P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能
|
摘要
从钒渣钠化焙烧后的含钒浸液中,采用2-乙基己基磷酸单-2-乙基己酯(P507)萃取-草酸反萃取-蒸发结晶新工艺制备了草酸氧钒,优化了草酸反萃取工艺的条件.研究结果表明,采用2. 0 mol/L草酸溶液,在水相与有机相体积比V(A)∶V(O)为1∶5时,于50℃下经过三级(理论)反萃取,钒的反萃取率可达到99. 98%,反萃取液中VOC_2O_4浓度可达290. 0 g/L以上.负载的反萃取液经膜过滤除去残留有机物后,再经蒸发结晶得到草酸氧钒.采用X射线衍射、X射线能谱、热场发射扫描电子显微镜及同步热分析等手段表征了草酸氧钒的物化性能,结果表明,草酸氧钒的结构为VOC_2O_4·2H_2O,粒度分布均匀,结晶度高.
Vanadium oxalate is an ideal precursor used for the preparation of vanadium containing catalysts,advanced phase change material of VO_2,high performance VN and other vanadium based chemical products.Currently,few research on the preparation of VOC_2O_4 was found to be reported. In this study,highly pure vanadium oxalate was prepared through "extraction-stripping-evaporative crystallization " method using2-ethylhexyl dihydrogen phosphate( P507) as the extractant and H_2C_2O_4 as the stripping reagent from a vanadium leach solution obtained by sodium roasting and water leaching of vanadium titano-magnetite slags. V( Ⅳ)stripping from the loaded P507 solution with H_2C_2O_4 was emphatically studied and the stripping conditions were optimized. The result showed that vanadium could be almost completely( 99. 98%) stripped at an A/O ratio of 1 ∶ 5 and 50 ℃ using 2. 0 mol/L oxalic acid solution in three stages( theoretical). The concentration of VOC_2O_4 would reach 290 g/L in the loaded strip liquor. The vanadium oxalate was characterized by X-ray diffraction( XRD),energy dispersive spectrometer( EDS),field emission scanning electron microscope( SEM)and synchronous thermal analyzer( TGA-DSC). The result showed that vanadium oxalate was VOC_2O_4·2H_2O and it had high purity,good crystallinity and average particle size distribution.
Vanadium oxalate is an ideal precursor used for the preparation of vanadium containing catalysts,advanced phase change material of VO_2,high performance VN and other vanadium based chemical products.Currently,few research on the preparation of VOC_2O_4 was found to be reported. In this study,highly pure vanadium oxalate was prepared through "extraction-stripping-evaporative crystallization " method using2-ethylhexyl dihydrogen phosphate( P507) as the extractant and H_2C_2O_4 as the stripping reagent from a vanadium leach solution obtained by sodium roasting and water leaching of vanadium titano-magnetite slags. V( Ⅳ)stripping from the loaded P507 solution with H_2C_2O_4 was emphatically studied and the stripping conditions were optimized. The result showed that vanadium could be almost completely( 99. 98%) stripped at an A/O ratio of 1 ∶ 5 and 50 ℃ using 2. 0 mol/L oxalic acid solution in three stages( theoretical). The concentration of VOC_2O_4 would reach 290 g/L in the loaded strip liquor. The vanadium oxalate was characterized by X-ray diffraction( XRD),energy dispersive spectrometer( EDS),field emission scanning electron microscope( SEM)and synchronous thermal analyzer( TGA-DSC). The result showed that vanadium oxalate was VOC_2O_4·2H_2O and it had high purity,good crystallinity and average particle size distribution.
引文
[1]Yang S.L.,Peng F.C.,Pan F.S.,Gao S.Z.,Mater.Rev.,2008,22(4),53-56(杨绍利,彭富昌,潘复生,高仕忠.材料导报,2008,22(4),53-56)
[2]Gao Z.M.,Zhang Y.F.,Wang Q.S.,Zhen J.Q.,J.Chin.Ele.Micro.Soc.,2017,36(2),103-112(高占明,张依福,王秋实,郑吉祺.电子显微学报,2017,36(2),103-112)
[3]Cao Y.L.,Jia D.Z.,Liu L.,Xiao D.Q.,Xin X.Q.,Chem.Res.Chinese Universities,2005,21(2),134-136
[4]Lin H.,Zou J.,Li Q.,Iron Steel Vanadium Titanium,2006,27(1),55-58,63(林华,邹建,李庆.钢铁钒钛,2006,27(1),55-58,63)
[5]Hao Q.L.,Shao Q.,Liu Q.Y.,Mod.Chem.Ind.,2014,34(11),51-54(郝巧兰,邵谦,刘青云.现代化工,2014,34(11),51-54)
[6]Ren Z.Z.,Huang W.G.,J.Funct.Mater.,2007,8,2112-2113(任哲峥,黄维刚.功能材料,2007,8,2112-2113)
[7]Wang A.R.,Yuan J.F.,Chin.J.Process Eng.,2017,17(3),558-564(王安仁,袁吉峰.过程工程学报,2017,17(3),558-564)
[8]Li Z.T.,Synthesis,Characterization and Electrochemical Performance of Vanadium-Based Materials,South China University of Technology,Guangzhou,2015(栗志同.钒基材料的合成、表征及其电化学性能研究,广州:华南理工大学,2015)
[9]Li Z.T.,Wang S.Q.,Synthesis and Electrochemical Performance of Porous Vanadium Oxide,http://www.paper.edu.cn(栗志同,王素清.多孔五氧化二钒的制备及其电化学性能研究,中国科技论文在线,http://www.paper.edu.cn)
[10]Ren D.X.,Cao Y.Z.,Chen C.,Ying Y.H.,Chem.Res.Chinese Universities,2012,28(5),768-774
[11]Huang W.G.,Lin H.,Tu M.J.,J.Funct.Mater.,2006,3(37),440-442(黄维刚,林华,涂铭旌.功能材料,2006,3(37),440-442)
[12]Wan L.F.,Iron Steel Vanadium Titanium,2016,37(3),56-60(万龙飞.钢铁钒钛,2016,37(3),56-60)
[13]Hao C.Z.,Kong X.F.,Yu M.A.,A Method to Prepare Highly Pure Vanadyl Oxalate Solid Product,CP 201710340156.8,2017-08-18(郝承志,孔祥风,于明爱.一种高纯草酸氧钒固体产品的制备方法,CP 201710340156.8,2017-08-18)
[14]Cao P.,Wan L.F.,Shen B.,Sun Z.H.,Li Q.W.,Pen Y.,Hu L.,A Method to Prepare Vanadyl Oxalate,CP 201200079205.4,2013-09-25(曹鹏,万隆飞,申彪,孙朝晖,李千文,彭毅,胡力.一种草酸氧钒的制备方法,CP 201200079205.4,2013-09-25)
[15]Bruyère V.I.E.,Morando P.J.,Blesa M.A.,J.Colloid.Interf.Sci.,1999,209,207-214
[16]Bruyère V.I.E.,Rodenas L.A.G.,Morando P.J.,Blesa M.A.,J.Chem.Soc.Dalton.,2001,24(24),3593-3597
[17]Zhang J.,Zhu Z.W.,Chen D.S.,Wang L.N.,Wang W.J.,Lei Z.,Chinese Journal of Rare Metals,2018,43(3),303-311(张健,朱兆武,陈德胜,王丽娜,王伟菁,雷泽.稀有金属,2018,43(3),303-311)
[18]Li L.J.,Chang F.Z.,Wang H.X.,Bai R.G.,Zhou X.,Yan H.,A Method to Prepare Vanadyl Oxalate,CP 201610775992.4,2017-02-08(李兰杰,常福增,王海旭,白瑞国,周欣,闫浩.一种草酸氧钒的制备方法,CP 201610775992.4,2017-02-08)
[19]Zhang Y.,Zhang T.A.,Dreisinger D.,Lv G.Z.,Can.Metall.Quart.,2017,56(5),1-13
[20]Liu Y.H.,Yang C.,Hydrometallurgy of China,2010,29(4),263-266(刘彦华,杨超.湿法冶金,2010,29(4),263-266)
[21]Li X.B.,Wei C.,Wu J.N.,Li C.X.,Li M.T.,Deng Z.G.,Xu H.S.,T.Nonferr.Metal.Soc.,2015,25(10),461-466
[22]Mehdi N.,Fereshteh R.,Ataollah B.,Ehsan V.,Sep.Purif.Technol.,2014,136,125-128
[23]Zhang G.Z.,Study on the Recovery of V,Cr,and Fe form the Chloride Solution by Solvent Extraction,the University of Chinese Academy of Sciences,Beijing,2017(张国之.酸性氯化物体系钒、铬、铁萃取分离基础研究,北京:中国科学院大学,2017)
[24]Li D.,Preparation of Vanadyl Sulfate with High Purity form Vanadium Hydrochloride Solutions in Shorter Process,The University of Chinese Academy of Sciences,Beijing,2017(李丹.含钒氯化物溶液短流程制备高纯硫酸氧钒研究,北京:中国科学院大学,2017)
[2]Gao Z.M.,Zhang Y.F.,Wang Q.S.,Zhen J.Q.,J.Chin.Ele.Micro.Soc.,2017,36(2),103-112(高占明,张依福,王秋实,郑吉祺.电子显微学报,2017,36(2),103-112)
[3]Cao Y.L.,Jia D.Z.,Liu L.,Xiao D.Q.,Xin X.Q.,Chem.Res.Chinese Universities,2005,21(2),134-136
[4]Lin H.,Zou J.,Li Q.,Iron Steel Vanadium Titanium,2006,27(1),55-58,63(林华,邹建,李庆.钢铁钒钛,2006,27(1),55-58,63)
[5]Hao Q.L.,Shao Q.,Liu Q.Y.,Mod.Chem.Ind.,2014,34(11),51-54(郝巧兰,邵谦,刘青云.现代化工,2014,34(11),51-54)
[6]Ren Z.Z.,Huang W.G.,J.Funct.Mater.,2007,8,2112-2113(任哲峥,黄维刚.功能材料,2007,8,2112-2113)
[7]Wang A.R.,Yuan J.F.,Chin.J.Process Eng.,2017,17(3),558-564(王安仁,袁吉峰.过程工程学报,2017,17(3),558-564)
[8]Li Z.T.,Synthesis,Characterization and Electrochemical Performance of Vanadium-Based Materials,South China University of Technology,Guangzhou,2015(栗志同.钒基材料的合成、表征及其电化学性能研究,广州:华南理工大学,2015)
[9]Li Z.T.,Wang S.Q.,Synthesis and Electrochemical Performance of Porous Vanadium Oxide,http://www.paper.edu.cn(栗志同,王素清.多孔五氧化二钒的制备及其电化学性能研究,中国科技论文在线,http://www.paper.edu.cn)
[10]Ren D.X.,Cao Y.Z.,Chen C.,Ying Y.H.,Chem.Res.Chinese Universities,2012,28(5),768-774
[11]Huang W.G.,Lin H.,Tu M.J.,J.Funct.Mater.,2006,3(37),440-442(黄维刚,林华,涂铭旌.功能材料,2006,3(37),440-442)
[12]Wan L.F.,Iron Steel Vanadium Titanium,2016,37(3),56-60(万龙飞.钢铁钒钛,2016,37(3),56-60)
[13]Hao C.Z.,Kong X.F.,Yu M.A.,A Method to Prepare Highly Pure Vanadyl Oxalate Solid Product,CP 201710340156.8,2017-08-18(郝承志,孔祥风,于明爱.一种高纯草酸氧钒固体产品的制备方法,CP 201710340156.8,2017-08-18)
[14]Cao P.,Wan L.F.,Shen B.,Sun Z.H.,Li Q.W.,Pen Y.,Hu L.,A Method to Prepare Vanadyl Oxalate,CP 201200079205.4,2013-09-25(曹鹏,万隆飞,申彪,孙朝晖,李千文,彭毅,胡力.一种草酸氧钒的制备方法,CP 201200079205.4,2013-09-25)
[15]Bruyère V.I.E.,Morando P.J.,Blesa M.A.,J.Colloid.Interf.Sci.,1999,209,207-214
[16]Bruyère V.I.E.,Rodenas L.A.G.,Morando P.J.,Blesa M.A.,J.Chem.Soc.Dalton.,2001,24(24),3593-3597
[17]Zhang J.,Zhu Z.W.,Chen D.S.,Wang L.N.,Wang W.J.,Lei Z.,Chinese Journal of Rare Metals,2018,43(3),303-311(张健,朱兆武,陈德胜,王丽娜,王伟菁,雷泽.稀有金属,2018,43(3),303-311)
[18]Li L.J.,Chang F.Z.,Wang H.X.,Bai R.G.,Zhou X.,Yan H.,A Method to Prepare Vanadyl Oxalate,CP 201610775992.4,2017-02-08(李兰杰,常福增,王海旭,白瑞国,周欣,闫浩.一种草酸氧钒的制备方法,CP 201610775992.4,2017-02-08)
[19]Zhang Y.,Zhang T.A.,Dreisinger D.,Lv G.Z.,Can.Metall.Quart.,2017,56(5),1-13
[20]Liu Y.H.,Yang C.,Hydrometallurgy of China,2010,29(4),263-266(刘彦华,杨超.湿法冶金,2010,29(4),263-266)
[21]Li X.B.,Wei C.,Wu J.N.,Li C.X.,Li M.T.,Deng Z.G.,Xu H.S.,T.Nonferr.Metal.Soc.,2015,25(10),461-466
[22]Mehdi N.,Fereshteh R.,Ataollah B.,Ehsan V.,Sep.Purif.Technol.,2014,136,125-128
[23]Zhang G.Z.,Study on the Recovery of V,Cr,and Fe form the Chloride Solution by Solvent Extraction,the University of Chinese Academy of Sciences,Beijing,2017(张国之.酸性氯化物体系钒、铬、铁萃取分离基础研究,北京:中国科学院大学,2017)
[24]Li D.,Preparation of Vanadyl Sulfate with High Purity form Vanadium Hydrochloride Solutions in Shorter Process,The University of Chinese Academy of Sciences,Beijing,2017(李丹.含钒氯化物溶液短流程制备高纯硫酸氧钒研究,北京:中国科学院大学,2017)