伯胺N_(1923)从离子吸附型稀土浸出液中萃取分离稀土与铝
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摘要
离子吸附型稀土浸出液中共存杂质铝的含量随矿床产地和浸取条件而变化,其浓度有时与稀土属于同一数量级,而铝对稀土的分离纯化过程影响严重。因此,稀土与铝的分离具有重要意义。本文研究了伯胺N_(1923)萃取分离稀土与铝的性能,结果表明:N_(1923)-煤油-异辛醇有机相可以从离子吸附型稀土浸出液中直接萃取稀土,而铝及其他低价金属离子留在水相;其分离系数可以达到10~5。少量进入有机相的铝继续用(NH_4)_2SO_4溶液反洗(O/A=1∶1),使负载有机相中稀土与铝的比值大大增加,其分离系数随(NH_4)_2SO_4浓度的升高和溶液pH的下降而增大。确定的最佳浓度和pH分别为2%和1。有机相中的稀土经3 mol·L~(-1) NH_4Cl溶液反萃(O/A=2∶1),可以得到浓度大纯度高的稀土溶液;采用c_(Al)/c_(RE)=8.443的含铝稀土浸出液,经萃取、洗涤和反萃,可以得到浓度为4.3～13.34 g·L~(-1)的c_(Al)/c_(RE)=0.0023～0.0027的稀土溶液,稀土回收率大于96%。
The concentration of aluminum in the ion adsorption rare earth leachate varies with theorigin of the deposit and the leaching conditions, which sometimes is in the same magnitude as that of rare earth, and shows serious effect on the subsequent separation and purification of rare earth. Therefore, it is of great significance to separate rare earth from aluminum. The extraction separation performance of rare earth and aluminum by primary amine N_(1923) was studied, the results showed that N_(1923)-kerosene-isooctanol organic phase can directly extract rare earths from the leachate of rare earth ions, while keep aluminum and other low valence metal ions remaining in aqueous phase. The separation factor reaches at around 10~5. The aluminum in extracted organic phase is backwashed with 2% ammonium sulfate and pH value of 1(O/A ratio of 1∶1), resulting in a great increase of ratio of rare earth to aluminum in the loaded organic phase. It was demonstrated that the separation factor of RE to Al increases with the increase of ammonium sulfate concentration and with the decrease of solution pH value, the optimum concentration and pH were determined to be 2% and 1, respectively. The rare earth in the organic phase was stripped by 3 mol·L~(-1) ammonium chloride solution(O/A=2∶1) to obtain a rare earth solution with high purity and high concentration. Fora leachate with c_(Al~(3+))/c_(RE~(3+))=8.443, a rare earth solution with c_(Al~(3+))/c_(RE~(3+))=0.0023～0.0027 at the concentration of 4.3～13.34 g·L~(-1) can be obtained via extracting with N_(1923), washing with ammonium sulfate solution and striping with ammonium chloride solution, and the recovery rate of rare earth is over 96%.
The concentration of aluminum in the ion adsorption rare earth leachate varies with theorigin of the deposit and the leaching conditions, which sometimes is in the same magnitude as that of rare earth, and shows serious effect on the subsequent separation and purification of rare earth. Therefore, it is of great significance to separate rare earth from aluminum. The extraction separation performance of rare earth and aluminum by primary amine N_(1923) was studied, the results showed that N_(1923)-kerosene-isooctanol organic phase can directly extract rare earths from the leachate of rare earth ions, while keep aluminum and other low valence metal ions remaining in aqueous phase. The separation factor reaches at around 10~5. The aluminum in extracted organic phase is backwashed with 2% ammonium sulfate and pH value of 1(O/A ratio of 1∶1), resulting in a great increase of ratio of rare earth to aluminum in the loaded organic phase. It was demonstrated that the separation factor of RE to Al increases with the increase of ammonium sulfate concentration and with the decrease of solution pH value, the optimum concentration and pH were determined to be 2% and 1, respectively. The rare earth in the organic phase was stripped by 3 mol·L~(-1) ammonium chloride solution(O/A=2∶1) to obtain a rare earth solution with high purity and high concentration. Fora leachate with c_(Al~(3+))/c_(RE~(3+))=8.443, a rare earth solution with c_(Al~(3+))/c_(RE~(3+))=0.0023～0.0027 at the concentration of 4.3～13.34 g·L~(-1) can be obtained via extracting with N_(1923), washing with ammonium sulfate solution and striping with ammonium chloride solution, and the recovery rate of rare earth is over 96%.
引文
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[12]贾江涛,张亚文,吴声,廖春生,严纯华,刘均云.铝在稀土萃取分离流程中的分布及分离方法研究(I)[J].稀土,2001,22(2):10.Jia J T,Zhang Y W,Wu S,Liao C S,Yan C H,Liu JY.Distribution and separation of aluminum in the rare earth solvent extraction separation processes(I)[J].Chinese Rare Earths,2001,22(2):10.
[13]李标国,周永芬,李俊然,刘兴芝,徐光宪.高纯氧化镧的制备[J].稀有金属,1984,8(6):56.Li B G,Zhou Y F,Li J R,Liu X Z,Xu G X.Preparation of high-purity lanthanum oxide[J].Chinese Journal of Rare Metals,1984,8(6):56.
[14]Wu W Y,Zhang F Y,Bian X,Xue S F,Yin S H,Zheng Q.Effect of loaded organic phase containing mixtures of silicon and aluminum,single iron on extraction of lanthanum in saponification P507-HCl system[J].J.Rare Earths,2013,31(7):722.
[15]Wu W Y,Li D,Zhao Z H,Jian J l,Zhang F Y,Yin SH.Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system[J].J.Rare Earths,2010,28(s1):174.
[16]王珊,赵治华,桑晓云,王英杰,卢国贞.P507-盐酸-煤油萃取体系中去除氯化镨钕溶液中铝的工艺研究[J].科技创新导报,2015,12(20):81.Wang S,Zhao Z H,Sang X Y,Wang Y J,Lu G Z.P507-hydrochloric acid-kerosene extraction system to remove aluminum from praseodymium neodymium chloride solution[J].Science and Technology Innovation Herald,2015,12(20):81.
[17]Huang X W,Dong J S,Wang L S,Feng Z Y,Xue QN,Meng X L.Selective recovery of rare earth elements from ion-adsorption rare earth element ores by stepwise extraction with HEH(EHP)and HDEHP[J].Green Chem.,2017,19(5):1345.
[18]Yang X L,Qiu T S.Influence of aluminum ions distribution on the removal of aluminum from rare earth solutions using saponified naphthenic acid[J].Sep.Purif.Tech.,2017,186:290.
[19]刘志强,朱薇,郭秋松.高铝稀土料液萃取除铝工艺的研究[J].材料研究与应用,2012,6(4):256.Liu Z Q,Zhu W,Guo Q S.Study on process of extracting aluminum from high-alumina rare earth solution[J].Materials Research and Application.,2012,6(4):256.
[20]李剑虹,张兴,常宏涛,吴文远.环烷酸改性合成氯代环烷酸萃取体系分离稀土和铝[J].矿产综合利用,2010,29(5):43.Li J H,Zhang X,Chang H T,Wu W Y.Research on extraction separation of rare-earths and aluminum by chloronaphthenic acid system[J].Multipurpose Utilization of Mineral Resources,2010,29(5):43.
[21]李剑虹,张兴.改性环烷酸萃取体系分离稀土和铝的优越性[J].金属矿山,2011,23(7):98.Li J H,Zhang X.Superiority research on rare earth and aluminium separation in modified naphthenic acid extraction system[J].Metal Mine.,2011,23(7):98.
[22]李剑虹,张兴,徐莹,吴文远.氯代环烷酸体系萃取单一稀土和铝分配比及分离系数的研究[J].稀有金属,2010,34(5):776.Li J H,Zhang X,Xu Y,Wu W Y.Distribution ratio and separation coefficient of single rare earth and aluminium in chloronaphthenic acid system[J].Chinese Journal of Rare Metals,2010,34(5):776.
[23]Jiang D D,Song N Z,Liao S F,Lian Y,Ma J T,Jia Q.Study on the synergistic extraction of vanadium by mixtures of acidic organophosphorus extractants and primary amine N1923[J].Sep.Purif.Tech.,2015,156:835.
[24]Sun P,Huang K,Liu H Z.Separation of V and Cr in alkaline aqueous solution using acidified primary amine N1923[J].Hydrometallurgy,2016,165:370.
[25]Li D Q.Extraction and separation of rare earth,in:G.X.Xu(Ed.),Rare Earth(second ed.)[M].Beijing:Metallurgy Industry Press,1995.563.
[26]Amaral J C B S,Morais C A.Thorium and uranium extraction from rare earth elements in monazite sulfuric acid leach liquor through solvent extraction[J].Miner.Eng.,2010,23(6):498.
[27]Li M Y,He Z M,Zhou L.Removal of iron from industrial grade aluminum sulfate by primary amine extraction system[J].Hydrometallurgy,2011,106(3-4):170.
[28]徐光宪.稀土(上册)[M].北京:冶金工业出版社,1995.Xu G X.Rare Earth(Volume 1)[M].Beijing:Metallurgical Industry Press,1995.
[2]池汝安,田君.风化壳淋积型稀土矿化工冶金[M].北京:科学出版社,2006.Chi R A,Tian J.Hydrometallurgy of the Weathered Crust Elution-Deposited Rare Earth Ores[M].Beijing:Science Press,2006.
[3]许秋华,孙园园,周雪珍,刘艳珠,李静,李永绣.离子吸附型稀土资源绿色提取[J].中国稀土学报,2016,34(6):650.Xu Q H,Sun Y Y,Zhou X Z,Liu Y Z,Li J,Li Y X.Green extraction of ion-adsorption rare earth resources[J].Journal of Chinese Society of Rare Earths,2016,34(6):650.
[4]欧阳克氙,饶国华,姚慧琴,毛燕红.南方稀土矿抑铝浸出研究[J].稀有金属与硬质合金,2003,31(4):1.Ouyang K X,Rao G H,Yao H Q,Mao Y H.Study of southern RE ore leaching by aluminum inhibition[J].Rare Metals and Cemented Carbides,2003,31(4):1.
[5]He Z Y,Zhang Q Y,Yu J X,Zhou F,Xu Y L,Xu ZG,Chen Z,Chi R A.Kinetics of column leaching of rare earth and aluminum from weathered crust elution-deposited rare earth ore with ammonium salt solutions[J].Hydrometallurgy,2016,163:33.
[6]许秋华,杨丽芬,张丽,李翠翠,王大山,周新木,周雪珍,李永绣.基于浸取p H依赖性的离子吸附型稀土分类及高效浸取方法[J].无机化学学报,2018,34(1):112.Xu Q H,Yang L F,Zhang L,Li C C,Wang D S,Zhou X M,Zhou X Z,Li Y X.Classification and high efficient leaching of ion adsorption rare earth based on its p H dependence[J].Chinese Journal of Inorganic Chemistry,2018,34(1):112.
[7]李永绣,许秋华,王悦,谢爱玲,侯潇,周雪珍,周新木,刘艳珠,李静,李东平.一种提高离子型稀土浸取率和尾矿安全性的方法[P].中国专利:CN103695670A,2014.Li Y X,Xu Q H,Wang Y,Xie A L,Hou X,Zhou XZ,Zhou X M,Liu Y Z,Li J,Li D P.Method for the high efficiency leaching of ion adsorption rare earths using aluminum sulfate as leaching reagent[P].China Patent:CN201610821052.4,2016.
[8]吴文远,边雪.稀土冶金技术[M].北京:科学出版社,2012.140.Wu W Y,Bian X.Rare Earth Metallurgy Technology[M].Beijing:Science Press,2012.140.
[9]李秀芬,池汝安.稀土矿淋出液除杂工艺的研究[J].矿产综利用,1997,10(2):10.Li X F,Chi R A.Study on removing impurities in the exchanged liquor of rare earth ores[J].Multipurpose U-tilization of Mineral Resources,1997,10(2):10.
[10]赵治华,桑晓云,张文斌,郝高慧,段春坤,李冬.离心沉降法去除稀土溶液中杂质铝和铁[J].稀土,2007,28(6):95.Zhao Z H,Sang X Y,Zhang W B,Hao G H,Duan CK,Li D.Application of centrifuging sedimentation on removing aluminumand iron from rare earth solution[J].Chinese Rare Earths,2007,28(6):95.
[11]Chi R A,Xu Z G.A solution chemistry approach to the study of rare earth elementprecipitation by oxalic acid[J].Metall.Mater.Trans.B,1999,30(2):189.
[12]贾江涛,张亚文,吴声,廖春生,严纯华,刘均云.铝在稀土萃取分离流程中的分布及分离方法研究(I)[J].稀土,2001,22(2):10.Jia J T,Zhang Y W,Wu S,Liao C S,Yan C H,Liu JY.Distribution and separation of aluminum in the rare earth solvent extraction separation processes(I)[J].Chinese Rare Earths,2001,22(2):10.
[13]李标国,周永芬,李俊然,刘兴芝,徐光宪.高纯氧化镧的制备[J].稀有金属,1984,8(6):56.Li B G,Zhou Y F,Li J R,Liu X Z,Xu G X.Preparation of high-purity lanthanum oxide[J].Chinese Journal of Rare Metals,1984,8(6):56.
[14]Wu W Y,Zhang F Y,Bian X,Xue S F,Yin S H,Zheng Q.Effect of loaded organic phase containing mixtures of silicon and aluminum,single iron on extraction of lanthanum in saponification P507-HCl system[J].J.Rare Earths,2013,31(7):722.
[15]Wu W Y,Li D,Zhao Z H,Jian J l,Zhang F Y,Yin SH.Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system[J].J.Rare Earths,2010,28(s1):174.
[16]王珊,赵治华,桑晓云,王英杰,卢国贞.P507-盐酸-煤油萃取体系中去除氯化镨钕溶液中铝的工艺研究[J].科技创新导报,2015,12(20):81.Wang S,Zhao Z H,Sang X Y,Wang Y J,Lu G Z.P507-hydrochloric acid-kerosene extraction system to remove aluminum from praseodymium neodymium chloride solution[J].Science and Technology Innovation Herald,2015,12(20):81.
[17]Huang X W,Dong J S,Wang L S,Feng Z Y,Xue QN,Meng X L.Selective recovery of rare earth elements from ion-adsorption rare earth element ores by stepwise extraction with HEH(EHP)and HDEHP[J].Green Chem.,2017,19(5):1345.
[18]Yang X L,Qiu T S.Influence of aluminum ions distribution on the removal of aluminum from rare earth solutions using saponified naphthenic acid[J].Sep.Purif.Tech.,2017,186:290.
[19]刘志强,朱薇,郭秋松.高铝稀土料液萃取除铝工艺的研究[J].材料研究与应用,2012,6(4):256.Liu Z Q,Zhu W,Guo Q S.Study on process of extracting aluminum from high-alumina rare earth solution[J].Materials Research and Application.,2012,6(4):256.
[20]李剑虹,张兴,常宏涛,吴文远.环烷酸改性合成氯代环烷酸萃取体系分离稀土和铝[J].矿产综合利用,2010,29(5):43.Li J H,Zhang X,Chang H T,Wu W Y.Research on extraction separation of rare-earths and aluminum by chloronaphthenic acid system[J].Multipurpose Utilization of Mineral Resources,2010,29(5):43.
[21]李剑虹,张兴.改性环烷酸萃取体系分离稀土和铝的优越性[J].金属矿山,2011,23(7):98.Li J H,Zhang X.Superiority research on rare earth and aluminium separation in modified naphthenic acid extraction system[J].Metal Mine.,2011,23(7):98.
[22]李剑虹,张兴,徐莹,吴文远.氯代环烷酸体系萃取单一稀土和铝分配比及分离系数的研究[J].稀有金属,2010,34(5):776.Li J H,Zhang X,Xu Y,Wu W Y.Distribution ratio and separation coefficient of single rare earth and aluminium in chloronaphthenic acid system[J].Chinese Journal of Rare Metals,2010,34(5):776.
[23]Jiang D D,Song N Z,Liao S F,Lian Y,Ma J T,Jia Q.Study on the synergistic extraction of vanadium by mixtures of acidic organophosphorus extractants and primary amine N1923[J].Sep.Purif.Tech.,2015,156:835.
[24]Sun P,Huang K,Liu H Z.Separation of V and Cr in alkaline aqueous solution using acidified primary amine N1923[J].Hydrometallurgy,2016,165:370.
[25]Li D Q.Extraction and separation of rare earth,in:G.X.Xu(Ed.),Rare Earth(second ed.)[M].Beijing:Metallurgy Industry Press,1995.563.
[26]Amaral J C B S,Morais C A.Thorium and uranium extraction from rare earth elements in monazite sulfuric acid leach liquor through solvent extraction[J].Miner.Eng.,2010,23(6):498.
[27]Li M Y,He Z M,Zhou L.Removal of iron from industrial grade aluminum sulfate by primary amine extraction system[J].Hydrometallurgy,2011,106(3-4):170.
[28]徐光宪.稀土(上册)[M].北京:冶金工业出版社,1995.Xu G X.Rare Earth(Volume 1)[M].Beijing:Metallurgical Industry Press,1995.
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