溶解态钼钒深度分离技术研究现状与展望

黄艳芳; 史坤鹏; 刘兵兵; 苏胜鹏; 韩桂洪

doi:10.13779/j.cnki.issn1001-0076.2021.05.010

溶解态钼钒深度分离技术研究现状与展望

郑州大学化工学院, 河南郑州 450001

基金项目:
国家自然科学基金（U2004215，51974280，51774252）；河南省高校科技创新人才项目（20HASTIT012）

详细信息

作者简介: 黄艳芳(1983-), 女, 河南许昌人, 副教授, 主要从事化工冶金固废资源利用研究

通讯作者: 韩桂洪(1981-), 男, 河北昌黎人, 教授, 主要从事矿产资源综合利用、浮选理论与新方法, E-mail: hanguihong@zzu.edu.cn

中图分类号: TD983;TF803.2⁺3

收稿日期: 2021-08-13

刊出日期: 2021-10-25

Research Status and Prospect of Deep Separation Technology for Dissolved Molybdenum and Vanadium

School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China

More Information

Corresponding author: HAN Guihong, hanguihong@zzu.edu.cn

Received Date: 13 August 2021

Publish Date: 25 October 2021

摘要

摘要:
钼、钒作为重要的战略金属，在国民经济、国防军工等领域具有难以替代的关键作用。随着功能材料、电子元器件等尖端技术领域的快速发展，大批催化剂、靶材进入报废期，随之产生大量富含Mo/V等战略金属的固体废弃物。上述二次资源中钼、钒等有价金属含量高，经济价值大，且部分固体废弃物被列为危废，实现二次资源中钼、钒的选择性分离及资源化利用，对缓解环保压力、保障国家资源安全、国防安全和战略性新兴产业发展需求意义重大。本文系统分析了我国钼、钒矿产资源及二次资源概况；重点探讨了溶解态（游离离子）钼、钒选择性深度分离技术的研究现状，归纳总结了常见钼、钒分离技术如化学沉淀、离子交换、溶剂萃取的方法原理、过程特点及发展空间；最后提出采用离子浮选/溶剂萃取耦合技术（即浮游萃取）强化钼、钒选择性深度分离的建议，并对未来钼、钒分离技术的发展前景进行展望。
- 钼钒分离 /
- 化学沉淀 /
- 离子交换 /
- 溶剂萃取 /
- 浮游萃取
Abstract:
Molybdenum and vanadium, as important strategic metals, play an irreplaceable key role in the national economy, national defense and military industry and other fields. With the rapid development of cutting-edge technology fields, such as functional materials and electronic components, a large number of spent catalysts and targets were produced, resulting in a large amount of solid waste containing Mo/V and other strategic metals. The secondary resources mentioned above containing high content of valuable metals such as molybdenum and vanadium have great economic value, but part of the solid waste wasdefined as hazardous waste. It is of great significance for relieving the pressure on environmental protection, ensuring national resource security, national defense security, and the development needs of strategic emerging industries torealize elective separation and resource utilization of molybdenum and vanadium in the secondary resources. This paper systematically analyzed the general situation of our country's molybdenum and vanadium mineral resources and secondary resources, focused on the research progress of deep selective separation technique for dissolved molybdenum and vanadium, summarized the common principle of the method, process characteristics and development directionof molybdenum and vanadium separation technology.Finally, a feasible strategy by using ion flotation/solvent extraction coupling technology(floating-extraction) to enhance the selective deep separation of molybdenum and vanadium was proposed, and the development prospects of the separation technology were prospected.
- separation of molybdenum and vanadium /
- chemical precipitation /
- ion exchange /
- solvent extraction /
- floating-extraction

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图 1 2020年全球钼、钒储量及中国钼、钒矿品位分布

Figure 1.

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图 2 废HDS催化剂化学成分及浸出液金属离子浓度

Figure 2.

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图 3 MoO₄^2-和VO₄^2-(1 g/L)在不同pH条件下离子形态特征

Figure 3.

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图 4 硫化沉淀法原理示意图

Figure 4.

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图 5 离子交换法分离钼、钒示意图

Figure 5.

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图 6 N263萃取钼、钒示意图

Figure 6.

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图 7 N263萃取钼、钒原理

Figure 7.

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图 8 浮游萃取分离钼、钒过程示意图

Figure 8.

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表 1 Mo(Ⅵ)-V(Ⅴ)-H₂O体系中的化学反应常数

Table 1. Chemical reaction constants in Mo(Ⅵ)-V(Ⅴ)-H₂O system

化学反应	物种浓度的计算公式	编号
MoO₄^2-+H⁺=HMoO₄^-	[HMoO₄^-]=10^3.49[MoO₄^2-][H⁺]	1
MoO₄^2-+2H⁺=H₂MoO₄	[H₂MoO₄]=10^7.29[MoO₄^2-][H⁺]²	2
7MoO₄^2-+8H⁺=Mo₇O₂₄^6-+4H₂O	[Mo₇O₂₄^6-]=10^52.79[MoO₄_2-]₇[H⁺]⁸	3
7MoO₄^2-+9H⁺=HMo₇O₂₄^5-+4H₂O	[HMo₇O₂₄^5-]=10^57.50[MoO₄^2-]₇[H⁺]9	4
8MoO₄^2-+12H⁺=Mo₈O₂₆^4-+6H₂O	[Mo₈O₂₆^4-]=10^71.49[MoO₄^2-]₈[H⁺]¹²	5
VO₄^3-+H⁺=HVO₄^2-	[HVO₄^2-]=10^13.36[VO₄^3-][H⁺]	6
VO₄^3-+2H⁺=H₂VO₄^-	[H₂VO₄^-]=10^21.31[VO₄^3-][H⁺]²	7
4VO₄^3-+8H⁺=V₄O₁₂^4-+4H₂O	[V₄O₁₂4-]=10^95.11[VO₄^3-]₄[H⁺]⁸	8
10VO₄^3-+25H⁺=HV₁₀O₂₈^5-+12H₂O	[HV₁₀O₂₈^5-]=10^270.89[VO₄^3-]₁₀[H⁺]²⁵	9
10VO₄^3-+26H⁺=H₂V₁₀O₂₈^4-+12H₂O	[H₂V₁₀O₂₈^4-]=10^274.49[VO₄^3-]₁₀[H⁺]²⁶	10
VO₄^3-+4H⁺=VO²⁺+2H₂O	[VO²⁺]=10^28.23[VO₄^3-][H⁺]⁴	11

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表 2 常见钼、钒分离方法比较

Table 2. Comparison of several methods for separation ofmolybdenum and vanadium

分离方法	处理对象	原理	操作条件及效果	技术优势	发展空间	参考文献
化学沉淀	高浓度金属溶液	加入沉淀剂，使Mo/V发生沉淀	溶液pH=8.9，通入H₂S沉淀Mo，Mo的析出率达99.8%；溶液pH=0.75，Mo=14.58 g/L，加入氨水、加热产生MoO₃沉淀，Mo回收率达99%；温度为40 ℃、80 ℃时，分别加入氢氧化钡、铝酸钡，V、Mo析出率为94.8%和92.6%；	操作简单经济成本低	开发新型沉淀剂提高沉淀效率	[23, 36, 37]
离子交换	适中浓度金属溶液	树脂选择性吸附Mo/V，解吸剂解析树脂	溶液pH=7.18，Mo=50 g/L，树脂DP-1吸附V，去除率达99.84%；溶液pH=1.2，Mo=0.2 g/L，树脂AG1-x8吸附Mo，吸附容量为176 mg/g；溶液pH=9.25，Mo/V与Mo/W的摩尔比大于40，树脂D403吸附W、V，W、V去除率为90%、99.4%；	回收率高选择性好	提高树脂饱和容量和循环利用率	[22, 40, 41]
溶剂萃取	高浓度金属溶液	萃取剂先萃取Mo/V，反萃剂依次反萃出Mo/V	溶液pH=8.5，Mo=100 g/L，V=10 g/L，N263萃取V，萃取率达99.6%；溶液pH=1.5，Mo=256.7 mg/L，V₂O₅=1.83 g/L，P507萃取Mo、V，Mo、V萃取率为98.96%、98.72%；溶液pH=2，PEG2000共萃取Mo、V，萃取率均为95%以上；溶液pH为0.7~0.75，由L35、Triton X-100、PEG2000和硫酸钠混合成的离子液体萃取，Mo和V萃取率分别大于90%和小于20%；	选择性好分离效率高	开发新型萃取剂简化萃取工艺调控第三相生成	[46-50]

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