Liquid–liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding

Abstract

Liquid–liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.

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Abbreviations

CMPO:

Carbamoyl-methyl phosphine oxide

TBP:

Tributyl phosphate

TODGA:

N,N,N′,N′-Tetra(n-octyl)diglycolamide

TTA:

Thenoyltrifluoroacetone

References

  1. 1.

    Plechkova N, Seddon RK (2008) Applications of ionic liquids in the chemical industry. Chem Soc Rev 37:123

    Article  CAS  Google Scholar 

  2. 2.

    Wilkes SJ (2002) A short history of ionic liquids - from molten salts to neoteric solvents. Green Chem 4:73

    Article  CAS  Google Scholar 

  3. 3.

    Dietz LM (2006) Ionic liquids as extraction solvents: where do we stand? Sep Sci Technol 41:2047

    Article  CAS  Google Scholar 

  4. 4.

    Binnemans K (2007) Lanthanides and actinides in ionic liquids. Chem Rev 107:2592

    Article  CAS  Google Scholar 

  5. 5.

    Mudring VA, Tang S (2010) Ionic liquids for lanthanide and actinide chemistry. Eur J Inorg Chem. 2569

  6. 6.

    Lohithakshan VK, Aggarwal KS (2008) Solvent extraction studies of Pu(IV) with CMPO in 1-octyl3-methylimidazolium hexafluorophosphate (C8mimPF6) room temperature ionic liquid (RTIL). Radiochim Acta 96:93

    Article  CAS  Google Scholar 

  7. 7.

    Zuo Y, Liu Y, Chen J, Li QD (2008) The separation of Cerium(IV) from nitric acid solutions containing thorium(IV) and lanthanides(III) using pure [C8mim]PF6 as extracting phase. Ind Eng Chem Res 47:2349

    Article  CAS  Google Scholar 

  8. 8.

    Swatloski PR, Holbrey DJ, Rogers DR (2003) Ionic liquids are not always green: hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate. Green Chem 5:361

    Article  CAS  Google Scholar 

  9. 9.

    Germani R, Mancini VM, Savelli G, Spreti N (2007) Mercury extraction by ionic liquids: temperature and alkyl chain length effect. Tetrahedron Lett 48:1767

    Article  CAS  Google Scholar 

  10. 10.

    Papaiconomou N, Lee MJ, Salminen J, von Stosch M, Prausnitz MJ (2008) Selective extraction of copper, mercury, silver and palladium ions from water using hydrophobic ionic liquids. Ind Eng Chem Res 47:5080

    Article  CAS  Google Scholar 

  11. 11.

    Holbrey DJ, Visser EA, Spear KS, Reichert MW, Swatloski PR, Broker AG, Rogers DR (2003) Mercury(II) partitioning from aqueous solutions with a new, hydrophobic ethylene-glycol functionalized bis-imidazolium ionic liquid. Green Chem 5:129

    Article  CAS  Google Scholar 

  12. 12.

    Visser EA, Swatloski PR, Reichert MW, Mayton R, Sheff S, Wierzbicki A, Davis HJ, Rogers DR (2001) Task-specific ionic liquids for the extraction of metal ions from aqueous solutions. Chem Commun. 135

  13. 13.

    Kozonoi N, Ikeda Y (2007) Extraction mechanism of metal ion from aqueous solution to the hydrophobic ionic liquid 1-butyl-3-methylimidazolium nonafluorobutanesulfonate. Monatsh Chem 138:1145

    Article  CAS  Google Scholar 

  14. 14.

    Rout A, Venkatesan K, Srinivasan VK, Rao PVR (2010) Unusual extraction of plutonium(IV) from uranium(VI) and americium(III) using phosphonate based task specific ionic liquid. Radiochim Acta 98:459

    Article  CAS  Google Scholar 

  15. 15.

    Ouadi A, Gadenne B, Hesemann P, Moreau EJJ, Billard I, Gaillard C, Mekki S, Moutiers G (2006) Task-specific ionic liquids bearing 2-hydroxybenzylamine units: synthesis and americium extraction studies. Chem Eur J 12:3074

    Article  CAS  Google Scholar 

  16. 16.

    Ouadi A, Klimchuk O, Gaillard C, Billard I (2007) Solvent extraction of U(VI) by task-specific ionic liquids bearing phosphoryl groups. Green Chem 9:1160

    Article  CAS  Google Scholar 

  17. 17.

    Dai S, Ju HY, Barnes EC (1999) Solvent extraction of strontium nitrate by a crown ether using room temperature ionic liquids. J Chem Soc Dalton Trans. 1201

  18. 18.

    Rios DL PA, Hernadez-Fernandez JF, Lozano JL, Moreno IJ, Godinez C (2010) Removal of metal ions from aqueous solutions by extraction with ionic liquids. J Chem Eng Data 55:605

    Article  Google Scholar 

  19. 19.

    Egorov MV, Djigailo ID, Momotenko SD, Chernyshov VD, Torocheshnikova II, Smirnova VS, Pletnev VI (2010) Task specific ionic liquid trioctylmethylammonium salicylate as extraction solvent for transition metal ions. Talanta 80:1177

    Article  CAS  Google Scholar 

  20. 20.

    Dietz M, Dzielawa AJ (2001) Ion-exchange as a mode of cation transfer into room-temperature ionic liquids containing crown ethers: implications for the 'greenness' of ionic liquids as diluents in liquid-liquid extraction. Chem Commun. 2124

  21. 21.

    Dietz LM, Dzielawa AJ, Laszak I, Young AB, Jensen PM (2003) Influence of solvent structural variation on the mechanism of facilitated ion transfer into room-temperature ionic liquids. Green Chem 5:682

    Article  CAS  Google Scholar 

  22. 22.

    Luo H, Dai S, Bonnesen VP, Buchanan CA, Holbrey DJ, Bridges JN, Rogers DR (2004) Extraction of cesium ions from aqueous solutions using calix[4]arene-(tert-octylbenzo-crown-6) in ionic liquids. Anal Chem 76:3078

    Article  CAS  Google Scholar 

  23. 23.

    Dietz LM, Stepinski CD (2008) Anion concentration-dependent partitioning mechanism in the extraction of uranium into room-temperature ionic liquids. Talanta 75:598

    Article  CAS  Google Scholar 

  24. 24.

    Billard I, Ouadi A, Jobin E, Champion J, Gaillard C, Georg S (2010) Understanding extraction mechanism in ionic liquids: UO 2+2 /HNO3/TBP/C4-mimTf2N as a case study. submitted

  25. 25.

    Schultz WW, Navratil DJ (1984) Science and technology of tributyl phosphate, vol I. CRC Press, Boca Raton

    Google Scholar 

  26. 26.

    Visser EA, Rogers DR (2003) Room-temperature ionic liquids: new solvents for f-element separations and associated solution chemistry. J Solid State Chem 171:109

    Article  CAS  Google Scholar 

  27. 27.

    Rout A, Venkatesan AK, Srinivasan VK, Rao VRP (2009) Extraction of americium(III) from nitric acid medium by CMPO-TBP extractants in ionic liquid diluent. Radiochim Acta 97:719

    Article  CAS  Google Scholar 

  28. 28.

    Nakashima K, Kubota F, Maruyama T, Goto M (2005) Feasibility of ionic liquids as alternative separation media for industrial solvent extraction processes. Ind Eng Chem Res 44:4368

    Article  CAS  Google Scholar 

  29. 29.

    Shimojo K, Kurahashi K, Naganawa H (2008) Extraction behavior of lanthanides using diglycolamide derivative TODGA in ionic liquids. Dalton Trans. 5083

  30. 30.

    Wei TG, Yang Z, Chen JC (2003) Room temperature ionic liquid as a novel medium for liquid–liquid extraction of metal ions. Anal Chim Acta 488:183

    Article  CAS  Google Scholar 

  31. 31.

    Stepinski CD, Jensen PM, Dzielawa AJ, Dietz LM (2005) Synergistic effects in the facilitated transfer of metal ions into room-temperature ionic liquids. Green Chem 7:151

    Article  CAS  Google Scholar 

  32. 32.

    Chun S, Dzyuba VS, Bartsch AR, Adams M (2001) Influence of structural variation in room-temperature ionic liquids on the selectivity and efficiency of competitive alkali metal salt extraction by a crown-ether. Anal Chem 73:3737

    Article  CAS  Google Scholar 

  33. 33.

    Luo H, Dai S, Bonnesen VP, Haverlock JT, Moyer AB, Buchanan CA (2006) A striking effect of ionic liquid anions in the extraction of Sr2+ and Cs+ by dicylcohexano-18-crown-6. Solv Extr Ion Exch 24:19

    Article  CAS  Google Scholar 

  34. 34.

    Luo H, Dai S, Bonnesen VP (2004) Solvent extraction of Sr2+ and Cs+ based on room temperature ionic liquids containing monoaza-substituted crown ethers. Anal Chem 76:2773

    Article  CAS  Google Scholar 

  35. 35.

    Dietz LM, Jakab S, Yamato K, Bartsch AR (2008) Stereochemical effects on the mode of facilitated ion transfer into room-temperature ionic liquids. Green Chem 10:174

    Article  CAS  Google Scholar 

  36. 36.

    Freire GM, Santos FLMNB, Fernandes MA, Coutinho PJA, Marrucho MI (2007) An overview of the mutual solubilities of water-imidazolium based ionic liquids systems. Fluid Phase Equilib 261:449

    Article  CAS  Google Scholar 

  37. 37.

    Visser EA, Swatloski PR, Reichert MW, Griffin TS, Rogers DR (2000) Traditional extractants in nontraditional solvents: groups 1 and 2 extraction by crown-ethers in room-temperature ionic liquids. Ind Eng Chem Res 39:3596

    Article  CAS  Google Scholar 

  38. 38.

    Billard I, Gaillard C, Hennig C (2007) Dissolution of UO2, UO3 and of some lanthanide oxides in BumimTf2N: effect of acid and water and formation of UO2(NO3)3-. Dalton Trans. 4214

  39. 39.

    Toh ISL, McFarlane J, Tsouris C, DePaoli WD, Luo H, Dai S (2006) Room-temperature ionic liquids in liquid–liquid extraction: effects of solubility in aqueous solution on surface properties. Solv Extr Ion Exch 24:33

    Article  CAS  Google Scholar 

  40. 40.

    Gutowski EK, Broker AG, Willauer DH, Huddleston GJ, Swatloski PR, Holbrey DJ, Rogers DR (2003) Controlling the aqueous miscibility of ionic liquids: aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle, metathesis and separations. J Am Chem Soc 125:6632

    Article  CAS  Google Scholar 

  41. 41.

    Visser EA, Jensen PM, Laszak I, Nash LK, Choppin RG, Rogers DR (2003) Uranyl coordination environment in hydrophobic ionic liquids: an in situ investigation. Inorg Chem 42:2197

    Article  CAS  Google Scholar 

  42. 42.

    Jensen PM, Dzielawa AJ, Rickert P, Dietz LM (2002) EXAFS investigations of the mechanism of facilitated ion transfer into a room-temperature ionic liquid. J Am Chem Soc 124:10664

    Article  CAS  Google Scholar 

  43. 43.

    Jensen PM, Neuefeind J, Beitz VJ, Skanthakumar S, Soderholm L (2003) Mechanisms of metal ion transfer into room-temperature ionic liquids: the role of anion exchange. J Am Chem Soc 125:15466

    Article  CAS  Google Scholar 

  44. 44.

    Billard I, Gaillard C (2009) Actinide and lanthanide speciation in imidazolium-based ionic liquids. Radiochim Acta 97:355

    Article  CAS  Google Scholar 

  45. 45.

    Cocalia AV, Jensen PM, Holbrey DJ, Spear KS, Stepinski CD, Rogers DR (2005) Identical extraction behavior and coordination of trivalent or hexavalent f-element cation using ionic liquid and molecular solvents. Dalton Trans. 1966

  46. 46.

    Gupta KK, Achuthan VP, Ramanujam A, Mathur NJ (2003) Effect of diluents on the extraction of Sr2+ from HNO3 solutions with dicyclohexano-18-crown-6. Solv Extr Ion Exch 21:53

    Article  CAS  Google Scholar 

  47. 47.

    Dietz LM, Stepinski CD (2005) A ternary mechanism for the facilitated transfer of metal ions into room temperature ionic liquids: implications for the greenness of RTILs as extraction solvents. Green Chem 7:747

    Article  CAS  Google Scholar 

  48. 48.

    Hirayama N, Deguchi M, Kawasumi H, Honjo T (2005) Use of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids as chelate extraction solvent with 4, 4, 4-trifluoro-1-(2-thienyl)-1, 3-butanedione. Talanta 65:255

    Article  CAS  Google Scholar 

  49. 49.

    Shimojo K, Goto M (2004) Solvent extraction and stripping of silver ions in room-temperature ionic liquids containing calixarenes. Anal Chem 76:5039

    Article  CAS  Google Scholar 

  50. 50.

    Wei TG, Chen CJ, Yang Z (2003) Studies on liquid–liquid extraction of copper ion with room temperature ionic liquid. J Chin Chem Soc 50:1123

    CAS  Google Scholar 

  51. 51.

    Odinets LI, Sharova VE, Artyshin IO, Lyssenko AK, Nelyubina VY, Myasoedova VG, Molochnikova PN, Zakharchenro AE (2010) Novel class of functionalized ionic liquids with grafted CMPO-moieties for actinides and rare-earth elements recovery. Dalton Trans 39:4170

    Article  CAS  Google Scholar 

  52. 52.

    Ouadi A, Jobin E, Klimchuk O, Gaillard C, Billard I (2010) CMPO functionalized task specific ionic liquid for actinide and lanthanide extraction. submitted

  53. 53.

    Luo H, Dai S, Bonnesen VP, Buchanan CA (2006) Separation of fission products based on ionic liquids: task specific ionic liquids containing an aza-crown ether fragment. J Alloys Compd 418:195

    Article  CAS  Google Scholar 

  54. 54.

    Miroshnichenko S, Ternova D, Billard I, Ouadi A, Klimchuk O, Kalchenko V (2010) Synthesis of new calixarene-phosphine oxides and their extraction properties in ionic liquids. Phosphorus, sulfur and silicon and the related elements accepted

  55. 55.

    Jin MC, Shreeve MJ (2004) Bridged di(alkyl- and 4, 4, 4-trifluorobutylimidazolium) quaternary salts based on p-tert-butylcalix[4]arene. Inorg Chem 43:7532

    Article  CAS  Google Scholar 

  56. 56.

    Giernoth R (2010) Task specific ionic liquids. Angew Chem Int Ed 49:2834

    Article  CAS  Google Scholar 

  57. 57.

    Davis HJ (2004) Task-specific ionic liquids. Chem Lett 33:1072

    Article  CAS  Google Scholar 

  58. 58.

    Zhao D, Fei Z, Ohlin AC, Laurenczy G, Dyson JP (2004) Dual-functionalised ionic liquids: synthesis and characterization of imidazolium salts with a nitrile functionalised anion. Chem Commun. 2500

  59. 59.

    Sun X, Ji Y, Chen J, Li D (2010) An engineering purpose preparation strategy for ammonium type ionic liquid with high purity. AIChE 56:989

    CAS  Google Scholar 

  60. 60.

    Tindale JJ, Hartlen DK, Alizadeh A, Workentin SM, Ragogna JP (2010) Maleimide modified phosphonium ionic liquids a template towards multi task specific ionic liquids. Chem Eur J 16:9068

    Article  CAS  Google Scholar 

  61. 61.

    Lenarcik B, Kierzkowska A (2006) The influence of alkyl chain length and steric effect on extraction of zinc(II) complexes with 1-alkyl-2-methylimidazoles. Solv Extr Ion Exch 24:433

    Article  CAS  Google Scholar 

  62. 62.

    Mehdi H, Binnemans K, Ecke VK, Meervelt VL, Nockemann P (2010) Hydrophobic ionic liquids with strongly coordinating anions. Chem Commun 46:234

    Article  CAS  Google Scholar 

  63. 63.

    Katritsky RA, Singh S, Kirichenko K, Smiglak M, Holbrey DJ, Reichert MW, Spear KS, Rogers DR (2006) In search of ionic liquids incorporating azolate anions. Chem Eur J 12:4630

    Article  Google Scholar 

  64. 64.

    Chaumont A, Wipff G (2003) Solvation of M3+ lanthanide cations in room-temperature ionic liquids. A molecular dynamics investigation. Phys Chem Chem Phys 5:3481

    Article  CAS  Google Scholar 

  65. 65.

    Schurhammer R, Wipff G (2007) Solvation of uranium hexachloro complexes in room temperature ionic liquids. A molecular dynamics investigation in two liquids. J Phys Chem B 111:4659

    Article  CAS  Google Scholar 

  66. 66.

    Chaumont A, Wipff G (2007) Solvation of big spherical solutes in room temperature ionic liquids and at their interface: a molecular dynamics simulation study. J Mol Liq 131/132:36

    Article  Google Scholar 

  67. 67.

    Sun X, Ji Y, Chen J, Ma J (2009) Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation. J Rare Earths 27:932

    Article  Google Scholar 

  68. 68.

    Mekki S, Wai MC, Billard I, Moutiers G, Yen HC, Wang SJ, Ouadi A, Gaillard C, Hesemann P (2005) Cu(II) extraction by supercritical fluid carbon dioxide from a room temperature ionic liquid using fluorinated b-diketones. Green Chem 7:421

    Article  CAS  Google Scholar 

  69. 69.

    Mekki S, Wai MC, Billard I, Moutiers G, Burt J, Yen HC, Wang SJ, Gaillard C, Ouadi A, Hesemann P (2006) Extraction of lanthanides from aqueous solutions using room temperature ionic liquids and supercritical carbon dioxide in conjunction. Chem Eur J 12:1760

    Article  CAS  Google Scholar 

  70. 70.

    Wang SJ, Sheaff NC, Yoon B, Addleman SR, Wai MC (2009) Extraction of uranium from aqueous solutions by using ionic liquid and supercritical carbon dioxide in conjunction. Chem Eur J 15:4458

    Article  CAS  Google Scholar 

  71. 71.

    Sun X, Ji Y, Hu F, He B, Chen J, Li D (2010) The inner synergistic effect of bifunctional ionic liquid extractant for solvent extraction. Talanta 81:1877

    Article  CAS  Google Scholar 

  72. 72.

    Turanov NA, Karandashev KV, Baulin EV (2008) Effect of ionic liquids on the extraction of rare earth elements by bidendate neutral organophosphorus compounds from chloride solutions. Russ J Inorg Chem 53:970

    Article  Google Scholar 

  73. 73.

    Stepinski CD, Vandegrift FG, Shkrob AI, Wishart FJ, Kerr K, Dietz M, Qadah DDT, Garvey LS (2010) Extraction of tetra-oxo anions into a hydrophobic ionic liquid based solvent without concomitant ion exchange. Ind Eng Chem Res 49:5863

    Article  CAS  Google Scholar 

  74. 74.

    Li W, Zhang Z, Zhang J, Han B, Wang B, Hou M, Xie Y (2006) Micropolarity and aggregation behavior in ionic liquid + organic solvent solutions. Fluid Phase Equilib 248:211

    Article  CAS  Google Scholar 

  75. 75.

    Deetlefs M, Hardacre C, Nieuwenhuyzen M, Sheppard O, Soper KA (2005) Structure of ionic liquid-benzene mixtures. J Phys Chem B 109:1593

    Article  CAS  Google Scholar 

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Correspondence to Isabelle Billard.

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Published in the special issue Radioanalytics - Dedicated to Marie Skłodowska-Curie with Guest Editors Boguslaw Buszewski and Philippe Garrigues.

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Billard, I., Ouadi, A. & Gaillard, C. Liquid–liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding. Anal Bioanal Chem 400, 1555–1566 (2011). https://doi.org/10.1007/s00216-010-4478-x

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Keywords

  • Actinides
  • Lanthanides
  • Liquid–liquid extraction
  • Ionic liquids