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Homogenous recycling of transuranium elements from irradiated fast reactor fuel by the EURO-GANEX solvent extraction process

  • Rikard Malmbeck , Daniel Magnusson , Stéphane Bourg , Michael Carrott , Andreas Geist EMAIL logo , Xavier Hérès , Manuel Miguirditchian , Giuseppe Modolo , Udo Müllich , Christian Sorel , Robin Taylor and Andreas Wilden
Published/Copyright: May 27, 2019
Radiochimica Acta
From the journal Radiochimica Acta Volume 107 Issue 9-11

Abstract

The EURO-GANEX process was developed for co-separating transuranium elements from irradiated nuclear fuels. A hot flow-sheet trial was performed in a counter-current centrifugal contactor setup, using a genuine high active feed solution. Irradiated mixed (carbide, nitride) U80Pu20 fast reactor fuel containing 20 % Pu was thermally treated to oxidise it to the oxide form which was then dissolved in HNO3. From this solution uranium was separated to >99.9 % in a primary solvent extraction cycle using 1.0 mol/L DEHiBA (N,N-di(2-ethylhexyl)isobutyramide in TPH (hydrogenated tetrapropene) as the organic phase. The raffinate solution from this process, containing 10 g/L Pu, was further processed in a second cycle of solvent extraction. In this EURO-GANEX flow-sheet, TRU and fission product lanthanides were firstly co-extracted into a solvent composed of 0.2 mol/L TODGA (N,N,N′,N′-tetra-n-octyl diglycolamide) and 0.5 mol/L DMDOHEMA (N,N′-dimethyl-N,N′-dioctyl-2-(2-hexyloxy-ethyl) malonamide) dissolved in Exxsol D80, separating them from most other fission and corrosion products. Subsequently, the TRU were selectively stripped from the collected loaded solvent using a solution containing 0.055 mol/L SO3-Ph-BTP (2,6-bis(5,6-di(3-sulphophenyl)-1,2,4-triazin-3-yl)pyridine tetrasodium salt) and 1 mol/L AHA (acetohydroxamic acid) in 0.5 mol/L HNO3; lanthanides were finally stripped using 0.01 mol/L HNO3. Approximately 99.9 % of the TRU and less than 0.1 % of the lanthanides were found in the product solution, which also contained the major fractions of Zr and Mo.

Keywords: Homogeneous recycling; TRU separation; solvent extraction; centrifugal contactor

Acknowledgement

Financial support for this research was provided by the European Commission via the following projects: ACSEPT (contract № FP7-CP-2007-211267), SACSESS (contract № FP7-Fission-2012-323282) and GENIORS (Horizon 2020 grant agreement № 755171).

References

1. The Nuclear Fuel Report. World Nuclear Association (2017).Search in Google Scholar

2. Poinssot, C., Bourg, S., Ouvrier, N., Combernoux, N., Rostaing, C., Vargas-Gonzalez, M., Bruno, J.: Assessment of the environmental footprint of nuclear energy systems. Comparison between closed and open fuel cycles. Energy 69, 199 (2014).10.1016/j.energy.2014.02.069Search in Google Scholar

3. Poinssot, C., Bourg, S., Boullis, B.: Improving the nuclear energy sustainability by decreasing its environmental footprint. Guidelines from life cycle assessment simulations. Progr. Nucl. Energy 92, 234 (2016).10.1016/j.pnucene.2015.10.012Search in Google Scholar

4. Modolo, G., Geist, A., Miguirditchian, M.: Minor actinide separations in the reprocessing of spent nuclear fuels: recent advances in Europe. In: R. Taylor (Ed.), Reprocessing and Recycling of Spent Nuclear Fuel (2015), Woodhead Publishing, Cambridge, UK.10.1016/B978-1-78242-212-9.00010-1Search in Google Scholar

5. Homogeneous versus heterogeneous recycling of transuranics in fast nuclear reactors. NEA No. 7077, OECD, Nuclear Energy Agency (NEA), Paris (2012).Search in Google Scholar

6. State-of-the-art report on the progress of nuclear fuel cycle chemistry. NEA No. 7267, OECD, Nuclear Energy Agency (NEA), Paris (2018).Search in Google Scholar

7. Aneheim, E., Ekberg, C., Fermvik, A., Foreman, M. R. S., Retegan, T., Skarnemark, G.: A TBP/BTBP-based GANEX separation process. Part 1: feasibility. Solvent Extr. Ion Exc. 28, 437 (2010).10.1080/07366299.2010.480930Search in Google Scholar

8. Aneheim, E., Ekberg, C., Foreman, M. R. S.: A TBP/BTBP-based GANEX separation process – part 3: fission product handling. Solvent Extr. Ion Exc. 31, 237 (2013).10.1080/07366299.2012.757158Search in Google Scholar

9. Halleröd, J., Ekberg, C., Löfström-Engdahl, E., Aneheim, E.: Development of the Chalmers grouped actinide extraction process. Nukleonika 60, 829 (2015).10.1515/nuka-2015-0115Search in Google Scholar

10. Foreman, M. R. S., Hudson, M. J., Drew, M. G. B., Hill, C., Madic, C.: Complexes formed between the quadridentate, heterocyclic molecules 6,6′-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and lanthanides(III): implications for the partitioning of actinides(III) and lanthanides(III). Dalton Trans. 1645 (2006).10.1039/B511321KSearch in Google Scholar PubMed

11. Geist, A., Hill, C., Modolo, G., Foreman, M. R. S. J., Weigl, M., Gompper, K., Hudson, M. J., Madic, C.: 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 Exc. 24, 463 (2006).10.1080/07366290600761936Search in Google Scholar

12. Todd, T. A., Vienna, J. D., Bresee, J. C., Gray, K., Kung, S., Paviet, P.: The United States material recovery and waste form development program. In Proc. Internat. Conf. GLOBAL 2015 (Nuclear Fuel Cycle for a Low-carbon Future), Paris, France, 20–24 September 2015; pp 1664–1669.Search in Google Scholar

13. Runde, W. H., Mincher, B. J.: Higher oxidation states of americium: preparation, characterization and use for separations. Chem. Rev. 111, 5723 (2011).10.1021/cr100181fSearch in Google Scholar PubMed

14. Mincher, B. J., Martin, L. R., Schmitt, N. C.: Diamylamylphosphonate solvent extraction of Am(VI) from nuclear fuel raffinate simulant solution. Solvent Extr. Ion Exc. 30, 445 (2012).10.1080/07366299.2012.671108Search in Google Scholar

15. Adnet, J.-M., Miguirditchian, M., Hill, C., Hérès, X., Lecomte, M., Masson, M., Brossard, P., Baron, P.: Development of new hydrometallurgical processes for actinide recovery: GANEX concept. In Proc. Internat. Conf. GLOBAL 2005 (Nuclear Energy Systems for Future Generation and Global Sustainability), Tsukuba, Japan, 9–13 October 2005.Search in Google Scholar

16. Miguirditchian, M., Chareyre, L., Hérès, X., Hill, C., Baron, P., Masson, M.: GANEX: adaptation of the DIAMEX-SANEX process for the group actinide separation. In Proc. Internat. Conf. GLOBAL 2007 (Advanced Nuclear Fuel Cycles and Systems), Boise, Idaho, USA, 9–13 September 2007.Search in Google Scholar

17. Miguirditchian, M., Sorel, C., Camès, B., Bisel, I., Baron, P., Espinoux, D., Calor, J.-N., Viallesoubranne, C., Lorrain, B., Masson, M.: HA demonstration in the Atalante facility of the GANEX 1st cycle for the selective extraction of uranium from HLW. In Proc. Internat. Conf. GLOBAL 2009 (The Nuclear Fuel Cycle: Sustainable Options & Industrial Perspectives), Paris, France, 6–11 September 2009.Search in Google Scholar

18. Berthon, L., Morel, J. M., Zorz, N., Nicol, C., Virelizier, H., Madic, C.: DIAMEX process for minor actinide partitioning: hydrolytic and radiolytic degradations of malonamide extractants. Sep. Sci. Technol. 36, 709 (2001).10.1081/SS-100103616Search in Google Scholar

19. Miguirditchian, M., Roussel, H., Chareyre, L., Baron, P., Espinoux, D., Calor, J.-N., Viallesoubranne, C., Lorrain, B., Masson, M.: HA demonstration in the Atalante facility of the GANEX 2nd cycle for the grouped TRU extraction. In Proc. Internat. Conf. GLOBAL 2009 (The Nuclear Fuel Cycle: Sustainable Options & Industrial Perspectives), Paris, France, 6–11 September 2009.Search in Google Scholar

20. 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.: ACSEPT – partitioning technologies and actinide science: towards pilot facilities in Europe. Nucl. Eng. Des. 241, 3427 (2011).10.1016/j.nucengdes.2011.03.011Search in Google Scholar

21. Sasaki, Y., Sugo, Y., Suzuki, S., Tachimori, S.: The novel extractants, diglycolamides, for the extraction of lanthanides and actinides in HNO3/n-dodecane system. Solvent Extr. Ion Exc. 19, 91 (2001).10.1081/SEI-100001376Search in Google Scholar

22. Carrott, M., Geist, A., Hérès, X., Lange, S., Malmbeck, R., Miguirditchian, M., Modolo, G., Wilden, A., Taylor, R.: Distribution of plutonium, americium and interfering fission products between nitric acid and a mixed organic phase of TODGA and DMDOHEMA in kerosene, and implications for the design of the “EURO-GANEX” process. Hydrometallurgy 152, 139 (2015).10.1016/j.hydromet.2014.12.019Search in Google Scholar

23. Carrott, M. J., Gregson, C. R., Taylor, R. J.: Neptunium extraction and stability in the GANEX solvent: 0.2 M TODGA/0.5 M DMDOHEMA/kerosene. Solvent Extr. Ion Exc. 31, 463 (2013).10.1080/07366299.2012.735559Search in Google Scholar

24. Bell, K., Geist, A., McLachlan, F., Modolo, G., Taylor, R., Wilden, A.: Nitric acid extraction into TODGA. Proc. Chem. 7, 152 (2012).10.1016/j.proche.2012.10.026Search in Google Scholar

25. Bell, K., Carpentier, C., Carrott, M., Geist, A., Gregson, C., Hérès, X., Magnusson, D., Malmbeck, R., McLachlan, F., Modolo, G., Müllich, U., Sypula, M., Taylor, R., Wilden, A.: Progress towards the development of a new GANEX process. Proc. Chem. 7, 392 (2012).10.1016/j.proche.2012.10.061Search in Google Scholar

26. Brown, J., McLachlan, F., Sarsfield, M., Taylor, R., Modolo, G., Wilden, A.: Plutonium loading of prospective grouped actinide extraction (GANEX) solvent systems based on diglycolamide extractants. Solvent Extr. Ion Exc. 30, 127 (2012).10.1080/07366299.2011.609378Search in Google Scholar

27. Cuillerdier, C., Musikas, C., Hoel, P., Nigond, L., Vitart, X.: Malonamides as new extractants for nuclear waste solutions. Sep. Sci. Technol. 26, 1229 (1991).10.1080/01496399108050526Search in Google Scholar

28. Sypula, M., Wilden, A., Schreinemachers, C., Malmbeck, R., Geist, A., Taylor, R., Modolo, G.: Use of polyaminocarboxylic acids as hydrophilic masking agents for fission products in actinide partitioning processes. Solvent Extr. Ion Exc. 30, 748 (2012).10.1080/07366299.2012.700591Search in Google Scholar

29. Geist, A., Müllich, U., Magnusson, D., Kaden, P., Modolo, G., Wilden, A., Zevaco, T.: 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 Exc. 30, 433 (2012).10.1080/07366299.2012.671111Search in Google Scholar

30. Carrott, M. J., Fox, O. D., Maher, C. J., Mason, C., Taylor, R. J., Sinkov, S. I., Choppin, G. R.: Solvent extraction behavior of plutonium (IV) ions in the presence of simple hydroxamic acids. Solvent Extr. Ion Exc. 25, 723 (2007).10.1080/07366290701634560Search in Google Scholar

31. Carrott, M., Bell, K., Brown, J., Geist, A., Gregson, C., Hérès, X., Maher, C., Malmbeck, R., Mason, C., Modolo, G., Müllich, U., Sarsfield, M., Wilden, A., Taylor, R.: Development of a new flowsheet for co-separating the transuranic actinides: the “EURO-GANEX” process. Solvent Extr. Ion Exc. 32, 447 (2014).10.1080/07366299.2014.896580Search in Google Scholar

32. Carrott, M., Maher, C., Mason, C., Sarsfield, M., Taylor, R.: “TRU-SANEX”: a variation on the EURO-GANEX and i-SANEX processes for heterogeneous recycling of actinides Np-Cm. Sep. Sci. Technol. 51, 2198 (2016).10.1080/01496395.2016.1202979Search in Google Scholar

33. Peakall, K. A., Antill, J. E.: Oxidation of uranium dioxide in air at 350–1000 °C. J. Nucl. Mater. 2, 194 (1960).10.1016/0022-3115(60)90051-9Search in Google Scholar

34. Bisson, J., Dinh, B., Huron, P., Huel, C.: PAREX, a numerical code in the service of La Hague plant operations. Proc. Chem. 21, 117 (2016).10.1016/j.proche.2016.10.017Search in Google Scholar

35. Miguirditchian, M., Sorel, C., Camès, B., Bisel, I., Baron, P.: Extraction of uranium(VI) by N,N’-di-(2-ethylhexyl)isobutyramide (DEHIBA): from the batch experimental data to the countercurrent process. Proc. Internat. Solvent Extr. Conf. (ISEC 2008), Moyer, B. A., Ed. Tucson, Arizona, USA, 15–19 September 2008.Search in Google Scholar

36. Sorel, C., Montuir, M., Balaguer, C., Baron, P., Dinh, B., Hérès, X., Pacary, V., Roussel, H.: A powerful tool to model and simulate solvent extraction operations. Proc. Internat. Solvent Extr. Conf. (ISEC 2011), Santiago, Chile, 3–7 October 2011.Search in Google Scholar

37. Moeyaert, P., Abiad, L., Sorel, C., Dufrêche, J. F., Ruas, A., Moisy, P., Miguirditchian, M.: Density and activity of pertechnetic acid aqueous solutions at T=298.15 K. J. Chem. Thermodyn. 91, 94 (2015).10.1016/j.jct.2015.07.006Search in Google Scholar

38. Moeyaert, P., Dumas, T., Guillaumont, D., Kvashnina, K., Sorel, C., Miguirditchian, M., Moisy, P., Dufrêche, J.-F.: Modeling and speciation study of uranium(VI) and technetium(VII) coextraction with DEHiBA. Inorg. Chem. 55, 6511 (2016).10.1021/acs.inorgchem.6b00595Search in Google Scholar PubMed

39. Drake, V. A.: Extraction chemistry of neptunium. In: W. W. Schulz, L. L. Burger, J. D. Navratil, K. P. Bender (Eds.), Science and Technology of Tributyl Phosphate (1990), CRC Press, Boca Raton, Florida.Search in Google Scholar

40. Moulin, J. P.: On the kinetics of redox reaction of neptunium in nitric acid – oxidation of neptunium(IV) to neptunium(V) – oxidation of neptunium(V) to neptunium(VI) by nitric acid, catalyzed by nitrous acid. CEA-R-4912, Commissariat à l’Énergie Atomique, France (1978).Search in Google Scholar

41. Chen, H., Taylor, R., Jobson, M., Woodhead, D., Masters, A.: Development and validation of a flowsheet simulation model for neptunium extraction in an advanced PUREX process. Solvent Extr. Ion Exc. 34, 297 (2016).10.1080/07366299.2016.1185853Search in Google Scholar

42. Chen, H., Taylor, R. J., Jobson, M., Woodhead, D. A., Boxall, C., Masters, A. J., Edwards, S.: Simulation of neptunium extraction in an advanced PUREX process – model improvement. Solvent Extr. Ion Exc. 35, 1 (2017).10.1080/07366299.2016.1273684Search in Google Scholar

43. Moeyaert, P., Miguirditchian, M., Masson, M., Dinh, B., Hérès, X., De Sio, S., Sorel, C.: Experimental and modelling study of ruthenium extraction with tri-n-butylphosphate in the PUREX process. Chem. Eng. Sci. 158, 580 (2017).10.1016/j.ces.2016.10.035Search in Google Scholar

44. Modolo, G., Asp, H., Vijgen, H., Malmbeck, R., Magnusson, D., Sorel, C.: Demonstration of a TODGA-based continuous counter-current extraction process for the partitioning of actinides from a simulated PUREX raffinate, part II: centrifugal contactor runs. Solvent Extr. Ion Exc. 26, 62 (2008).10.1080/07366290701784175Search in Google Scholar

45. Magnusson, D., Christiansen, B., Glatz, J. P., Malmbeck, R., Modolo, G., Serrano-Purroy, D., Sorel, C.: Demonstration of a TODGA based extraction process for the partitioning of minor actinides from a PUREX raffinate. Part III: centrifugal contactor run using genuine fuel solution. Solvent Extr. Ion Exc. 27, 26 (2009).10.1080/07366290802544726Search in Google Scholar

46. Serrano-Purroy, D., Baron, P., Christiansen, B., Malmbeck, R., Sorel, C., Glatz, J. P.: Recovery of minor actinides from HLLW using the DIAMEX process. Radiochim. Acta 93, 351 (2005).10.1524/ract.93.6.351.65642Search in Google Scholar

47. Geist, A., Gompper, K.: Miniature DIAMEX processes in a hollow fibre module micro-plant: process development and optimisation. Radiochim. Acta 96, 211 (2008).10.1524/ract.2008.1481Search in Google Scholar

48. Malmbeck, R., Magnusson, D., Geist, A.: Modified diglycolamides for grouped actinide separation. J. Radioanal. Nucl. Chem. 314, 2531 (2017).10.1007/s10967-017-5614-2Search in Google Scholar

49. Madic, C., Hudson, M. J.: High-level liquid waste partitioning by means of completely incinerable extractants. EUR 18038, European Commission, Luxembourg (1998).Search in Google Scholar

50. Macerata, E., Mossini, E., Scaravaggi, S., Mariani, M., Mele, A., Panzeri, W., Boubals, N., Berthon, L., Charbonnel, M.-C., Sansone, F., Arduini, A., Casnati, A.: Hydrophilic clicked 2,6-bis-triazolyl-pyridines endowed with high actinide selectivity and radiochemical stability: toward a closed nuclear fuel cycle. J. Amer. Chem. Soc. 138, 7232 (2016).10.1021/jacs.6b03106Search in Google Scholar PubMed

51. Wagner, C., Mossini, E., Macerata, E., Mariani, M., Arduini, A., Casnati, A., Geist, A., Panak, P. J.: Time-resolved laser fluorescence spectroscopy study of the coordination chemistry of a hydrophilic CHON [1,2,3-triazol-4-yl]pyridine ligand with Cm(III) and Eu(III). Inorg. Chem. 56, 2135 (2017).10.1021/acs.inorgchem.6b02788Search in Google Scholar PubMed

52. Traister, G. L., Schilt, A. A.: Water-soluble sulfonated chromogenic reagents of the ferroin type and determination of iron and copper in water, blood serum, and beer with the tetraammonium salt of 2,4-bis(5,6-diphenyl-1,2,4-triazin-3-yl)pyridinetetrasulfonic acid. Anal. Chem. 48, 1216 (1976).10.1021/ac50002a039Search in Google Scholar PubMed

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

Received: 2018-12-05
Accepted: 2019-04-25
Published Online: 2019-05-27
Published in Print: 2019-09-25

©2019 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Editorial: 150 years of the Periodic Table of Chemical Elements
  3. Part A: Actinides and Transactinides
  4. Evolution of the periodic table through the synthesis of new elements
  5. Nuclear and chemical characterization of heavy actinides
  6. Direct mass measurements and ionization potential measurements of the actinides
  7. Relativity in the electronic structure of the heaviest elements and its influence on periodicities in properties
  8. The periodic table – an experimenter’s guide to transactinide chemistry
  9. Synthesis and properties of isotopes of the transactinides
  10. Part B: Nuclear Energy
  11. Homogenous recycling of transuranium elements from irradiated fast reactor fuel by the EURO-GANEX solvent extraction process
  12. Separation of trivalent actinides and lanthanides using various ‘N’, ‘S’ and mixed ‘N,O’ donor ligands: a review
  13. Separation of actinides from lanthanides associated with spent nuclear fuel reprocessing in China: current status and future perspectives
  14. Contamination of Fukushima Daiichi Nuclear Power Station with actinide elements
  15. Protactinium(V) in aqueous solution: a light actinide without actinyl moiety
  16. What do we know about actinides-proteins interactions?
  17. Part C: Medical Radionuclides
  18. Positron-emitting radionuclides for applications, with special emphasis on their production methodologies for medical use
  19. Radiochlorine: an underutilized halogen tool
  20. Radiobromine and radioiodine for medical applications
  21. Radiochemical aspects of alpha emitting radionuclides for medical application
  22. Chelators and metal complex stability for radiopharmaceutical applications
https://doi.org/10.1515/ract-2018-3089
Keywords for this article
Homogeneous recycling; TRU separation; solvent extraction; centrifugal contactor

Articles in the same Issue

  1. Frontmatter
  2. Editorial: 150 years of the Periodic Table of Chemical Elements
  3. Part A: Actinides and Transactinides
  4. Evolution of the periodic table through the synthesis of new elements
  5. Nuclear and chemical characterization of heavy actinides
  6. Direct mass measurements and ionization potential measurements of the actinides
  7. Relativity in the electronic structure of the heaviest elements and its influence on periodicities in properties
  8. The periodic table – an experimenter’s guide to transactinide chemistry
  9. Synthesis and properties of isotopes of the transactinides
  10. Part B: Nuclear Energy
  11. Homogenous recycling of transuranium elements from irradiated fast reactor fuel by the EURO-GANEX solvent extraction process
  12. Separation of trivalent actinides and lanthanides using various ‘N’, ‘S’ and mixed ‘N,O’ donor ligands: a review
  13. Separation of actinides from lanthanides associated with spent nuclear fuel reprocessing in China: current status and future perspectives
  14. Contamination of Fukushima Daiichi Nuclear Power Station with actinide elements
  15. Protactinium(V) in aqueous solution: a light actinide without actinyl moiety
  16. What do we know about actinides-proteins interactions?
  17. Part C: Medical Radionuclides
  18. Positron-emitting radionuclides for applications, with special emphasis on their production methodologies for medical use
  19. Radiochlorine: an underutilized halogen tool
  20. Radiobromine and radioiodine for medical applications
  21. Radiochemical aspects of alpha emitting radionuclides for medical application
  22. Chelators and metal complex stability for radiopharmaceutical applications
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