃TiFe₂O₈[J]. Calphad, 2024, 85: 102671. doi: 10.1016/j.calphad.2024.102671