Speciation of palladium in nuclear fuel reprocessing operation
Transcript of Speciation of palladium in nuclear fuel reprocessing operation
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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