钒渣提钒浸出液的钒铬分离研究进展

王正豪

doi:10.7513/j.issn.1004-7638.2025.01.002

钒渣提钒浸出液的钒铬分离研究进展

doi: 10.7513/j.issn.1004-7638.2025.01.002

王正豪^{1, 2,}

1.
中南大学冶金与环境学院, 湖南长沙 410083
2.
国家重金属污染防治工程技术研究中心, 湖南长沙 410083

基金项目: 国家自然科学基金委创新研究群体项目（52121004）；国家自然科学基金青年科学基金项目（52404372）；中国博士后科学基金面上项目（2024M753671）；中国博士后科学基金国家资助计划（GZC20242056）。

详细信息

作者简介:
王正豪，1995年出生，男，云南文山人，博士后，主要从事有色金属冶金，E-mail：zhwangcsu@163.com

中图分类号: TF841.3
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- 文章访问数: 147
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- 被引次数: 0
出版历程
- 收稿日期: 2024-08-03
- 刊出日期: 2025-02-27

Recent progress developments on vanadium and chromium separation in vanadium extraction leachate from vanadium slag

WANG Zhenghao^{1, 2
,}

1.
School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan, China
2.
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha 410083, Hunan, China

摘要

摘要: 钒铬在自然界中常以伴生矿物—钒钛磁铁矿的形式共存，这一特性在资源提取阶段对钒铬的高效分离构成了显著的技术挑战，鉴于这一问题，系统分析了目前提钒工艺中普遍采用的几种钒铬分离技术，如化学沉淀法、离子交换法和溶剂萃取法等在应用过程中表现出的优势和存在的问题。指出探索更加高效、经济的钒铬分离方法是当前研究的重点，同时，未来的钒铬分离技术上应加强环保技术的研究与应用，解决分离过程中产生的废水、废渣等环境问题，从而实现高效、绿色、可持续生产。
- 钒渣 /
- 提取 /
- 钒铬分离 /
- 溶剂萃取
Abstract: Vanadium and chromium commonly coexist in nature as associated minerals in vanadium-titanium magnetite, which presents a significant technical challenge for their efficient separation during resource extraction. In light of this issue, several commonly employed vanadium and chromium separation techniques in current vanadium extraction processes, such as chemical precipitation, ion exchange, and solvent extraction, have been systematically analyzed in terms of their advantages and existing problems during application. It was emphasized that the development of more efficient and economical vanadium and chromium separation methods remains a key focus of current research. Furthermore, future vanadium and chromium separation technologies should prioritize the research and application of environmentally friendly techniques to address the environmental issues, such as wastewater and waste residue, generated during the separation process, thereby enabling efficient, green, and sustainable production.
- vanadium slag /
- extraction /
- vanadium-chromium separation /
- solvent extraction

HTML全文

图 1 钒渣回收V₂O₅工艺

Figure 1. V₂O₅ recovery process from vanadium slag

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图 2 水解过程的机理示意^[27]

Figure 2. Schematic diagram of the mechanism of the hydrolysis process^[27]

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图 3 DDTC络合法分步回收V−Cr−Fe示意^[29]

Figure 3. Schematic diagram of V−Cr−Fe ternary slime stepwise recovery using DDTC^[29]

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图 4 V(Ⅴ)和Cr(Ⅵ)在ZrO₂上的选择性吸附机制示意^[35]

Figure 4. Schematic representation of the selective adsorption mechanism of V(Ⅴ) and Cr(Ⅵ) on ZrO₂^[35]

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图 5 较高浓度SO₄²⁻下P204萃取Cr(Ⅲ)的反应路径^[40]

Figure 5. Reaction pathway of Cr(Ⅲ) extraction under higher SO₄²⁻ concentrations^[40]

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图 6 三液相体系分离高铬钒渣酸浸出液中的V(Ⅴ)和Cr(Ⅵ)机理^[50]

Figure 6. Mechanism of separation of V(Ⅴ) and Cr(Ⅵ) from acid leach solution of HCVS by three liquid phase system^[50]

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表 1 钒渣提钒方法及其浸出液中钒铬浓度

Table 1. Vanadium extraction methods from vanadium slag and the vanadium-chromium concentration in leaching solution

提取方法	元素价态	浓度/（g·L^–1)
提取方法	元素价态	V	Cr
钠化焙烧-水浸^[20]	V(Ⅴ), Cr(Ⅵ)	14.00	11.20
CaO焙烧- H₂SO₄浸出^[21]	V(Ⅴ), Cr(Ⅵ)	0.24	0.001
MnCO₃焙烧-H₂SO₄浸出^[22]	V(Ⅴ), Cr(Ⅵ)	10.30	0.008
钛白废酸压力浸出^[23]	V(Ⅴ), Cr(Ⅵ)	7.06	1.96
MgO焙烧-H₂SO₄浸出^[24]	V(Ⅴ), Cr(Ⅵ)	8.31	0.005
选择性氧化焙烧-压力酸浸^[18]	V(Ⅳ), Cr(Ⅲ)	9.01	1.94
硫酸焙烧-水浸^[16]	V(Ⅳ), Cr(Ⅲ)	11.8	3.36
压力酸浸^[17]	V(Ⅳ), Cr(Ⅲ)	4.79	1.05

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表 2 不同沉淀钒、铬方法的对比

Table 2. Comparison of different methods of precipitating V and Cr

沉淀方法	沉淀产物	优点	缺点
铵盐沉钒	APV	用于钒浓度较高的溶液；可获得不同形貌的沉淀产物	会产生较多含有氨氮的废水
水解沉钒	xNa₂O∙yV₂O₅∙zH₂O	操作简单，生产周期短，生产成本低，允许钒浓度在较大范围波动	产品纯度较低，酸耗大
铁盐沉钒	FeVO₄	用于铬含量较低的含钒溶液	产品纯度低；不适用于钒含量较高的溶液
钙盐沉钒	Ca(VO₃)₂	用于钒浓度较低的溶液	杂质含量要求高，沉淀后产生废物较多
络合沉钒	VO(DDTC)₂	用于铁锰浓度较低的溶液，钒铬分离系数大	钒的提纯步骤较多
钡盐沉铬	BaCrO₃	用于钒浓度较高的含铬溶液	沉淀物含重金属
磷酸盐沉铬	CrPO₄	用于铬含量较高的溶液；可选择性沉淀铬	钒损失较大，产品纯度不高

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表 3 常用于吸附V或Cr的离子交换树脂^[31]

Table 3. Common ion exchange resins used for adsorption of V or Cr^[31]

种类	功能基团	吸附离子	吸附容量 /(mg·g⁻¹)
ZGA414	—N(CH₃)₂·H₂O	H₂V₁₀O₂₈⁴⁻	150*
IRA400	—N⁺R₃	HVO₄²⁻	9.8
D751	—N(CH₃)₂C₂H₄OH	H₂VO₄⁻	61.1
D314	—N(CH₃)₂	V₁₀O₂₈⁶⁻	98*
TP207	C₄H₇NO₄	Cr³⁺	20.6
D453	—N(CH₃)₂	VO²⁺	36.9
注：*处的单位为g/L

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表 4 不同种类萃取剂的研究现状

Table 4. Research status on different types of extractants

种类	酸性萃取剂	中性和螯合萃取剂	碱性萃取剂
常用萃取剂	P204、P507、C272	TBP、C923、MIBK	伯胺（N1923）、叔胺（N235、TOA）、季铵盐（A336、N263）
常用萃取体系	硫酸、盐酸体系	盐酸体系	酸性体系、碱性体系
萃取钒铬价态	V(Ⅳ)、Cr(Ⅲ)	V(Ⅴ)、Cr(Ⅵ)	V(Ⅳ)、V(Ⅴ)、Cr(Ⅵ)
萃取机理	阳离子交换	中性络合萃取	阴离子交换、中性络合萃取
优点	饱和容量大；无乳化现象、易分层；萃取剂再生效果好	易反萃；用于盐酸体系选择性好	适用范围广；物化性质稳定；选择性好
缺点	对V(Ⅴ)和Fe(Ⅲ)选择性差，萃取前需要进行预处理；易腐蚀设备	多级萃取后黏度增加；循环使用出现第三相	易出现第三相；需多级逆流萃取；反萃剂用量大

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表 5 溶剂萃取钒和铬的萃取剂和萃取效率

Table 5. Extraction agent and extraction efficiency for solvent extraction of vanadium and chromium

浓度/(g·L⁻¹)		萃取剂	萃取效率/%			参考文献
V	Cr	萃取剂	V	Cr	β_V/Cr	参考文献
6.2	11.7	N1923	65.0	0.85		[46]
1.0	1.0	酸化N1923			94.38	[48]
5.0	1.7	N263	98.4	98.1		[50]
12.00	6.48	LK-N21	90	90		[52]
2.26	0.32	[C₈mim][PF₆]			56	[53]
20.48	3.62	P507	99.91	95.40		[54]

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