1. | PAGE 1 CEA | 10 AVRIL 2012 URANIUM (III) AND PLUTONIUM (III) PRECIPITATION IN MOLTEN CHLORIDE Pu Futures - 15-20 July 2012 J.F. Vigier 1,2, A. Laplace 1, T. Plet 1, C. Renard 2 and F. Abraham 2 1 CEA, Nuclear Energy Division, RadioChemistry & Processes Department, SCPS/LEPS, F-30207 Bagnols sur Cèze, France. 2 Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, Univ. Lille Nord de France, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d’Ascq Cedex, France. 4 JUIN 2016 | PAGE 1 CEA | 10 AVRIL 2012

2. I – Context II – Procedure and objectives III – Simulating system : Nd(III)-Ce(III) IV – Coconversion U(III)-Pu(III) 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 2 SUMMARY

3. I - CONTEXT 4 JUIN 2016 | PAGE 3 CEA | 10 AVRIL 2012

4. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 4 An z+ FP z+ II – Reductive Extraction An z+ FP z+ Al Fluoride An 0 An 3+ Al LiCl-CaCl 2 An 0 HFH2OH2O Fluoride LiCl-CaCl 2 AnO 2 III – Oxidative Back- extraction IV - Conversion I - Dissolution Pyrochemical process for nuclear spent fuel recycling An 3+ I - CONTEXT

5. II – PROCEDURE AND OBJECTIVES 4 JUIN 2016 | PAGE 5 PuFututres | 15-20 July 2012

6. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 6 II – PROCEDURE AND OBJECTIVES Conversion in molten salt An 3+ For Nuclear fuel re-fabrication O 2- 1 - Quantitative 2 - Oxide Form AnO 2 3 - Solid solution (U,Pu,MA)O 2 LiCl-CaCl 2 (700°C) H 2 O (g) → O 2- (salt) + 2HCl (g) Ar + H 2 O Ar + HCl O 2-

7. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 7 Ar+H 2 O LiCl-CaCl 2 700°C Ar+HCl Uranium Plutonium LiCl-CaCl 2 Precipitate II – PROCEDURE AND OBJECTIVES

8. III - Nd(III)-Ce(III) PRECIPITATION BY WET ARGON SPARGING 4 JUIN 2016 | PAGE 8 CEA | 10 AVRIL 2012

9. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 9 Lanthanide precipitate III - Nd(III)-Ce(III) PRECIPITATION BY WET ARGON SPARGING ICP analysis : 99.9% conversion rate conversion study for different ratio Ce/Nd X Nd = Nd / Ce+Nd X Nd = 0 X Nd = 0.25 X Nd = 0.50 X Nd = 0.75 X Nd = 1

10. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 10 NdOCl x Nd =1 20µm NdOCl NdCl 3(salt) + H 2 O (g) → NdOCl (ppt) + 2HCl (g) III - Nd(III)-Ce(III) PRECIPITATION BY WET ARGON SPARGING Intensity (a. u.)

11. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 11 CeO 2 x Nd =1 CeOCl x Nd =0 x Nd =0.25 x Nd =0.50 x Nd =0.75 Ce 1-x Nd x O 2-0.5X 20µm CeOCl CeO 2 CeCl 3(salt) + H 2 O (g) → CeOCl (ppt) + 2HCl (g) CeCl 3(salt) + 2H 2 O (g) → CeO 2(ppt) + 3HCl (g) + ½H 2 80% 20% Ce 1-y Nd y OCl III - Nd(III)-Ce(III) PRECIPITATION BY WET ARGON SPARGING Intensity (a. u.)

12. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 12 Nd(III)-Ce(III) precipitation : Partially oxidative method III - Nd(III)-Ce(III) PRECIPITATION BY WET ARGON SPARGING 1 - Quantitative 2 - Oxide Form LnO 2 3 - Solid solution OK OK calcination OK

13. IV – U(III)-Pu(III) PRECIPITATION BY WET ARGON SPARGING 4 JUIN 2016 | PAGE 13 CEA | 10 AVRIL 2012

14. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 14 Actinide precipitate ICP - alpha spectrometry analysis : Conversion rate > 99.9% conversion rate conversion study for different X Pu = Pu / U+Pu X Pu = 1 X Pu = 0.75 X Pu = 0.50 X Pu = 0.20 X Pu = 0 IV – U(III)-Pu(III) PRECIPITATION BY WET ARGON SPARGING Uranium volatilization 10-15%

15. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 15 a=5.470(1) UO 2 U3O8U3O8 3.75% Theoritical gain: 3.95% UCl 3(salt) + 2H 2 O (g) → UO 2(ppt) + 3HCl (g) + ½H 2 IV – U(III) PRECIPITATION BY WET ARGON SPARGING TGA (%) Temperature (°C)

16. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 16 UO 2 PuO 2 x Pu =0 x Pu =0.20 x Pu =0.50 x Pu =0.75 Intermediate sample X Pu U 3+ Pu 3+ 0.75< 1%70% 0.5< 1%76% 0.2< 1%61% U 3+ U 4+ UO 2 e-e- 2O 2- Pu 3+ Pu 4+ PuO 2 e-e- 2O 2- standard IV – U(III)-Pu(III) PRECIPITATION BY WET ARGON SPARGING E(V) Intensity (a. u.)

17. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 17 x Pu =0 x Pu =0.20 x Pu =0.50 x Pu =0.75 x Pu =1 UO 2 PuO 2 PuOCl Pu III oxidation is “catalyzed” by UO 2 stardard IV – U(III)-Pu(III) PRECIPITATION BY WET ARGON SPARGING Intensity (a. u.)

18. 4 JUIN 2016PuFututres | 15-20 July 2012 | PAGE 18 IV – U(III)-Pu(III) PRECIPITATION BY WET ARGON SPARGING U(III)-Pu(III) precipitation 1 - Quantitative 2 - Oxide Form AnO 2 3 - Solid solution OK

19. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 19 Conclusion -Wet argon is a promising conversion method -U(III) and Pu(III) coconversion lead to UO 2 and PuO 2 mixture (moderate oxidative conditions) Perspectives -U(III)-Am(III) coconversion study -Uranium volatilization minimization CONCLUSION

20. 4 JUIN 2016Pu Futures | 15-20 July 2012 | PAGE 20 THANK YOU FOR YOUR ATTENTION