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Modelling and simulation of molybdenum extraction byHDEHP ion-exchanger and DMDOHEMA solvating

extractantV Vanel, C Marie, M T Duchesne, X Hérès, V Pacary, L Berthon, D Rudloff,

M Bertrand, S. Watanabe

To cite this version:V Vanel, C Marie, M T Duchesne, X Hérès, V Pacary, et al.. Modelling and simulation of molybdenumextraction by HDEHP ion-exchanger and DMDOHEMA solvating extractant. ISEC 2014 - 20thInternational Solvent Extraction Conference, Sep 2014, Würzburg, Germany. �cea-02997814�

| PAGE 1CEA | 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

10 NOVEMBRE 2020 | PAGE 1CEA | 10 AVRIL 2012

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)

Conclusion - prospects

| PAGE 3

The EXAm process and the Mo stripping step

The EXAm process aims at recovering americium alone from the PUREX raffinate

TEDGAHNO3

Am Extraction Cm Scrubbing

Feed solutionPUREX raffinate

FP

Cm

Heavy Ln

DMDOHEMASolvating ext.

HDEHPAcidic ext.

Solventcleanup

Ln stripping

Mo stripping

Am selective stripping

CitricAcid

+ NaOH

HNO3 > 4M

Mo+Ru

Am + light LnLight Ln

Oxalic acidTEDGA

Light Ln

+ Fe

Am

pH 3HNO3 > 4M

pH 2 - 3

DTPA

+ TEDGA

Step 1 Step 2

Step 3Step 4

Step 5

CEA | SEPTEMBER 8th, 2014

CEA | SEPTEMBER 8th, 2014 | PAGE 4

How does the Mo stripping step work?

TEDGAHNO3

Am Extraction Cm Scrubbing

Feed solutionPUREX raffinate

FP

Cm

Heavy Ln

DMDOHEMASolvating ext.

HDEHPAcidic ext.

Solventcleanup

Ln stripping

Mo stripping

Am selective stripping

CitricAcid

+ NaOH

HNO3 > 4M

Mo+Ru

Am + light LnLight Ln

Oxalic acidTEDGA

Light Ln

+ Fe

Am

pH 3HNO3 > 4M

pH 2 - 3

DTPA

+ TEDGA

Step 1 Step 2

Step 3Step 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+

Citric acid: complexing power vs. acid buffer

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

Reference : ???

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

Neutral species

CEA | SEPTEMBER 8th, 2014| PAGE 8

Modelling of Mo(VI) behavior

D(Mo)

pH

Anionic ( )2

4MoOCationic ( )2

2MoO

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 ( )3MoO

pH ~ 1 pH ~ 4

Chemical

reaction Formula Log(K)

3

2

2 / MoOMoO 233

2

2

2

2 / HMoOMoOMoOKMoO 1.9

2

43 / MoOMoO 22

4

2

433 / HMoOMoOMoOKMoO 8.1

Cation

exchanger

242

2222

H

HDEHPMoOKHDEHPDEHPMoO ec 4.7

Solvating

extractant 4343 HDEHPMoOKHDEHPMoO es 5.5

Anion

exchanger 242

4222

HHDEHPMoOKHDEHPDEHPMoO ea 13.6

CEA | 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 %

Model seems to be representative of Mo behavior

CEA | SEPTEMBER 8th, 2014 | PAGE 11

Implementation in the PAREX code

D(Mo)

pH

Anionic ( )2

4MoOCationic ( )2

2MoO

Working point

Solvating extractant ( )3MoO

pH ~ 1 pH ~ 4

| 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)

Thank you for your attention!

| 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

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recyclage

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Centre de Marcoule | BP17171 | 30207 Bagnols-sur-Cèze Cedex

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Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 01910 NOVEMBRE 2020

| PAGE 15

CEA | 10 AVRIL 2012