Speciation of palladium in nuclear fuel reprocessing operation

HAL Id: cea-02338559

https://hal-cea.archives-ouvertes.fr/cea-02338559

Submitted on 24 Feb 2020

HAL is a multi-disciplinary open access

archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Speciation of palladium in nuclear fuel reprocessing

operation

B. Simon, C. Bouyer, S. de Sio, A. Chagnes, L. Berthon

To cite this version:

B. Simon, C. Bouyer, S. de Sio, A. Chagnes, L. Berthon. Speciation of palladium in nuclear fuel repro-cessing operation. 5th International Conference on Methods and Materials for Separation Processes ”Separation Science - Theory and Practice”, Aug 2018, Kudowa-Zdrój, Poland. �cea-02338559�

www.cea.fr

CEA Marcoule / Nuclear Energy Division,

Research Department on Mining and Fuel Recycling Processes

Unit of dissolution and separation processes

Speciation of palladium

in nuclear fuel

reprocessing operation

Bénédicte SIMON, Christine BOUYER, Stéphanie DE SIO,

Alexandre CHAGNES, Laurence BERTHON

PUREX process = hydrometallurgical process

Selective extraction of U and Pu present in the spent nuclear fuel by an organic

phase TBP-TPH

Palladium = fission product

FP insolubles

Pd

soluble :

(Pd)

Pu

PF

U

Extraction

Washing

Partition

Re-extr. U

Recycling

(solvent treatment)

Load

U,Pu,PF

Organic phase

TBP 30% / TPH

Dissolution

HNO

₃

Spent fuel:

U, Pu, FP

Glass matrix

Pd insoluble

(Pd)

TBP

How to cope with aging equipment:



Presence of precipitate with palladium

De SIO et al., Procedia Chemistry, 21, 2016, 17-23

Industrial solid

Characterization

by XRD powder diffraction

Role of the radiolysis

Objective of the study

Understanding the formation of Pd precipitates in liquid-liquid extraction

cycles

 Identification of the compounds responsible for the precipitation of Pd



_orga



_aq



_S,1



_S,2 φaq Pd(II) HNO3 orga Pd(TBP)2(NO3)2 + TBP + TPH



-irradiation

500 kGy

Precipitate



_S,1

Precipitate



_S,2

Industrial precipitate

18

26

36

40

2



(°)

Inten

sity

(a.u

.)

 Speciation of precipitates formed

by



-irradiation

 Extraction of Pd(II) in presence of

degradation product (DP) of the

solvent

S,1 S,2 18° 26° 36° 40° 1er _saut 2ème _saut -CH3 -CH3 TMS P-O-CH2 -(TBP et DBP) -150 ppm CN -172 ppm C=O Int e nsity ( a .u. )

Binding energy (eV)

339,9  0,3 338,9  0,3 502.9 505.0 507.0 513.1 519.2 526.9 528.9 Mai00117.d: +MS 500.9 502.9 505.0 506.9 514.1 526.9 528.9 530.9 Mai00142.d: +MS 504.5 511.5 516.3 518.5522.6 525.0 528.9 530.9 oct00003.d: +MS 0.0 0.2 0.4 0.6 0.8 5 x10 Intens. 0 1 2 3 5 x10 0 2 4 6 4 x10 500 505 510 515 520 525 530 m/z _S,1 _S,2 Pd(CN)2 [Pd2(pyr)3(CN)3]+ [Pd2(pyr)3(CN)2]+ [Pd2(pyr)3(CN)3]+ [Pd2(pyr)3(CN)2]+ XPS XRD RMN ATG ESI-MS

Precipitate



_S,1

Precipitate



_S,2 φaq Pd φorganique TBP in dodecane + degradation product

degradation

product

Pd(II)

Identification of palladium

species formed with

degradation products

(solid/complexe)

4000 3500 3000 2500 2000 1500 1000 500 précipité 2 Absor ba nce nombre d'onde (cm-1) précipité 4 palladium cyanure CN Pd-N ou Pd-C IRFT Pd(CN)2 S,2 S,1 wavenumber (cm-1₎

How to explain the presence of precipitate

Functions present in the precipitates



_S,1

et



_S,2

Pd(CN)

₂

with X = H

₂

O, CN, others functions

S. J. Hibble, A. M. Chippindale, E. J. Bilbé, E. Marelli, P. J. F. Harris and A. C. Hannon,

Inorg. Chem., 2011, 50, 104–113.

Pd-carboxylate

Organic compounds

and

Phosphorous

compounds

(TBP / HDBP)

Presence at least of 2 different compounds

XRD, XPS, ATG, ESI-MS XPS, FTIR, NMR NMR, XPS, FTIR, ESI-MS

Precipitate



_S,1

Precipitate



_S,2

Published manuscript : “Characterization of palladium species after -irradiation of a

TBP-alkane-Pd(NO3)2 system “

RSC Adv., 2018, 8, 21513-21527

Characterization of precipitates formed by

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nc

e

wavenumber (cm

-1

)

Initial conditions:



_aq

:

Pd(NO

₃

)

₂

, HNO

₃

3 mol.L

-1



_orga

:

variable composition

Degradation products from TBP or dodecane allowing the

formation of precipitates

TBP 100 %

TBP 30% - dodecane

dodecane 100 %

C



N

Pd-N / Pd-C

O-C=O

P-O-C

CH-CH



_S,2,dodecane



_{S,2,TBP-dodecane}



_S,2,TBP

NH

₂

P=O

Origin of degradation products leading to the

formation of precipitates

φaq HNO₃ orga TBP – dodecane



-irradiation

500 kGy

φaq HNO3 + DP orga TBP – dodecane + DP



_aq

irradiated



_orga

irradiated

Pd(NO

₃

)

₂

Pd(NO

₃

)

₂

Initial conditions:



_orga

:

TBP 1 mol/L

-1

_{- dodecane}



_aq

:

HNO

₃



_pp,orga



_pp,aq Stirring Rest

Irradiation without Pd :

Irradiation with Pd :



_orga



_aq



_S,1



_S,2 φaq Pd(II) HNO3 _orga Pd(TBP)2(NO3)2 + TBP + TPH



-irradiation

500 kGy



_S,2 Stirring Rest

Distribution of degradation products leading to

precipitation of palladium

Precipitates



_pp,orga

and



_pp,aq

et



_S,2

similar

CN, Pd-C/Pd-N

 Pd(CN)

₂

Functions O=C-O

NH

₂

, P=O et P-O-C

For



_pp,orga

CH-CH

_alcane



_pp,orga



_pp,aq



_S,2

Degradation products responsible for the precipitation of Pd

present in



_aq

et



_orga

C



N

Pd-N / Pd-C

O-C=O

C



N

O-C=O

C



N

O-C=O

P-O-C

P-O-C

CH-CH

CH-CH

NH

₂

P=O

NH

₂

P=O

NH

₂

P=O

P-O-C



_pp,orga



_pp,aq 4000 3500 3000 2500 2000 1500 1000 500

wavenumber (cm

-1

)

Absor

ba

nce

Infra-red of



_pp,orga

et



_pp,aq

after the addition of

Pd(NO

₃

)

₂

Extraction of Pd(II) in the presence of degradation

products (DP)

D. Lesage, 1995 L. Berthon et M. C. Charbonnel, 2009 Tripathi et Sumathi, 1999

R-

CH=CH

-R’

(C

4

H

9

O)

3

P=O

(TBP)

Functions

from TBP

(C

4

H

9

O)

₂

(OH)P=O

C

n

H

2n+2 (alkane) + HNO3 + H₂O + O₂

Functions

derived

from

alkanes

R-

NO

2

R-

ONO

2

R-

OH

R-

COOH

Common

functions for TBP

or dodecane

H

₃

PO

₄

R-

CO

-R’

(C

4

H

9

O)(OH)

₂

P=O

Bibliographic review

on the degradation of TBP -TPH

D. Lesage, 1995 L. Berthon et M. C. Charbonnel, 2009 Tripathi et Sumathi, 1999

DP tested:

5-dodecene

dodecanoïc acid

1-dodecanol

5-dodecanone

Extraction of Pd(II) in the presence of degradation

products (DP)

R-

CH=CH

-R’

(C

4

H

9

O)

3

P=O

(TBP)

Functions

from TBP

(C

4

H

9

O)

₂

(OH)P=O

C

n

H

2n+2 (alkane) + HNO3 + H₂O + O₂

Functions

derived

from

alkanes

R-

NO

2

R-

ONO

2

R-

OH

R-

COOH

Common

functions for TBP

or dodecane

H

₃

PO

₄

R-

CO

-R’

(C

4

H

9

O)(OH)

₂

P=O

Bibliographic review

on the degradation of TBP -TPH

D. Lesage, 1995 L. Berthon et M. C. Charbonnel, 2009 Tripathi et Sumathi, 1999

R-

CH=CH

-R’

(C

4

H

9

O)

3

P=O

(TBP)

(C

4

H

9

O)

₂

(OH)P=O

C

n

H

2n+2 (alcane) + HNO₃ + H2O + O2

R-

NO

2

R-

ONO

2

R-

OH

R-

COOH

H

₃

PO

₄

R-

CO

-R’

(C

4

H

9

O)(OH)

₂

P=O

Identification of palladium species formed with these

DPs (solids / complexes)

Aqueous phase:

HNO

₃

+ Pd(II)

Organic phase:

TBP 1 mol.L

-1

_{in dodecane}

+ addition of DP

Pd

Only 5-dodecene:

1.

D

_Pd

(TBP+alkene) >> D

_Pd

(undoped)

2.

Presence black powder at the interphase :

Pd et PdO (XRD powder and XPS)

Extraction of Pd(II) in the presence of degradation

products (DP)

Bibliographic review

on the degradation of TBP -TPH

Functions

from TBP

Functions

derived

from

alkanes

Common

functions for TBP

or dodecane

DP tested:

5-dodecene

dodecanoïc acid

1-dodecanol

5-dodecanone

𝐷

_𝑃𝑑

=

[𝑃𝑑]

𝑜𝑟𝑔𝑎

[𝑃𝑑]

_𝑎𝑞

D

_Pd

D

_Pd (undoped)



_orga

of TBP-Pd :

Initials conditions:

_aq: Pd(II), HNO₃

orga: TBP 1 mol/L in dodecane

with or without 5-dodecene

1800 1700 1600 1500 1400 1300 1200 1100 NO 3 Absorbance wavenumber (cm-1) TBP-Pd just after ext

HNO 3

P=O

_free P=O_bounded NO 3

Infra-red of



_orga

after Pd(II) extraction in presence of

absence of 5-dodecane



_orga

of TBP-Pd :



_orga

of TBP-Pd-5-dodecene :

Presence of C=O at 1718 cm

-1

 function RCOH, R-CO-R’ or R-COOH

NMN : presence of ketone

ESI-MS : complexes different from

Pd(TBP)

₂

(NO

₃

)

₂

 Palladium complexes different with or without

alkene

1800 1700 1600 1500 1400 1300 1200 1100 NO 3 NO 3 Absorbance wavenumber (cm-1) TBP-Pd-alkene just after ext

TBP-Pd just after ext

HNO 3 NO 3 P=O_free P=O_bounded P=O_free P=O_bounded NO 3 HNO 3 C=O Initials conditions: _aq: Pd(II), HNO₃

orga: TBP 1 mol/L in dodecane

with or without 5-dodecene

Infra-red of



_orga

after Pd(II) extraction in presence of

absence of 5-dodecane



_orga

of TBP-Pd :

Evolution 

_orga

of TBP-Pd-alkene :

Functions C=O: C

te

_{between t}

0

et 7 days

Disapperence of nitrate vibration bands

(1527 cm

-1

₎

ESI-MS : Presence of a mixed

complexe of Pd-TBP-5-dodecene

Hyp : mixed complexes Pd-TBP-C

₁₂

H

₂₄

Formation of C=O in presence of alkene



_orga

of TBP-Pd-5-dodecene :

Presence of C=O at 1718 cm

-1

 function RCOH, R-CO-R’ or R-COOH

NMN : presence of ketone

ESI-MS : complexes different from

Pd(TBP)

₂

(NO

₃

)

₂

 Palladium complexes different with or without

alkene

1800 1700 1600 1500 1400 1300 1200 1100 CH 2 CH 2 NO 3 NO 3 Absorbance wavenumber (cm-1) TBP-Pd-alkene 7 days after ext

TBP-Pd-alkene just after ext

TBP-Pd just after ext

HNO 3 NO 3 NO 3

P=O

_free

P=O

_free P=O_bounded

P=O

_free P=O_bounded NO 3 HNO 3 HNO 3 C=O C=O P=O_bounded Initials conditions: _aq: Pd(II), HNO₃

orga: TBP 1 mol/L in dodecane

with or without 5-dodecene

Infra-red of



_orga

after Pd(II) extraction in presence of

absence of 5-dodecane

20 40 60 80 0 200000 400000 600000 800000 1000000 1200000 others molecules TBP 5-dodecene Int en sity (a .u. )

retention time (min) dodecane N° Attribution 1 6-dodecanone 2 5-dodecanone 3 3-dodecanone 4 2-dodecanone 5 ?

5-dodecene

5-dodecanone

_6-dodecanone

Pd(II)

Pd(0)

Oxydo-reduction reaction:

39,0 39,5 40,0 40,5 41,0 41,5 42,0 0 10000 20000 30000 40000 3 3 2 5 Int en sity (a .u. )

retention time (min) 1

Characterization by GC-MS of an organic phase of

TBP-dodecane-Pd-5-dodecene

Initials conditions:

HNO

₃

, Pd(II), HNO

₂

,

Ketone

Pd(NO₃)₂ HNO₃ HNO₂



2-butanone



_{S,5-dodecanone}



_{S,2-dodecanone}

Mixture without

stirring

2-butanone

(DP from TBP)

No

precipitate

Pd(NO₃)₂ HNO₃ HNO₂

Mixture stirred

T

_amb

2- dodecanone

or

5-dodecanone

(DP from

dodecane)

without ketone: no solid formation

without HNO

₂

: no solid formation

Stirred mixture

100°C

M. Nonomura, Toxicol. Environ. Chem., 1987, 17, 47–57



_S,2



_{S,5-dodecanone}



_{S,2-dodecanone}



_S,2-butanone

C



N

Pd-N / Pd-C

Presence of C



N in

the 3 solids

whatever the length

of the chain and the

position of C=O,

formation of

Pd(CN)

₂ Pd(NO3)2 HNO3 HNO2 R-CO-R’

Ketone and HNO

₂

: precursors in the

Pd(CN)

₂

formation

obtained by -irradiation

Initials conditions:

HNO

₃

, Pd(II), HNO

₂

,

Ketone

4000 3500 3000 2500 2000 1500 1000 500

wavenumber (cm

-1

)

Absor

ba

nce

 Characterization of precipitates of palladium in {TBP-TPH-HNO

₃

} irradiated

Several compounds : Pd(CN)

₂

, Pd(COOR)

₂

, TBP, HDBP, Amine

DP come from TBP or dodecane

DP leading to the precipitation of Pd present in



_aq

and



_orga

Pd(CN)

₂

R-NH

₂

Pd(COOR)

₂

(C

4

H

9

O)

2

(OH)P=O

Alkane

TBP

Irradiation Irradiation Irradiation Irradiation R-CH=CH-R’ Pd2+ R-CO-R₁’ _R’’-COOH R₃-OH R₂-NO2 R1-ONO2 HNO₂ D HCN oxo-oxime deshydration deshydration Pd2+ Pd2+ Pd2+ M. Nonomura, Toxicol. Environ. Chem., 1987, 17, 47–57 H. Modler and M. Nonomura, Toxicol. Environ. Chem., 1995, 48, 155–175. V. I. Bakhmutov, Dalton Trans., 2005, 11, 1989 S. K. Ritter, Chem. Enginnering News, 2016, 94, 20-21 S. D. Kirik, Acta Crystallogr. C, 2004, 60, 449-450

 Suggestion of mechanisms formation of precipitates

Irradiation or

 Prospects: suggestion of NH

₂

mechanism formation

Commissariat à l’énergie atomique et aux énergies alternatives Centre de Marcoule | 30207 Bagnols-sur-Cèze Cedex T. +33 (0)4 66 79 50 60

Etablissement public à caractère industriel et commercial | RCS Paris B 775

| PAGE 19

CEA | 10 AVRIL 2012

CEA/ DEN/MAR/DMRC/SPDS/LDPS

 Christine BOUYER

 Nicole RAYMOND

CEA/DEN/MAR/DMRC/SPDS/LILA

 Laurence BERTHON

 Georges SAINT-LOUIS

 Nathalie BOUBALS

 Claude BERTHON

 Thomas DUMAS

CEA/DEN/MAR/DMRC/SPDS/LCPE

 Cécile MARIE

 Eugen ANDREIADIS

CEA/DEN/MAR/DMRC/SA2I/LMAC

 Emmanuelle BRACKX

CEA/DEN/DANS/DPC/SCCME/LECA

 Frédéric MISERQUE

Université de Lorraine

 Alexandre CHAGNES

ORANO Cycle

 Stéphanie DE SIO

CEA/DEN/MAR/DE2D/SEVT/LDMC

 Nicolas MASSONI