Euro-GANEX SYSTEM BEHAVIOR UNDER GAMMA RADIATION

Transcription

1 Euro-GAEX SYSTEM BEHAVIR UDER GAMMA RADIATI H. Galán, A. úñez, J.Cobos High Level Waste Unit, CIEMAT, Spain

2 Introduction: GAEX Concept Spent fuel EUR-GAEX Pu, p, Am, Cm U extraction An + Ln extraction An stripping Ln stripping U FP Ln GAEX 1 st cycle M. Miguirditchian et al., GLBAL, Paris, France, 2009, pp GAEX 2 nd (TRU) cycle

3 Introduction: Euro-GAEX flowsheet Co-Extraction C 8H 17 TDGA DMDHEMA C6 H 13 Pu, p, Am, Cm SF solution H H H CDTA An + Ln extraction An stripping Ln stripping H 5.9 M H 3 S 3 a Hydro-BTP S 3 a Ln and FP Pu, p, Am, Cm FP AHA H H Ln Carrott, M. et al., Solvent Extr. Ion Exch. 2014, 32(5), 447. Carrott, M. et al., Hydrometallurgy, 152, 139. S 3 a 0.5M H 3 S 3 a GAEX 2 nd (TRU) cycle Geist, A. et al., Solvent Extr. Ion Exch. 2012, 30, 433. Sypula, M. et al., Solvent Extr. Ion Exch. 2012, 30, 748.

4 Introduction: Process development Extraction process development Euro-GAEX process System selection Design and synthesis of ligands Extracting and complexing properties Industrial diluents High affinity and selectivity Good kinetics, viscosity, reversibility, etc Low synthesis cost of simple molecules Process development and optimization Stability: recyclability Hot test Scale-up Safe long-term performance Industrial application

5 bjetives: Euro-GAEX stability studies Co-Extraction Stability studies C 8H 17 TDGA DMDHEMA C6 H 13 SF solution Sugo, Y. et al. Radiochimia Acta 2002, 90, 161. G. Modolo et al, Solv. Extr. Ion Exch., 2007, 25, 703. Galán H., et al. Procedia Chemistry, 2012, 195. Christopher, A. et al, Solv. Extr. Ion Exch.,, 1. Berthon, L et al. Separation Science and Technology 2001, 3656, 709. Berthon, L. et al. Solvent Extr. Ion Exch: A series of Advances 2010, 19, PT Chapter 8, 429. Pu, p, Am, Cm H H H CDTA An + Ln extraction An stripping Ln stripping H 5.9 M H 3 S 3 a Hydro-BTP S 3 a FP AHA H H Ln S 3 a 0.5M H 3 S 3 a GAEX 2 nd (TRU) cycle

6 Stability studies performed after gamma radiation C 8H 17 ÁYADE Irradiation Facility External 60 Co Sources TDGA DMDHEMA C6 H 13 Characterization of solvent after gamma radiation: Behavior the degraded solvents: Extraction and back-extraction of Ln/An/FP. Composition of the degraded solvents: Extracting agents concentration. Degradation compounds (DCs). The phisico-chemical changes and mass transferences.

7 GAMMA irradiation experiments Fresh GAEX pre-equilibrated with 5 M H 3 TDGA DMDHEMA C 8H 17 TDGA DMDHEMA C6 H 13 GAEX Euro-GAEX 0.2 M TDGA 0.5 M DMDHEMA Fresh samples. In (100)% Kerosene (K) In (95:5)% K/octanol Parallel studies with TDGA and DMDHEMA separately 60 Co 1000 kgy Hydrolytic/chemical degradation. Aging control samples kept in the lab at 20ºC. Radiolytic degradation. Gamma irradiation at ( 60 Co, áyade) kgy, at kgy/h. T D GAEX Aging, 0 kgy

8 Extraction properties after gamma radiation Am(III)/Eu(III) extraction by reference, aged and irradiated GAEX samples (at 1.78 kgy/h). GAEX (100)% K Am TDGA Eu TDGA GAEX (95:5)% ok/octanol TDGA DAm* TDGA DEu* DMDHEMA DAm* DMDHEMA DEu* D M(III) Am DMDHEMA Am GAEX Eu DMDHEMA Eu GAEX DM(III) GAEX DAm GAEX DAm* GAEX DEu GAEX DEu* After rganics: high 0.2 mol/l doses of TDGA organic 0.5 GAEX DMDHEMA solvent or both keeps (GAEX) the in Ln(III)/An(III) (100)% or (95:5)% co-extraction K/ctanol. Aqueous: 241 Am(III) and 152 Eu(III) in 5 mol/l H 3 or (*) 241 Am(III), 152 Eu(III), 237 p(vi) and 238 Pu(IV).

9 Extraction properties after gamma radiation Extraction of elements presents in a HAR solution by fresh, aged and irradiated GAEX solvent (1000 kgy, 1.78 kgy/h) Weak decrease of Ln(III) extraction. Increase of extraction of other metal, such as Rh and Sn. Decrease some FP extraction (Zr and Pd), but an increase of others (Mo) Distribution ratios Fresh Aging Irradiated rganic phase: 0.2 mol/l TDGA and 0.5 mol/l DMDHEMA in K pre-equilibrated with 5 mol/l H 3. Aqueous phase: 10% of simulated HAR solution (H 3 5 mol/l) in H 3 5 mol/l. Ln thers PF thers Ce Gd d Sm Pd Cd Sr Cu Mo Ru Cr Rh Sn Eu La Pr Y Ba Cr Zr Rh Cd Sn Cu Ru

10 Back-extraction properties after gamma radiation Ln(III)/An(III) back-extraction from a loaded irradiated GAEX solvent (1000 kgy, 1.78 kgy/h). Ln back-extraction at higher nitric acid concentration. SF Ln/An could be affected. More difficult quantitative back-extraction of Ln/An. Am rg_irrad Am rg_fresh Am rg_fresh Eu rg_irrad Eu rg_fresh Eu rg_fresh It should be cheeked by using the corresponding aqueous phase (hydro-btp) [M] org,bq/ml 1000 [H 3 ], mol/l rganic phase 1000 [M] aq,bq/ml Aqueous phase [H 3 ], mol/l Extrac step 1 step 2 step 3 step 4 step 5 step 6 rganic phase: 0.2 mol/l TDGA and 0.5 mol/l DMDHEMA in 100% K pre-equilibrated with 5 mol/l H 3. Aqueous phase: Extrac, 10% of HAR solution in H 3 5 mol/l; back-extraction steps, 1.0 and, 0.01 mol/l H 3. 1 Extrac step 1 step 2 step 3 step 4 step 5 step

11 Back-extraction properties after gamma radiation Ln(III)/An(III) back-extraction from a loaded irradiated GAEX solvent (1000 kgy, 1.78 kgy/h) Ln back-extraction at higher nitric acid concentration. SF Ln/An could be affected. More difficult quantitative back-extraction of Ln/An. Ln/An/FP back-extraction from a loaded irradiated GAEX solvent (1000 kgy, 1.78 kgy/h) Ln back-extraction at higher nitric acid concentration. SF Ln/An could be affected. More difficult quantitative back-extraction of Ln/An. The composition of the system should explain the difference observed

12 Remaining extracting agents concentration Quantitative analysis by HPLC-DAD of TDGA and DMDHEMA. More than 50% degradation for both extracting agents. Presence of octanol reduces partially the extractant degradation. [C], mm TDGA alone DMDHEMA alone [C], mm TDGA alone DMDHEMA alone 600 TDGA (GAEX) DMDHEMA (GAEX) 600 TDGA (GAEX) DMDHEMA (GAEX) % K 100 (95:5)% K/ctanol 0 Fresh Aging (0 kgy) 100 kgy 1000 kgy 0 Fresh Aging (0 kgy) 100 kgy 1000 kgy Loading capacity study for Ln(III) and Pu(IV)!!!

13 Composition of degraded organic GAEX solvents HPLC-DAD qualitative studies after irradiation (1000 kgy, 1.78 kgy/h). Same qualitative degradation of ligands alone and as part of GAEX solvent. Higher number of signals in presence of octanol: hydrolytic degradation. (100)% K, 1000 kgy TDGA TDGA DMDHEMA DMDHEMA. DMDHEMA GAEX solvent TDGA

14 Identification of degradation compounds (DCs) HPLC-MS (APCI + ) qualitative studies after gamma irradiation H C 6 H 13 H C 6 H 13 DMDHEMA H C 6 H 13 TDGA GAEX (100)% K 1000 kgy, 1.78 kgy/h Galán H., et al. Procedia Chemistry, 2012, 195. Berthon, L et al. Separation Science and Technology 2001, 3656, pp. 709.

15 DMDHEMA degradation compounds Identification of DCs by HPLC-MS 3 of them (1-3), reduce partially the efficiency of solvents based on DMDHEMA. DMDHEMA C 6 H 13 H H C 6 H 13 C 6 H 13 H ew possible structures H C 6 H 13 H C 6 H 13 Berthon, L. et al. Solvent Extr. Ion Exch: A series of Advances 2010, 19, PT Chapter 8, 429. Berthon, L et al. Separation Science and Technology 2001, 3656, pp H H C 6 H 13 H C 6 H 13

16 TDGA degradation compounds Identification of DCs by HPLC-MS Effects on solvent formulation 3 of them (3-5), D Ln/An(III) > 1 at 3 mol/l H 3. TDGA At least 1 of them (2), troubles in Ln backextraction. 2 of them (4 and 5), possible troubles in SF Ln/An. H H H D Am = D Eu = 277 D Am = 3.5 D Eu = 30 H H D Am = 1.5 D Eu = 1.6 H H H A. úñez et. al. Global, H. Galán et.al. Procedia Chemistry 2012, 195.

17 Phisico-chemical stability of organic GAEX solvent Insoluble drops and precipitates after irradiation up to 1000 kgy (95:5)% K/ctanol DMDHEMA TDGA GAEX Mass transference studies Analysis of insolubilities Drops 100% K 1000 kgy 0 kgy 1000 kgy 0 kgy GAEX GAEX Precipitate Drop

18 Phisico-chemical stability of org. GAEX solvent Mass transferences between phases after irradiation HPLC-DAD chromatograms (95:5)% K/ctanol DMDHEMA TDGA GAEX DMDHEMA TDGA 1000 kgy rganic phase contact with 5 mol/l H 3. o evidence of mass Aqueous transferences phase!!! 100% K 1000 kgy 0 kgy GAEX o evidence of mass transference!!! contact with 5 mol/l H 3.

19 Responsible of insolubilities Analysis by HPLC-MS(APCI) + of insolubilities of GAEX solvent DMDHEMA 100% K GAEX 1000 kgy TDGA Analysis of insolubilities DMDHEMA 100% K Insoluble drop, DMDHEMA 1000 kgy H H White precipite GAEX 1000 kgy TDGA Insoluble drop GAEX 1000 kgy Amine DCs should be removed from degraded solvent

20 What can we conclude about Euro-GAEX stability? It keeps the co-extraction of Ln/An after gamma radiation. High D Ln/An after 1000 kgy. Important reduction in TDGA and DMDHEMA concentration: ctanol: higher remaining concentration but lower D Am/Eu. At least 7 DCs of TDGA and 5 of DMDHEMA are formed. It can be affected: SF An/Ln. Stripping Ln. Properties of of DCS Responsible of insolubilities: Aggregates of protonated MectylH and (ctyl) 2 H.

21 Future work ngoing studies about: Extraction properties: LC Pu(IV), SF An/Ln and Ln back-extraction with the corresponding aqueous phase. Effects of DCs on degraded solvent. Cleaning up experiments: MectylH and (ctyl) 2 H. Interaction between all solvents related along the Euro-GAEX process. Simulating an operative cycle: Interaction between all phases/solvents involved in. Looking for the limits of the systems.

22 Acknowledgment Ana úñez, HLW Unit at Ciemat. Rosa Sedano, UAM (SiDI) Pedro Valdivieso and Mario Rodriguez, áyade Facility s group Laureano Anta, Sofía Durán, Lorena Serrano, HLW Unit at Ciemat.

23 Thank you for your attention

24 Composition of degraded org. GAEX solvents HPLC-DAD qualitative studies after irradiation (1000 kgy, 1.78 kgy/h). Same qualitative degradation for TDGA and DMDHEMA alone and in the GAEX. Higher number of signals for GAEX solvent in presence of octanol: hydrolytic degradation. (95:5)% K/ctanol, 1000 kgy TDGA TDGA DMDHEMA DMDHEMA. DMDHEMA GAEX solvent TDGA

25 Remaining extracting agent concentration Ln(III) loading capacity of after irradiation (1000 KGy, 1.50 kgy/h). C 8H 17 TDGA DMDHEMA C6 H mol/l TDGA 0.5 mol/l DMDHEMA In kerosene (K) 1 [Eu] org, M Fresh 1000 kgy Fresh 1000 kgy Any unexpected change! [Eu] aq, M 4 mm 8 mm 16 mm 32 mm 64 mm 128 mm rganic Solution: 0.2 M TDGA + 0.5M DMDHEMA in 100%K. Aqueous solution [H 3 ] = 4 M and Eu(III) concentrations from M to M, spiked with 152 Eu (1000 Bq/mL).

26 Responsible of Insolubilities Analysis by HPLC-MS(APCI) + of insolubilities of GAEX solvent DMDHEMA 100% K GAEX 1000 kgy TDGA Analysis of insolubilities H C 6 H 13 Insoluble drop, DMDHEMA 1000 kgy H H White precipite GAEX 1000 kgy H Insoluble drop GAEX 1000 kgy Amine DCs should be removed from degraded solvent