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Development and demonstration of a new SANEX process for - - PowerPoint PPT Presentation

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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)

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SLIDE 1

The 10th OECD/NEA Information Exchange Meeting

  • n Actinide and Fission Product P&T, Mito, Japan, 6-10 October 2008

Mitglied der Helmholtz-Gemeinschaft

  • G. Modolo1, M. Sypula1, A. Geist2, C. Hill3, C. Sorel3, R. Malmbeck4,
  • D. Magnusson5, M. R. St. J Foreman5

Development and demonstration of a new SANEX process for actinide(III)/lanthanide(III) separation using a mixture of CyMe4BTBP and TODGA as selective extractant

1Forschungszentrum Jülich GmbH (FZJ), Jülich, Germany 2Forschungszentrum Karlsruhe (FZK), Karlsruhe, Germany 3CEA, Marcoule, France 4 Institute for Transuranium Elements (ITU) Karlsruhe, Germany 5Chalmers University, Gothenburg, Sweden

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SLIDE 2

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 CyMe4BTBP, an effective extracting agent for An(III)/Ln(III) Optimisation studies and CC tests using centrifugal contactors Conclusions and Outlook

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SLIDE 3

Am/Cm separation Am Cm

4

PUREX

Pu U Np

1

spent fuel

European hydrometallurgical separation strategy (Newpart to Europart, 1996 - 2007)

An(III) + Ln(III) co-extraction FP Ac

2

DIAMEX

An(III)/Ln(III) separation Ln

3

SANEX

High Active Raffinate (HAR)

HAR

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SLIDE 4

Co-extraction of Actinides(III) and Lanthanides(III)

Am/Cm separation Am Cm An(III)/Ln(III) separation Ln An(III) + Ln(III) co-extraction FP Ac

2 3 4

Recovery rates: Am + Cm + Ln > 99.99%, low non-Ln impurities

Modolo et al, Part I, Solv. Extr. Ion Exch., 25, 703-721 (2007) 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

TODGA + TBP Wor

  • rk done in

k done in EUR EUROPART

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SLIDE 5

An(III) + Ln(III) co-extraction Am/Cm separation Am Cm An(III)/Ln(III) separation Ln Sp Ak

2 3 4

BTPs

Separation of Actinides(III) from Lanthanides(III)

Dithiophosphinic acids

Low hydrolytic stability at HNO3 > 1 M HNO3 Needs a synergist, which complicates regeneration CC tests with real HAR gave promising results Low hydrolytic and radiolytic stability NEWPART PARTNEW

SANEX Call for improvements

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SLIDE 6
  • 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,
  • Bis-diazine-pyridine,
  • Hemi-BTPs

N N N N N N N N N N N N N

Require synergists (carboxylic acid) to extract at higher acidity Separation of Actinides(III) from Lanthanides(III) Main achievements during EUROPART

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SLIDE 7
  • Nitrogen containing ligands (heterocyclic rings)

☺ Very good extraction efficiency for

BATPs

N N N N N N N

CyMe4-BTP ☺ DAm > 1; SFAm/Eu > 1000 Low solubility Radiolytic instability No An(III) stripping

Separation of Actinides(III) from Lanthanides(III) Main achievements during EUROPART

N N N N N N N N

CyMe4-BTBP ☺ DAm > 1; SFAm/Eu > 100 ☺ High hydrolytic stability Kinetics is slow Radiolytic stability Low solubility

BATBPs

N N N N N N N N

C5-BTBP ☺ DAm > 1; SFAm/Eu > 100 Hydrolytic Instability

BTBPs

slide-8
SLIDE 8

N N N N N N N N

O N O O N

0.015 M CyMe 4BTBP + 0.25 M DMDOHEMA in n-octanol Geist, Hill, Modolo, Foreman, Weigl, Gompper, Hudson, Madic,

  • Solv. Extr. Ion Exch., 24, 463–483 (2006)

Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe4BTBP + DMDOHEMA

Flow sheet proposed by CEA (C. Sorel)

Element Y La Ce Pr Nd Sm Eu Gd

252Cf 241Am 244Cm 152Eu

mg/L 56 209 397 204 764 151 140 78 traces

Composition of synthetic SANEX feed (generated during TODGA/TBP test)

Spent solvent

Extraction Scrubbing

9 1 12

Feed

SANEX (An +Ln), HNO3 1.3 M 10 mL/h

Scrub

HNO3 0.7 M 10 mL/h

Raffinate Ln(III) Solvent

0.015 M CyMe4BTBP + 0.25 M DMDOHEMA in n-octanol 10 mL/h

Stripping

16 13

Strip

Glycolic acid 0.5 M, pH = 4 10 mL/h

An(III) Product Spent solvent

Extraction Scrubbing

9 1 12

Feed

SANEX (An +Ln), HNO3 1.3 M 10 mL/h

Scrub

HNO3 0.7 M 10 mL/h

Raffinate Ln(III) Solvent

0.015 M CyMe4BTBP + 0.25 M DMDOHEMA in n-octanol 10 mL/h

Stripping

16 13

Strip

Glycolic acid 0.5 M, pH = 4 10 mL/h

An(III) Product

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SLIDE 9

Separation of Actinides(III) from Lanthanides(III) Kinetic tests in test tubes with CyMe4BTBP + DMDOHEMA

conditions Organic phase Aqueous phase A/O ratio Extraction 0.015 M CyMe4-BTBP + 0.25 M DMDOHEMA in octanol SANEX feed 1.15 M HNO3 0.5 Scrubbing Loaded organic phase from extraction 0.8 M HNO3 1 Stripping Loaded organic phase from extraction 0.5 M Glycolic acid set to pH 4 1

0.001 0.01 0.1 1 10 100 2 4 6 8 10 12 14

Mixing time (minutes) Distribution ratio DM(III)

1 10 100 1000

Ce Eu Gd La Nd Pr Sm Y Am SFAm/Eu

Extraction

0.001 0.01 0.1 1 10 100 2 4 6 8 10 12 14

Mixing time (minutes) Distribution ratio DM(III)

1 10 100 1000

Ce Eu Gd La Nd Pr Sm Y Am SFAm/Eu

Scrubbing

0.001 0.01 0.1 1 10 5 10 15 20

Mixing time (minutes) Distribution ratio DAm(III)

Stripping

Element Y La Ce Pr Nd Sm Eu Gd

252Cf 241Am 244Cm 152Eu

mg/L 56 209 397 204 764 151 140 78 traces

SANEX Feed

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SLIDE 10

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 Batch Test EX eq

Organic phase: 0.015 M CyMe4-BTBP + 0.25 M DMDOHEMA in 1-octanol Aqueous phase: SANEX Feed, A/O ratio = 2 , Mixing time 15 min, 22°C

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SLIDE 11

Separation of Actinides(III) from Lanthanides(III) Single centrifuge kinetic tests

Too slo

  • 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 modifica Needs modification tion

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 Batch Test EX eq

Organic phase: 0.015 M CyMe4-BTBP + 0.25 M DMDOHEMA in 1-octanol Aqueous phase: SANEX Feed, A/O ratio = 2 , Mixing time 15 min, 22°C

Sample DEu DAm γ DAm α DCm DCf SFAm/Eu SFAm/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

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SLIDE 12

Separation of Actinides(III) from Lanthanides(III) Results of hot BTBP/DMDOHEMA (ITU 2008, CC)

~30 Cm ~80 Am ~50 Gd ~25 Eu ~70 Sm ~20 Pm ~600 Nd ~150 Pr ~300 Ce ~200 La ~50 Y Concentration [ppm] Element ~30 Cm ~80 Am ~50 Gd ~25 Eu ~70 Sm ~20 Pm ~600 Nd ~150 Pr ~300 Ce ~200 La ~50 Y Concentration [ppm] Element

Feed: Product fraction from the TODGA/TBP Acidity adjusted to 2 M (from 0.12) Ln(III) > 99.9 % Eu-153 ∼ 99.9 Am-243 ∼ 0.01 % Cm-244 ∼ 0.07 % An(III) < detec. limit Ln(III) < detec. limit Am-243 > 99.9 % Cm-244 ∼ 99.9 % Eu-153 ∼ 0.1 % Ln(III) < 0.01 %

  • > 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

Magnusson, Christiansen, Foreman, Geist, Glatz, Malmbeck, Modolo, Serranno-Purroy, Sorel,

  • Solv. Extr. Ion Exch.

submitted

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SLIDE 13

Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

Organic phase: 0.015 mol/L CyMe4BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO3, traces of 241Am and 152Eu, 22 °C

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SLIDE 14

Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

Organic phase: 0.015 mol/L CyMe4BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO3, traces of 241Am and 152Eu, 22 °C

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SLIDE 15

Separation of Actinides(III) from Lanthanides(III) Optimisation studies, influence of TODGA

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

Organic phase: 0.015 mol/L CyMe4BTBP + variable TODGA in n-octanol Aqueous phase: variable HNO3, traces of 241Am and 152Eu, 22 °C

slide-16
SLIDE 16

Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe4BTBP

N N N N N N N N

Organic phase: 0.015 mol/L CyMe4BTBP in n-octanol Aqueous phase: 1.0 mol/L HNO3, traces of 241Am and 152Eu, 22 °C

Kinetic of extraction

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SLIDE 17

Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe4BTBP

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

+

0.005 M Organic phase: 0.015 mol/L CyMe4BTBP (+ 0.005 mol/L TODGA) in n-octanol Aqueous phase: 1.0 mol/L HNO3, traces of 241Am and 152Eu, 22 °C

Kinetic of extraction

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SLIDE 18

Separation of Actinides(III) from Lanthanides(III) Optimisation studies with CyMe4BTBP

N N N N N N N N

O N O O N

+

0.25 M Organic phase: 0.015 mol/L CyMe4BTBP without and with (0.005 mol/L TODGA or 0.25 mol/L DMDOHEMA) in n-octanol Aqueous phase: 1.0 mol/L HNO3, traces of 241Am and 152Eu, 22 °C

Kinetic of extraction

0.25 M

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SLIDE 19

Separation of Actinides(III) from Lanthanides(III) Single centrifuge kinetic tests

N N N N N N N N

Extraction from SANEX feed Stripping w ith glycolic acid

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SLIDE 20

Separation of Actinides(III) from Lanthanides(III) Results of spiked BTBP/TODGA (FZJ 2008, CC)

Element Concentration (mg/L) Nuclide/Activity (MBq/L) Am traces Am-241 (2.5) Cm traces Cm-244 (2.4) Cf traces Cf-252 (1.6) Ce 383 Eu 129 Eu-152 (3.3) Gd 85 La 205 Nd 716 Pr 192 Sm 142 Y 55

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

Ln(III) > 99.9 % Eu-152 ∼ 99.9 % Am-241 ∼ 0.08 % Cm-244 ∼ 0.32 % Cf-252 ∼ detec. limit An(III) ∼ detec. limit Ln(III) ∼ detec. limit Am-241 > 99.9 % Cm-244 ∼ 99.7 % Cf-252 > 99.9 % Eu-152 ∼ 0.8 % Ln(III) < 0.1 % Y(III) ∼ 3.2%

  • >99.9% of the An(III) in the product, < 0.5 % Ln (mass)
  • The Ln remained in the raffinate,
  • No detectable Ln or An in the spent organic phase
slide-21
SLIDE 21

Separation of Actinides(III) from Lanthanides(III) Results of spiked BTBP/TODGA (FZJ 2008, CC)

N N N N N N N N

H17C8 N C O C N C8H17 O O C8H17 C8H17

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SLIDE 22

An(III) + Ln(III) co-extraction Am/Cm separation Am Cm An(III)/Ln(III) separation Ln FP Ac

2 3 4

Modolo, Odoj, European Patent 1664359B1, (2007)

Cl P S SH Cl

P O O O O

+

SeparationfactorAm/Cm∼ 8- 10

LUCA

Lanthaniden Und Curium/Americium separation

Separation of Americium(III) from Curium(III)

Modolo, Nabet, Solv. Extr. Ion Exch., 23, 359-373 (2005)

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SLIDE 23

Separation of Americium(III) from Curium(III) LUCA demonstration

Extraction - Scrubbing Stripping

7 1 16

Feed

HNO3 0.08 M NaNO3 0.5 M Am-241 3.1 MBq Cm-244 3.0 MBq Cf-252 1.9 MBq Eu-152 4.0 MBq Eu 100 mg/L 35 mL/h

Scrub

HNO3 0.23 M NaNO3 0.5 M 15 mL/h 24 17

Strip

HNO3 0.7 M 35 mL/h

Am(III) Product Spent solvent Raffinat

Solvent

(ClPh)2PSSH 0.4 M TEHP 0.15 M tert.-butylbenzene/ isoctane 20% 35 mL/h

Flow sheet designed by FZK (A.Geist)

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SLIDE 24

Separation of Americium(III) from Curium(III) LUCA demonstration

Extraction - Scrubbing Stripping

7 1 16

Feed

HNO3 0.08 M NaNO3 0.5 M Am-241 3.1 MBq Cm-244 3.0 MBq Cf-252 1.9 MBq Eu-152 4.0 MBq Eu 100 mg/L 35 mL/h

Scrub

HNO3 0.23 M NaNO3 0.5 M 15 mL/h 24 17

Strip

HNO3 0.7 M 35 mL/h

Am(III) Product Spent solvent Raffinat

Solvent

(ClPh)2PSSH 0.4 M TEHP 0.15 M tert.-butylbenzene/ isoctane 20% 35 mL/h

Am(III) ∼0.2 % Am(III) ∼ below d.l. Cm(III) > 99.9 % Cf(III) > 99.9 % Eu(III) > 99.9 % Am(III) ∼99.8 % Cm(III) ∼ below d.l.

  • >99.9% of the Am(III) extraction, no Cm(III) contamination
  • The Ln + Cm(III) + Cf(III) remained in the raffinate,
  • Stripping can easily be optimized
slide-25
SLIDE 25

Conclusions

CyMe4BTBP is a promising extractant for An(III)/Ln(III) Kinetic of extraction is low, can be improved by a phase transfer catalyst such as DMDOHEMA or TODGA Optimisation studies leads to the development of reversible extraction processes Hot CyMe4BTBP + DMDOHEMA extraction process Spiked CyMe4BTBP + TODGA extraction process Am(III)/Cm(III) separation is possible by the LUCA process

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SLIDE 26

Outlook

Hot CyMe4BTBP + TODGA demonstration Hot Am(III)/Cm(III) demonstration

FP 7 ACSEPT 2008-2011 (Actinide reCycling by SEparation and Transmutation)

LWRs PUREX U Product Pu Product

U, Np, Pu, Am, Cm

U Pu Np

LWRs PUREX U Product Pu Product

U, Np, Pu, Am, Cm

U Pu Np

LWRs PUREX U Product Pu Product

U, Np, Pu, Am, Cm

U Pu Np

LWRs PUREX U Product Pu Product

U, Np, Pu, Am, Cm

U Pu Np

An(III) selective extraction (SANEX) Am, Cm Product

Am, Cm

An(III) selective extraction (SANEX) Am, Cm Product

Am

An(III) selective extraction (SANEX) Am, Cm Product

Am

An(III) selective extraction (SANEX) Am, Cm Product

Am

An(III) + Ln(III) co-extraction An(III)/Ln(III) separation Am, Cm Product

Am, Cm

3 Step Process

An(III) + Ln(III) co-extraction An(III)/Ln(III) separation Am, Cm Product

Am

An(III) + Ln(III) co-extraction An(III)/Ln(III) separation Am, Cm Product

Am

3 Step Process

An(III) + Ln(III) co-extraction An(III)/Ln(III) separation Am, Cm Product

Am

An(III) selective Stripping (innovative SANEX) Am, Cm Product

Am,Cm

An(III) selective Stripping (innovative SANEX) Am, Cm Product

Am

An(III) selective Stripping (innovative SANEX) Am, Cm Product

Am

An(III) selective Stripping (innovative SANEX) Am, Cm Product

Am

2 Step Processes 2 Step Processes Challenge

(See Poster III-7: C. Hill et al.)

slide-27
SLIDE 27

Acknowledgement

The European Commission is acknow ledged for the financial support during EUROPART (FI6W-CT-2003-508 854) and ACSEPT (FP-7-CP-2007-211267)

Thank y hank you f

  • u for y
  • r your
  • ur

attention… ttention…