CH4还原氮化V2O3制备VN

夏三元; 姜涛; 陈泊键; 温婧; 杨广东; 刘孟霞

doi:10.7513/j.issn.1004-7638.2024.05.003

CH₄还原氮化V₂O₃制备VN

doi: 10.7513/j.issn.1004-7638.2024.05.003

东北大学冶金学院, 辽宁沈阳110819

基金项目: 国家自然科学基金项目（52174277，52374300，52204309）。

详细信息

作者简介:
夏三元，1999年出生，男，河北邢台人，硕士研究生，主要从事VN制备工艺研究，E-mail：554804131@qq.com

通讯作者:
姜涛，1973年出生，男，辽宁本溪人，教授，博士生导师，主要从事冶金资源综合利用研究，E-mail：jiangt@smm.neu.edu.cn

中图分类号: TF841.3
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出版历程
- 收稿日期: 2024-04-02
- 网络出版日期: 2024-10-30
- 刊出日期: 2024-10-30

Preparation of VN by reduction nitriding V₂O₃ with CH₄

School of Metallurgy, Northeastern University, Shenyang 110819, Liaoning, China

摘要

摘要: 通过热力学计算和试验工艺结合的方式，探究了利用CH₄作为还原剂碳热还原、氮化制备VN的工艺条件以及反应过程。结果表明：在CH₄流量0.1 L/min、1150 ℃保温2 h并继续渗氮2 h的条件下，成功合成了氮、碳含量分别为14.2%、3.35%的VN产物，符合国家VN16(GB/T 20567-2020)氮化钒产品标准。反应过程中的物相转变过程为V₂O₃→V₈C₇→VN，并且CH₄在高温条件下分解产生的高活性炭与H₂均有利于碳化反应的进行，能有效提高反应速率。
- 氮化钒 /
- 三氧化二钒 /
- 甲烷 /
- 还原氮化 /
- 物相转变
Abstract: In this paper, the process conditions and reaction process of using CH₄ instead of traditional carbon thermal reduction to prepare VN is explored by combining thermodynamic calculation and experimental process exploration. The results showed that the VN products with nitrogen and carbon contents of 14.2% and 3.35% were successfully synthesized under the conditions of CH₄ flow rate of 0.1 L/min, heating at 1150 ℃ for 2 h and continuous nitriding for 2 h, which met the national standard of VN16 (GB/T 20567-2020) for vanadium nitride product. The phase transition process during the reaction is V₂O₃→V₈C₇→VN, and the high activated carbon and hydrogen produced by methane decomposition at high temperature are beneficial to the carbonization reaction and effectively improve the reaction rate.
- VN /
- V₂O₃ /
- CH₄ /
- reduction nitridation /
- phase transitions

HTML全文

图 1 钒氧化物在CH₄气氛下还原氮化过程中涉及的反应ΔG^θ-T曲线

Figure 1. Reaction ΔG^θ-T curve involved in reductive nitridation of vanadium oxide in methane atmosphere

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图 2 不同气体比例下碳含量变化

(a)无N₂；(b) CH₄:N₂=3:1；(c) CH₄:N₂=3:2；(d) CH₄:N₂=1:1

Figure 2. Change of carbon content under different gas ratios

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图 3 (a)试验流程； (b)还原氮化过程升温制度

1-质量流量计；2-计算机；3-分析天平；4-尾气排放管路；5-钨丝篮；6-炉膛保温段；7-电炉管壁

Figure 3. (a) Experimental flow chart, (b) temperature rising system in reduction nitriding process

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图 4 不同反应温度条件下反应物的失重曲线以及物相图谱

(a)失重曲线；(b)1050 ℃条件下阶段Ⅱ产物图谱；(c)产物物相图谱

Figure 4. Weight loss curves and phase diagrams of reactants at different reaction temperatures

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图 5 0.1 L/min CH₄条件下V₂O₃于1150 ℃保温2 h反应产物微观形貌与元素含量

(a)微观形貌；(b)~(e)V、N、C、O元素分布；(f)能谱分析

Figure 5. Morphology and element content distribution of V₂O₃ reaction products at 1150 ℃ for 2 h in 0.1 L/min methane

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图 6 (a)失重曲线；(b)不同CH₄流量下试验产物物相图谱；(c)不同CH₄流量对应VN产物的C、N含量

Figure 6. (a) Weight loss curve, (b) phase diagram of experimental products under different CH₄ flow rates, (c) C and N contents of vanadium carbonitride products under different CH₄flow rates

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图 7 不同渗氮时间下氮含量变化

Figure 7. Changes of nitrogen content with different nitriding time

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图 8 分步碳、氮化试验产物物相图谱（a）及局部对比(b)

Figure 8. Phase diagram and local enlargement of products of step-by-step carbonitriding experiment(a) phase diagram, (b) comparison diagram

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图 9 氮化试验产物微观形貌及元素含量

Figure 9. Morphology and element content of nitriding experimental product

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图 10 单一CH₄、C参与V₂O₃碳化反应产物物相图谱

Figure 10. Phase diagram of single CH₄ and C participating in V₂O₃ carbonization reaction product

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图 11 H₂配碳还原与单一H₂、碳还原对比失重及对应产物物相图谱

Figure 11. Comparative weight loss of single H₂, carbon and H₂/C blending and the phase diagram of corresponding products

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图 12 H₂+N₂、N₂氮化增重曲线对比及其对应产物形貌

Figure 12. Nitriding versus weight gain curve and its corresponding product picture

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表 1 试验方案

Table 1. Experimental scheme

方案	反应物	气氛组成	甲烷流量 /(L·min⁻¹)	温度/℃	保温时间/h	渗氮时间/h
1	V₂O₃	CH₄+N₂	0.1	950	2	0
2	V₂O₃	CH₄+N₂	0.1	1000	2	0
3	V₂O₃	CH₄+N₂	0.1	1050	2	0
4	V₂O₃	CH₄+N₂	0.1	1100	2	0
5	V₂O₃	CH₄+N₂	0.1	1150	2	0
6	V₂O₃	CH₄+N₂	0.15	1150	2	0
7	V₂O₃	CH₄+N₂	0.2	1150	2	0
8	V₂O₃	CH₄+N₂	0.25	1150	2	0
9	V₂O₃	CH₄+N₂	0.05	1150	2	0
10	V₂O₃	CH₄+N₂	0.1	1150	2	1
11	V₂O₃	CH₄+N₂	0.1	1150	2	2
12	V₂O₃	CH₄+N₂	0.1	1150	2	3
13	V₂O₃	CH₄+N₂	0.1	1150	2	4
14	V₂O₃	CH₄	0.1	1150	2	0
15	VC	N₂		1150	2	0
16	V₂O₃+C	H₂		1150	2
17	V₂O₃+C			1150	2
18	V₂O₃	H₂		1150	2
19	VC	N₂		1150	2
20	VC	N₂+H₂		1150	2

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参考文献(17)

[1]	Zhou Zhenyu. Study on the basis and application of deep vanadium extraction and carbon preservation in vanadium-bearing molten iron combined blowing converter [D]. Chongqing: Chongqing University, 2019. (周振宇. 含钒铁水复吹转炉深提钒和保碳的基础及应用研究[D]. 重庆: 重庆大学, 2019. Zhou Zhenyu. Study on the basis and application of deep vanadium extraction and carbon preservation in vanadium-bearing molten iron combined blowing converter [D]. Chongqing: Chongqing University, 2019.
[2]	Tan Ruobin. Development and application of vanadium, vanadium compounds and vanadium alloys[J]. Vanadium and Titanium, 1995(1):1-10. (谭若斌. 钒、钒化合物、钒合金的开发应用[J]. 钒钛, 1995(1):1-10. Tan Ruobin. Development and application of vanadium, vanadium compounds and vanadium alloys[J]. Vanadium and Titanium, 1995（1）: 1-10.
[3]	Duan Xinhui, Srinivasakannan C, Zhang H, et al. Process optimization of the preparation of vanadium nitride from vanadium pentoxide[J]. Arabian Journal for Science and Engineering, 2015, 40(8): 2133-2139.
[4]	Xu Rui, Wu Yuedong, Zhang Guohua. Preparation of high purity vanadium nitride by magnesiothermic reduction of V₂O₃ followed by nitriding in N₂ atmosphere[J]. Transactions of Nonferrous Metals Society of China, 2019, 29(8): 1776-1783. (徐瑞, 吴跃东, 张国华. 用镁热还原法制备高纯氮化钒[J]. 中国有色金属学会学报, 2019, 29(8): 1776-1783. Xu Rui, Wu Yuedong, Zhang Guohua. Preparation of high purity vanadium nitride by magnesiothermic reduction of V₂O₃ followed by nitriding in N₂ atmosphere[J]. Transactions of Nonferrous Metals Society of China, 2019, 29(8): 1776-1783.
[5]	Mechnik V A, Bondarenko N A, Kuzin N O. Influence of the addition of vanadium nitride on the structure and specifications of a diamond–(Fe–Cu–Ni–Sn) composite system[J]. Frict. Wear, 2018, 39 (2) : 108-113.
[6]	Wu Yuedong, Zhang Guohua, Zhou Guozhi. A novel process to synthesize high-quality ferrovanadium nitride[J]. Metallurgical and Materials Transactions, 2016,47(6):3405-3412. (吴跃东, 张国华, 周国治. 合成高质量氮化钒铁的新工艺[J]. 冶金材料学报, 2016,47(6):3405-3412. doi: 10.1007/s11663-016-0793-8 Wu Yuedong, Zhang Guohua, Zhou Guozhi. A novel process to synthesize high-quality ferrovanadium nitride[J]. Metallurgical and Materials Transactions, 2016, 47（6）: 3405-3412. doi: 10.1007/s11663-016-0793-8
[7]	Zhong Yu, Chao Dongliang, Deng Shengjue, et al. Confining sulfur in integrated composite scaffold with highly porous carbon fibers/vanadium nitride arrays for high-performance lithium-sulfur batteries[J]. Advanced Functional Materials, 2018,28(38):1706391. (钟宇, 晁栋梁, 邓胜珏, 等. 高性能锂硫电池用多孔碳纤维/氮化钒阵列集成复合支架中的硫限制[J]. 先进功能材料, 2018,28(38):1706391. doi: 10.1002/adfm.201706391 Zhong Yu, Chao Dongliang, Deng Shengjue, et al. Confining sulfur in integrated composite scaffold with highly porous carbon fibers/vanadium nitride arrays for high-performance lithium-sulfur batteries[J]. Advanced Functional Materials, 2018, 28（38）: 1706391. doi: 10.1002/adfm.201706391
[8]	Tao Jun, Tao Ran, Yan Baijun. Experimental measurements of activity coefficients of vanadium in liquid iron[J]. Nonferrous Metals Science and Engineering, 2017,8(1):11-14. (陶俊, 陶然, 闫柏军. 钒在铁液中活度系数的实验研究[J]. 有色金属科学与工程, 2017,8(1):11-14. Tao Jun, Tao Ran, Yan Baijun. Experimental measurements of activity coefficients of vanadium in liquid iron[J]. Nonferrous Metals Science and Engineering, 2017, 8（1）: 11-14.
[9]	Bondarchuk O, Morel A, Bélanger D, et al. Thin films of pure vanadium nitride: Evidence for anomalous non–faradaic capacitance[J]. Journal of Power Sources, 2016,324(5):439-446.
[10]	Wang Baohua, Wu Chunliang, Lu Yongjie, et al. Study on industrial production of high-nitrogen content VN-alloy[J]. Nonferrous Metals, 2019(7):64-67. (王宝华, 吴春亮, 卢永杰, 等. 工业生产高氮氮化钒合金的研究[J]. 有色金属(冶炼部分), 2019(7):64-67. Wang Baohua, Wu Chunliang, Lu Yongjie, et al. Study on industrial production of high-nitrogen content VN-alloy[J]. Nonferrous Metals, 2019（7）: 64-67.
[11]	Chu Zhiqiang, Guo Xueyi, Tian Qinghua, et al. Preparation of vanadium nitride by carbothermic reduction and nitrogenization[J]. Materials Science and Engineering of Powder Metallurgy, 2015,20(6):965-970. (储志强, 郭学益, 田庆华, 等. 碳热还原氮化法制备氮化钒[J]. 粉末冶金材料科学与工程, 2015,20(6):965-970. doi: 10.3969/j.issn.1673-0224.2015.06.022 Chu Zhiqiang, Guo Xueyi, Tian Qinghua, et al. Preparation of vanadium nitride by carbothermic reduction and nitrogenization[J]. Materials Science and Engineering of Powder Metallurgy, 2015, 20（6）: 965-970. doi: 10.3969/j.issn.1673-0224.2015.06.022
[12]	Yin Qi. Mechanism study on preparation of vanadium nitride by carbothermal reduction nitridation method[D]. Kunming: Kunming University of Science and Technology, 2023. (尹奇. 碳热还原氮化法制备氮化钒的机理研究[D]. 昆明: 昆明理工大学, 2023. Yin Qi. Mechanism study on preparation of vanadium nitride by carbothermal reduction nitridation method[D]. Kunming: Kunming University of Science and Technology, 2023.
[13]	Zhao Shiqiang. Study on the preparation of V(N, O) powder by reduction of V₂O₅ with ammonia at low temperatures[J]. Nonferrous Metals Science and Engineering, 2019,10(5):28-34. (赵世强. 氨气还原氮化五氧化二钒制备V(N, O)粉体与机理研究[J]. 有色金属科学与工程, 2019,10(5):28-34. Zhao Shiqiang. Study on the preparation of V(N, O) powder by reduction of V₂O₅ with ammonia at low temperatures[J]. Nonferrous Metals Science and Engineering, 2019, 10（5）: 28-34.
[14]	Fu Mingkai, Jin Jiahui, Ma Haitao, et al. Thermodynamic analysis of novel vanadium redox materials for solar thermochemical ammonia synthesis from N₂ and CH₄[J]. International Journal of Hydrogen Energy, 2020,45(4):2569-2577. doi: 10.1016/j.ijhydene.2019.11.122
[15]	Rodrı́guez P, Brito J L, Albornoz A, et al. Comparison of vanadium carbide and nitride catalysts for hydrotreating[J]. Catalysis Communications, 2004,5(2):79-82. doi: 10.1016/j.catcom.2003.11.011
[16]	Choi Jeong Gil, Ha Joseph, Hong Jin Who. Synthesis and catalytic properties of vanadium interstitial compounds[J]. Applied Catalysis A: General, 1998,168(1):47-56. doi: 10.1016/S0926-860X(97)00332-3
[17]	Gao Feng. Fundamental study on preparing vanadium nitride and carbide by carbothermal reduction and nitridation of V₂O₃[D]. Shenyang: Northeastern University, 2006. (高锋. 三氧化二钒碳热还原氮化制备碳氮化钒的基础研究[D]. 沈阳: 东北大学, 2006. Gao Feng. Fundamental study on preparing vanadium nitride and carbide by carbothermal reduction and nitridation of V₂O₃[D]. Shenyang: Northeastern University, 2006.