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

• Autorzy: Kaufholz P. , Sadowski F. , Wilden A. , Modolo G. , Lewis F. W. , Smith A. W. , Harwood L. M.

Identyfikatory

DOI

10.1515/nuka-2015-0120

• Konferencja: International Workshop “Towards safe and optimized separation processes, a challenge for nuclear scientists” (FP7 European Collaborative Project SACSESS) (22-24.04.2015 ; Warsaw, Poland)
• Języki publikacji: EN

Abstrakty

EN

The novel hydrophilic back-extraction agent TS-BTPhen (3,3',3'',3'''-[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,N',N'-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 signifi cant 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 infl uence 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,N',N'-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.

Słowa kluczowe

EN

Am-Cm separation; TODGA; TS-BTPhen; liquid-liquid extraction

• Wydawca: Institute of Nuclear Chemistry and Technology
• Czasopismo: Nukleonika
• Rocznik: 2015
• Tom: Vol. 60, No. 4, part 2
• Strony: 815--820
• Opis fizyczny: Bibliogr. 22 poz., rys.

Twórcy

autor

Kaufholz P.

• Institut für Energie- und Klimaforschung, Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Forschungszentrum Jülich GmbH (FZJ), 524 25 Jülich, Germany, Tel.: [phone], Fax: [phone]

autor

Sadowski F.

• Institut für Energie- und Klimaforschung, Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Forschungszentrum Jülich GmbH (FZJ), 524 25 Jülich, Germany, Tel.: [phone], Fax: [phone]

autor

Wilden A.

• Institut für Energie- und Klimaforschung, Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Forschungszentrum Jülich GmbH (FZJ), 524 25 Jülich, Germany, Tel.: [phone], Fax: [phone]

autor

Modolo G.

• Institut für Energie- und Klimaforschung, Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Forschungszentrum Jülich GmbH (FZJ), 524 25 Jülich, Germany, Tel.: [phone], Fax: [phone]

autor

Lewis F. W.

• Department of Applied Sciences, Faculty of Health and Life Sciences, Northumbria University, Newcastle upon Tyne NE1 8ST, United Kingdom

autor

Smith A. W.

• Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, United Kingdom

autor

Harwood L. M.

• Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, United Kingdom

Bibliografia

• 1. NEA. (2011). Potential benefits 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). 6,6'-Bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo[1,2,4]triazin-3-yl)[2,2']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). Demonstrationof 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 raffinate 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 flowsheet 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 2,6-bis(1,2,4-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-1,2,4-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 raffinate 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). Modified diglycolamides for the An(III) + Ln(III) co-separation: Evaluation by solvent extractionand time-resolved laser fluorescence 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 fl uorescence spectroscopy. Dalton Trans., 43, 2684–2694. DOI: 10.1039/c3dt52204k.