从含钒酸浸液中萃取提钒的研究进展

项新月; 叶国华; 朱思琴; 荣一阳; 张云; 宋昌溆

doi:10.13779/j.cnki.issn1001-0076.2023.07.008

从含钒酸浸液中萃取提钒的研究进展

昆明理工大学国土资源工程学院，云南昆明 650093

基金项目: 国家自然科学基金项目（51964028）

详细信息

作者简介: 项新月（1999—），女，湖北黄冈人，硕士研究生，研究方向为钒的提取，E-mail：xinyue_xiang@163.com

通讯作者: 叶国华（1981—），男，博士，副教授，长期从事钒资源的物理分选与化学提取研究，E-mail：ghye581@163.com。

中图分类号: TF804.2；TF841.3

收稿日期: 2022-12-29

刊出日期: 2023-10-25

Solvent Extraction of Vanadium from Vanadium−bearing Acid Leaching Solution

Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China

More Information

Corresponding author: YE Guohua, ghye581@163.com

Received Date: 29 December 2022

Publish Date: 25 October 2023

摘要

摘要:
针对含钒酸浸液净化与富集的难题，评述了其萃取提钒的研究进展。常规萃取时，酸性磷类萃取剂具有萃钒效率高、分相快等优点，但其除杂不彻底，且需消耗大量的酸；碱性胺类萃取剂具有较好选择性，且除杂彻底，但易产生第三相；螯合萃取剂能缩短萃取流程，萃余液中的游离酸还可循环使用，具有良好经济效益，但其降解问题仍未得到解决。新型萃取方法中，液膜萃取工艺简单、传质效率高、金属离子富集比高，但存在萃取流程长、药剂用量大、有机相损失多等缺点；离子液体具有许多优势，但由于其制备成本高，尚无法大规模投产应用；微乳液萃取具有分离速度快、分离效率高和选择性好的优点，但会产生氨氮废水；近年来协同萃取被广泛研究，但如何有效抑制拮抗作用使其充分发挥作用，尚需进一步研究。
- 钒 /
- 酸浸 /
- 萃取 /
- 萃取剂 /
- 液膜萃取 /
- 离子液体
Abstract:
Aiming at the problem of vanadium purification and enrichment for vanadium-containing acid leaching solution, the research progress of vanadium extraction is reviewed. In conventional extraction, acidic phosphorus extractant has the advantages of high efficiency of vanadium extraction and fast phase separation, but its impurity removal is not complete and requires a large amount of acid. The alkaline amine extractant has good selectivity and thorough impurity removal, but it is easy to produce the third phase. Chelating extractant can shorten the extraction process, and the free acid in the raffinate can also be recycled, which has good economic benefits, but its degradation problem has not been solved. Among the new extraction methods, the liquid membrane extraction process is simple, the mass transfer efficiency is high, and the metal ion enrichment ratio is high. However, it has the disadvantages of long extraction process, large dosage of reagents, and high organic phase loss. Ionic liquids have many advantages, but they cannot be put into large−scale production and application due to their high preparation cost. Microemulsion extraction has the advantages of fast separation speed, high separation efficiency, and good selectivity, but it will produce ammonia nitrogen wastewater. In recent years, synergistic extraction has been widely studied, but how to effectively inhibit its antagonistic effect and make it fully play its role needs further study.
- vanadium /
- acid leaching /
- solvent extraction /
- acidic phosphorus extractant /
- liquid membrane extraction /
- ionic liquid

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图 1 V-H₂O，E-pH图^[14]

Figure 1.

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图 2 离子液体阳离子化学结构^[28]

Figure 2.

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表 1 溶液在不同pH下的主要反应平衡式

Table 1. Main reaction equilibrium equations of solution at different pH

序号	方程式	pH范围
1	2(VO₄)^3–+2H⁺＝(V₂O₇)^4–+H₂O	10.0≤pH≤12.0
2	2(V₂O₇)^4–+4H⁺＝(V₄O₁₂)^4–+2H₂O	pH=9.0
3	5(V₄O₁₂)^4–+8H⁺＝2(V₁₀O₂₈)^6–+4H₂O	pH≤7.0
4	3(H₂V₁₀O₂₈)^4–+H₂O＝3(H₂V₁₀O₂₈)^5–+3H⁺	1.8≤pH≤6.5
5	6(H₂V₁₀O₂₈)^4–+24H⁺＝5H₂V₁₂O₃₁+13H₂O	pH=1.6
6	(H₂V₁₀O₂₈)^4–+14H⁺＝10VO₂⁺+8H₂O	pH＜1.0

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表 2 溶剂萃取法的种类及优缺点

Table 2. Types, advantages and disadvantages of solvent extraction

萃取方法	主要萃取剂种类	优点	缺点
常规酸性磷类萃取法	P204、P507	萃取率高，技术成熟	易挥发、易产生第三相、钒铁难分离
常规碱性胺类萃取法	伯胺:N1923	萃取率高，技术成熟，选择性好，除杂彻底，不易产生第三相，适用分离钒铬	易挥发、易燃易爆
	叔胺:N235	萃取率高，技术成熟，选择性好，除杂彻底，不易产生第三相，钒铁分离效果极佳
	季胺：N263、Aliquat-336	萃取率高，技术成熟，选择性好，除杂彻底，不易产生第三相，有望实现萃取剂循环利用
常规螯合类萃取法	喹啉类：Kelexl00	选择性好，萃取率高	除杂不彻底、污染环境
常规螯合类萃取法	羟肟类萃取剂：Lix984、M5640 HBLl01	选择性好，萃取率高	化学稳定性较差、除杂不彻底、价格昂贵
液膜萃取法	乳液液膜：D2EHPA作载体	工艺流程短、萃取效率高、选择性好	乳化液的形成、破乳困难，膜稳定性差
液膜萃取法	支撑液膜：N235作载体	工艺流程短、萃取效率高、选择性好	乳化液的形成、破乳困难，膜稳定性差
离子液体萃取法	阴离子：卤素离子、四氟硼酸根离子、六氟磷酸根离子	低挥发性、功能可调、环保	成本高
离子液体萃取法	阳离子：季铵盐类、季磷盐类、咪唑类、吡啶类	低挥发性、功能可调、环保	成本高
微乳液萃取法	W/O、Aliquat 336	克服了乳化液膜的缺点、分离V、P效果好	易产生高盐、氨氮废水、成本高
协同萃取法	NaCl-P204	萃取效率高、除杂彻底	部分有毒易挥发易燃易爆，易产生污染
	D2EHPA-PC88A
	D2EHPA-TBP-磺化煤油
	P507-N235-磺化煤油
	Cyanex272-N235

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