Presentation at
9th OECD/NEA
P&T IEM
Nimes，FranceAn Overview of CRIEPI Pyroprocessing Activities
Tadashi Inoue
CRIEPI
2-11-1, Iwato-kita, Komae-shiTokyoE-mail;inouet@criepi.denken.or.jp
presented by Tadafumi Koyama, CRIEPI

1Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceObjective of R & D on Pyroprocessing in CRIEPIObjective :To propose effective scenario and method for SF treatment
for establishment of a fuel cycle including fast reactor cycle
Target of R & D on pyroprocessing:
1. To establish the compact method for treating various
kinds of oxides fuel2. To establish the effective fuel cycle for fast reactor
3. To establish the technology for recovering TRUs for
HLLW from aqueous reprocessing
2

Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceMetal Fuel Cycle Integrated with Oxide Fuel Treatment

MiningLWR Fuel Cycle

Metal Fuel FR Cycle

Oxide fuel fabrication

Pyro-reprocessing

U, Pu

UUU, Pu, MA, FP

Enrichment
LWR

Metal Fuel FR

Spent MOX, etc.
U, Pu, MA, FPU

U, Pu, MAU, Pu, MA

MOX

PUREX Reprocessing(UO2 recovery),ElectrochemicalReduction

Metal Fuel Fabrication

MA, (U, Pu)

HLW
Pyro-partitioning

3Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceProcess Flow of Pyroprocessing
Metal Fuel FR

Pyro-reprocessing

U-Pu-Zr / FP

Spent metal fuelFast Reactor
U, U-Pu/ salt, Cd

Electrorefining
MAU,

Cathode U-Pu
process

TRU
Extract

Fuelfabrication

Metal Fuel
U-Zr
U-Pu-Zr

U-Pu / FP
MA / FP

chlorination
HLW

denitration

Spent Oxide fuelUO2
separation

Electroreduction

Waste
treatment

U-Pu

fresh MOX fuelPre-treatment
4Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceOverview of Collaboration with domestic and overseas organizations
CRIEPIRole: Developing process technology
Extending to engineering scale
development○Process technology by use of molten
salt and liquid metal

INL
Mass tracking in ER
Government support
program (Contract

JAEA(JAERI)
Plutonium（Electrorefining, Fuel fabrication
For irradiation)(1996 - )○Installation of experimental facility/equipment
by use of actinides and genuine materialbasis)- Metal fuel cycle: 2subjects- Electrochemical
reduction of oxide fuel: 2subjects○Design study of facility/equipment forcommercial base

JAEA(JNC)

ITU(EU-Germany)
TRU/Genuine material（1989 )Contribution to EUROPART

Kyoto University
Research Reactor

Plutonium(Series demonstrationof process)(2000 -Uranium(1990 -)

at CPF)

Other collaborations
・Toshiba（1987-）

・DOE/ANL(1989-1994)
・Rockwell International/U. of Missouri（1988-1995）
・AEAT（1997-2000）

Participation to cooperation research: EUROPART
Bi-lateral information exchange agreements: BNFL, CEA
5Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceJoint study with JAEA: Basics of Electrorefining with Pu
Recovery rate into Cd cathode：1.2t-An/y（per one electrorefiner）→Equivalent cathode current density
125mA/cm2stirrer/ lead

Steel crucible(120mmf)
li quid Cd cathode(120g, 40mmf)
mol ten sal t(1.2kg, 60mm-H)
li quid Cd anode(1.4kg, 16mm-H)

Cd ingot with U+Pu
（Cd：120g、U+Pu：14.7g）
Cd

50mm

Concentration in LCC（wt.%）

10%

0.25%
Pu/U in salt：4.39

8%

0.20%
Pu

6%

0.15%
Am
0.10%

4%
U
2%

0.05%

0%
0%

2%

4%

6%

0.00%
8% 10% 12%

Passes charge converted to HM content

Composition change of Cd cathode(U,Pu)Cd11(U,Pu)Cd6

Electrorefiner for Pu separation(U,Pu:100g)
Central Research Institute of Electric Power Industry

6

9th OECD/NEA P&T IEM, Nimes, FranceJoint study with JAEA: Series verification of pyroprocess with Pu
Evaluation of material balance through reduction to casting（Oxide reduction

UO2(U,Pu)O2（Electrorefiner)

U- Pu（Distillation）

U、Pu

Uー＋（Injection casting）

U+Pu+Zr（Re-oxidation）

UO2(U,Pu)O 2ーAnode Cd Cathode
Solid Cathode

Salt・CdU 3+LiCl/Li

Li Reduction /Electroreduction

3+LiCl-KCl Pu

Electrorefineing(500℃）(650℃)

Distillation(500－1500℃)

Sampling(1500℃）

Oxidation(500℃)

Metal fuel cycle
Oxide fuel cycle

Central Research Institute of Electric Power Industry

7

9th OECD/NEA P&T IEM, Nimes, FranceJoint Study with JRC-ITU: Test with HLLW and Metal Fuels

Caisson with high purity Ar atmosphere andmanipulating operating system

Dismantling and transfer to hot cell after
experience with non irradiated TRUcontaining material

Set up of caisson in hot cell-0.8

U,Pu,Zr濃度
バルク
salt
溶融塩

alloy合金"スラリー"層Slurrylayer（塩とZr粉末）withsalt and Zr

溶融塩中Diffusion
拡散層layer in salt

Cross section after anodic
dissolution of U-Pu-Zr-MA-0.9
anode potential (V vs Ag/AgCl)

Concentrationof U,Pu,Zr

-1.0

-1.1

-1.2

-1.3
Run2-exp

Run3-exp

RUN2-calc

RUN3-calc-1.401000

2000

3000
4000
5000
electric charge passed (C)Model of anodic dissolution and anode potential change

6000

7000

8000

Uranium deposit

Pu,MA,U in cadmium

8Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceEngineering Technology development: High-throughput Electrode
U collection rate based on the solid cathodeca.8.8g-U/h/L (at unit volume of electrode)

After the improvement withclearance, scraper, etc.,
more than 40 g-U/h/L was achieved

0.73kg-U

Uranium metal recovered（ca.5kg）
Central Research Institute of Electric Power Industry

99th OECD/NEA P&T IEM, Nimes, FranceEngineering Technology development: Transport technology & Equipments
7000

PYRO-STATION : Pyroprocess Scaled-up Test Apparatus for Industrialization

溶融金属輸送試験装置
Cdバ ッ フ ァ Transportタン クMetal
Test Rig

溶融塩バ ッ フ ァ タン ク546N
重量測定エ リア不溶解残渣
処理エ リア(500 ×1000 )

φ784

2000

(800 ×800 )蒸留装置(1000 ×1000 )陽極操作エ リア
陽極操作エ リア(500 ×800 )

溶融塩輸送試験装置

Salt Transport Test Rig(500 ×800 )

電解精製槽
Electrorefiner

Ar atmosphere Large Glove Box
Salt Transport Rig
Central Research Institute of Electric Power Industry

Metal Transport & Distillation Rig

10

9th OECD/NEA P&T IEM, Nimes, FranceEngineering Technology development: Metal/Salt Contactor for TRU recovery
The separation experiments were carried out with Ce,Gd, Y as substitutes of U, Pu(MA), REs , respectively.

The flow rates of the experiments were about 3 litersof both salt and Cd in 1-3 hr.

The concentration of each solute was found to reachsteady state immediately.
As expected, effectiveextraction were achieved at high agitation speed andlow flow rate.

In the case of low flow rate experiment, more than
97% of Ce and Gd (substituted for actinides) wererecovered in one stage.

Further experiments are now under way with using 3staged extractor.
Single stage counter-current extraction
Central Research Institute of Electric Power Industry

11

9th OECD/NEA P&T IEM, Nimes, FranceDevelopment of Oxide Fuel Treatment : flowsheet development
Storage
Decladded spent fuelResidual oxide

Fuel Fabrication～ 0.5Ｖ
CathodeAnode

Metal reduced～ 3VCathode～ 0.5Ｖ

AnodeAnodeSolidCathodeliquid

UO2 transfer
U,TRU
In CdUCs, Sr, I, etc. dissolution

O-ion
transfer

UO2

LiCl or LiCl/KCl

LiCl or CaCl2

U3+,FP

TRUn+
LiCl/KCl
Salt

Waste with AL, ALE
Salt
Waste treatment by zeolite

Salt waste
Central Research Institute of Electric Power Industry

Actinide recovery bymulti-stage extraction

Waste treatment by zeolite

Salt waste

129th OECD/NEA P&T IEM, Nimes, FranceDevelopment of Oxide Fuel Treatment: experimental achievements
Electrowinning of UO2 in LiCl-KCl

SEM image of UO2 deposit(Radial cross section)

Electrochemical reduction

Reduction of MOX (55U-5Np-40Pu) wasconfirmed with small scale

Reduction of UO2 in larger scale
was confirmed in ~100g scale

50mm
内周部の拡大Magnified

40mm
13Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceObjectives of irradiation of metal fuel
Fuel performance to be verified for commercial use
Item

Objective

Target value

Target for oxide

Burn upCost-effective

ca. 200GWd/t

ca. 200GWd/t

Linear heat rateCore-compactness

ca. 500W/cm

ca.450W/cm

High temperature

Heat efficiency >40%

Cladding temp. ≧650C

Cladding temp.≧675C

MA-transmutation

Environmental
friendly

Several %/year

70-80% compared withmetal fuelList of irradiation test of metal fuelANL record

JOYO. planned

Phenix-METAPHIX-

Item of verification

High B.U., High LHT

High temp. operation

MA transmutation

Fuel composition

U-Pu-Zr

U-Pu-Zr

U-Pu-MA(RE)-Zr

Fabrication

Injection casting

Injection casting

Arc-melting

Number of pins

ca. 600 pins

ca. 10 pins

9 pinsMax. cladding temp. Less than 600 ℃

More than 650 C

Less than 580 C

Max. burn-up

ca. 200GWd/t

ca. 200GWd/t

ca.100GWd/t

Linear heat rat

450 ～ 500 W/cm

ca. 500 W/cm

ca. 350 W/cm

Schedule

Finished( ～’95)

Fab.：’03 ～’06
Irrad.：’07 ～’15

Fab. finished(～’94)
Irrad.；’03 ～’1014

Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FrancePhenix irradiation of MA-metal fuel - METAPHIX - Irradiation of metal fuel pin with U-Pu-Zr contained minor actinides(Np,Am,Cm)
and rare earths- Fuel fabrication, PIE and recycling with pyro-process in ITU
Irradiation

2003

2004

2.4 at.%Start→

7.0 at.%Start→

11.0 at.%

Start→

2005

2006

2007

2008

Trans.

PIE→→Trans.

PIE→→→

Trans

2009

2010

U-Pu-Zr-MA-REﾞ
PIE

MA; Np, Am, Cm
RE; Ce, Nd, Y, Gd→(Fabricated by arc-melting)- Finished the non-destructive analysis on pins with 2.4at% burnup at PHENIX＜Configuration of capsule＞＜Pin configuration＞
A・C：U-Pu-Zr、B：U-Pu-Zr-MA-RE

Irradiation of 3 pins in the same capsule at different burnup

1 79 38 082 85

1 00 1 00 1 04 67

16.55ΦAB

MOX Driver pin

CN a - b ondin g gas ple num

23Metal fuel pin withMA⇒4 35

4 35＜Appearance after irradiation＞
M O Xdrive rNo failure and no visual deformation
H e - bo nd in g

Composition of region B, wt%⇒Pin1 : U-19Pu-10Zr
Pin2 : U-19Pu-10Zr-2MA -2RE
Pin3 : U-19Pu-10Zr-5MA -5RE

Transport to ITU for destructive analysis etc.
Collaboration with ITU15Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceMetal fuel development -Fabrication of fuel pins for JOYO irradiation- Installed electrorefiner for reduction and separation, Injection casting in former JAERI- Fabricated U-Pu-Zr rod- Fabricate 10pins until 2007, and put into the core of JOYO at 2008, low, medium and high B.U.

42Φ

⇒⇒
5mm

Cathode product（Cd-Pu-U）

30μm

U-Pu ingot

Cd distillation

Casting test
(U-10%Pu-10%Zr)⇒⇒

fuel fabrication apparatus
Collaboration with JAEA(JAERI) 16
Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceEngineering scale model of injection casting for U-Zr

Casting furnace

Mold Loading
equipment ofPressurestorage tankAppearance of casting furnace (U-Zr : 20kg/batch）

Quartzmold

Inside view during casting

Molds injected U-Zr

Heel and dross in crucible- 20kg/batch ：～400mm length, 50～60slugs/batch
17Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceFuture study
Outline:- Verification of process by use of genuine material- Development of engineering scale model- Safeguard and material accounting- Irradiation of metal fuelR&D item:- Verification of pyro-process by use of irradiated metal alloy atPHENIX- Verification of reduction process by use of spent oxide fuel- Development of engineering scale model of electrorefiner, TRU
extractor, waste treatment & solidification- Safeguard and material accounting measures- Design study of reprocessing facility and economic analysis
18

Central Research Institute of Electric Power Industry

9th OECD/NEA P&T IEM, Nimes, FranceProcess Flow of Pyroprocessing of Metal Fuel Cycle

Spent metal fuel

UPu,U,MARE

U/Pu/MAPu,U,MANM

Decladding &Chopping(U-Pu-Zr)+MA, FP

Zr

AM,AEM
RE,I

U,Pu,MA-Cd

Distillation ofsalt and Cd
U,Pu,MA

Fuel fabrication

Distillation

Electrorefining

Fresh metal fuelU metal with salt

(Injection casting)U metalSpent salt
(LiCl-KCl + U,Pu,MA,FP)

Spent salt

Salt purified

Cd-U,Pu,MA

Multistage countercurrent extraction(Actinide recovery)

Fresh U、Zr

Pu+MA recovery into
Cd from salt
Quartz mold used

Cd-Li
Salt with FP

Recycled Spent salt(LiCl-KCl + FP)
salt
Zeolite＋FP+ LiCl-KCl
Zeolite column(FP decontamination)

Zeolitecontained FPRecycle
Central Research Institute of Electric Power Industry

Zeolite absorbed
alkali and alkaline
earth FP in salt

Salt waste
solidification

Boric acid, Al2O3
Sodalite

199th OECD/NEA P&T IEM, Nimes, France