Actinide stripping by a hydrophilic BTP ligand in aqueous ... · Actinide stripping by a...
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Actinide stripping by a hydrophilic BTP ligandin aqueous HNO3 from TODGA containingorganic phase.
L. Steczek1, J. Narbutt1, M. Rejnis1, P. Moisy2, M. Ch. Charbonnel2
1 Institute of Nuclear Chemistry and Technology, 2 Alternative Energies and Atomic Energy Commission
First SACSESS International Workshop: ‘Towards safe and optimised separation processes, a challenge for nuclear
scientists’ 22-24.04.2015 Warsaw
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Bibliography ‐ Aromatic poly‐N‐dentate ligands
The simplest aromatic poly-N-dentate ligand is 2,2'-bipyridil
Affinity to protonate nitrogen atoms decreases in the order:
> >
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The Choice of Selected ligand Lipophilic poly-N-nitrogen ligands are broadly studied asselective extractants for separation of long-lived actinides fromirradiated nuclear fuel. In the last years, the research wasfocused on the derivatives of bis-triazinyl pyridine (BTP) whichselectively extract actinides(III) from lanthanides(III) fromaqueous HNO3 solutions to organic solvents. Moreover, selectivestripping of minor actinides can be done also, using a hydrophilicligand, e.g. SO3-Ph-BTP delivered by Technocomm Ltd (UK).
NN
NN N
NN SO3H
SO3HHO
3S
HO3S
HSO3PhBTP
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Bibliography Complexes of An(III), Ln(III) with HSO3PhBTP
β Cm Euβ1 5,4 5,2
β2 9,3 8
β3 12,2 10,2
Stability constant of An with SO3‐Ph‐BTP ligand ← TRLFS, An3+ forms more stable complexes than Ln3+. Complexes (1:1), (1:2) and (1:3) were observed
Stability constants of Cm and Eu with SO3‐Ph‐BTP ligand; at pH 3 (TRLFS)
Ch.M. Ruff, U. Müllich, A. Geist, P. J. Panak, Dalton Trans., 2012, 41, 14594
Distribution ratio of Am (0.5 M NH4NO3 + HNO3 (pH 1)/ 0.2 M TODGA in kerosene A. Geist et al., Solv. Extr. Ion Exch.,30: 433–444, 2012
0.01
0.1
1
10
100
0 0.002 0.004 0.006 0.008 0.01
DA
m
HSO3PhBTP mol · L-1
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Liquid‐liquid Extraction of Actinides with TODGA
In certain separation schemes under study (innovative-SANEX)the f-block elements are extracted together from acidic PUREXraffinate to the organic phase using e.g. lipophlilic tri-O-dentateligand, TODGA.
TODGA-2
-1.5-1
-0.50
0.51
1.52
2.5
-1 -0.5 0 0.5 1log
D0
log [HNO3]
Th(IV)Pu(IV)UO2(VI)
0.2 M TODGA
Yuji Sasakia*, Yasuhiro Tsubataa, Yoshihiro Kitatsujia, Yumi, SolventExtraction and Ion Exchange Volume 31, Issue 4, 2013 401-415
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Principle of the LLE Method
n221
0 ......1 Lβ+Lβ+Lβ=DD
n
An4+ + sTODGA + uNO3- = [An(TODGA)s(NO3)u]4-u
An4+ + uNO3- = [An(NO3)u]4-u
An4+ + kBTP = [An(hsBTP)k]4-4k
hsBTP4- + aH+ = [hsBTP(H+)a]4-a
where hsBTP = SO3PhBTP
u3
su3s
NOTODGAAnNOTODGAAn )(Kex=
kBTPk
k
i
u3unitrate
u
i
0
hsBTPK+NOK+
D
1,
1][1
u
u
u3l
uNOAnAn
NOTODGAAn
1
43 ])([][
])([D0=
D=
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Method of the determination of the Distribution coefficient
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0
500
1000
1500
2000
2500
0.4 2.4 4.4 6.4
c/s
MeV
02000400060008000100001200014000160001800020000
0 20 40 60 80 100c/s
keV
alpha spectrometry gamma spectrometry
spectrophotometry spectrophotometry
Complex Arsenazo(III)-Th 660 nm Complex Arsenazo(III)-UO2(2+) 655 nm
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Purification of ligand
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0.1
1
10
0 0.01 0.02 0.03
D
HSO3PhBTP mol ∙ L‐1
SO3H‐Ph‐BTP contaminated SO43‐
SO3‐Ph‐BTP purified
Ligand has to be additional purify in case of the presence sulphate which form relatively strong complexes with An(IV)
Test with BaCl2 can generate large amount of white powder
Neutralization wiht NaOH until pH = 7
Solubilization in MeOH at leastthree times
Evaporation or precipitation with acetone
Müllich, Udo, Geist, Andreas, Zevaco, Thomas EP 2 377 861 A1
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Preliminary experimentsExperiments with Th(IV), Pu(IV)
UO22+ ,PuO2
2+, NpO22+
At pH 1 we observed the formation of the complex with Pu(VI) and reduction
0
0.1
0.2
0.3
0.4
800 820 840 860 880
Optical den
sity
nm
Pu(VI)
Pu(VI)LInstability of The complextime30 min
0.001 M Pu(VI), HSO3PhBTP 0-0.15 M, pH 1
reduction
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-0,5
0
0,5
1
1,5
2
2,5
3
3,5
-5 -4 -3 -2 -1 0
log HSO3PhBTP
log
D0/
D-1
Am(III)Th(IV)U(VI)
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Extraction of An as a function of ligand
Extraction of Th(IV), Am(III) and UO22+ by TODGA in
5% octanol-keresone from acidic aqueous solution.Temperature of extraction 25 ºC , time 30 min, O/A =1
UO22+ Th Am
C Anmol/L 0.0002 0.0001 trace
C NO3- 1 1 1
Phaseaqueous 0.15 M 0.15 M
HNO3
0.015 M HNO3
Phaseorganic
0.6 M TODGA
0.06 M TODGA
0.1 M TODGA
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Results ‐ Extraction of Americium from acidic solution HSO3PhBTP and NaNO3
-0.50
0.51
1.52
2.53
3.5
-5 -4 -3 -2 -1 0
log(
D0/
D-1
)
log (HSO3PhBTP)
0.5 M HNO3 0.15 M HNO30.01 M HNO3 0.5M HNO3 with Pu1 M HNO3 avec Pu
k=2
k=1
Phase organic: 0.1 M TODGA and 0.06 M TODGA when Am was measured with Pu
acidity log β1 log β2
0.02 5.27 ±0.54
8.24 ±1.01
0.15 4.76 ±0.45
8.73 ±1.03
0.5 4.70 ±0.51
8.48±1.04
1.0 5.21 ±1.01
9.74 ±2.01
3.0 In progress In progress
A. Geist, U. Mullich, G. Modolo, A. Wilden ACTINIDE AND FISSION PRODUCT PARTITIONING AND TRANSMUTATION, ISBN 978-92-64-99174-3, © OECD 2012 (1-9)
β Cm Euβ1 5,4 5,2β2 9,3 8β3 12,2 10,2
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Results ‐ Extraction of Plutoniumfrom acidic solution HSO3PhBTP and NaNO3
CPu(VI) = 0.1 mM, 1.0 M (H, Na)NO3TODGA = 0.06 M in kerosene/5% octanol
-1.5-1
-0.50
0.51
1.52
2.5
-4 -3 -2 -1 0
D0/
D-1
log(HSO3PhBTP)
0.5 M HNO3 France 1 M HNO3
k=2
k=1
acidity log β1 log β2
0.5 5.01 ±(0.51)
8.98 ±(1.01)
1.0 4.34 ±(0.51)
8.80 ±(1.02)
3.0 In progress In progress
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Results ‐ Extraction of Uranium(VI) and Thorium(IV) from acidic solution HSO3PhBTP and NaNO3
log K1 = 2.660.15 M HNO3TODGA 0.6 M
tgα=1
preliminary results log K1 = 3.63 log K2 = 6,000.15 M HNO3TODGA 0.06 M
Th(IV)
00,20,40,60,8
11,21,41,61,8
-2,5 -2 -1,5 -1 -0,5 0
log HSO3PhBTP
log
D0/
D-1
Th(IV)
UO2(2+)
00,10,20,30,40,50,60,70,80,9
-2,5 -2 -1,5 -1 -0,5 0
log HSO3PhBTP
log
D0/
D-1
UO2(2+)
k=2k=1
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Conclusion
Am3+,Th4+, Pu4+ forms complexes 1:1, 1:2 and UO22+,
1:1 under the conditions of experiments. No evidence of the complexes 1:3 under the conditions of
experiments. The results for Am3+ are in accordance with the data
existed for Cm(III) and Eu(III). The order of the conditional stability constants for the
complexes 1:1 is Pu4+ ~ Am3+ > Th4+ > UO22+.
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ACKNOWLEDGEMENTS
Prof J. Narbutt
M. RejnisK. Lyczko
Dr. Philippe MoisyDr. M. Ch. Charbonnel
L. BerthonC. BerthonN. BoubalsT. DumasD. GuillaumontP. GuilbaudC. TamainL. GuerinN. ZorzS. PetitR. BurgaudI. DantilleS. MostaphaO.PecheurM. AudrasM. Autillo
LN1 L18M. GuigueJ. VermeulenJ. Maurin
Prof. G. Zakrzewska KołtuniewiczA. MiśkiewiczM. ButaD. GajdaA. AbramowskaW. OlszewskaP. NieściórK. Kiegiel