P507萃取纯化V(IV)制备高纯钒电解液的研究
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摘要
全钒氧化还原液流电池具有清洁、高效、安全、寿命长等优点,是一种新型的储能技术,成为目前研究的热点,其中高纯钒电解液的制备是研究的关键。以钒渣钠化焙烧后的含钒浸液为原料,通过"酸化-还原-萃取-反萃"一步纯化制备了高纯钒电解液。研究了V(IV)萃取及其与主要杂质元素硅和铝的分离效果,获得钒萃取纯化的优化条件为:P507浓度为30%, pH=1.8～2.0。温度对钒萃取影响较小;萃取过程中,钒与铝硅分离效果好;根据V(IV)的萃取和反萃分配曲线绘制了McCabe Thiele图,在pH=2.0、相比O/A为1∶1条件下,以30%(体积分数)的P507经两级(理论级)萃取,含钒20.9 g·L~(-1)的料液中的钒基本萃取完全,萃取率大于98%;硫酸溶液能够很好地反萃钒,通过控制H_2SO_4浓度和相比,经两级逆流反萃和去除夹带有机相后制得了高质量的硫酸氧钒电解液。
Vanadium redox battery was a new technology for energy storage with many advantages, such as environmental friendship, high efficiency, good safety, longer cycling life, and currently, it became a hot research topic. One of the key research areas was the preparation of highly pure vanadium electrolyte which was important for improving the battery performance. In this study, a highly pure VOSO_4 electrolyte was prepared through acidification, reduction, and solvent extraction with P507 as the extractant using a vanadium water leach solution obtained by sodium roasting and leaching processes of vanadium slag. The extraction of V(IV) and its separation from the main impurities of aluminum and silicon were studied. The results showed that the optimum conditions for V(IV) extraction and separation from the impurities were 30%(volume fraction) P507 at pH=1.8～2.0. Temperature had insignificant effect on V(IV) extraction. Based on the V(IV) extraction and stripping distribution isotherms, McCabe Thiele diagrams were constructed. It was demonstrated that two theoretical stages were required to completely extract vanadium from the leach solution containing 20.9 g·L~(-1) V(IV) at an O/A ratio of 1∶1 and pH 2.0 using 30% P507. Sulfuric acid solution could be used for the vanadium stripping. A vanadium electrolyte with high quality was obtained via vanadium stripping in two counter-current stages after organic removal.
Vanadium redox battery was a new technology for energy storage with many advantages, such as environmental friendship, high efficiency, good safety, longer cycling life, and currently, it became a hot research topic. One of the key research areas was the preparation of highly pure vanadium electrolyte which was important for improving the battery performance. In this study, a highly pure VOSO_4 electrolyte was prepared through acidification, reduction, and solvent extraction with P507 as the extractant using a vanadium water leach solution obtained by sodium roasting and leaching processes of vanadium slag. The extraction of V(IV) and its separation from the main impurities of aluminum and silicon were studied. The results showed that the optimum conditions for V(IV) extraction and separation from the impurities were 30%(volume fraction) P507 at pH=1.8～2.0. Temperature had insignificant effect on V(IV) extraction. Based on the V(IV) extraction and stripping distribution isotherms, McCabe Thiele diagrams were constructed. It was demonstrated that two theoretical stages were required to completely extract vanadium from the leach solution containing 20.9 g·L~(-1) V(IV) at an O/A ratio of 1∶1 and pH 2.0 using 30% P507. Sulfuric acid solution could be used for the vanadium stripping. A vanadium electrolyte with high quality was obtained via vanadium stripping in two counter-current stages after organic removal.
引文
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[9] Wang S Y.Modification of the Vanadium Redox Flow Battery Electrode Materials and Design of the Stack Structure [D].Lanzhou:Lanzhou Jiaotong University,2014.6.(王双印.全钒氧化还原液流电池电极材料的改性及电堆结构设 [D].兰州:兰州交通大学,2014.6.)
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[13] Zhan G G.Preparation of High Purity V2O5 and Its Application in Vanadium Batteries[D].Chengdu:Xihua University,2017.8.(张贵刚.高纯V2O5的制备及其在钒电池中的应用 [D].成都:西华大学,2017.8.)
[14] Wang Y W,Guan Q.Study on the preparation technology of VOSO4 for vanadium battery with high purity V2O5 [J].Guangdong Chemical Industry,2014,(23):62.(王远望,官清.高纯V2O5制备钒电池用VOSO4的工艺研究 [J].广东化工,2014,(23):62.)
[15] Wang Y W,Luo H B,Peng R H.Study on the green preparation technology of VOSO4 for vanadium battery [J].Iron Steel Vanadium Titanium,2016,37(3):30.(王远望,罗海波,彭荣华.钒电池用 VOSO4绿色制备工艺研究 [J].钢铁钒钛,2016,37(3):30.)
[16] Chen T B,Jia X M,Huang Y,Liu Z C,Xiang Q L,Li P Y.Fractional extraction separation of uranium and vanadium in sulfuric acid system [J].Hydrometallurgy of China,2018,37(2):105.(陈天宝,贾秀敏,黄永,刘忠臣,向秋林,李培佑.硫酸体系中铀、 钒分步萃取分离试验研究 [J].湿法冶金,2018,37(2):105.)
[17] Zhang Y,Zhang T A.Extraction of vanadium from the leaching solution from converter vanadium slag without roasting using N1923 [J].Nonferrous Metals Science and Engineering,2015,6(6):14.(张莹,张廷安.N1923萃取钒渣无焙烧浸出液中钒的实验探究 [J].有色金属科学与工程,2015,6(6):14.)
[18] Zhang G Z.Study on the Recovery of V,Cr,and Fe form the Chloride Solution by Solvent Extraction [D].Beijing:The University of Chinese Academy of Sciences,2017.84.(张国之.酸性氯化物体系钒、 铬、 铁萃取分离基础研究 [D].北京:中国科学院大学,2017.84.)
[19] Chen C,Zhang Y M,Bao S X,Huang J,Yang X.Separation and enrichment of vanadium from stone coal acidic leach solution using tertiary amine N235 [J].Chinese Journal of Rare Metals,2017,41(4):422.(谌纯,张一敏,包申旭,黄晶,杨晓.叔胺N235从石煤酸浸液中分离富集钒 [J].稀有金属,2017,41(4):422.)
[20] Li D.Preparation of Vanadyl Sulfate with High Purity form Vanadium Hydrochloride Solutions in Shorter Process [D].Beijing:The University of Chinese Academy of Sciences,2017.76.(李丹.含钒氯化物溶液短流程制备高纯硫酸氧钒研究 [D].北京:中国科学院大学,2017.76.)
[21] Sun C.Study on the Extraction of Vanadium Pentoxide from Stone Coal Ore [D].Shenyang:Northeastern University,2009.1.(孙聪.从石煤矿中提取五氧化二钒的工艺研究 [D].沈阳:东北大学,2009.1.)
[22] Wang J D,Chen J Y.Handbook of Solvent Extraction [M].Beijing:Chemical Industry Press,2001.185.(汪家鼎,陈家镛.溶剂萃取手册 [M].北京:化学工业出版社.2001.185.)
[23] Sheng M W,Zhu C L,Li H L.P507-Kerosene system in extraction separation of vanadium and molybdenum [J].Multipurpose Utilization of Mineral Resources,2007,4:14.(沈明伟,朱昌洛,李华伦.P507-煤油体系在钒钼萃取分离中的试验研究 [J].矿产综合利用,2007,4:14.)
[24] Zhang F Y.Effect of Silicon & Iron on Extracting Rare Earth in Saponification P507 System [D].Shenyang:Northeastern University,2011.27.(张丰云.硅、 铁对皂化P507萃取稀土过程的影响 [D].沈阳:东北大学,2011.27.)
[25] Hu G P,Chen D S,Wang L N,Liu J C,Zhao H X,Liu Y H,Qi T,Zhang C Q,Yu P.Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA [J].Separation and Purification Technology,2014,125:59.
[26] Li X B,Chang W,Wu J.Co-extraction and selective stripping of vanadium (IV) and molybdenum(VI) from sulphruric acid soltuion using 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester [J].Separation and Purification Technology,2011,86:64.
[2] Wu E H.Fundamental Research on the Reduction-melting Separation Process for Metalized Oellets of Vanadium-Bearing Titanomagnetite Concentrates [D].Beijing:University of Science and Technology Beijing,2016.1.(吴恩辉.钒钛铁精矿金属化球团还原熔分工艺基础研究 [D].北京:北京科技大学,2016.1.)
[3] Zhao H Y.Analysis of vanadium resources utilization and demand for vanadium in China [J].Conservation and Utilization of Mineral Resources,2014,(2):54.(赵海燕.钒资源利用概况及我国钒市场需求分析 [J].矿产保护与利用,2014,(2):54.)
[4] Hao W B,Dai Z L,Guo Q S,Wei Q,Li Y X.Vanadium precipitation process by ammonium salts in acid leaching vanadium-rich solution after vanadium extracting from stone coal [J].Metal Mine,2014,(6):75.(郝文彬,戴子林,郭秋松,危青,李云霄.石煤直接酸浸提钒富液铵盐沉钒工艺研究 [J].金属矿山,2014,(6):75.)
[5] Skyllas-Kazacos,Limantari Y.Kinetics of the chemical dissolution of vanadium pentoxide in acidic bromide solutions [J].Journal of Applied Electrochemistry,2004,34(7):681.
[6] Sum E,Rychcik M,Skyllas-Kazacos M.Investigation of the V(V)/V(IV) system for use in the positive half-cell of a redox battery [J].Journal of Power Sources,1985,16(2):85.
[7] Llewellyn P,Grossmith F,Fane A,Skyllas-Kazacos M.Membrane evaluation for vanadium redox cell in journal of the eletrochemical society [J].Electochemical Soc Inc South Main Street,Pennington,1987,65:49.
[8] Mao F J.The research on the preparation of vanadyl sulfate for vanadium battery system [J].Sichuan Chemical Industry,2015,(1):1.(毛凤娇.钒电池用硫酸氧钒的制备研究 [J].四川化工,2015,(1):1.)
[9] Wang S Y.Modification of the Vanadium Redox Flow Battery Electrode Materials and Design of the Stack Structure [D].Lanzhou:Lanzhou Jiaotong University,2014.6.(王双印.全钒氧化还原液流电池电极材料的改性及电堆结构设 [D].兰州:兰州交通大学,2014.6.)
[10] Zhu P P.Influence of Impurity Ions on the Electrolyte Stability and Electrochemical Performance of Vanadium Redox Flow Battery [D].Shenyang:Shenyang Ligong University,2014.18.(朱朋朋.杂质离子对全钒液流电池电解液稳定性及电化学性能的影响 [D].沈阳:沈阳理工大学,2014.18.)
[11] Duan C Q.Handbook of Modern Chemical Reagents.Volume 1,General Reagents [M].Beijing:Chemical Industry Press,1988.55.(段长强.现代化学试剂手册.第一分册,通用试剂 [M].北京:化学工业出版社,1988.55.)
[12] Yang T X,Chen Y.Vanadyl sulfate preparation and determination of its vanadium [J].Journal of Mianyang Normal University,2013,(11):64.(杨通秀,陈英.硫酸氧钒的制备及硫酸氧钒中钒的测定 [J].绵阳师范学院学报,2013,(11):64.)
[13] Zhan G G.Preparation of High Purity V2O5 and Its Application in Vanadium Batteries[D].Chengdu:Xihua University,2017.8.(张贵刚.高纯V2O5的制备及其在钒电池中的应用 [D].成都:西华大学,2017.8.)
[14] Wang Y W,Guan Q.Study on the preparation technology of VOSO4 for vanadium battery with high purity V2O5 [J].Guangdong Chemical Industry,2014,(23):62.(王远望,官清.高纯V2O5制备钒电池用VOSO4的工艺研究 [J].广东化工,2014,(23):62.)
[15] Wang Y W,Luo H B,Peng R H.Study on the green preparation technology of VOSO4 for vanadium battery [J].Iron Steel Vanadium Titanium,2016,37(3):30.(王远望,罗海波,彭荣华.钒电池用 VOSO4绿色制备工艺研究 [J].钢铁钒钛,2016,37(3):30.)
[16] Chen T B,Jia X M,Huang Y,Liu Z C,Xiang Q L,Li P Y.Fractional extraction separation of uranium and vanadium in sulfuric acid system [J].Hydrometallurgy of China,2018,37(2):105.(陈天宝,贾秀敏,黄永,刘忠臣,向秋林,李培佑.硫酸体系中铀、 钒分步萃取分离试验研究 [J].湿法冶金,2018,37(2):105.)
[17] Zhang Y,Zhang T A.Extraction of vanadium from the leaching solution from converter vanadium slag without roasting using N1923 [J].Nonferrous Metals Science and Engineering,2015,6(6):14.(张莹,张廷安.N1923萃取钒渣无焙烧浸出液中钒的实验探究 [J].有色金属科学与工程,2015,6(6):14.)
[18] Zhang G Z.Study on the Recovery of V,Cr,and Fe form the Chloride Solution by Solvent Extraction [D].Beijing:The University of Chinese Academy of Sciences,2017.84.(张国之.酸性氯化物体系钒、 铬、 铁萃取分离基础研究 [D].北京:中国科学院大学,2017.84.)
[19] Chen C,Zhang Y M,Bao S X,Huang J,Yang X.Separation and enrichment of vanadium from stone coal acidic leach solution using tertiary amine N235 [J].Chinese Journal of Rare Metals,2017,41(4):422.(谌纯,张一敏,包申旭,黄晶,杨晓.叔胺N235从石煤酸浸液中分离富集钒 [J].稀有金属,2017,41(4):422.)
[20] Li D.Preparation of Vanadyl Sulfate with High Purity form Vanadium Hydrochloride Solutions in Shorter Process [D].Beijing:The University of Chinese Academy of Sciences,2017.76.(李丹.含钒氯化物溶液短流程制备高纯硫酸氧钒研究 [D].北京:中国科学院大学,2017.76.)
[21] Sun C.Study on the Extraction of Vanadium Pentoxide from Stone Coal Ore [D].Shenyang:Northeastern University,2009.1.(孙聪.从石煤矿中提取五氧化二钒的工艺研究 [D].沈阳:东北大学,2009.1.)
[22] Wang J D,Chen J Y.Handbook of Solvent Extraction [M].Beijing:Chemical Industry Press,2001.185.(汪家鼎,陈家镛.溶剂萃取手册 [M].北京:化学工业出版社.2001.185.)
[23] Sheng M W,Zhu C L,Li H L.P507-Kerosene system in extraction separation of vanadium and molybdenum [J].Multipurpose Utilization of Mineral Resources,2007,4:14.(沈明伟,朱昌洛,李华伦.P507-煤油体系在钒钼萃取分离中的试验研究 [J].矿产综合利用,2007,4:14.)
[24] Zhang F Y.Effect of Silicon & Iron on Extracting Rare Earth in Saponification P507 System [D].Shenyang:Northeastern University,2011.27.(张丰云.硅、 铁对皂化P507萃取稀土过程的影响 [D].沈阳:东北大学,2011.27.)
[25] Hu G P,Chen D S,Wang L N,Liu J C,Zhao H X,Liu Y H,Qi T,Zhang C Q,Yu P.Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA [J].Separation and Purification Technology,2014,125:59.
[26] Li X B,Chang W,Wu J.Co-extraction and selective stripping of vanadium (IV) and molybdenum(VI) from sulphruric acid soltuion using 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester [J].Separation and Purification Technology,2011,86:64.