Maintaining parallel flows in microsystem during solvent extraction of concentrated Uranium(VI) solutions a solution for the screening of extractive molecules

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Maintaining parallel flows in microsystem during solvent

extraction of concentrated Uranium(VI) solutions a

solution for the screening of extractive molecules

J-P. Jasmin

To cite this version:

J-P. Jasmin. Maintaining parallel flows in microsystem during solvent extraction of concentrated Ura-nium(VI) solutions a solution for the screening of extractive molecules. BIT’s 5th Annual Conference of AnalytiX 2017, Mar 2017, Fukuoka, Japan. �cea-02438340�

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Jean-Philippe JASMIN

Den—Service d’Etudes Analytiques et de Réactivité des

Surfaces (SEARS), CEA

jean-philippe.jasmin@cea.fr

MAINTAINING PARALLEL FLOWS IN

MICROSYSTEM DURING SOLVENT EXTRACTION

OF CONCENTRATED URANIUM(VI) SOLUTIONS:

A SOLUTION FOR THE SCREENING OF

EXTRACTIVE MOLECULES

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THE PUREX PROCESS

PUREX: Plutonium and Uranium Recovery Extraction

 Recycling part of the spent nuclear fuel  Uranium and plutonium

 Based on liquid–liquid extraction ion-exchange Nuclear plant purpose

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NEW EXTRACTIVE MOLECULES REQUIREMENT

TBP: Historically used Monoamide: next generation of extractive molecules

 CHON principle respected  Incinerable

 Easy U/Pu separation  Highly effective

 Phosphorous atom

 Degradation products hardly manageable  Redox U/Pu separation

Assets and drawbacks: Assets and drawbacks:

Extractant U/Pu Settling Separation [HNO₃]=5 M Monoamide + U/Pu [HNO₃]= 5 M U/Pu Organic phase Monoamide tested

Current screening procedure :

Screening procedure of the monoamide is fastidious and costly due to:

• synthesis, • purification,

• use of radiochemicals

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OBJECTIVES

(REACH) Volumes Product waste Operator exposure Costs

Classic hydrodynamic

principles conserved

[1] [1] Whitesides, Nature, 2006, 442, 368-373

Microfluidics for the screening

Conception of a uniquescreening tool for the monoamides

featuring:

• Few manipulations

• Low amount of reagents (radionuclides and extractant) • Limited generated wastes

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EXPERIMENTAL SET-UP

Outlets Microsyringe pump

Syringe

Microchip

PEEK Capillaries Y–Y shaped microchip

Parallel flow



Resistance toward corrosive products (concentrated acid, solvents, radionuclides)



High interfacial area A’ = A/V = 104_m-1  Channel geometry

Height H = 100 µm Width W = 40 µm Length L = 12 cm  Pyrex glass microchips (IMT, Japan)

Phase separation

Interface

• Parallel flows

• Centered interface Phase separation Experimental conditions

𝒕_𝐚𝐪 = 𝒉 𝑾 𝑳 𝑸_𝐚𝐪

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HYDRODYNAMICS CONTROL FOR ONE CHEMICAL SYSTEM

[U(VI)] = 10-4 _{M in [HNO}

3] = 3 M / µaq = 1,22 ± 0,01 mPa.s

Flow patterns of the biphasic system

30 % TBP in n-dodecane (v/v) / µ_org = 1,97 ± 0,01 mPa.s

𝑈𝑂

₂2+

+ 2𝑁𝑂

₃−

+ 2𝑇𝐵𝑃 → 𝑈𝑂

₂

𝑁𝑂

_{3 2}

. 2𝑇𝐵𝑃

Extraction equilibrium Non-centered interface Centered interface Instable flows Good separation

𝑸

_𝐨𝐫𝐠

𝐐

_𝐚𝐪

≈

µ

_𝐚𝐪

µ

_𝐨𝐫𝐠

Simple case: U-TBP reference chemical system

 Only one extractant

 Low concentration of uranium  Viscosities unchanged

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Qorg Qaq ≈

µaq

µorg _{𝐼𝑛𝑙𝑒𝑡}

SPECIFICITY OF HYDRODYNAMICS CONTROL FOR THE

SCREENING OF EXTRACTANTS

[8] Maruyama et al., Analyst, 2004, 129, 1008-1013 [9] Ban et al., J Nucl Sci Tech, 2011, 48, 1313-1318

Partition-wall

Shallow microchannel Deep microchannel

More difficult, if:

 Several extractants with different viscosities

 the viscosities evolve along the stream because high concentrations

Partition walls[8] _{Asymmetrical chip}[9]

W1 W2 Commercial microchip Outlets Limitations: • Challenging conception

• Impact on the interfacial area

• Specific geometry for one chemical system

L_org,Outlet L_aq,Outlet Qorg Qaq ≈ µaq µorg _{𝑂𝑢𝑡𝑙𝑒𝑡}× 𝐿aq 𝐿org _{𝑂𝑢𝑡𝑙𝑒𝑡}

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STRATEGY

Main requirement for the screening tool:  Same device for a wide range of molecules  Screening with high U and Pu concentrations

( ≥ 10 g/L)

 Each molecule owns a specific viscosity  The viscosities evolve between inlets and the

outlets

Main challenges

Conception strategy for the screening tool:

N O N O N O N O N O N O N O N O

Molecule MOEHA DEHDMBA

Formula Viscosity at 1.4 M in THP (mPa.s) 4.02 ± 0.01 8.04 ± 0.01

 Two monoamides known for their respectively low and high viscosities were used

 U(VI) in [HNO₃] = 5 M

 [Monoamide] = 1.4 M in THP

Two objectives:

 Parallel flows and centered interface for any

monoamide

 Compare the efficiency of the monoamides

𝑈𝑂₂2+_{+ 2𝑁𝑂}

3−+ 2𝑚𝑜𝑛𝑜𝑎𝑚𝑖𝑑𝑒 → 𝑈𝑂2 𝑁𝑂3 2. 2𝑚𝑜𝑛𝑜𝑎𝑚𝑖𝑑𝑒

Extraction equilibrium

Parameters

Screening tool specifications

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STRATEGY

Determination of a common hydrodynamic protocole for monoamides

Common Contact time:

𝒕𝐚𝐪 =𝒉 𝑾 𝑳_𝑸

𝐚𝐪

Common Length ratio:

𝑳_aq 𝑳_org

𝑶𝒖𝒕𝒍𝒆𝒕

Flow rate ratio Range:

𝑸_𝐨𝐫𝐠 𝐐_𝐚𝐪

Inlet stream control _{Outlet stream control}

Mass transfer control

Qorg Qaq ≈ µaq µorg _{𝑂𝑢𝑡𝑙𝑒𝑡} × 𝐿aq 𝐿org _{𝑂𝑢𝑡𝑙𝑒𝑡} Qorg Qaq ≈ µaq µorg _{𝐼𝑛𝑙𝑒𝑡} Specific Flow rate

𝐐

_𝐨𝐫𝐠

µ

_𝐨𝐫𝐠

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0,0 0,5 1,0 1,5 2,0 0 50 100 150 200 µaq (m P a .s) [U(VI)]_aq,Initial(g.L-1₎

1st _{step: Determination of the suitable flow rate ratio}

 With the aqueous and organic phase initial viscosities: µ𝐚𝐪

µ_{𝐨𝐫𝐠 𝑰𝒏𝒍𝒆𝒕} ≈

𝑸𝐨𝐫𝐠 𝐐_{𝐚𝐪 𝑰𝒏𝒍𝒆𝒕}

Any inlet flow rate ratiocan be determined knowing the organic phase viscosity Evolution of the aqueous phase viscosity [HNO3] = 5 M with [U(VI)].

𝟒. 𝟎𝟐 ≤ µ_𝐨𝐫𝐠 ≤ 𝟖. 𝟎𝟒 mPa.s

MICROFLUIDIC SCREENING TOOL FOR MONOAMIDES

Flow rate ratio Range:

𝑸_𝐨𝐫𝐠 𝐐_𝐚𝐪 0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0 20 40 60 80 μaq /μorg ≈ Qorg /Q aq [U(VI)]_initiale(g/L)

Evolution of the aqueous flow rate ratio for MOEHA and DEHDMBA at 1.4 M with [HNO3] = 5 M depending on [U(VI)].

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2cd _{step: Determination of the suitable Outlet length ratio}

 With batch experiments according to:

The outlet length ratio is determined with the batch extraction yields

Monoamide MOEHA DEHDMBA

µ_𝒂𝒒 µ_{𝒐𝒓𝒈 𝑰𝒏𝒍𝒆𝒕}≈ Qorg Qaq 0.34 0.17 µaq µorg _{𝐎𝐮𝐭𝐥𝐞𝐭} 0.20 0.07 𝑳_𝒂𝒒 𝑳_𝒐𝒓𝒈 2.5 1.7 𝑸_𝐨𝐫𝐠 𝐐_𝐚𝐪

≈

µ_𝐚𝐪 µ_𝐨𝐫𝐠 _{𝑶𝒖𝒕𝒍𝒆𝒕}

×

𝑳_𝒂𝒒 𝑳_𝒐𝒓𝒈 0 5 10 15 20 25 30 0 20 40 60 80 100 µorg (m P a .s) [U(VI)]org(g.L-1)

Evolution of the organic phases viscosities with [U(VI)] in the organic phase after extraction, Vorg/Vaq= 1, T = 293 K. [DEHDMBA]

= 1.4 M (red) and [MOEHA] = 1.4 M (green), (diluted in THP)

0,0 0,5 1,0 1,5 2,0 0 50 100 150 200 µaq (m P a .s) [U(VI)]_aq(g.L-1₎

Evolution of the aqueous phase viscosity [HNO3] = 5 M with [U(VI)].

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MICROFLUIDIC SCREENING TOOL FOR MONOAMIDES

𝑳_aq 𝑳_org 𝑶𝒖𝒕𝒍𝒆𝒕 𝑽_𝐨𝐫𝐠 𝑽_𝐚𝐪

=

𝑸_𝐨𝐫𝐠 𝐐_𝐚𝐪

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 With solvent extraction experiments in microsystem with:

Equilibrium reached in 3 seconds

or with a maximum flow rate of Q

_aq

= 0.3 mL.h

-1

0 20 40 60 80 100 0 1 2 3 4 5 RU, D E H D M B A , 12 cm (20 g. L -1) ( %) t_aq(s) 0 20 40 60 80 100 0 1 2 3 4 5 RU, M O E H A ,12 cm (20 g.L -1) ( %) t_aq(s)  Chip length: 12 cm

 Flow rates ratio: 𝟎. 𝟏𝟕and 𝟎. 𝟑𝟒  Outlet length ratio: L_aq = 2 x L_org

Extraction kinetic profils obtained with [DEHDMBA] = 1.4 M, [MOEHA] = 1.4 M . With ICC-DY15 (12 cm), [U(VI)] =20 g.L-1_in

[HNO3] = 5 M and [monoamide] = 1.4 M, and Laq,Outlet/Lorg,Outlet= 2, T = 293 K.

MICROFLUIDIC SCREENING TOOL FOR MONOAMIDES

3rd _{step: Determination of a suitable contact time}

Common Contact time:

𝒕𝐚𝐪 =𝒉 𝑾 𝑳_𝑸

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MICROFLUIDIC SCREENING TOOL FOR MONOAMIDES

𝑅

_𝑁

=

𝑅

𝐶ℎ𝑖𝑝

100 ×

𝐐

_𝐐

𝐨𝐫𝐠 𝐚𝐪 Normalized Yield  Chip length: 12 cm

 Flow rates ratio: 𝟎. 𝟏𝟕and 𝟎. 𝟑𝟒  Outlet length ratio: L_aq = 2 x L_org  Aqueous flow rate: Q_aq = 0.3 mL.h-1 Hydrodynamic parameters

Flow rate ratio Range: 0.17 ≤ 𝑸_𝐐𝐨𝐫𝐠

𝐚𝐪 ≤ 0.34

𝑳_aq 𝑳_org 𝑶𝒖𝒕𝒍𝒆𝒕 = 2 Common Contact time: 𝒕𝐚𝐪 = 3s (𝑸𝐚𝐪 = 0.3 mL.h-1)

1

st

_Objective:

_{Parallel flows and centered interface for any monoamide}

2

cd

_Objective:

_{Compare the efficiency of the monoamides}

Specific viscosity

Specific Flow rate

µ

_org

Q

_org

 U(VI) in [HNO₃] = 5 M

 [Monoamide] = 1.4 M in THP

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Validation of the method for [U(VI)] =20 g.L

-1 0 20 40 60 80 100 A B C E x tra ctio n y ield in b a tch (1/1 ) (%) Conventional screening 0 0,5 1 1,5 2 2,5 3 A B C Norm a liz e d y ield Microfluidic screening Screening of 3 monoamides A, B, C

Same relative performances as batch experiments

ICC-DY15 (12cm), [U(VI)] =20 g.L-1 _{in [HNO}

3] = 5 M and

[monoamide] = 1.4 M, and Vaq/Vorg= 1, T = 293 K.

ICC-DY15 (12cm), [U(VI)] =20 g.L-1 _{in [HNO}

3] = 5 M and

[monoamide] = 1.4 M, and L_aq,_Outlet/L_org,Outlet= 2, T = 293 K.

MICROFLUIDIC SCREENING TOOL FOR MONOAMIDES

Monoamide _A _B _C Viscosity at 1.4 M in THP (mPa.s) 6.07 5.6 5.45 0,0 0,1 0,2 0,3 0,4 4 5 6 7 8 Qorg /Q aq µ_1.4M(mPa.s)

flow rate ratio evolution depending on the viscosity of the organic phase containing monoamide diluted 1.4 M in THP with [U(VI)]Initial= 20 g.L-1

𝑅_𝑁 = 𝑅𝐶ℎ𝑖𝑝 100 × Q_Qorg

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CONCLUSION AND PERSPECTIVES

Conclusion

Perspectives



Only 20 µL of solution are need



CFD simulation (COMSOL) for the design of a custom-made chip

•

Asymetrical geometry

•

More suitable length of microchip

•

Test with U(VI) and Pu(IV)

Microfluidic screening tool

20 µL

need

𝐐𝐚𝐪 = 𝟎. 𝟑 𝐦𝐋/𝐡 𝑳aq≈ 𝟐 𝑳org 𝐭𝐚𝐪 = 𝟑 𝐬 Aqueous flow rate Contact time Length ratio Parameters 8.04 6.07 5.454.02 0 0,1 0,2 0,3 0,4 0 ₂₀ 40 ₆₀ 80 ₁₀₀ μaq / μor g ≈ Qor g /Q aq

[U(VI)]_{aq, initial}

Establishment of a viscosity/phase ratio diagram

flow rate ratio evolution depending on the viscosity of the organic phase containing monoamide diluted 1.4 M in THP and [U(VI)]_Initialin aqueous phase.

Monoamide viscosity

Extraction Efficiency



Screening method can be applicable with large range of uranium concentration

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