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

Submitted on 24 Feb 2020

HAL is a multi-disciplinary open accessarchive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come fromteaching and research institutions in France orabroad, or from public or private research centers.

L’archive ouverte pluridisciplinaire HAL, estdestinée au dépôt et à la diffusion de documentsscientifiques de niveau recherche, publiés ou non,émanant des établissements d’enseignement et derecherche français ou étrangers, des laboratoirespublics ou privés.

Speciation of palladium in nuclear fuel reprocessingoperation

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

| PAGE 1

Bénédicte SIMON, Christine BOUYER, Stéphanie DE SIO,

Alexandre CHAGNES, Laurence BERTHON

Kudowa Zdròj, August 26-30, 2018

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 2

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

HNO3

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

Context: PUREX process

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 3

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 (°)

Inte

nsity (

a.u

.)

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018

Speciation of precipitates formed

by -irradiation

| PAGE 4

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

CN

-172 ppm

C=O

Inte

ns

ity (

a.u

.)

Binding energy (eV)

339,9 0,3

338,9 0,3

502.9

505.0

507.0513.1 519.2

526.9

528.9

Mai00117.d: +MS

500.9

502.9

505.0

506.9514.1

526.9

528.9

530.9

Mai00142.d: +MS

504.5511.5

516.3

518.5 522.6

525.0

528.9

530.9

oct00003.d: +MS

0.0

0.2

0.4

0.6

0.8

5x10

Intens.

0

1

2

3

5x10

0

2

4

6

4x10

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

Ab

sorb

an

ce

nombre d'onde (cm-1)

précipité 4

palladium cyanure

CN

Pd-N

ou

Pd-C

IRFT

Pd(CN)2

S,2

S,1

wavenumber (cm-1)

How to explain the presence of precipitate

in liquide-liquid extraction cycles ?

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 5

Functions present in the precipitates S,1 et S,2

Pd(CN)2

with X = H2O, 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

-irradiation

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018

4000 3500 3000 2500 2000 1500 1000 500

Ab

so

rban

ce

wavenumber (cm-1)

| PAGE 6

Initial conditions:

aq: Pd(NO3)2, HNO3 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 %

CN

Pd-N / Pd-C

O-C=O

P-O-C

CH-CH

S,2,dodecane

S,2,TBP-dodecane

S,2,TBP

NH2

P=O

Origin of degradation products leading to the

formation of precipitates

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 7

φaq

HNO3

orga

TBP –

dodecane

-irradiation 500 kGy

φaq

HNO3

+ DP

orga

TBP –

dodecane

+ DP

aq irradiated

orga irradiated

Pd(NO3)2

Pd(NO3)2 Initial conditions:

orga: TBP 1 mol/L-1- dodecane

aq: HNO3

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

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018

Precipitates pp,orga and pp,aq et S,2 similar

CN, Pd-C/Pd-N

Pd(CN)2

Functions O=C-O

NH2, P=O et P-O-C

For pp,orga

CH-CHalcane

| PAGE 8

pp,orga

pp,aq

S,2

Degradation products responsible for the precipitation of Pd

present in aq et orga

CN

Pd-N / Pd-C

O-C=O

CN

O-C=O

CN

O-C=O

P-O-C

P-O-C

CH-CH

CH-CH

NH2

P=O

NH2

P=O

NH2

P=O

P-O-C

pp,orga pp,aq 4000 3500 3000 2500 2000 1500 1000 500

wavenumber (cm-1)

Ab

so

rban

ce

Infra-red of pp,orga et pp,aq after the addition of

Pd(NO3)2

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 9

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’

(C4H9O)3P=O (TBP)

Functions

from TBP

(C4H9O)2(OH)P=O

CnH2n+2

(alkane) + HNO3

+ H2O

+ O2

Functions

derived

from

alkanes

R-NO2

R-ONO2

R-OH

R-COOH

Common

functions for TBP

or dodecane

H3PO4

R-CO-R’

(C4H9O)(OH)2P=O

Bibliographic review

on the degradation of TBP -TPH

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 10

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’

(C4H9O)3P=O (TBP)

Functions

from TBP

(C4H9O)2(OH)P=O

CnH2n+2

(alkane) + HNO3

+ H2O

+ O2

Functions

derived

from

alkanes

R-NO2

R-ONO2

R-OH

R-COOH

Common

functions for TBP

or dodecane

H3PO4

R-CO-R’

(C4H9O)(OH)2P=O

Bibliographic review

on the degradation of TBP -TPH

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 11

D. Lesage, 1995

L. Berthon et M. C.

Charbonnel, 2009

Tripathi et Sumathi, 1999

R-CH=CH-R’

(C4H9O)3P=O (TBP)

(C4H9O)2(OH)P=O

CnH2n+2

(alcane) + HNO3

+ H2O

+ O2

R-NO2

R-ONO2

R-OH

R-COOH H3PO4

R-CO-R’

(C4H9O)(OH)2P=O

Identification of palladium species formed with these

DPs (solids / complexes)

Aqueous phase:

HNO3 + Pd(II)

Organic phase:

TBP 1 mol.L-1 in dodecane

+ addition of DP

Pd

Only 5-dodecene: 1. DPd(TBP+alkene) >> DPd(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

𝐷𝑃𝑑 = [𝑃𝑑]𝑜𝑟𝑔𝑎

[𝑃𝑑]𝑎𝑞

DPd

DPd (undoped)

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 12

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

NO3

Absorbance

wavenumber (cm-1)

TBP-Pd

just after ext

HNO3

P=Ofree

P=Obounded

NO3

Infra-red of orga after Pd(II) extraction in presence of

absence of 5-dodecane

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 13

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(NO3)2

Palladium complexes different with or without

alkene

1800 1700 1600 1500 1400 1300 1200 1100

NO3

NO3

Absorbance

wavenumber (cm-1)

TBP-Pd-alkene

just after ext

TBP-Pd

just after ext

HNO3

NO3

P=Ofree

P=Obounded

P=Ofree

P=Obounded

NO3

HNO3C=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

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 14

orga of TBP-Pd :

Evolution orga of TBP-Pd-alkene :

Functions C=O: Cte between t0 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-C12H24

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(NO3)2

Palladium complexes different with or without

alkene

1800 1700 1600 1500 1400 1300 1200 1100

CH2

CH2

NO3

NO3

Absorbance

wavenumber (cm-1)

TBP-Pd-alkene

7 days after ext

TBP-Pd-alkene

just after ext

TBP-Pd

just after ext

HNO3

NO3

NO3

P=Ofree

P=Ofree

P=Obounded

P=Ofree

P=Obounded

NO3

HNO3

HNO3

C=O

C=O

P=Obounded

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

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018

20 40 60 80

0

200000

400000

600000

800000

1000000

1200000

others

molecules

TBP

5-dodecene

Inte

nsity (

a.u

.)

retention time (min)

dodecane

| PAGE 15

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

33

2

5

Inte

nsity (

a.u

.)

retention time (min)

1

Characterization by GC-MS of an organic phase of

TBP-dodecane-Pd-5-dodecene

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 16

Initials conditions:

HNO3, Pd(II), HNO2,

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

Tamb

2- dodecanone

or

5-dodecanone

(DP from

dodecane)

without ketone: no solid formation without HNO2: no solid formation

Stirred mixture

100°C

M. Nonomura,

Toxicol. Environ.

Chem., 1987, 17,

47–57

Behavior of ketone in presence of palladium

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 17

S,2

S,5-dodecanone

S,2-dodecanone

S,2-butanone

CN

Pd-N / Pd-C

Presence of CN 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 HNO2: precursors in the

Pd(CN)2 formation

obtained by -irradiation

Initials conditions:

HNO3, Pd(II), HNO2,

Ketone

4000 3500 3000 2500 2000 1500 1000 500

wavenumber (cm-1)

Absorb

ance

Infra-red of S,2-dodecanone , S,5-dodecanone et S,2-butanone

Nuclear Energy Division - Marcoule

Research Department on Mining and Fuel Recycling Processes 26-30 August 2018 | PAGE 18

Characterization of precipitates of palladium in {TBP-TPH-HNO3} 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 Pd(COOR)2

(C4H9O)2(OH)P=O R-NH2

Alkane TBP Irradiation

Irradiation Irradiation

Irradiation

R-CH=CH-R’ Pd2+

R-CO-R1’ R3-OH R’’-COOH

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 NH2 mechanism formation

Conclusions and Prospects

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

685 019

| 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

Thank you for your attention