Partitioningof Fissile Materials and Radiotoxic
Materials from Spent Nuclear Fuel.
RIAR current and future activities

M.V.Kormilitsyn, A.V.Bychkov
RIAR, RUSSIA

9th IEM on Actinide and Fission Products Partitioning and Transmutation
Nimes, France, 25-29 September 2006

Russian programs on partitioning (some history)
In 1980-s – partitioning of Np from SNF was implemented
into MAYAK Plant, separation of Am+Cm/REE andextraction of Cs+Sr were tested on real HLW
1993-2001 – Minatom Program “RECYCLE”:
Participants: MAYAK Reprocessing Plant, Bochvar Institute,Kurchatov Institute, RIAR, IPPE, Moscow Institute ofPhysical Chemistry of RAS
Main tasks¾ Separation and collecting of I, Tc, Am¾ Development of reactor conceptions of FP and MA
incineration (transmutation)
1999 (until now) – FS and R&D of advanced RT-2
Reprocessing Plant Concepts and following Concepts for
future LWR reprocessing plantTechnologies
Advanced (or extended) PUREX, Fluoride Volatility
technology, DDP, supercritical CO2 extraction, others
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Russian programs on partitioning (some history)
2003-2006 – Preparation of new Russian Program “Construction ofthe BN-800 FR with CFC demonstration”
Start of Pu fuel cycle in Russia (MOX fuel) and utilization of accumulated“power grade” Pu
Possible technologies for MOX fuel production
RIAR – pyrochemical + vi-packing with Am burning
Bochvar Institute – codeposition GRANAT technology and pelletizing
Possible technologies for MOX fuel reprocessing demonstration
RIAR – pyrochemical reprocessing with MA partitioning and vi-packing
Bochvar Inst. – simplified PUREX, GRANAT and pelletizing (nopartitioning)
Russian State Duma supported this Program as innovative Program
2000 (until now) – Program of BREST fast reactor
Main approaches to BREST fuel cycle
So-called “on-site” closed fuel cycle (i.e. location of fuel cycle
facility on the same site with reactor unit) Pyrochemical reprocessing
Homogeneous recycle of MA in frame of BREST close fuel cycle
3Russian programs on partitioning
2006
Partitioning will be included into new integrated
conception:NEW
TECHNOLOGICALPLATFORM

Commercial Fast Reactors withClosed Fuel Cycle (included P&T)
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Comments:
New look on Advanced Fuel Cycle Concepts
PARTITIONING is most important component of FC
not Spent Fuel REPROCESSING,
but Spent Fuel PARTITIONING,
i.e. P&T Nuclear Fuel Cycle
It include: CLOSING, PARTITIONING, RECYCLING,IRRADIATION/TRANSMUTATION and WASTESTREATMENTIn such approach the REACTOR units are only one ofpeer components of Fuel Cycle
5International cooperation in the field of advanced FC.
Russian research needs. RIAR view
Fuel production

Reprocessing

P&T

Advan- Cladd.
Concept Fundaced
Materials Studies mentalStudies

MOX

other

China

pellet/vibro?

-------France-MAoxide-Am,Cm
recovery

Pyro/
RTIL’s+ ?

FSCmIndia-Met/Th?
Carbide?

?

?

?

?

?

?

JapanMOXvibro-ODSFS

MAKorea-Pyro+ ?

--USEU

MA met. Metalliz. MA/REE?
/ vibro- separ.
DUPICVibro?

-

MOX / MA/REE Pyro/nitrides? separ. Fluorex/
MoO42-MAnitride-----

RTIL’s--MSR fuel--Cm

Blue – current and past activities, red – planning, discussing and desired, black –without RIAR, but in any case – in all topics and cases RIAR is ready to participate

6Since 1992 RIAR has been performing
the R&D DOVITA program¾ Dry technologies for MA fuel reprocessing andpreparation¾ Oxide fuel application as the most widely studied one¾ Vibropacking automated technology of the fuel pinproduction¾ Integrated disposition of fuel reprocessing and fuelelement refabrication facilities on the same site withthe reactor¾ TA The whole complex of approaches will permit acreation of the compact plant for Transmutation ofActinides
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RIAR DOVITA experience in addingof minor actinides in fuel compositions
9 Pyrochemical technology of adding Np into oxide fuel (520%) has been developed
9 Performance of vi-pack (U,Np)O2 fuel has been validatedexperimentally to a burn-up of ~20% in BOR-60
9 No evidence of significant difference in performance of(U,Np)O2 fuel pins with compared with UO2 or MOX fuel has
been noticed

Microstructure andmacrostructure ofirradiated (U, Np)O2 fuel,919% burn-up

Pyrochemical process of Am codeposition with MOX fuel (25%) has been developed

9 Methods of Am/REE separation in melts has been tested(AMBOINE-1)
9 Special vi-pack targets containing Am oxide with UO2 orinert matrix have been developed (AMBOINE-1)
9 Transmutation of Np, Am, Cm is being studied in BOR-60
8Oxides with MA. AMBOINE-1 Program incollaboration with CEA
The Program has started in December 2001.
Study of Am recycling and separation from RRE bypyrochemistry
Development and fabrication of BOR-60 fuel pins with(UAm)O2 in core and with UAmO2+MgO in axial blankets.
The Program is completed.
The BOR-60 experimental fuel pin has been
fabricated.
Investigations on Am/REE separation by selectiveoxide precipitation in molten salts have been carried out.
The possibility of the Program continuation – AMBOINE-2 including comparative study of different fabrication
techniques (vi-pack, sol-gel, GRANAT) and further
9irradiation in the BOR-60 reactor is under discussion.

Main part of RIAR activities related to P&T
are carrying out in frame of ISTCDOVITA fuel cycle

Integrated
projects
ISTC 17ISTC 272

PuO2

UO2

NpO2

H o m o g e n e o u s re c y c lin g

Targets with MA
ISTC 2680

FAs production
AFBR reactor
Targetassemblies

FAs

Partially treatment without
reprocessing(U, Pu, Np)O2(Am, Cm)O2 +residual REE

Pyrochemical reprocessing
Phosphate concentrate ofFP’s to preparing for storage

H e te ro g e n e o u s re c y c lin g

Targets production

Fuel and fuel pins production

Pyrochemicalpartitioning
ISTC 279
ISTC 3231p
ISTC 3261

Inert matrix or UO2(Am, Cm)O2

Used chloride salts containingof residual Cs-137 and Sr

10Nitrides with MA. “MATINE: Study of MA
Transmutation in Nitrides: modeling andmeasurements of out-of-pile properties”.
ISTC Project#2680
On May 2004 the Project has started.
Participants - IPPE, Bochvar Institute, RIAR.
Collaborators - CEA (France) and KTH (Sweden).
Objectives
performance modeling of (Pu,Am,Cm,Zr)N (with ZrN=5565%, Pu/Am/Cm=40/50/10) fuel under irradiation in ADS fast
spectrum up to high burn-up in order to compare relative
performance of helium, sodium and lead-bismuth bonded pins.
Two different fuel forms (pellet and vibropacked).
Experimental study of PuZrN properties .
The Program continuation – ISTC Project #3608 MATINE-2 including in particular the fabrication of (Pu,Am,Cm,Zr)N microtargets (containing about 1 g of Cm-244) by vi-pack technique andfurther irradiation in the BOR-60 reactor - is under preparation.
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ISTC Project # 3261

Study of Cm thermodynamics in molten chlorides
Objectives
Reactions of formation for oxygen Cm compounds- equilibrium constants for reactions of Cm oxygen compounds
formation versus temperature;- equilibrium constants for reactions of Cm oxygen compounds
formation versus the inverse effective radius of solvent cathion
Reactions of formation for oxygen-free Cm compounds- standard potential for redox pair versus temperature;- standard potential for redox pair versus the inverse effective
radius of solvent cation
Simulation of Cm behavior in molten chlorides
Pourbaix diagrams

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ISTC Project # 3261

Study of Cm thermodynamics in molten chlorides
Investigation methods•Thermodynamics of formation for oxygen Cm compounds

Potentiometric titration with oxygen pumpadvantage - small concentration of Cm in melt

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ISTC Project # 3261

Study of Cm thermodynamics in molten chlorides
Investigation methods•Thermodynamics of formation of oxygen-free Cmcompounds
Method of EMF
Cyclic Voltammetry
Chroho Potentiometry

necessary request - Cm concentration in melt must be morethan 3%wt
(interaction of Cm with melt is negligible)•Simulation of Cm behavior in molten chlorides

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ISTC Project # 3261

Study of Cm thermodynamics in molten chlorides

Conditions

Molten salts
LiCl-KCl, NaCl-CsCl, NaCl-KCl•Temperature range
450oC - 850oC•Cm content
10-4 – 10-2 mol/kg (Potentiometric titration)(2 – 5)*10-1 mol/kg (EMF, Cyclic Voltammetry, ChrohoPotentiometry)

Collaborators – ITU, CIEMAT, KTH, (CEA)
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ISTC Partner Project # 3231 (RIAR-KAERI)
Separation of MA from REE on a liquid metallic cathode inmolten chlorides

Objectives:
Task 1: Polarization curves on electrodeposition of actinides
and lanthanides on bismuth and cadmium cathodes
Task 2. Electrodeposition tests for effective separation ofactinides and lanthanides on liquid-metal cathodes
Task 3. Effect of uranium content in molten salt toelectrodeposition and separation of actinides and lanthanides
on liquid metallic cathode-Actinides - U, Np, Am, Cm,-REE -Nd, La, Ce-Systems: - Bi / LiCl-KCl and Cd / LiCl-KCl16

Future ISTC proposals forstudies
Continuation of recently investigated subjects:
Molten Salt chemistry of Am and Cm for fluorides
Phase II for ISTC 3261

Partitioning of MA/REE in molten fluorides
with liquid cathodes

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Application of Room Temperature Ionic
Liquids for Separation of TPE and REE
RIAR proposal for ISTC project

The R&D program includes the following stages:
selection of the RTIL with a rather wide
electrochemical window, study of its properties,
study of solubility of the TPEs and REEs salts
with different anions (NO3-, Cl-, F-, CN-) in the chosen
RTILs
study of composition of the complexes andelectrochemical behavior of the TPEs and REEs in thechosen RTILs
study of TPE and REE cathodic deposition in thealloy form with transient metals (Zn, Cu, Ni, Al andothers) and/or on a liquid metallic cathodes (Ga, Hg)
study of separation Al and actinides from
Al-An-alloys by Al electrorefining process
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ISTC Project proposals from RIAR:
Preparation of monographs related to P&T andadvanced fuel cycle
V.Nickolaev, E.Karelin, R.Kuznetsov, Yu.Toporov. Technology ofTransplutonium Elements – second edition and translation toEnglish and publishing
V.Radchenko, M.Ryabinin, etc. Physical Metallurgy ofTransplutonium Elements – preparation of Russian and Englisheditions
A.Mayorshin Fuel elements with vibropacked oxide fuel –preparation of Russian and English editions
O.Skiba, A.Bychkov, V.Ivanov. Pyroelectrochemical process innuclear fuel cycle – preparation of Russian and English editions
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Research area of pyrochemical (non-aqueous)
methods for MA/FP partitioning development
Melts/
media

Electrochemical methods
Liquidcathodes

Solidcathodes

Chlorides

Cd, Bi, Ga

Al,

Fluorides

Bi, Ga,Al, Pb-Cl- /F-Cd, Bi,Ga, Al, Pb

Molibdates
RTIL

AnodicE/Chem.
dissolu- oxidetion
titration

OxidesPrecipitation

Metallization+++++++-Al+++--+Ga, Hg

Zn, Cu,Ni, Al, …

+-+--+ Methods of Volatility of Fluorides and /or Chlorides

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New Russian Initiative P&T Group
Main objective
To establish New Russian National R&D P&T Program
Form of coordination and cooperation
Multi-lateral Frame Agreement between different
Russian R&D Institutes and Organization
Initiative Participants
RIAR (Dimitrovgrad)
Kurchatov Institute (Moscow)
IPPE (Obninsk)
JINR (Dubna)
Chlopin Institute (Petersburg)…
List is open ….

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