Thorium molten salts, theory and practice

Paul Madden (Oxford, UK) & Mathieu Salanne & Maximilien Levesque (UPMC, France)

Euratom Project, 13 Groups Molten Salt Fast Reactor

WP2: MSFR whole system

Thermal power (MWth) Electric power (MWe) Fuel Molten salt initial composition (mol%) Fertile Blanket Molten salt initial composition (mol%) Melting point (C) Input/output operating temp. (C)

3000 1500 LiF-ThF4-233UF4 with 77.5 % LiF or LiF-ThF4-(Pu-MA)F3 LiF-ThF4 (77.5%-22.5%) 565 625-775

Fuel Salt Volume (m3)

18 9 out of the core 9 in the core

7.3

Blanket Salt Volume (m3)

Total fuel salt cycle in the system 3.9 s

Fission products extraction

Motivation Control physicochemical properties of the salt (control deposit, erosion and corrosion phenomena's) Keep good neutronic properties Physical Separation Gas Reprocessing Unit through bubbling extraction Extract Kr, Xe, He and particles in suspension Chemical Separation Pyrochemical Reprocessing Unit Located on-site, but outside the reactor vessel

Discussion by Sylvie Delpech (Tuesday 4pm)

The complexity of the flow inside the cavity involves a coupled Thermal-Hydraulic & Neutronics approach:

Fluid velocity

Temperature

Elsa Merle-Lucotte (Wednesday 10am)

Hence need various thermodynamic, transport and chemical properties of multi-component molten salts over a wide range of temperatures

e.g. Melting points, heat capacities, thermal conductivity......... chemical activity coefficients

Phase diagram of LiF:ThF4

Liquid

Physical properties
Physical properties for LiF-78%mol-ThF4-22%mol (ISTC Project No. #3749)
Formula Density (g/cm3) Kinematic Viscosity (m/s) Dynamic viscosity (Pa.s) Thermal Conductivity (W/m/K) Calorific capacity Cp (J/kg/K) 4,094 8,82 10-4 (T(K)-1008) 5,54 10-8 exp{3689/T(K)} (g/cm3)5,54 10-5 exp{3689/T(K)} Value at 700C 4,1249 2,4610-6 10,110-3 Validity Range, C [620-850] [625-846] [625-846]

0,928 + 8,39710-5T(K)
(-1,111 + 0,00278 T(K)) 103

1,0097
1594

[618-747]
[594-634]

Hence need various thermodynamic, transport and chemical properties of multi-component molten salts over a wide range of temperatures and compositions

e.g. Solubilities, heat capacities, thermal conductivity......... chemical activities

Such datasets do not exist!!

4th progress meeting - EVOL Project

Thermodynamic modelling of ternary system from data for binary subsystems 26 -28 June 2013, Grenoble e.g. by O. Bene & R. Konings (ITU, Karlsruhe)
Sub-binary systems

Experimental data: Phase transition points Enthalpy of mixing Li3ThF7 enthalpy of fusion ThF4 enthalpy of fusion Phase transition points (Barton et al.) No experimental data available on ThF4-PuF3 system. Phase diagram optimized based on similarity with ThF4-CeF3 system.

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4th progress meeting - EVOL Project 26 -28 June 2013, Grenoble

LiF-ThF4-PuF3 ternary system

Tmin=818,14 K LiF-ThF4-PuF3 (69.628.6-1.8)

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Approach via atomistic simulation

Perform realistic Molecular Dynamics simulations, with polarizable, deformable ionic interaction models

model parameters from first-principles electronic structure calculations

-- i.e. predictive simulations (no experimental input)

A general methodology applicable to a wide variety of ionic liquids

Output of simulations is a trajectory of the ions in the fluid in a given thermodynamic state

Liquid-vapour interface in LiF:ThF4 By averaging functions of positions and

velocities can calculate observable properties validate, predict, interpret

Molten LaCl3 (1300K) diffraction structure

X-rays(Okamoto)

EXAFS

Transport Properties of LiF:ThF4

Viscosity
Conductivity

Figure of Merit for heat transfer

Can link observable properties to underlying atomic scale structure - interpretation of different material behaviours

3LiF:BeF2

LiF:BeF2

of LiF:BeF mixtures 2 BeFViscosity X-ray diffraction (Narten) 2

Thermodynamic Activity Coeff. Separability of fission products

LiCl/KCl solvent

Increase cell voltage -> deposition of M3+

Activity coefficients

Gtot

Transmutation
by changing the interaction potential U()

Transmutation of U3+ into Sc3+

99.9% separability requires E = 0.149 V

Conclusion:
the modelling methodology is generally applicable, capable of predicting material properties and of helping to interpret material behaviour the accuracy has been validated on molten salts of interest