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Modelling and simulation of molybdenum extraction by HDEHP ion-exchanger and DMDOHEMA solvating
extractant
V Vanel, C Marie, M Duchesne, X Hérès, V Pacary, L Berthon, D Rudloff, M Bertrand, S. Watanabe
To cite this version:
V Vanel, C Marie, M Duchesne, X Hérès, V Pacary, et al.. Modelling and simulation of molybdenum extraction by HDEHP ion-exchanger and DMDOHEMA solvating extractant. ISEC 2014 - 20th International Solvent Extraction Conference, Sep 2014, Würzburg, Germany. �cea-02997814�
| PAGE 1 CEA | 10 AVRIL 2012
Modelling and simulation of
molybdenum extraction by
HDEHP ion-exchanger and
DMDOHEMA solvating
extractant
Monday, September 8th, 2014
ISEC 2014 – Nuclear Chemistry For Sustainable Fuel Cycles |V. Vanel, C. Marie, M. T. Duchesne, X. Hérès, V. Pacary, L. Berthon, D. Rudloff, M. Bertrand, S. Watanabe
CEA | SEPTEMBER 8th, 2014 | PAGE 2
Contents
Introduction
The EXAm process and the Mo stripping step
How does the Mo stripping step work?
Approach adopted to build the model
Modelling of Mo behavior
Comparison with experimental results
Batch experiments
Implementation in the PAREX code
Cold tests (G1 facility, Marcoule)
| PAGE 3
The EXAm process and the Mo stripping step
The EXAm process aims at recovering americium alone from the PUREX raffinate
TEDGA HNO3 Am Extraction Cm Scrubbing Feed solution PUREX raffinate FP Cm Heavy Ln DMDOHEMA Solvating ext. HDEHP Acidic ext. Solvent cleanup Ln stripping Mo stripping Am selective stripping Citric Acid + NaOH HNO3> 4M Mo+Ru Am + light Ln Light Ln Oxalic acid TEDGA Light Ln + Fe Am pH 3 HNO3> 4M pH 2 - 3 DTPA + TEDGA Step 1 Step 2 Step 3 Step 4 Step 5 CEA | SEPTEMBER 8th, 2014
CEA | SEPTEMBER 8th, 2014 | PAGE 4
How does the Mo stripping step work?
TEDGA HNO3 Am Extraction Cm Scrubbing Feed solution PUREX raffinate FP
Cm
Heavy Ln DMDOHEMA Solvating ext. HDEHP Acidic ext.Solvent
cleanup Ln stripping Mo stripping Am selective stripping CitricAcid
+ NaOHHNO
3> 4M
Mo+Ru Am + light Ln Light LnOxalic acid
TEDGA Light Ln + Fe AmpH
3
HNO3 > 4M pH 2 - 3 DTPA+ TEDGA
Step 1
Step 2
Step 3
Step 4
Step 5
Am La, Ce, Pr, Nd Mo, Ru Fe H+ ~ 0.6M H+ ~ 0.1M H+Change from an acidic medium (4 – 5 M) to weak acidic conditions (pH 2 – 3) Neutralization of extracted acid by NaOH
Recombination of extracted complexes in the organic phase 4 – 5 M: predominant effect of DMDOHEMA (solvating extractant)
pH 2 – 3: predominant effect of HDEHP (cationic exchanger) => release of H+
Stripping of Mo
~ 0.03M H+
CEA | SEPTEMBER 8th, 2014 | PAGE 5
Approach adopted to build the model
Determination of constants on batch experiments
First validation of the model on a cold test (G1 facility at Marcoule)
Reference : Marie C., Watanabe S., Vanel V., Duchesne M.-T., Zorz N., Berthon L. Behaviour of Molybdenum (VI) and Iron(III) in {HDEHP-DMDOHEMA-nitric acid} liquid-liquid extraction systems. Paper in preparation
CEA | SEPTEMBER 4th, 2012 | PAGE 6
Modelling of Mo(VI) behavior
CEA | SEPTEMBER 8th, 2014 | PAGE 7
Modelling of Mo(VI) behavior
Ref : Tkac P., Paulenova A. Speciation of molybdenum(VI) in aqueous and organic phases of selected extracting systems, Separation Science and Technology, Vol. 43, p. 2641 – 2657, 08/2008.
Cationic species
Anionic species
CEA | SEPTEMBER 8th, 2014
| PAGE 8
Modelling of Mo(VI) behavior
D(Mo) pH Anionic ( )2 4 MoO Cationic ( )2 2 MoO Working point
Ref : étude d’un procédé de valorisation du molybdène par extraction par solvant organosphosphore, C. Brassier, thèse CEA-R-5689, 1995
Solvating extractant ( )MoO3
Chemical
reaction Formula Log(K)
3 2 2 / MoO MoO
2 3
3
2 2 2 2 / H MoO MoO MoO K MoO 1.9 2 4 3 / MoO MoO
2
2 4 2 4 3 3 / K MoO MoO MoO H
MoO 8.1 Cation exchanger
2 4 2 2 2 2 2 H HDEHP MoO K HDEHP DEHP MoO ec 4.7 Solvating extractant
4 3 43HDEHP K MoO HDEHP
MoO es 5.5 Anion exchanger
2 4 2 4 2 2 2 K MoO HDEHP H HDEHP DEHP MoO ea 13.6CEA | SEPTEMBER 8th, 2014 | PAGE 9
Modelling of Mo(VI) behavior
CEA | SEPTEMBER 8th, 2014 | PAGE 10
Modelling of Mo(VI) behavior
+0.8 % +0.3 % -0.6 % -5.7 % +2.6 % +0.75 % -1.4 %
CEA | SEPTEMBER 8th, 2014 | PAGE 11
Implementation in the PAREX code
D(Mo) pH Anionic ( )2 4 MoO Cationic ( )2 2 MoO Working point Solvating extractant ( )MoO3
| PAGE 12
Cold test (G1 facility, Marcoule)
CEA | SEPTEMBER 8th, 2014 | PAGE 13
Cold test (G1 facility, Marcoule): trace amounts of Am
CEA | SEPTEMBER 4th, 2012 | PAGE 14
Conclusions - prospects
Conclusions :
Modelling quite representative for Am, La, Ce, Pr, Nd and Mo in weak acidic conditions
Use of models to propose flowsheets for hot tests, both in trace and macroscopic amounts of actinides.
Prospects :
Implement the complete model in the PAREX code
Compare the model to future hot tests (trace and macroscopic amounts of actinides)
| PAGE 15
CEA | 10 AVRIL 2012
Direction de l’énergie nucléaire
Département de radiochimie des procédés Service de modélisation et de chimie des procédés de séparation
Laboratoire de modélisation des procédés de recyclage
Commissariat à l’énergie atomique et aux énergies alternatives Centre de Marcoule| BP17171| 30207 Bagnols-sur-Cèze Cedex T. +33 (0)4 66 79 77 00 |F. +33 (0)4 66 79 63 25
Etablissement public à caractère industriel et commercial |RCS Paris B 775 685 019
10 NOVEMBRE 2020 | PAGE 15
