CE.VAUDEY AREVA BUA Technical Direction 25/02/2013

NOCHAR polymers: an aqueous and organic liquid

solidification process for Cadarache LOR (Liquides Organiques Radioactifs)

CE.VAUDEY

AREVA BUA Technical Direction25/02/2013

WM2013– C-E.Vaudey – 02/2013 p.3

NOCHAR polymers: a solidification process for Cadarache LOR

Summary

Introduction Waste handling Cadarache LOR waste streams characteristics

Method and experimental device

Results and discussion

Conclusion and outlook

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Introduction Waste handling

For VLLW and LLW handling in France : 2 options- Incineration at CENTRACO facility

- Disposal facility on ANDRA sites

Waste acceptance in a radwaste route- Adequacy Waste characteristics/Radwaste route specifications

- In case of incompatible : necessary to find an alternative solution

A waste pre-treatment process

Cadarache LOR waste streams characteristics 2 radioactive scintillation cocktails

LOR 20 LOR 75

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LOR 20 LOR 75

Volume (L) and Mass (kg) 208L and 206kg 137L and 137kgComposition 11% Xylene

1.6% Mesitylene0.4% Diphenyloxazole

0.1% TBP91.4% Water

8.6% TBP 91.4% Water

Physical chemistry characteristics

1.7 mg.g-1 Chloride0.61 mg.g-1 Fluoride0.9 mg.g-1 Sulfate

1.3 mg.g-1 Chloride0.23 mg.g-1 Fluoride2.1 mg.g-1 Sulfate

Radiological characterisctics

Spectra Am-241 Co-60Cs-137

H-3

Am-241Pu-241Cs-137

Mass activity AAlpha = 3.78x108 Bq.g-1

ABeta/Gamma = 5.55x105 Bq.g-1

ATritium = 3.47x106 Bq.g-1

AAlpha = 8.67x108 Bq.g-1

ABeta/Gamma = 8.62x103 Bq.g-1

LLW (mass activity equal to some kBq.g-1) + Organic and aqueous components + Presence of significant quantities of tritium, chlorine and fluorine

Needs of a pre-treatment : NOCHAR polymers as solidification process

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Method and experimental device NOCHAR polymers

N910 for organic liquids solidification N960 for aqueous liquids solidification

Implementing of polymers technology = 2 main steps mixing waste/polymer curing during 24h to 48h

Process specificities For N910 : Creation of permanent chemical bonds between organic liquids and

polymer For N960 : Creation of strong mechanical bonds between aqueous liquids and

polymer Final product = immobilised solid stable under radiation, non-toxic, not

dangerous, non-corrosive and non-biodegradable Evaluation of formulation validity : approach in 3 steps

Identification of the ideal polymer formulation with a Waste/Polymer mass ratio 1:1 Increase of Waste/Polymer mass ratio Observations, evaluations of residual liquid presence/absence and manual exudation

tests

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Results and discussion

Ideal polymer formulation?

3 types of results- Sticky, doughy, glistening with presence of residual moisture or waste

- Dry sample- Dry sample with presence of polymer N910 excess

Ideal polymer formulation = Dry sample

Mass ratio N960 : N910

1 : 0

0.85 : 0.15

0.70 : 0.30

0.50 : 0.50

0.25 : 0.75

LOR 20 LOR 75Mass ratio N960 : N910

1 : 0

0.75 : 0.25

0.50 : 0.50

0.25 : 0.75

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Ideal Waste/Polymer mass ratio? For ideal polymer formulation, 3 ratios

- 1 : 1 -> Dry sample

- 2 : 1 -> Sticky, doughy, glistening with presence of residual moisture

- 4 : 1 -> Sticky, doughy, glistening with presence of residual waste Ideal Waste/Polymer mass ratio = 1 : 1


0.50 : 0.50

LOR 20 LOR 75

0.25 : 0.75

LOR 20 Mass ratio N960 : N910

0.50 : 0.50 0.25 : 0.75

LOR 75LOR 20

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Observations, evaluations of residual liquid presence/absence and manual exudation tests ?

For ideal polymer formulation and Waste/Polymer mass ratio 1 :1

After a curing of 1 and 20h, no moisture and no waste desorption under exudation test


0.50 : 0.50 0.25 : 0.75LOR 20 LOR 75

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Discussion

For LOR 20 Ideal formulation : N910/N960 mass ratio equal to 0.50 : 0.50

N910 absorption power higher than the N960 one Ideal Waste/Polymer mass ratio equal to 1 : 1

Xylene and mesitylene composed of a benzenic ring and methyl groups

-> Limited number of free carbon atoms

-> Negative effects on the reactive mechanism which occurs during the Waste/Polymer mixing to form covalent bonds between the two products

For LOR 75

Ideal formulation : N910/N960 mass ratio equal to 0.25 : 0.75

N910 absorption power higher than the N960 one Ideal Waste/Polymer mass ratio equal to 1:1

Nature of the organic product (TBP)

-> Negative effects on the reactive mechanism which occurs during the Waste/Polymer mixing to form covalent bonds between the two products

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Conclusion and Outlook

For Cadarache LOR waste, pre-treatment by polymer adapted

Polymers = suitable solidification matrix for a final acceptance in storage on ANDRA sites

To consolidate this conclusion, 3 future steps Optimisation of the adapted formulations by tests Realisation of a waste field study based on

- the experimental data collected during this study,

- the potential adequate between pre-treated Cadarache LOR waste streams characteristics and ANDRA specifications,

- the ANDRA agreement principle on VLLW, LLW and ILW immobilised by polymers

Final product conditioned in homogenous waste package (waste immobilised by polymers placed in cement matrix)

Final product conditioned in heterogeneous waste at 10% for the waste immobilised by polymers and at 20% for the waste immobilised by polymers placed in cement matrix

Preparation of an ANDRA agreement file for Cadarache LOR waste streams pre-treated by NOCHAR polymers

CE.VAUDEY AREVA BUA Technical Direction 25/02/2013

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