P204萃取提钒的应用现状与发展趋势

胡渝杰; 叶国华; 唐悦; 陶媛媛

doi:10.3969/j.issn.1000-6532.2023.03.011

P204萃取提钒的应用现状与发展趋势

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（51964028，51304090）

详细信息

作者简介: 胡渝杰（1997- ），男，硕士研究生，研究方向为金属钒钛的提取

通讯作者: 叶国华（1981-），男，博士，副教授，研究方向为金属冶金。

中图分类号: TD951

收稿日期: 2020-04-06

刊出日期: 2023-06-25

Current Status and Development Trend of Vanadium Extraction by P204 Extraction

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

More Information

Corresponding author: Ye Guohua, ghye581@163.com

Received Date: 06 April 2020

Publish Date: 25 June 2023

摘要

摘要:
这是一篇冶金工程领域的论文。有机磷类萃取剂D2EHPA（P204）非常广泛地应用于钒的萃取中，首先阐述了钒在浸液中的存在形式影响萃取的效果，V（IV）在溶液中主要以VO²⁺的形式稳定存在于强酸性溶液中；pH值逐渐增大时，V（V）多以H₂V₁₀O₂₈ ^4-、HV₁₀O₂₈ ^5-的形式存在。其次本文以近几年来有机磷类萃取剂P204的研究为基础，分析了有机磷类萃取剂P204的构效关系，发现与磷酰基相邻的基团类型相比，空间位阻效应作为次要因素同样重要，基于氢键作用，萃取剂分子之间会产生二聚体甚至多聚体，从而改变萃取剂分子的结构与性质。最后对P204萃钒的研发与应用进展以及对相关领域的未来进行了展望，指出了P204萃取剂今后的研究方向。
- 冶金工程 /
- 提钒 /
- P204 /
- 溶剂萃取 /
- 应用进展
Abstract:
This is a paper in the field of metallurgical engineering. Organophosphorus class extractant D2EHPA (P204) is very widely used in vanadium extraction. Firstly, the form of vanadium present in the leach solution affects the effect of extraction, V(IV) is mainly stable in solution in the form of VO²⁺ in a strongly acidic solution; when the pH value gradually increases, V(V) mostly exists in the form of H₂V₁₀O₂₈ ^4- and HV₁₀O₂₈ ^5-. Secondly, based on the research of organophosphorus extractant P204 in recent years, this paper analyzes the conformational relationship of organophosphorus extractant P204 and finds that the spatial site resistance effect is equally important as a secondary factor compared with the type of phosphoryl adjacent groups, based on the hydrogen bonding effect, the extractant molecules will produce dimers or even multimers between them, thus changing the structure and properties of the extractant molecules. Finally, the progress of the development and application of P204 extractive vanadium and the outlook on the future of the related fields are presented, pointing out the future research directions of P204 extractive agents.
- Metallurgical engineering /
- Vanadium extraction /
- P204 /
- Solvent extraction /
- Applications and advances

HTML全文

表 1 常用萃取剂的分类

Table 1. Classification of common extractants

类型	试剂	简称	水溶度/(g·L^-1)	使用途径
烷基磷酸	二(2_乙基己酸)磷酸	D2EHPA(P204)	0.02	有色金属和核燃料广泛使用
伯胺叔胺	仲碳伯胺三烷基叔胺	N1923		萃取稀土
伯胺叔胺	仲碳伯胺三烷基叔胺	N235	0.01	从H₂SO₄中提铀
叔胺季胺盐	三辛胺三辛基甲基氯化铵	TOA		萃取铀
叔胺季胺盐	三辛胺三辛基甲基氯化铵	N263
烷基膦酸烷基次膦酸	2_乙基己基磷酸_单_2_乙基己基酯双(2,4,4_三甲基戊基)膦酸	EHEHPA(P507)	0.029	稀土分组和重稀土分离
烷基膦酸烷基次膦酸	2_乙基己基磷酸_单_2_乙基己基酯双(2,4,4_三甲基戊基)膦酸	Cyanex272

下载: 导出CSV

参考文献(51)

[1]	漆明鉴. 从石煤中提钒现状及前景[J]. 湿法冶金, 1999(4):1-10. QI M J. Status and prospects of vanadium extraction from quarry coal[J]. Hydrometallurgy, 1999(4):1-10. doi: 10.13355/j.cnki.sfyj.1999.04.001 QI M J. Status and prospects of vanadium extraction from quarry coal [J]. Hydrometallurgy, 1999(4): 1-10. doi: 10.13355/j.cnki.sfyj.1999.04.001
[2]	R. K. Biswas, M. G. K. Mondal. Kinetics of VO₂₊ extraction by D2EHPA[J]. Hydrometallurgy, 2003, 69(1):117-133.
[3]	徐正震, 梁精龙, 李慧, 等. 含钒废弃物中钒的回收研究现状及展望[J]. 矿产综合利用, 2020(3):8-13. XU Z Z, LIANG J L, LI H, et al. Research status and prospects of vanadium recovery in vanadium containing wastes[J]. Multipurpose Utilization of Mineral Resources, 2020(3):8-13. doi: 10.3969/j.issn.1000-6532.2020.03.002 XU Z Z, LIANG J L, LI H, et al. Research status and prospects of vanadium recovery in vanadium containing wastes[J]. Multipurpose Utilization of Mineral Resources, 2020(3): 8-13. . doi: 10.3969/j.issn.1000-6532.2020.03.002
[4]	邴桔. 从石煤中提取五氧化二钒的工艺研究 [D]. 长沙: 中南大学, 2008. BING J. Process study for the extraction of vanadium pentoxide from quarry coal [D]. Changsha: Central South University (CSU), 2008.
[5]	胡建锋. 从废钒触媒中提钒新工艺的研究 [D]. 昆明: 昆明理工大学, 2006. HU J F. Research on a new process for vanadium extraction from spent vanadium catalysts [D]. Kunming: Kunming University of science and techlonogy, 2006.
[6]	WEI C, DENG Z G, et al. Selective solvent extraction of vanadium over iron from a stone coal/black shale acid leach solution by D2EHPA/TBP[J]. Hydrometallurgy, 2011.
[7]	余德麒, 施正伦. 石煤灰渣二次焙烧稀酸浸出提钒工艺条件 [J]. 过程工程学报, 2010, 14(8): 673-678. YU D Q, SHI Z L. Vanadium extraction process conditions for dilute acid leaching of coal fly ash slag by secondary roasting [J]. Journal of Process Engineering, 2010, (8)14: 673-678.
[8]	祁健, 黄荣艳, 石立新. 萃取提钒工艺研究进展[J]. 北方钒钛, 2013(Z1):26-29. QI J, HUANG R Y, SHI L X. Advances in extractive processes for vanadium extraction[J]. Vanadium and Titanium North, 2013(Z1):26-29. QI J, HUANG R Y, SHI L X. Advances in extractive processes for vanadium extraction [J]. Vanadium and Titanium North, 2013(Z1): 26-29.
[9]	ZENG L, LI Q, XIAO L. Extraction of vanadium from the leach solution of stone coal using ion exchange resin[J]. Hydrometallurgy, 2009, 97(3-4):194-197. doi: 10.1016/j.hydromet.2009.03.005
[10]	郑汝伟, 包申旭, 张一敏. CL-P204萃淋树脂对溶液中钒的吸附性能研究[J]. 有色金属(冶炼部分), 2017(1):45-48. ZHENG R W, BAO S X, ZHANG Y M. Study on the adsorption properties of CL-P204 extractive resin on vanadium in solution[J]. Non-Ferrous Metals(Extractive Metallurgy), 2017(1):45-48. ZHENG R W, BAO S X, ZHANG Y M. Study on the adsorption properties of CL-P204 extractive resin on vanadium in solution [J]. Non-Ferrous Metals(Extractive Metallurgy), 2017(1): 45-48.
[11]	ZENG L, CHENG C Y. A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts: Part I: Metallurgical processes[J]. Hydrometallurgy, 2009, 98:10-20. doi: 10.1016/j.hydromet.2009.03.012
[12]	LI X B, LI Z G, et al. Solvent extraction of vanadium from a stone coal acidic leach solution using D2EHPA/TBP: Continuous testing[J]. Hydrometallurgy, 2015, 154:45-46.
[13]	鲁兆伶. 用酸法从石煤中提取五氧化二钒的试验研究与工业实践[J]. 湿法冶金, 2002, 21(4):175-183. LU Z L. Experimental study and industrial practice for the extraction of vanadium pentoxide from petrified coal using the acid method[J]. Hydrometallurgy, 2002, 21(4):175-183. doi: 10.3969/j.issn.1009-2617.2002.04.002 LU Z L. Experimental study and industrial practice for the extraction of vanadium pentoxide from petrified coal using the acid method [J]. Hydrometallurgy, 2002, 21(4): 175-183. doi: 10.3969/j.issn.1009-2617.2002.04.002
[14]	胡建锋, 朱云. P204萃取硫酸体系中钒的性能研究[J]. 稀有金属, 2007(3):367-370. HU J F, ZHU Y. Performance study of vanadium in P204 extracted sulfuric acid system[J]. Rare Metal, 2007(3):367-370. doi: 10.3969/j.issn.0258-7076.2007.03.018 HU J F, ZHU Y. Performance study of vanadium in P204 extracted sulfuric acid system [J]. Rare Metal, 2007(3): 367-370. doi: 10.3969/j.issn.0258-7076.2007.03.018
[15]	Tavakoli M R, Dreisinger D B. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants[J]. Hydrometallurgy, 2014, 141:17-23. doi: 10.1016/j.hydromet.2013.10.008
[16]	LI W, ZHANG Y, LIU T, et al. Comparison of ion exchange and solvent extraction in recovering vanadium from sulfuric acid leach solutions of stone coal [J]. Hydrometallurgy, 2013, 131-132.
[17]	Navarro, R, Guzman, J, Saucedo I, et al. Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction process[J]. Waste Management, 2007, 27(3):425-438. doi: 10.1016/j.wasman.2006.02.002
[18]	刘峰. 从含钒酸浸液萃取钒并短流程制备高纯V₂O₅基础研究 [D]. 天津: 天津大学, 2014. LIU F. Basic research on the extraction of vanadium from vanadium-containing acid leachate and short-flow preparation of high purity V₂O₅ [D]. Tianjin: Tianjin University, 2014.
[19]	王非. 氟化物强化石煤提钒机理研究 [D]. 武汉: 武汉科技大学, 2014. WANG F. Study on the mechanism of vanadium extraction from fluoride-strengthened quartz coal [D]. Wuhan: Wuhan University of Science and Technology, 2014.
[20]	薛丽华. 从含钒钢渣酸浸液中萃取钒的试验研究 [D]. 昆明: 昆明理工大学, 2008. XUE L H. Pilot study on the extraction of vanadium from acid leach solution of vanadium-containing steel slags [D]. Kunming: Kunming University of Science and Technology, 2008.
[21]	胡艺博, 叶国华, 左琪. 石煤钒矿酸浸液提钒萃取剂的研究进展与前景[J]. 矿产综合利用, 2020(1):10-15. HU Y B, YE G H, ZUO Q. Research progress and prospect of vanadium extractant for acid leach solution of stone coal vanadium ore[J]. Multipurpose Utilization of Mineral Resources, 2020(1):10-15. doi: 10.3969/j.issn.1000-6532.2020.01.002 HU Y B, YE G H, ZUO Q. Research progress and prospect of vanadium extractant for acid leach solution of stone coal vanadium ore[J]. Multipurpose Utilization of Mineral Resources, 2020(1): 10-15. doi: 10.3969/j.issn.1000-6532.2020.01.002
[22]	张菊花, 张力, 张伟. 溶剂萃取法净化含钒溶液的研究现状[J]. 材料与冶金学报, 2013, 12(3):189-196. ZHANG J H, ZHANG L, ZHANG W. Current status of research on the purification of vanadium-containing solutions by solvent extraction method[J]. Journal of Materials and Metallurgy, 2013, 12(3):189-196. doi: 10.14186/j.cnki.1671-6620.2013.03.014 ZHANG J H, ZHANG L, ZHANG W. Current status of research on the purification of vanadium-containing solutions by solvent extraction method [J]. Journal of Materials and Metallurgy, 2013, 12(3): 189-196. doi: 10.14186/j.cnki.1671-6620.2013.03.014
[23]	DENG Z, WEI C, LI M, et al. Technology of extracting vanadium and removing iron from stone-coal oxygen pressure acid-leaching solution[J]. Chinese Journal of Rare Metals, 2009, 33(2):290-296.
[24]	曹耀华, 高照国, 刘红召. 萃取法从含钒酸浸液中提取钒的研究[J]. 河南化工, 2007, 24(6):20-23. CAO Y H, GAO Z G, LIU H Z. Extraction of vanadium from acidic leachates containing vanadium by extraction method[J]. Henan Chemical, 2007, 24(6):20-23. doi: 10.3969/j.issn.1003-3467.2007.06.007 CAO Y H, GAO Z G, LIU H Z. Extraction of vanadium from acidic leachates containing vanadium by extraction method [J]. Henan Chemical, 2007, 24(6): 20-23. doi: 10.3969/j.issn.1003-3467.2007.06.007
[25]	LI W, ZHANG Y M, HUANG J. Comparison of ion exchange and solvent extraction in recovering vanadium from sulfuric acid leach solutions of stone coal[J]. Hydrometallurgy, 2013(131/132):1-7.
[26]	AMESH P, SUNEESH A S, VENKATESAN K A, et al. Preparation and ion exchange studies of cesium and strontium on sodium iron titanate [J]. Separation and Purification Technology, 2020, 238(1).
[27]	THI Hong Nguyen, LEE Man Seung. Recovery of molybdenum and vanadium with high purity from sulfuric acid leach solution of spent hydrodesulfurization catalysts by ion exchanged[J]. Hydrometallurgy, 2014(147/148):142-148.
[28]	胡艺博. 从低品位石煤钒矿中提取五氧化二钒的研究 [D]. 昆明: 昆明理工大学, 2019. HU Y B. Research on the extraction of vanadium pentoxide from low-grade sphalerite vanadium ore [D]. Kunming: Kunming University of Science and Techlonogy, 2019.
[29]	吕天然, 王凌云, 周海涛. 酸性有机磷萃取剂对镓的萃取研究[J]. 山东化工, 2019(12):9-12. LV T R, WANG L Y, ZHOU H T. Extraction of gallium by acidic organophosphorus extractants[J]. Shandong Chemical Industry, 2019(12):9-12. doi: 10.3969/j.issn.1008-021X.2019.12.006 LV T R, WANG L Y, ZHOU H T. Extraction of gallium by acidic organophosphorus extractants [J]. Shandong Chemical Industry, 2019(12): 9-12. doi: 10.3969/j.issn.1008-021X.2019.12.006
[30]	Amesh P, Suneesh A S, Venkatesan K A, et al. Preparation and Ion exchange studies of cesium and strontium on sodium iron titanate[J]. Separation and Purification Technology, 2019, 238(1):63-93.
[31]	Kumari A, Panda R, Lee J Y, et al. Extraction of rare earth metals(REMs) from chloride medium by organo-metallic complexationusing D2EHPA[J]. Separation and Purification Technology, 2019, 227(15):56-80.
[32]	魏昶. 有机磷类萃取剂结构-性能关系及萃取钒基础研究 [R]. 国家自然科学基金结题报告. 昆明: 昆明理工大学. 2015: 10–20. WEI C. Structure-property relationship of organophosphorus extractants and basic research on vanadium extraction [R]. National Natural Science Foundation of China Final Report. Kunming: Kunming university of science and technology. 2015: 10-20.
[33]	徐志高, 王力军, 吴延科, 等. DIBK-P204体系萃取锆铪的热力学研究[J]. 稀有金属, 2013, 37(2):266-271. XU Z G, WANG L J, WU Y K, et al. Thermodynamic study of extracted hafnium zirconium in DIBK-P204 system[J]. Rare Metal, 2013, 37(2):266-271. doi: 10.3969/j.issn.0258-7076.2013.02.015 XU Z G, WANG L J, WU Y K, et al. Thermodynamic study of extracted hafnium zirconium in DIBK-P204 system [J]. Rare Metal, 2013, 37(2): 266-271. doi: 10.3969/j.issn.0258-7076.2013.02.015
[34]	朱军, 郭继科, 马晶. 从含钒石煤酸浸液中溶剂萃取钒的试验研究 [J]. 湿法冶金, 2011, 30(4): 293-297. ZHU J, GUO J K, MA J. Pilot study on the solvent extraction of vanadium from vanadylitic coal acid leach solution [J]. Hydrometallurgy, 011, 30(4): 293-297.
[35]	陈向阳, 兰新哲. 从石煤酸浸液中萃取钒的实验研究[J]. 化学工程, 2010, 38(10):146-149. CHEN X Y, LAN X Z. Experimental study on the extraction of vanadium from lignite leach solution[J]. Chemical Engineering, 2010, 38(10):146-149. doi: 10.3969/j.issn.1005-9954.2010.10.032 CHEN X Y, LAN X Z. Experimental study on the extraction of vanadium from lignite leach solution [J]. Chemical Engineering, 2010, 38(10): 146-149. doi: 10.3969/j.issn.1005-9954.2010.10.032
[36]	YE G, HU Y, TONG X, et al. Extraction of vanadium from direct acid leaching solution of clay vanadium ore using solvent extraction with N235[J]. Hydrometallurgy, 2018, 177:27-33. doi: 10.1016/j.hydromet.2018.02.004
[37]	钱强. 溶剂萃取在湿法冶金中的应用进展[J]. 中国资源综合利用, 2007, 25(10):14015-15. QIAN Q. Advances in solvent extraction for hydrometallurgical applications[J]. Comprehensive Utilization of Resources in China, 2007, 25(10):14015-15. doi: 10.3969/j.issn.1008-9500.2007.10.012 QIAN Q. Advances in solvent extraction for hydrometallurgical applications [J]. Comprehensive Utilization of Resources in China, 2007, 25(10): 14015. doi: 10.3969/j.issn.1008-9500.2007.10.012
[38]	李尚勇, 谢刚, 俞小花. 从含钒浸出液中萃取钒的研究现状[J]. 有色金属, 2011(1):100-104. LI S Y, XIE G, YU X H. Current status of the extraction of vanadium from vanadium-containing leachates[J]. Non-Ferrous Metals, 2011(1):100-104. LI S Y, XIE G, YU X H. Current status of the extraction of vanadium from vanadium-containing leachates [J]. Non-Ferrous Metals, 2011(1): 100-104. .
[39]	魏昶, 李存兄, 李旻廷, 等. 在压力场下从石煤中浸取钒和浸出渣综合利用[J]. 矿冶, 2009(3):37-43. WEI. C, LI C X, LI M T. Integrated utilization of vanadium leaching and leach residue from quarry coal in pressure fields[J]. Mining and Metallurgy, 2009(3):37-43. doi: 10.3969/j.issn.1005-7854.2009.03.009 WEI. C, LI C X, LI M T. Integrated utilization of vanadium leaching and leach residue from quarry coal in pressure fields [J]. Mining and Metallurgy, 2009(3): 37-43. doi: 10.3969/j.issn.1005-7854.2009.03.009
[40]	杨绍文, 曹耀华, 高照国, 等. 从钒精矿中湿法提取五氧化二钒新工艺研究[J]. 湿法冶金, 2011(1):33-36. YANG S W, CAO Y H, GAO Z G. New process for the wet extraction of vanadium pentoxide from vanadium concentrates[J]. Hydrometallurgy, 2011(1):33-36. doi: 10.3969/j.issn.1009-2617.2011.01.009 YANG S W, CAO Y H, GAO Z G. New process for the wet extraction of vanadium pentoxide from vanadium concentrates [J]. Hydrometallurgy, 2011(1): 33-36. doi: 10.3969/j.issn.1009-2617.2011.01.009
[41]	冯雪茹, 吕国志, 张廷安, 等. P204萃取硫酸体系中V(Ⅳ), Fe(Ⅲ)的分离性能研究[J]. 钢铁钒钛, 2017, 38(2):23-29. FENG X R, LV G Z, ZHANG T A. Separation performance of V(IV), Fe(III) in P204 extracted sulfuric acid system[J]. Steel, Vanadium and Titanium, 2017, 38(2):23-29. doi: 10.7513/j.issn.1004-7638.2017.02.004 FENG X R, LV G Z, ZHANG T A. Separation performance of V(IV), Fe(III) in P204 extracted sulfuric acid system [J]. Steel, Vanadium and Titanium, 2017, 38(2): 23-29. doi: 10.7513/j.issn.1004-7638.2017.02.004
[42]	曹继. 石煤中五氧化二钒的提取新工艺研究[ D]. 长沙: 湖南大学, 2011. CAO J. New extraction process of vanadium pentoxide from petrocoal [D]. Changsha: Hunan University, 2011.
[43]	Seyed Mohammad Razavi, ALI Haghtalab, ALI Reza Khanchi. Thermodynamic modeling of the solvent extraction equilibrium for the recovery of vanadium (V) from acidic sulfate solutions using Di-(2-ethylhexyl) phosphoric acid[J]. Fluid Phase Equilibria, 2018, 474(25):20-31.
[44]	SHI Q H, ZHANG Y M, HUANG J, et al. Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A[J]. Separation and Purification Technology, 2017, 181:1-7. doi: 10.1016/j.seppur.2017.03.010
[45]	HU G P, CHEN D S, WANG L N, et al. Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA[J]. Separation and Purification Technology, 2014, 125(7):59-65.
[46]	Mehdi Noori, Fereshteh Rashchi, Ataollah Babakhani, et al. Selective recovery and separation of nickel and vanadium in sulfate media using mixtures of D2EHPA and Cyanex 272[J]. Separation and Purification Technology, 2014, 136(5):265-273.
[47]	LY X B, DENG Z G, WEI C, et al. Solvent extraction of vanadium from a stone coal acidic leach solution using D2EHPA/TBP: Continuous testing[J]. Hydrometallurgy, 2015, 154:40-46. doi: 10.1016/j.hydromet.2014.11.008
[48]	MA Y Q, WANG X W, WANG M Y, et al. Separation of V(IV) and Fe(III) from the acid leach solution of stone coal by D2EHPA/TBP[J]. Hydrometallurgy, 2015, 153:38-45. doi: 10.1016/j.hydromet.2015.02.003
[49]	CHEN D S, ZHAO H X, HU G P, et al. An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite[J]. Journal of Hazardous Materials, 2015, 294(30):35-40.
[50]	LI X B, WEI C, DENG Z G, et al. Selective solvent extraction of vanadium over iron from a stone coal/black shale acid leach solution by D2EHPA/TBP[J]. Hydrometallurgy, 2010, 105(3):359-363.
[51]	LIU H, ZHANG Y M, HUANG J, et al. Selective separation and recovery of vanadium from a multiple impurity acid leaching solution of stone coal by emulsion liquid membrane using di-(2-ethylhexyl)phosphoric acid[J]. Chemical Engineering Research and Design, 2017, 122:289-297. doi: 10.1016/j.cherd.2017.04.026