2055-27 Joint ICTP/IAEA School on Physics and Technology of Fast Reactors Systemsindico.ictp.it/event/a08209/session/51/contribution/30/... · 2014-05-05 · Joint ICTP/IAEA School

2055-27

Joint ICTP/IAEA School on Physics and Technology of Fast ReactorsSystems

Dominique Warin

9 - 20 November 2009

CEA / Nuclear Energy DivisionRadiochemistry and Processes Department

MarcouleFrance

————————————[email protected]

Advanced partitioning of MOX fuels by aqueous route (1)

————————————[email protected]————————————[email protected]

CEA / Nuclear Energy Division 2009 IAEA/ICTP School on Physics and Technology of Fast Reactor Systems, Trieste 17-18/11/2009

Advanced partitioning of MOX fuels by aqueous route (1)

Dominique Warin

CEA / Nuclear Energy DivisionRadiochemistry and Processes Department

Marcoule, [email protected]

IAEA/ICTP School onPhysics and Technology of Fast Reactor Systems


CEA/Nuclear Energy Directorate missions

INTERNATIONAL COLLABORATIONS : Europe (SNEINTERNATIONAL COLLABORATIONS : Europe (SNE--TP), USA (GNEP), TP), USA (GNEP), JapanJapan, China,, China,……

A WORLD CLASS LABORATORY FOR SUSTAINABLE A WORLD CLASS LABORATORY FOR SUSTAINABLE NUCLEAR FISSION ENERGY DEVELOPMENTNUCLEAR FISSION ENERGY DEVELOPMENT

● R and D in support of existing LW Reactors (material ageing, fuels, power plant life time, safety,...)

R and D for innovative future GEN IV Fast Neutron ReactorsBasic nuclear science and technology studies, materialsThermal and fast neutron Test ReactorsSimulation program

REACTORSREACTORS

● R and D in support of existing reprocessing plants (Areva La Hague,Sellafield, Rokkasho Mura,..) and for future recycling plantsR and D for nuclear waste management (1991 and 2006 French Acts)

● Hot radioactive facilities

FUEL CYCLEFUEL CYCLE


CADARACHE

Nuclear reactors• Core design, neutronics• Fuels• Nuclear technology• Test reactors for PWRs,

(RJH 2014)

Nuclear fuel cycle• Radiochemistry, reprocessing• Fuel cycle technology• Long term waste management• Na fast test reactor (Phénix,

ASTRID 2020)• Decommissioning

SACLAY

Nuclear materialsSimulation, codesNuclear physics

and chemistry

GRENOBLE

Thermo hydraulics

DEN

CEA/ Nuclear Energy Directorate organization

MARCOULE

SACLAY

MARCOULE

CADARACHE

GRENOBLE

4500 staff, 900 M4500 staff, 900 M€€//yearyear


Final waste radiotoxicity

0,1

1

10

100

1000

10000

10 100 1000 10000 100000 1000000Temps (années)

Rad

ioto

xici

té re

lativ

e

GLASSESFPs ONLY

GLASSESFPs + MAs

SPENT FUEL

TIME after unloading (years)

U ore


0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

5 ans

10 ans

30 ans

50 ans

100 ans

200 ans

300 ans

500 ans

1000 ans

2000 ansCM244

PU238

PU240

PU239

AM241

AM243

BA137M

CS137

SR_90

_Y_90F

EU154F

CS134F

PR144F

RH106F

Contributions to residual heat (UOX spent fuel)


Actinide recycling : what fuel cycle option ?

R T

U

U PuU and Pu recycled,

COEX

FP&MAR TU

UU and Pu recycled,

PUREX

Pu

FP&MA

R T

U

MAU Pu

FP

MA heterogeneousrecycling

MA homogeneousrecycling

R T

U

FP

U Pu AM

MA : Np, Am, Cm


– Reference route• Solvent extraction, PUREX Process

• How to reprocess spent nuclear fuels?• Which industrial technology?

– Criteria• Safety, performance, cost, secondary waste…

How to partition Np, Am and Cm ?

• Already mastered at the industrial scale• La Hague plant (AREVA NC)

UP3 plant: 800 tons reprocessed / year» High separation yields achieved» Few technological waste generated


LLRN recovery by solvent extraction

SPENT FUEL

Uranium and Plutonium

Fission, Activation,and Corrosion Products

PUREXPUREX

COMPLEMENTARYSTEPS

COMPLEMENTARYSTEPS

Cm

Am

Np

Minor Actinides

A possible route…


Reprocessing process : requirements

PUREXSPENT FUEL

1. RECOVER 2. PURIFY

1. CONCENTRATE 2. CONFINE

URANIUM PLUTONIUM

WASTE

SAFETY

RELIABILITY

FLEXIBILITY

COST


Reprocessing requirements and constraints

• High recovery yields (99.9 %)• High purification yields (106)• Low amount of secondary waste…

• Confinment• Shielding• Criticality risk• Nuclear material accounting• Radiolysis…


The PUREX Process

U, Pu, FPs,MAssolution

HULLS

SPENT FUEL HNO3

TBP

FPs, MAs

U

Pu

DISSOLUTION EXTRACTION

TriButylPhospahte TBP


PUREX, the reference since 1950’s…

• TBP, a selective and strong molecule

• High recovery /purification yields(99.9 % U &Pu recovered, DFs ~ 107)

• Low secondary waste amount• No extreme conditions, no severe materials issues• A heavy work for development

WHY ?


PUREX : some important steps

• U.S.A. 1950s (Savannah, Hanford)

• UK 1953 (Windscale)

• France 1958 (Marcoule, UP1)1967 (La Hague, UP2)1976 (La Hague, UP2-HAO) (UOX)1989 (La Hague, UP3)1994 (La Hague, UP2-800)

• UK 1994 (Sellafield, THORP)

• Japan 2007 (Rokkashomura)


PUREX main steps

1. DISSOLVE

2. EXTRACT

3. CONDITION


PUREX Process : 1. « HEAD-END »

GOAL : SOLUBILIZE ALL THE SPENT FUEL COMPONENTS STEPS : SHEARING- DISSOLUTION-CLARIFICATION DOWNSTREAMS :

1 – DISSOLUTION LIQUOR (U, Pu, P.F., A.M.) ] to next steps

2 - "HULLS " (and end-pieces) (AP) ⎫ ⎬ to be conditionned 3 – DISSOLUTION RESIDUES (noble metals, ...) ⎭

4 – GASEOUS EFFLUENTS (gaseous FPs) ] to be purified

before release


PUREX Dissolution mechanisms

UO2 Dissolution : ΔH = - 420 J/kg< 2M : UO2 + 8/3 HNO3 → UO2 (NO3)2 + 2/3 NO + 4/3 H2O

> 8M : UO2 + 4 HNO3 → UO2 (NO3)2 + 2 NO2 + 2 H2OUO2 + 3 HNO3 → UO2 (NO3)2 + ½ NO + ½ NO2 + 3/2 H2O

PuO2 Dissolution :PuO2 + 4 HNO3 → Pu (NO3)4 + 2 H2O (very slow)


PUREX Volatile Radionuclides

Iodine (I2) [129I]

Carbone (CO2) [14C]

Tritium (HTO) [3H]

Krypton (Kr) [85Kr]

To be considered too :- NO/NO2


The principle of solvent extraction

Step1Preparation

Step 3Separation

Step 2Emulsion

Organic solution

Aqueous solution( ) [ ]

[ ] aq

org

MM

=DKorD


Extraction of a specie

[ ] [ ] [ ][ ] [ ] [ ] ...21

...21++++++

=complexcomplexMcomplexcomplexMDM

Mixer-Settler (MS)

Pulsed Column (PC)(M)aq (M)org

Very diverse mechanisms:

- solvatation (complexes)

- ion exchange (anions, cations)

- chelation (all organic species)

(all aqueous species)

For two elements, M1 and M2 to be separated :

2

1

21

M

M/MM D

D FS =


« Non compensated « extraction

• « Passive extraction », solvation of a lipophiliccompound in the organic phase

M

Organic Phase

Aqueous Phase

( )M M

MKex

⎯⎯⎯ →⎯ ⎯⎯⎯ ⎯←


• Solvatation of a neutral complex:(acid or metallic salt in the initial aqueous solution)

• Uranyl nitrate by TBP

( )en

MK-n EMA An E e M ex

⎯⎯⎯ →⎯++ ⎯⎯⎯ ⎯←+

Mn+

Organic Phase

Aqueous PhaseMn+

Mn+

A-

A-

A-

A-

A-

( ) [ ][ ] [ ] [ ] [ ] [ ]n-e

Mn-en

enex

AED

AEMEMAMK

⋅=

⋅⋅=

+

« Non compensated « extraction


• Cation exchange

• Am3+ by HDEHP

++ +⎯⎯⎯⎯ →⎯ ⎯⎯ ⎯←+ H n (HA)MA

K HA m M n-mn

exn

( )[ ][ ][ ][ ]

[ ][ ]m

n M

m n

n nmn

exHA

H.D HA.M

H.HAMA K+

+

+− ==

Ion Exchange extraction

Mn+

Phase organique

Phase aqueuseMn+

Mn+

A-A-

H+ H+

H+

Mn+

Organic Phase

Aqueous PhaseMn+

Mn+

A-A-

H+ H+

H+


+

Cationmétallique

Complexant azoté(TPTZ,Py, ...)

Complexecationique

Extractantéchangeur cationique(acide carboxylique, ...) Complexe neutre

+

M M

M

(n+)(n+)

+

Cationmétallique

Complexant azoté(TPTZ,Py, ...)

Complexecationique

Extractantéchangeur cationique(acide carboxylique, ...) Complexe neutre

+

M MM

MM

(n+)(n+)

ORGANIC PHASE

AQUEOUS PHASE

Synergistic extraction

LIGAND CATIONIC COMPLEX

CATIONIC EXCHANGER(carboxylic acid)

NEUTRAL COMPLEX

METAL CATION


UO22+ by

TOPO/HDEHP

( )+

−

+

+⎯⎯⎯⎯ →⎯ ⎯⎯ ⎯←++ Hn HAAML HAm Le M nmne

n exK

( )[ ][ ][ ][ ] [ ]

[ ][ ] [ ]e m

n M

e m n

n nmne

exLHA

H.D LHA.MH.HAAML K

⋅=

⋅=

+

+

+−

PC8H17 C8H17

C8H17

O

O

OHPO

O

Synergistic extraction…


Uranyl Extraction by TBP

TBP 2 ,)NO(UOTBP 2NO 2UO 23232

2 ⇔++ −+


(UO22+)aq + 2 (NO3

-)aq + 2 (TBP)org (UO2(NO3)2 , 2TBP)org

Aqu

eous

phas

eO

rgan

icph

ase

Uranyl Extraction by TBP


Actinide extraction by TBP

OXIDATION STATE

III IV V VI

U X

Np X

Pu X X

Am

Cm

X

X


PUREX U-Pu Extraction operation

TBP 1.1 M

UO2+ ,Pu 4+, FPsFP

EXTRACTION

U, Pu

Operating conditions : [HNO3] rather high

[U]org rather high


PUREX with pulsed comumns : principle

P

Light phase inlet

Heavy phase outlet

Light phase outlet

Heavy phase inlet

plates


Atalante/L15a

b

From PUREX to COEX™: co-extraction principle (U-Pu-Np)

FP + MA

Extraction/scrubbing

Pu stripping U strippingNp scrubbing

Oxidizing

Extraction/scrubbing Pu stripping

OxidizingConcentration and

buffer storageReduction

UVI scrubbingAdjustment

Feed

Toco-conversion

U(IV)

U(IV)

To 2nd U cycle ?

U(VI),Pu(IV),Np(V,VI)

HAN

U(VI),Pu(III),Np(IV)

U(VI), Pu(IV), Np(V,VI) U(IV),U(VI),Pu(III),Np(IV)

U(IV),Pu(III),Np(IV)

Pu,U,NpU

FP

100% of initial Pu, NpU/Pu ~ 1 HAN

coana

Rectangle


FeedM1 + M2

Strippingsolution

StrippingSolution

M1

RaffinateM2

Extractant(s)Diluent Solvent treatment

EXTRACTION BACK-EXTRACTION

Solvent extraction

• Counter-current separation process


Industrial contactors

• Mixer-settlers• Pulsed columns

• Centrifugal contactors

Heavy Phase Outlet

Light Phase Intlet

Light Phase Outlet

Heavy Phase Intlet

Radial Vanes Rotor Orifice

Heavy Phase Weir

Heavy Phase Collector Ring

Annular Mixing Zone

Rotor

Interface

Light Phase Collector Ring

Light Phase Weir

Separating Zone

StationaryCylinder


Requirements for process development

• Extraction efficiency– Distribution ratios of separated elements

• Fast kinetics of mass transfer– Both at extraction and stripping steps

• Implementation in short time contactors

• Ligand stability– Both vs acidic hydrolysis and radiolysis

• High distribution ratios at the extraction step

>> 1 E(%) > 50%• Small distribution ratios at the stripping step

<< 1 E(%) < 50%• High selectivity: 1

DD

FS2M

1M

2/M1M >>=

AODM ×

AODM ×


Distribution ratio

Mn+

Organic Phase

Aqueous PhaseMn+

Mn+

A-

A-

A-

A-

A-

Y = DM.X[M]org

[M]aq

SATURATION LIMITY = DM.X[M]org

[M]aq

Y = DM.X[M]org

[M]aq

SATURATION LIMITY = DM.X[M]org

[M]aq

• DM depends on P, t°, [X], pH, I …

( ) [ ][ ] [ ]

org

aqM

M

orgaq

org

VV

D

D 100 VM VM

VM 100 %E

+⋅=

⋅+⋅⋅

⋅=tottot

tot

[ ][ ]

[ ] [ ] [ ][ ] [ ] [ ] ...2complex1complexM

...2complex1complexMD

MMD

M

M

++++++

=

∑∑

=Organic phase species

Aqueous phase species


Actinides properties

SYMBOL

OXIDATION STATES

CHEMICAL BEHAVIOR:Light actinides (Th to Pu): specific redox (PUREX basis)

Np recovery is achievable by PUREXHeavier actinides (from Am) behave like lanthanides

An(III) recovery requires new separation processes


Acidification

Scrub

Tc scrubbing (MS)

Complementaryextraction (MS)

Feed HAU, Pu, Np, P.F.HNO3 4.5 M

~1 L/h F.P. scrub

TBP 30%

Np < 0.1 % (d.l.), F.P.

2 extractions (PC) F.P. scrub (PC)

U, Pu, Np( > 99%)

TBP 30%

Np Extraction demonstration hot run

- ~ 15 kg of UOX fuel,52 GWd/t

- CEA Marcoule- April 2005

Np < 0.5 % (d.l.), F.P.

4 m highPulsed columns


Partitioning research steps

A true challenge : a sophisticated partitioning chemistry under highly radioactive conditions

Fundamental research : a wide co-operative framework- exploration : new extracting systems- fundamentals : in-depth study of mechanisms at work

Applied research :- process design- lab experiments on actual spent fuel

material- « demonstration » experiments :

integration, representativeness, long-lasting performance

A few hundreds

of new molecules

Scale : 1/10000

Scale : 1/100 à 1/1000

2009 IAEA/ICTP School on Physics and Technology of Fast Reactor Systems, Trieste 17-18/11/2009

Actinides Partitioning : the research path used

Spent fuel

U, Pu Np

Cm

AmLn

PUREXPUREX

SANEXSANEX

Fissionproducts DIAMEXDIAMEX CO-EXTRACTION

of An et LnCO-EXTRACTION

of An et Ln

PARTITIONINGbetween An & LnPARTITIONING

between An & Ln

1

H2

He3

Li4

Be5

B6

C7

N8

O9

F10

Ne11

Na12

Mg13

Al14

Si15

P16

S17

Cl18

A19

K20

Ca21

Sc22

Ti23

V24

Cr25

Mn26

Fe27

Co28

Ni29

Cu30

Zn31

Ga32

Ge33

As34

Se35

Br36

Kr37

Rb38

Sr39

Y40

Zr41

Nb42

Mo43

Tc44

Ru45

Rh46

Pd47

Ag48

Cd49

In50

Sn51

Sb52

Te53

I54

Xe55

Cs56

Ba Ln72

Hf73

Ta74

W75

Re76

Os77

Ir78

Pt79

Au80

Hg81

Tl82

Pb83

Bi84

Po85

At86

Rn87

Fr88

Ra An104

Rf105

Db106

Sg107

Bh108

Hs109

Mt110

Uun

LANTHANIDES

57

La58

Ce59

Pr60

Nd61

Pm62

Sm63

Eu64

Gd65

Tb66

Dy67

Ho68

Er69

Tm70

Yb71

Lu

ACTINIDES

89

Ac90

Th91

Pa92

U93

Np94

Pu95

Am96

Cm97

Bk98

Cf99

Es100

Fm101

Md102

No103

Lr

NOYAUX LOURDS PRODUITS D’ACTIVATION

PRODUITS DE FISSION PRODUITS DE FISSION ET D’ACTIVATION

N

O

C2H4N

O

C8H17

CH3CH3

C8H17OC6H13

DMDOHEMA

OP

OO O

HHDEHP


Two

step

str

ateg

yTw

o st

ep s

trat

egy

Am3+ and Cm3+ recovery : a 2-step strategy

Spent Fuel

U, Pu Np

Ln

PUREXPUREX

22

FissionProducts 11 CO-EXTRACTION

of MAs and LnCO-EXTRACTION

of MAs and Ln

SEPARATIONof MAs from LnSEPARATION

of MAs from Ln

TBPTBP

PO

OO

O

Am, Cm

(e.g., CMPO, TRUEX processesusing hard-donor ligands)

(e.g. SANEX, TALSPEAK processes using soft-donor ligands)


1991-2006 : Partitioning results

The results :Neptunium: recovery up to 99%, with modified PUREXAmericium and Curium: recovery up to 99.9%, with DIAMEX-SANEX

Proven processes and technologies which can be appliedto other partitioning schemes

Further steps will be required prior to any industrial implementation

Tested at CEA Atalante Marcoule hot labs on 15 kgs of EDF UOx spent fuel


DIAMEX demonstrative hot run, November 2005

Am ~ 0.015 %Cm < 0.002 %

extraction

(CP)(CP)

-

HEDTA

HNO3H2C2O4HEDTA

HNO3

FPRaffinate

extractionAn+ Ln

(CP)

ScrubbingFP

(CP)

Am, Cm, Ln> 99.9%

Back-extraction An-Ln (MS)

NaOHHEDTA

Solvent Treatment(ECRAN)

0.65 MDMDOHEMA/TPH

PUREX raffinate15 kg genuine fuel

Ln ~ 2.5 g/L

Am ~ 150 mg/LCm ~ 15 mg/L

V ~ 1 L/h4 m highPulsed columns HNO3

H2C2O4HEDTA

HNO3

extraction

(CP)

extractionAn+ Ln

(CP)

DIAMEXProductionAm, Cm, Ln


An

SolventDMDOHEMA 0.5 M

+ HDEHP 0.3 MTPH

Lnscrubbing

HNO3

extraction-scrubbing

HEDTACitric ac.

Ln stripping

LnHNO3

DIAMEXProductionAm, Cm, Ln~ 45 mL/h

NaOHHEDTA

HNO3

An stripping

Am, Cm < 0.01%

Am, Cm > 99.9%F.D.Ln ~ 80 Am < 0.06 %

Cm < 0.03 %

Raffinate

SANEX demonstrative hot run, December 2005

N

O

C 2H4

N

O

C 8H17

CH3CH3

C8H17O

C6H13

DM D O H EM A

OP

O

O O

H

HD EH P

N N

OOOO

O H O

O

H ED T A

N

O

C 2H4

N

O

C 8H17

CH3CH3

C8H17O

C6H13

DM D O H EM A

OP

O

O O

H

HD EH P

N N

OOOO

O H O

O

H ED T A


Fuel cycle, the MA heterogeneous recycling option

FPs

- U, Pu, Np by COEXTM

- Am (and Cm) separation : simplified DIAMEX-SANEX,…- Am (and Cm) recycled on dedicated « targets-blankets »

REACTOR TREATMENT

URANIUM

MAs

Pu,U,(Np) U


• Co-extraction An (III) and Ln (III) with TODGA, using HNO3 4N

• Selective back-extraction of An (III)• With polyamino-carboxylic hydrophile complexing agent

Simplified TODGA-SANEX process

NO

N

O O

C8H17

C8H17

C8H17

C8H17

Back Extr. Ln

Ln

Extr.

PF

TODGAAn + Ln

COEX Raffinate

DTPA pH 2 + NO3

Back Extr. An

An

10-3

10-2

10-1

1 00

1 01

1 02

1 03

1 04

10-2 10-1 10 0 101

U(VI)Np (IV )Np (V)Pu( III)Pu( IV)Am( III )Cm (I II)

D(A

n)

HNO3 concentra tion (M)

TO D GA con cent ra tion:0. 1M/ n-do deca ne

• Advantages : simple scheme, TODGA synthesis low cost• Drawbacks : high sensitivity of the Am-Cm back extraction step

to pH and temperature


Fuel cycle, the MA heterogeneous recycling option

FPs

- U, Pu, Np by COEXTM

- Am (and Cm) separation : (DIAMEX-SANEX), (SANEX-TODGA)…- Am (and Cm) recycled on dedicated « targets-blankets »

REACTOR TREATMENT

URANIUM

MAs

Pu,U,(Np) U


Actinide recycling : what fuel cycle option ?

R T

U

U PuU and Pu recycled,

COEX

FP&MAR TU

UU and Pu recycled,

PUREX

Pu

FP&MA

R T

U

MAU Pu

FP

MA heterogeneousrecycling

MA homogeneousrecycling

R T

U

FP

U Pu AM

MA : Np, Am, Cm


F.P.

DISSOLUTION

Spent fuel

1st stepU Extraction

Ln Stripping

Ln

WASTE

UPuNpAmCm ConversionDISSOLUTION

U

Pu+MA

2nd step An Stripping

Ln

RECYCLE

Fuel cycle, the MA homogeneous recycling option

The grouped actinide GANEX concept


The GANEX process

DIAMEX-SANEX

Monoamide

PF (dont Ln)

TRU + PF

HA spent fuel solution ∼ 4M HNO3

UDEHiBA

TRUHDEHP-

DMDOHEMAHEDTA/citric acid

N

O

PO

OHO

O

NCH3

C8H17

CH

NCH3

C8H17

O O

C2H4

OC6H13

Excellent compromise between complete Uranium extraction, and good U(VI)/Pu(IV) selectivity

Adaptation of the processalready demonstrated in 2005


1st step : U selective extraction

2nd step : Pu-Np-Am-Cmco-recovery (diamide-based process)

(performed successfully in November 2008)

GANEX demonstrative hot runs, 2008

(performed successfully in June 2008)

Solvent clean-up

Mono Amide

Extraction Scrubbing U stripping

FeedNp, Pu, Am, Cm + FPs

HNO3 Diluted HNO3

U

U > 99.9%


Heterogeneous multi-recycling

• Core : UPuO2

• “CCAM” : UAMO2 (AM =Np/Am/Cm)(minor actinide-loaded blankets)

PuU

MA

CORE CCAM


Recycling process : consolidation towards industrialization

NCH3

C8H17

NCH3

C8H17

O O

C2H4

OC6H13

ExtractantExtractantsynthesissynthesis

ModelingModeling((flowsheetflowsheet, sensitivity, operation), sensitivity, operation)

DMDOHEMA + HDEHP

RaffinatPUREX

Ln stripping

Ln

Extr-scrub.

PF

An(III) + Ln(III)

DTPA pH 3-4

An stripping Ln(III)

An

Core of the process demonstrated at small scale

Long term effectsLong term effects(solvent treatment)(solvent treatment)

EquipmentsEquipments(Implementation,(Implementation,extrapolation)extrapolation) In situ In situ

analysisanalysis(cations, (cations,

pH...)pH...)

Es sai Nd 17/11/2 005 suivi ANL , resultats analyses et calcul

0100200300400500600700800900

100011001200130014001500160017001800190020002100220023002400250026002700280029003000

17/1117:00

17/ 1118: 00

17/1119:00

17/ 1120: 00

17/1121:00

17/ 1122: 00

17/1123:00

18/ 1100: 00

18/1101:00

18/ 1102: 00

18/1103:00

18/ 1104: 00

18/1105:00

18/ 1106: 00

18/1107:00

18/ 1108: 00

18/1109:00

18/1110:00

Temps

[Nd

] (m

g.L

-1)

ANL APANL ASPAANL CPAnalyse CBA APAnalyse CBA ASPAAnalyse CBA CPCalcul APCalcul ASPACalcul CP

InterfaceInterfaceCoCo--conversionconversion

FP solution FP solution adaptedadaptedto vitrificationto vitrification

((ConcentConcent. Calcination). Calcination)


Modelling

• For what? – Reliable Calculation Codes

• Draft flowsheets in industrial scale• Minimise number of experimental tests, steps and measurements• Carry out operating analysis and transitory calculations

• How?– Phenomenological representation

• Main equilibria during MA selective stripping

DIAMEX-SANEX: • Extraction: M3+ + n (HDEHP) [M, 3DEHP,HDEHP] + 3 H+

• Complexation: M3+ + HEDTA (M,HEDTA) + 3 H+

SANEX-TODGA: • Extraction: M3+ + 3 NO3

- + 3 TODGA [M(NO3)3,3 TODGA]• Complexation: M3+ + HEDTA (M,HEDTA) + 3 H+

O

N

O

N

O

Am O N

OO

ON

O

NO

ONO

O

O

N

O

O

O

N

O

N

O

O

N

O

N

O

Am O N

OO

O NO

ON

OO

ON

O

NO

ONO

O

ONO

ON

OO

O

N

O

O N

O

O

Speciation in organic phase,

thermodynamics

Speciation in aqueous phase,

Thermodynamics

Interfacial reactionskinetics, thermodynamics

Radiolysis

Speciation in organic phase,

thermodynamics

Speciation in aqueous phase,

Thermodynamics

Interfacial reactionskinetics, thermodynamics

Radiolysis


Essai Diamex (CBP 22/11/05)Suivi Am

0102030405060708090

100110120130140150160170180190200

22/1108:00

22/1110:00

22/1112:00

22/1114:00

22/1116:00

22/1118:00

22/1120:00

22/1122:00

23/1100:00

23/1102:00

23/1104:00

23/1106:00

23/1108:00

23/1110:00

23/1112:00

23/1114:00

23/1116:00

conc

(mg/

L)

Piloting process and in-situ analysis

• Piloting process– Identifying sensitive parameters via sensitivity

analysis and transient calculations• pH, flowrate, temperature…

– Determine relevant points to be followed to detect serious malfunctioning

• [cation]

• In-situ measurements– Am and Nd

• Spectrophotometry adapted to « highactivity »

– Solvent• Assessment of miniaturized mass

spectrometers


Apparatus: adaptation

– To each step specificity• Solid Presence• Slow kinetics

– Implementing conditions• Example: comparison between DMDODHEMA andTBP

- Lower interfacial Tension- Higher Viscosity- Phase density difference, ajustable via extractant

concentration

– Hydrodynamics tests to perform in pulsed columns (smalldiameter)

• DMDOHEMA/HDEHP/TPH• TODGA/TBP/TPH


Extractant Synthesis

• New extractants: DMDOHEMA, TODGA, DEHiBA…– Identify malonamides capable of being synthetized at large scale (tons)– Cost assessment– Required purity

from kg to ton…


Solvent clean up

• Objective : assessment of long term solvent behaviour– Clean up efficiency destined to remove acidic degradation products issued from

hydrolysis/radiolysis

MARCOULE γ-Irradiation loop

Solvent studied:• DMDOHEMA/TPH• DMDOHEMA/HDEHP/TPH

Continuous long term runsSimulating 1-2 years of industrial operation

No significant impact on Hydraulicand Recovery performances

Yet to be tested:TODGADIAMEX-SANEX


Solvent clean up

• Need of solvent purification step• Recover pure diluent• Extractant concentration• Decontamination/some degradation products☹ Thermosensitive molecules

• Assessment• Evaporation under vacuum• Flash distillation• Supercritical carbon dioxide extraction


Innovative process : results to be obtained for 2012

Exploratory Research

Concepts selectedand validated

Demonstration experiments

Simplification« Consolidation »

Towards potential industrialization

Severalhundreds of moleculesassessed

Scale 1/10000

Scale 1/1000

integration, long-lasting performance

representativeness,

2012

2008

2005

2001

1993

NN

NN

NN

N N

ONH NHO O

OO

NOct Oct

NOctOct

OO

ONH NHO O

OO

NOct Oct

NOctOct

OO

Program in progress…

Documents

2055-27 Joint ICTP/IAEA School on Physics and Technology of Fast Reactors Systemsindico.ictp.it/event/a08209/session/51/contribution/30/... · 2014-05-05 · Joint ICTP/IAEA School