Partitioning Research at JRC - ITU
Recent Progress

J-P. Glatz, L. Casseyre, B. Christiansen, R. Malmbeck, M. Ougier, H. Ottmar,
D. Magnusson, J. Serp, D. Serrano-Purroy, P. Soucek, T. Inoue, K. Uozumi
9th Information Exchange Meeting on

Actinide andFission Product Partitioning & Transmutation
26. - 28. September 2006Nîmes, France

9th IEM 906

1

Partitioning activities at ITU
9 Institutional program: Partitioning and TransmutationÍactivities in the field of hydro- and pyro-reprocessingÍdemonstration of separation schemes on simulated andirradiated materials

9 Participation in European projects actually EUROPART
Ícontributions to hydro- and pyro-metallurgy WPs
Íjoint partnership with CRIEPI

9 contractual collaboration with CRIEPI since 1991Íreprocessing of the metallic fuels U,Pu,Zr with up to 5% An’sand Ln’sÍstudy processes on calcined - chlorinated HLW from PUREX typewasteÍstudy of direct electroreduction processes for the head-end
conversion of oxides to metal
9th IEM 906

2

ITU competences: P&TNew
Centrifugal
Contactor
Centrifugal
contactor
equipmentin hot cell
equipment

Aqueous partitioning• demonstrate minor actinide
separation schemes in view ofan industrial implementationPyrometallurgical reprocessing• reprocessing of new types offuels (e.g. metallic U,Pu,Zr,MA)and HLW• electroreduction of oxide fuels
PIE of innovative fuels

Chlorination equipment

Hot Cell Laboratory• CERMET, inert matrices, metallic fuels,

ThO2, nitrides, carbides etc.

Minor Actinide Laboratory• fabrication of minor actinide containing

fuels and targets for transmutation

9th IEM 906

3

Minor Actinide Laboratory
active operation started

Hot CellLaboratory
Pilotfacilityfor
pyrometallurgicalreprocessing

Pyro-reprocessing objectives¾ develop reprocessing schemes for genuine fuels¾ demonstrate co-recycling of all actinides (goal for

new generation reactor systems)¾ achieve an efficient separation of all actinides fromlanthanide fission products¾ set-up an efficient safeguarding technology¾ investigate appropriate head-end conversion

especially oxide to metal¾ study the recovery and the recycling of actinides(fuel re-fabrication)

9th IEM 906

4

Pyroprocessing of metallic fuels

An reduction potentials on different cathodic materials
-1

UPuAm

PuAm
La-1.2

NdLaPotential / V vs. Ag/AgCl-1.4

U-1.6

Pu-1.8Am-2

Nd
La-2.2sol. W

9th IEM 906

liq Bi, Cdsol. Al•more efficient An/Ln separation on solid cathodes (W and Al)•alloying with An stabilizes the deposit (liquid Cd ,Bi and Al)•Al unifies both advantages
5

Pyroprocessing of metallic fuels
Am and Nd valency in molten salt25
20

Nd(0)/Nd(III)
Am(0)/Am(III)15

I (mA)

105
0-2

-1.8
Nd(III)/Nd(II)Am(II)/Am(0)

-1.6
-1.4
Am(III)/Am(II)-1.2

Nd(II)/Nd(0)cyclovoltamograms of Nd and Am in liquid Cd
6-5-10-15

E (V/AgAgCl)

9th IEM 906-1

Electrolyses of U,Pu,Zr,Ln,MA alloy:

batch experiment involving 25 runs ( ~30g of fuel)Wt % in salt

UPu
AmZr
Y
CeNd
Gd
Al

Composition of the dissolved
deposit (mg)B e fo r e
Run 1Af te r
Run 1

B e fo r e
Run
11Afte rRun
11BeforeRun
14AfterRun
14

Run1

Run 7

Run 11

Run 142 .5 50 .9 60 .0 90 .0 1 60 .0 2 10 .1 7 70 .0 2 5-2 .1 4
1 .5 80 .1 70 .0 4 8
0 .0 4 7
0 .4 0 3
0 .0 4 8-0 .2 50 .6 5
0 .2 40 .0 5 60 .0 7 40 .0 7 8
0 .5 90 .0 6 9-0 .3 00 .5 00 .2 30 .0 9 60 .0 7 50 .0 8 5
0 .6 10 .0 7 3
-0.20
0.32
0.19
0.055
0.075
0.089
0.65
1.8*
-

0.30
0.27
0.19
0.075
0.078
0.091
0.65
1.8*-936
94.2
4.4
0.039
0.041
0.374
0.042
387
171386
91
99.95
8.8

512243
13.5
0.018
0.026
0.244
0.025
301
9.3
1193
70
99.96
43

223
203
9.95
0.015
0.024
0.183
0.018
173
8.2
674
80
99.9
42176
146
8.8
0.008
0.011
0.092
0.027
134
6.1
598
70
99.9
26

* added to the melt as GdCl3

Current density (mA/cm²)
Charge (C)Faradic efficiency (%)
m An/(m An + m Ln) (%)
m Am /m Ln•Gd has the lowest electrodeposition potential difference compared to Am•at Gd conc. corresponding to ~250 runs (300g of fuel) Am/Ln sepation still efficient9th IEM 906

7

actinide separation from U,Pu,Zr,MA,RE fuels
9 Adherent and compact deposit are obtained on solid Al witha good faradic yield (~ 90%)

9 Separation of MA from Ln: the cathodic potential can bechosen in order to collect selectively U, Pu, Am (Ec > -1. 25V
vs. Ag/AgCl 1 wt%)

9 Efficient An/Ln separation by electrolysis was demonstrated

for almost 30 g of U,Pu,Zr,MA,RE fuels

9 separation efficient after 25 electrolyses of the same salt

mixture (more than 6 months of experiments)

9 Selective grouped separation of actinides from “realistic” fueldemonstrated

9th IEM 906

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Direct electroreduction of irradiated FR
oxide fuelExperiments ongoing using SUPERFACT irradiatedfuel, fabricated by ITU:
2 pieces of (U0.74Pu0.24Am0.02)O2 and2 pieces of (U0.74Pu0.24Np0.02)O2
Crucible material: MgO
Electrolyte: LiCl + Li2O (T=650°C)
apparatus

Setup
insidethe pyro
caissonSet of electrodes

Experimental set-up
9th IEM 906

9

Direct electroreduction of irradiated FR
oxide fuelSalt samples takenfrom the top andbottom (incl. blackfuel deposit) of thecrucible

fuel loading

Crucible showing
a black reduced
fuel deposit on
the bottom

preliminary results
9th IEM 906

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Direct electroreduction of irradiated FR
oxide fuelr/ro = 0.35

r/ro = 0.44

Afterirradiation
1991
r/ro = 0.34

r/ro = 0.4

Afterstorage
2003

SEM examination of SUPERFACT fuel showing a strong
intergranular porosity due to fission gas release
9th IEM 906

11safeguards/non proliferation
 IAEA and EURATOM: effective flow sheet verification(FSV) at ITU to update the existing design forsafeguarding U and Pu, and to provide additional
information relevant to Np proliferation and safeguards issues are far lessdefined and investigated for pyroprocessing
 new schemes, approaches and analytical techniques
under development
K- X ray Fluorescence (K-XRF)
Neutron Coincidence Counting (NCC)High Resolution Gamma Spectrometry (HRGS)Calorimetry

9th IEM 906

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Application of radiometric techniques for MAs

Technique
K-XRF

NCC

Element/
isotopemeasuredNpAm
CmCm

Isotope
Minimum
contribution amount forApplicationto response*assay
Any sample type in liquid form
50 μgmassfractions of analyte
70 μg≥ 0.02 %.
100 μg244
For any type of Cm-containing
Cm. 90-95%
200 ng246

samples (liquid or solid) withPu/Cm ratios ≤ 1000

Cm: 5-10%

HRGS

Calorimetry

237

Np
241
Am243
AmAm
Cm

241

Am: 98%
Am: 2%
244
Cm: 99%243
Cm: 1%
243

500 μg
10 ng
100 ng5 mg**
200 μg*** For typical MA isotopic composition in spent LWR/FBR fuels** Can be lowered by factor of 10 when using microcalorimeters

9th IEM 906

13Liquid samples for absolutemeasurements.
Low FP content for 237Np assay.
Refractory MA fuels fortransmutation.
Combined with NCC/HRGS forinterpretation.

New analytical equipment for
Pyrometallurgical Processes
Objective: to install NDA assay system for a direct
non-destructive assay on irradiated samples

Status of the project- Design completed- Parts under manufacturing:
Glove box, NCC, plug andsupporting frame for shielding

9th IEM 906

Advanced NDA assay system
14

Pyro-Partitioning: outlook
9 reprocessing of irradiated Zr based metallic fuels; METAPHIX(collaboration with CRIEPI and CEA)
9 TRU recovery from Al cathode: depending on thesubsequent fuel type9 define limitations regarding the use of the salt bath
9 determine recovery rate of actinides: use of graphite anodes
9 clean-up of the salt and waste treatment
9 study of alternative methods for oxide fuel reduction(collaboration with CRIEPI)
9 basic thermodynamic data on Cm: collaboration with RIAR
Dimitrovgrad in ISTC project
9 integration study of the electrorefining process:collaboration CEA (S. Bourg, H. Boussier) -ITU
9th IEM 906

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METAPHIX irradiation experiment
Irradiation of U,Pu,Zr,Ln,MA alloys
3 capsules;
3 different compositions
under irradiation since November 2003 in thePHENIX reactor in Marcoule
1. 90 PEPD
2.4 % burn-up
unloaded: 8. August 2004
transport to ITU 25. September 2006
2. 3 cycles of 120 PEPD
7 % burn-up
unloaded: 20. July 2006
3. 5 cycles of 120 PEPD
11 % burn-up
to be unloaded beg. 2009
work initiated by CRIEPI,Japan; now trilateral project
CRIEPI, CEA, ITU
9th IEM 906

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Pyroprocessing: Tentative Test Plan1999

2000

2001

2002

Design & Construction
U-Pu-MA-RE-Zr

2003

2004

HLLWirradiated FR fuelDenitration

RecoveredTRUs

2008

2009 2010

23
MP2

MP1

Electroreduction

MP3

Electrorefining
Spent salt

Chlorinationelectrorefining
MS Extraction

Molten Salt Extraction

Molten Salt
Extraction

RecoveredTRUs

Recovered TRUs

Cd distillation

Cd distillation
U,Pu,MA

Development andmetal fuel TRU recovery
Installation ofExperimental Apparatus reprocessing
from HLLW
17

2007

Transport METAPHIX 1

Spent salt

9th IEM 906

2006

Pb-Shielding

Electrorefining

Recovered TRUs

2005

Recov.TRUs

Cd distillation
U,Pu,MAU,Pu,MA

FR MOX
electroreduction

METAPHIX
reprocessing