OECD Nuclear Energy Agency
9th IEM on P&TNîmes, 25-29 September 2006

Progress in Partitioning:
Activities in ATALANTE
P. BARON, B. LORRAIN, B. BOULLISRadiochemistry and Processes Department

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

1COMPLEMENTARY SEPARATIONS : WHICH PROCESSES ?

1. MAIN CRITERIA :- safety, efficiency, cost, secondary waste,…
- robust technical elements for 2006
2. REFERENCE ROUTE : SOLVENT EXTRACTION- used for U and Pu recovery- La Hague feedback :∗ high separation yields∗ low amount of technological waste
3.

ALTERNATIVE ROUTE: PYRO-PROCESSES(molten salts, high temperature)

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

2LLRNs recovery : CEA general flowsheet

Spent fuelI
Uranium andPlutonium

PUREX

Tc
Np

Cs
Fission Products

Additional
Additional
Separations
Separations

AmCm

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

3Np extraction : CBP hot run, april 2005
Feed HAU, Pu, Np, P.F.
HNO3 4.5 M~1 L/h2 extractions (PC)

F.P. scrub

F.P. scrub (PC)

Acidification

U, Pu, Np( >99%)

Tc scrubbing (MS)Scrub
TBP 30%Np < 0.1 % (d.l.), F.P.
TBP 30%~ 15 kg of UOX fuel
52 GWd/t

Complementaryextraction (MS)Np < 0.5 % (d.l.), F.P.
OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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ATALANTE « CBP » HOT CELL (commissioned 2003)

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

5

[U] in loaded solvent and scrubbing

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

6Np (g/L)[Np] in loaded solvent and scrubbing

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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ACTINIDE SEPARATION STRATEGY
Spent FuelOPO
O

Two step strategy

PUREX

Fission
Products

DIAMEX

Ln

SANEX

U, Pu, Np

O

TBP
TBP

CO-EXTRACTION
of MAs and Ln

Am, CmOECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

SEPARATION
of Mas from Ln

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DIAMEX, « CBP » hot run, November 2005
FeedHNO3H2C2O4HEDTAHNO3 4M
Am ~ 150 mg/L
Cm ~ 15 mg/L
Ln ~ 2.5 g/L
Mo, Zr, Fe
V ~ 1 L/h

NaOH 0.3M
HEDTA

Solvent Treatement

HNO31.8 M(ECRAN)HNO3,H2C2O4
HEDTA

1extraction
An+Ln
(CP)

extraction
An+Ln
(CP)

Back-extraction An-Ln-FP
scrubbing

HNO3 0.1 M(CP)

0.65 MDMDOHEMA/TPH
0,65 M dansAm, Cm, Ln :> 99.9%

2FP
Raffinate(MS)

3Am ~ 0.015 %Cm < 0.002 %123

Î [Am] and [ Nd] online measure

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

9[Am] on line measure
online scrubbing
predicted scrubbing
samples scrubbing
200
onlinesolvent
190 solvent
predicted
180 solvent
samples170
onlineproduction
160 production
samples
150 production
predicted
140130[Am] (mg/L)

120
110
100
90
80
70
60
50
40
30
20
100
22/11 22/11 22/11 22/11 22/11 22/11 22/11 22/11 23/11 23/11 23/11 23/11 23/11 23/11 23/11 23/11 23/11
08:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 00:00 02:00 04:00 06:00 08:00 10:00 12:00 14:00 16:00

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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The second step : An/Ln Separation
From
DIAMEX

An+LnExtr.

Desex. selective.AnLn

DesexLn

LnAnPFs.

O

The key : an An-selective complexant

OONNOOHEDTAOOThe difficulty : efficient only at low acid concentration
The solution proposed : an appropriate extractant system
OO

N
C8H17 C2H4DMDOHEMA O
C6H13NO

C8H17

HDEHP

O
PO

O
H

…and towards a single-cycle concept !
OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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SANEX Process, hot run, December 2005

Feed
HNO3 4 mol/L-1
45 mL/h

HNO3 0.5 mol.L-1

NaOH 1.5 mol.L-1
HEDTA 0.01 mol.L-1

extraction-scrubbing
Solvent
DMDOHEMA 0.5 M+ HDEHP 0.3 M/TPH
HNO3 0.01 M

Raffinate

Am, Cm < 0.01%
Lnscrubbing

AnAm, Cm > 99.9%
F.D.Ln ~ 80

An stripping

Ln stripping

HEDTA 0.5 mol.L-1
Citric ac. 0.5 mol.L-1
pH 3LnHNO3 1M

Am, Cm < 0.06 %OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

12Minor Actinide : Main results• Neptunium :Ö recovery yield : > 99 % (adaptation of PUREX process)• Américium et curium :Ö recovery yield : 99,9 % Am + Cm

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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HOW TO GO FURTHER ?
• DIAMEX-SANEX Optimization : single cycle !

• ALL-ACTINIDE GROUPED EXTRACTION– adapted DIAMEX-SANEX (with U, Pu,Np…)– other new molecules…

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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The GANEX Concept
RECYCLE
Spent fuel

DISSOLUTIONAn Conversion
U SEPARATIONUU +Pu+MA

EXTRACTION

An Stripping

F.P.

Ln Stripping

Ln
WASTE

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 200615

Preliminary Uranium extraction•U(VI) / other actinides separation, based on
selective mono-amide extraction of uranium.
lavage solvant

H2C

H3C
CO

C2H5
CH-C4H9Solution

Dissolution

HNO3N

DésextractionUextraction

CH2

CH-C4H9C2H5NaOH 0,3M

HNO3 3 M

RecyclagemonoamideU

HNO30,1 M

N,N-di(éthyl-2)hexyl-acétamide
Pu, Np, Am, CmP.F.

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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«Poly-actinide » oxalate coprecipitation
ATALANTE – L15

Continuous operation
Atalante/L15

1999 : U 70 % - Pu 30 %2003 : U, Pu,Np

2005 : U, Np, Pu, Am
U 78 % - Np 1% - Pu 20 % - Am 1 %OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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ACTINIDE RECOVERY BY SALT/METAL EXTRACTION :ATALANTE HOT RUNS, 2004
Assessment of the Pu-Am co- extraction & separation from F.Ps
by using salt/metal extraction in LiF-AlF3 / Al(Cu) at 830°C

Run 2 : Extraction (Al)Salt before extraction: LiF-AlF3 (8519.5 mole %) + PuF3 (11,1 wt%) +AmF3 (0,12 wt%) + CeF3 (2,50 wt%)
+ SmF3 (0,52 wt%) + EuF3 (0,51 wt%)
+ LaF3 (0,52 wt%)

High Temperature Salt/MetalContactor in glove-box (Atalante)

Salt before extraction

Alloy/Salt ratio = 1
Alloy ~ 15-17 g
Salt after extraction

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 200618

en résumé….
actinides, the main target !

Solvent extraction, a powerfull, clean, mature technology !
 Many options studied for An recovery :molecules and extraction processes have been
experimented at lab-scale and « large-lab » scale.
 co-precipitation, a very promising route to get An solidcompounds

Pyro-processesses : an attractive alternative !
 CEA launched a R&D program Encouraging results, to be pursued (technological issues!)

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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The ATALANTE facility…

From basic studies to demonstrative experiments …
… up to kgs of spent fuelOECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 200620

Pu industrial conversion : oxalic precipitation• 2 steps :– Pu(IV)(C2O4)2,6H2O precipitation– Calcination to PuO2
• Operated in La Hague plant (R4/T4)
Atalante/L15Pu(IV)

H2C2O4Filtration
PuO2
calcination

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 200621

All-actinide coprecipitation ?

QuadraticNdUOCNacHexagonalSame cristallographic site
For An(IV) and An(III)and solid solutions foroxides !
ba

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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PYROPROCESSES : THE ALTERNATIVE ROUTE• Frame :– launched in the frame of the french legislative act, Dec. 1991, on
the management of nuclear waste– since 2003, extended to Gen IV cycle studies• Very preliminary goal :- all actinide quantitative recovery (> 99 %)- with a “high enough” purity level- both electro-recovery and molten metals extraction

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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ACTINIDE RECOVERY BY SALT/METAL EXTRACTION :MAIN RESULTS> 98 wt% of Pu and Am have been transfered to the Al-based
alloy after one contact
Pure Al
Element M

DMSAm/MPu

273 ± 126

0,78 ± 0,47Am

213 ± 301Ce

0,162 ± 0,021315 ± 289

Sm0,043 ± 0,004

4954 ± 1139

Eu

< 0,029> 7345

La0,037100

DCm = 185+/-32 with pure Al (measured from Cm traces)
OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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SPENT FUEL REPROCESSING
Spent FuelUPUREX
PuFission
Products&MinorActinides

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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COMPLEMENTARY SEPARATIONS : THE MAIN TARGETS• MINOR ACTINIDES : Am - Cm - Np
(Mains contributors to long term radiotoxicity, after plutonium)• SOME FISSION PRODUCTS : I – Cs – Tc– Significant abundance of long-lived isotope– More « mobile » in repository conditions

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 2006

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ACTINIDE PARTITIONING : R&D SUCCESSIVE STEPS…
1. BASIC RESEARCH (very wide cooperative frame)- innovative : new extractant systems- fundamental : mecanism studies

Several hundred
new molecules

2. DEVELOPMENT- process design- hots runs with genuine spent fuelScale 1/10000

Scale 1/100 à 1/1000- demonstrative tests(integration, representativeness, robustness)

OECD Nuclear Energy Agency, 9th IEM on P&T, Nîmes, 25-29 September 200627