The 10 th OECD/NEA Information Exchange Meeting Mitglied der Helmholtz-Gemeinschaft on Actinide and Fission Product P&T, Mito, Japan, 6-10 October 2008 Development and demonstration of a new SANEX process for actinide(III)/lanthanide(III) separation using a mixture of CyMe 4 BTBP and TODGA as selective extractant G. Modolo 1 , M. Sypula 1 , A. Geist 2 , C. Hill 3 , C. Sorel 3 , R. Malmbeck 4 , D. Magnusson 5 , M. R. St. J Foreman 5 1 Forschungszentrum Jülich GmbH (FZJ), Jülich, Germany 2 Forschungszentrum Karlsruhe (FZK), Karlsruhe, Germany 3 CEA, Marcoule, France 4 Institute for Transuranium Elements (ITU) Karlsruhe, Germany 5 Chalmers University, Gothenburg, Sweden
Outline of the presentation � European hydrometallurgical separation strategy � TODGA/TBP process for co-extraction of An(III) + Ln(III) � Status of EUROPART research on An(III)/Ln(III) separation � CyMe 4 BTBP, an effective extracting agent for An(III)/Ln(III) � Optimisation studies and CC tests using centrifugal contactors � Conclusions and Outlook
European hydrometallurgical separation strategy (Newpart to Europart, 1996 - 2007) 1 2 3 4 An(III) + Ln(III) An(III)/Ln(III) Am/Cm PUREX co-extraction separation separation HAR Cm Pu Np Am U FP Ac Ln DIAMEX SANEX spent fuel High Active Raffinate (HAR)
Co-extraction of Actinides(III) and Lanthanides(III) 2 3 4 An(III) + Ln(III) An(III)/Ln(III) Am/Cm TODGA + TBP co-extraction separation separation Cm Am FP Ac Ln Recovery rates: Am + Cm + Ln > 99.99%, low non-Ln impurities Modolo et al, Part I, Solv. Extr. Ion Exch., 25, 703-721 (2007) Wor ork done in k done in EUR EUROPART Modolo et al, Part II, Solv. Extr. Ion Exch., 26 (1), 62 – 76 (2008 ) Magnusson et al, Part III, Solv. Extr. Ion Exch., in press
Separation of Actinides(III) from Lanthanides(III) 2 3 4 NEWPART An(III) + Ln(III) An(III)/Ln(III) Am/Cm co-extraction separation separation PARTNEW Cm Am Sp Ak Ln SANEX Dithiophosphinic acids BTPs � Low hydrolytic stability � CC tests with real HAR at HNO 3 > 1 M HNO 3 gave promising results � Needs a synergist, which � Low hydrolytic and complicates regeneration radiolytic stability Call for improvements
Separation of Actinides(III) from Lanthanides(III) Main achievements during EUROPART • Sulphur containing ligands (dithiophosphinic acids) � No improvement of systems developed during FP5 (PARTNEW) • Nitrogen containing ligands (heterocyclic rings) � No extraction efficiency for molecules such as • Pyridine-diazines, N N N N • Bis-diazine-pyridine, N N N N N N • Hemi-BTPs N N N Require synergists (carboxylic acid) to extract at higher acidity
Separation of Actinides(III) from Lanthanides(III) Main achievements during EUROPART • Nitrogen containing ligands (heterocyclic rings) ☺ Very good extraction efficiency for CyMe 4 -BTP ☺ D Am > 1; SF Am/Eu > 1000 N N � Low solubility N BATPs N N � Radiolytic instability N N � No An(III) stripping C5-BTBP N N BTBPs ☺ D Am > 1; SF Am/Eu > 100 N N � Hydrolytic Instability N N N N CyMe 4 -BTBP ☺ D Am > 1; SF Am/Eu > 100 N N ☺ High hydrolytic stability N N BATBPs N N � Kinetics is slow N N � Radiolytic stability � Low solubility
Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe 4 BTBP + DMDOHEMA N N O Geist, Hill, Modolo, Foreman, Weigl, N N Gompper, Hudson, Madic, N N N N Solv. Extr. Ion Exch., 24, 463–483 (2006) N N O O 0.015 M CyMe 4 BTBP + 0.25 M DMDOHEMA in n-octanol Solvent Solvent Feed Feed 0.015 M CyMe 4 BTBP 0.015 M CyMe 4 BTBP SANEX SANEX + 0.25 M DMDOHEMA + 0.25 M DMDOHEMA (An +Ln), (An +Ln), in n-octanol in n-octanol HNO 3 1.3 M HNO 3 1.3 M 10 mL/h 10 mL/h 10 mL/h 10 mL/h Spent Spent solvent solvent Stripping Stripping Extraction Extraction Scrubbing Scrubbing 1 1 9 9 12 12 13 13 16 16 Raffinate Raffinate An(III) Product An(III) Product Scrub Scrub Strip Strip Ln(III) Ln(III) HNO 3 0.7 M HNO 3 0.7 M Glycolic acid Glycolic acid 10 mL/h 10 mL/h 0.5 M, pH = 4 0.5 M, pH = 4 10 mL/h 10 mL/h Flow sheet proposed by CEA (C. Sorel) 252 Cf 241 Am 244 Cm 152 Eu Element Y La Ce Pr Nd Sm Eu Gd mg/L 56 209 397 204 764 151 140 78 traces Composition of synthetic SANEX feed (generated during TODGA/TBP test)
Separation of Actinides(III) from Lanthanides(III) Kinetic tests in test tubes with CyMe 4 BTBP + DMDOHEMA 100 1000 100 1000 Distribution ratio DM(III) 10 Distribution ratio DM(III) 10 Ce Ce 100 100 Eu Eu Gd Gd 1 1 La La Nd Nd Pr Pr 0.1 0.1 Sm Sm 10 10 Y Y Am Am 0.01 0.01 SFAm/Eu SFAm/Eu 0.001 1 0.001 1 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 Extraction Scrubbing Mixing time (minutes) Mixing time (minutes) 10 Stripping Aqueous A/O Distribution ratio D Am(III) conditions Organic phase phase ratio 1 0.015 M CyMe 4 -BTBP + 0.25 M SANEX feed Extraction 0.5 DMDOHEMA in octanol 1.15 M HNO 3 0.1 Scrubbing Loaded organic phase from extraction 0.8 M HNO 3 1 0.01 0.5 M Glycolic Stripping Loaded organic phase from extraction 1 acid set to pH 4 0.001 0 5 10 15 20 Mixing time (minutes) SANEX Feed 252 Cf 241 Am 244 Cm 152 Eu Element Y La Ce Pr Nd Sm Eu Gd mg/L 56 209 397 204 764 151 140 78 traces
Separation of Actinides(III) from Lanthanides(III) Single centrifuge kinetic tests Flow rate (mL/h) Test number Sample Organic phase Aqueous phase Test 1 EX 1 20 40 Test 2 EX 2 10 20 Test 3 EX 3 5 10 Organic phase: 0.015 M CyMe 4 -BTBP + 0.25 M DMDOHEMA in 1-octanol Batch Test EX eq Aqueous phase: SANEX Feed, A/O ratio = 2 , Mixing time 15 min, 22°C
Separation of Actinides(III) from Lanthanides(III) Single centrifuge kinetic tests Flow rate (mL/h) Test number Sample Organic phase Aqueous phase Test 1 EX 1 20 40 Test 2 EX 2 10 20 Test 3 EX 3 5 10 Organic phase: 0.015 M CyMe 4 -BTBP + 0.25 M DMDOHEMA in 1-octanol Batch Test EX eq Aqueous phase: SANEX Feed, A/O ratio = 2 , Mixing time 15 min, 22°C Sample D Eu D Am γ D Am α D Cm D Cf SF Am/Eu SF Am/Cm EX 1 0.05 0.62 0.58 0.35 0.61 13 1.65 EX 2 0.08 1.48 1.32 0.73 1.49 19 1.81 EX 3 0.11 2.48 2.02 1.20 2.38 21 1.68 EX eq 0.21 27 25 13 183 133 1.92 Too slo o slow kinetics (e kinetics (extr xtraction and stripping) action and stripping) to implement the cur to implement the current flo ent flow sheet w sheet Needs modification Needs modifica tion
Separation of Actinides(III) from Lanthanides(III) Results of hot BTBP/DMDOHEMA (ITU 2008, CC) Magnusson, Christiansen, Concentration Concentration Element Element Foreman, Geist, Glatz, Feed: Product fraction from the TODGA/TBP [ppm] [ppm] Malmbeck, Modolo, Acidity adjusted to 2 M (from 0.12) Y Y ~50 ~50 Serranno-Purroy, Sorel, La La ~200 ~200 Solv. Extr. Ion Exch. Ce Ce ~300 ~300 Pr Pr ~150 ~150 submitted Nd Nd ~600 ~600 Pm Pm ~20 ~20 Sm Sm ~70 ~70 Eu Eu ~25 ~25 Gd Gd ~50 ~50 Am Am ~80 ~80 An(III) < detec. limit Cm Cm ~30 ~30 Ln(III) < detec. limit Am-243 > 99.9 % Ln(III) > 99.9 % Cm-244 ∼ 99.9 % Eu-153 ∼ 99.9 Eu-153 ∼ 0.1 % Am-243 ∼ 0.01 % Ln(III) < 0.01 % Cm-244 ∼ 0.07 % � > 99.9% of the An(III) in the product � The Ln remained in the raffinate � No detectable Ln or An in the spent organic phase
Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA N N N N N N N N O O C 8 H 17 H 17 C 8 C O C N N C 8 H 17 C 8 H 17 Organic phase: 0.015 mol/L CyMe 4 BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA N N N N N N N N O O C 8 H 17 H 17 C 8 C O C N N C 8 H 17 C 8 H 17 Organic phase: 0.015 mol/L CyMe 4 BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA N N N N N N N N O O C 8 H 17 H 17 C 8 C O C N N C 8 H 17 C 8 H 17 Organic phase: 0.015 mol/L CyMe 4 BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe 4 BTBP Kinetic of extraction N N N N N N N N Organic phase: 0.015 mol/L CyMe 4 BTBP in n-octanol Aqueous phase: 1.0 mol/L HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe 4 BTBP Kinetic of extraction N N N N N N N N + O O C 8 H 17 H 17 C 8 C O C N N C 8 H 17 C 8 H 17 0.005 M Organic phase: 0.015 mol/L CyMe 4 BTBP (+ 0.005 mol/L TODGA) in n-octanol Aqueous phase: 1.0 mol/L HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe 4 BTBP Kinetic of extraction N N N N N N N N + O N N O O Organic phase: 0.015 mol/L CyMe 4 BTBP without and with 0.25 M 0.25 M (0.005 mol/L TODGA or 0.25 mol/L DMDOHEMA) in n-octanol Aqueous phase: 1.0 mol/L HNO 3 , traces of 241 Am and 152 Eu, 22 ° C
Separation of Actinides(III) from Lanthanides(III) Single centrifuge kinetic tests Extraction from SANEX feed N N N N N N N N Stripping w ith glycolic acid
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