TS-BTPhen as a promising hydrophilic complexing agent for selective Am(III) separation by solvent extraction

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Abstract

The novel hydrophilic back-extraction agent TS-BTPhen (3,3ʹ,3ʺ,3ʹʺ-[3-(1,10-phenanthroline-2,9-diyl)-1,2,4-triazine-5,5,6,6-tetrayl]tetrabenzenesulfonic acid) was tested for its selectivity towards Am(III) over Cm(III) and Eu(III) with a TODGA (N,N,Nʹ,Nʹ-tetraoctyldiglycolamide) based solvent. Batch experiments were carried out using TS-BTPhen dissolved in aqueous nitric acid solution with tracers of 152Eu, 241Am and 244Cm. A significant increase of the separation factor for Cm over Am from SFCm/Am = 1.6 up to SFCm/Am = 3.3 was observed compared to the use of a TODGA-nitric acid system alone. Furthermore, stripping was possible at high nitric acid concentrations (0.6-0.7 mol/L) resulting in a low sensitivity to acidity changes. The influence of the TS-BTPhen concentration was analyzed. A slope of -2 was expected taking into account literature stoichiometries of the lipophilic analogue CyMe4BTPhen. However, a slope of -1 was found. Batch stripping kinetics showed fast kinetics for the trivalent actinides. As an alternative organic ligand the methylated TODGA derivate Me-TODGA (2-methyl-N,N,Nʹ,Nʹ-tetraoctyldiglycolamide) was tested in combination with the hydrophilic TS-BTPhen. The Am(III) separation was achieved at even higher nitric acid concentrations compared to TODGA.

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  • 1. NEA. (2011). Potential benefi ts and impacts of advanced nuclear fuel cycles with actinide partitioning and transmutation. Issy-les-Moulineaux France: OECD-NEA. (NEA no. 6894).

  • 2. McKibben J. M. (1983). Chemistry of the PUREX process. In Americal Chemical Society 135th National Meeting 10 March 1983. Seattle Washington USA.

  • 3. Poinssot C. Rostaing C. Baron P. Warin D. & Boullis B. (2012). Main results of the French Program on Partitioning of Minor Actinides a Significant Improvement Towards Nuclear Waste Reduction. Procedia Chem. 7 358-366. DOI: 10.1016/j. proche.2012.10.056.

  • 4. Serrano-Purroy D. Baron P. Christiansen B. Malmbeck R. Sorel C. & Glatz J. P. (2005). Recovery of minor actinides from HLLW using the DIAMEX process. Radiochim. Acta 93 351-355. DOI: 10.1524/ ract.93.6.351.65642.

  • 5. Magnusson D. Christiansen B. Foreman M. R. S. Geist A. Glatz J. P. Malmbeck R. Modolo G. Serrano-Purroy D. & Sorel C. (2009). Demonstration of a SANEX process in centrifugal contactors using the CyMe4-BTBP molecule on a genuine fuel solution. Solvent Extr. Ion Exch. 27 97-106. DOI: 10.1080/07366290802672204.

  • 6. Geist A. Hill C. Modolo G. Foreman M. R. S. J. Weigl M. Gompper K. Hudson M. J. & Madic C. (2006). 66ʹ-Bis(5588-tetramethyl-5678- tetrahydro-benzo[124]triazin-3-yl)[22ʹ]bipyridine an effective extracting agent for the separation of americium(III) and curium(III) from the lanthanides. Solvent Extr. Ion Exch. 24 463-483. DOI: 10.1080/07366290600761936.

  • 7. Modolo G. Kluxen P. & Geist A. (2010). Demonstration of the LUCA process for the separation of americium(III) from curium(III) californium(III) and lanthanides(III) in acidic solution using a synergistic mixture of bis(chlorophenyl)dithiophosphinic acid and tris(2-ethylhexyl)phosphate. Radiochim. Acta 98 193-201. DOI: 10.1524/ract.2010.1708.

  • 8. Modolo G. Wilden A. Geist A. Magnusson D. & Malmbeck R. (2012). A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate. Radiochim. Acta 100 715-725. DOI: 10.1524/ract.2012.1962.

  • 9. Wilden A. Modolo G. Kaufholz P. Sadowski F. Lange S. Sypula M. Magnusson D. Muellich U. Geist A. & Bosbach D. (2015). Laboratory-scale counter-current centrifugal contactor demonstration of an innovative-SANEX process using a water soluble BTP. Solvent Extr. Ion Exch. 33 91-108. DOI: 10.1080/07366299.2014.952532.

  • 10. Wilden A. Modolo G. Schreinemachers C. Sadowski F. Lange S. Sypula M. Magnusson D. Geist A. Lewis F. W. Harwood L. M. & Hudson M. J. (2013). Direct selective extraction of actinides(III) from PUREX raffi nate using a mixture of CyMe4BTBP and TODGA as 1-cycle SANEX solvent. Part III: Demonstration of a laboratory-scale counter-current centrifugal contactor process. Solvent Extr. Ion Exch. 31 519-537. DOI: 10.1080/07366299.2013.775890.

  • 11. Rostaing C. Poinssot C. Warin D. Baron P. & Lorrain B. (2012). Development and validation of the EXAm separation process for single Am recycling. Procedia Chem. 7 367-373. DOI: 10.1016/j. proche.2012.10.057.

  • 12. Montuir M. Pacary V. Sorel C. Baron P. Bollesteros M. -J. Costenoble S. Espinoux D. Hérès X. & Rostaing C. (2012). Sensitivity of americium and curium splitting fl owsheet and running procedure. Procedia Chem. 7 275-281. DOI: 10.1016/j. proche.2012.10.044.

  • 13. Geist A. Müllich U. Magnusson D. Kaden P. Modolo G. Wilden A. & Zevaco T. (2012). Actinide(III)/lanthanide(III) separation via selective aqueous complexation of actinides(III) using a hydrophilic 26-bis(124-triazin-3-yl)-pyridine in nitric acid. Solvent Extr. Ion Exch. 30 433-444. DOI: 10.1080/07366299.2012.671111.

  • 14. Bell K. Geist A. McLachlan F. Modolo G. Taylor R. & Wilden A. (2012). Nitric acid extraction into TODGA. Procedia Chem. 7 152-159. DOI: 10.1016/j.proche.2012.10.026.

  • 15. Bourg S. Hill C. Caravaca C. Rhodes C. Ekberg C. Taylor R. Geist A. Modolo G. Cassayre L. Malmbeck R. Harrison M. de Angelis G. Espartero A. Bouvet S. & Ouvrier N. (2011). ACSEPT - Partitioning technologies and actinide science: Towards pilot facilities in Europe. Nucl. Eng. Des. 241 3427-3435. DOI: 10.1016/j.nucengdes.2011.03.011.

  • 16. Lewis F. W. Harwood L. M. Hudson M. J. Drew M. G. B. Hubscher-Bruder V. Videva V. Arnaud-Neu F. Stamberg K. & Vyas S. (2013). BTBPs versus BTPhens: Some reasons for their differences in properties concerning the partitioning of minor actinides and the advantages of BTPhens. Inorg. Chem. 52 4993-5005. DOI: 10.1021/ic3026842.

  • 17. Iqbal M. Huskens J. Verboom W. Sypula M. & Modolo G. (2010). Synthesis and Am/Eu extraction of novel TODGA derivatives. Supramol. Chem. 22 827-837. DOI: 10.1080/10610278.2010.506553.

  • 18. Lewis F. W. Harwood L. M. Hudson M. J. Geist A. Kozhevnikov V. N. Distler P. & John J. (2015). Hydrophilic sulfonated bis-124-triazine ligands are highly effective reagents for separating actinides(III) from lanthanides(III) via selective formation of aqueous actinide complexes. Chem. Sci. 4812-4821. DOI: 10.1039/C5SC01328C.

  • 19. Modolo G. Asp H. Schreinemachers C. & Vijgen H. (2007). Development of a TODGA based process for partitioning of actinides from a PUREX raffi nate Part I: Batch extraction optimization studies and stability tests. Solvent Extr. Ion Exch. 25 703-721. DOI: 10.1080/07366290701634578.

  • 20. Wilden A. Modolo G. Lange S. Sadowski F. Beele B. B. Skerencak-Frech A. Panak P. J. Iqbal M. Verboom W. Geist A. & Bosbach D. (2014). Modifi ed diglycolamides for the An(III) + Ln(III) co-separation: Evaluation by solvent extraction and time-resolved laser fl uorescence spectroscopy. Solvent Extr. Ion Exch. 32 119-137. DOI: 10.1080/07366299.2013.833791.

  • 21. Nash K. L. Madic C. Mathur J. N. & Lacquement J. (2006). The chemistry of actinide and transactinide elements. In L. R. Morss N. M. Edelstein J. Fuger & J. J. Katz (Eds.) Actinide separation science and technology (Chapter 24 pp. 2622-2798). Dordrecht The Netherlands: Springer.

  • 22. Bremer A. Whittaker D. M. Sharrad C. A. Geist A. & Panak P. J. (2014). Complexation of Cm(III) and Eu(III) with CyMe4-BTPhen and CyMe4-BTBP studied by time resolved laser fluorescence spectroscopy. Dalton Trans. 43 2684-2694. DOI: 10.1039/ c3dt52204k.

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