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Open problems in reprocessing of a molten salt reactor fuel.

Vladimir Lelek, Radim Vocka Nuclear Research Institute Rez, Czech Republic [email protected], [email protected]

Abstract.

The study of fuel cycle in a molten salt reactor (MSR) needs deeper understanding of chemical methods used for reprocessing of spent nuclear fuel and preparation of MSR fuel, as well as of the methods employed for reprocessing of MSR fuel itself. Assuming that all the reprocessing is done on the basis of electrorefining, we formulate some open questions that should be answered before a flow sheet diagram of the reactor is designed. Most of the questions concern phenomena taking place in the vicinity of an electrode, which influence the efficiency of the reprocessing and sensibility of element separation. Answer to these questions would be an important step forward in reactor setout.

607 Page 1 of 8 I. Introduction

Spent nuclear fuel contains highly radioactive isotopes and isotopes with a very long half-life (>IOOO years) which, if stored, could be potentially hazardous for environment. The main aim of the Molten Salt Demonstrational Transmuter (MSDT) is to proof the possibility of closing of the fuel cycle, that means of conversion of these radioactive isotopes (mainly plutonium and minor actinides) either to stable ones or to fission products with relatively short half-life (~30 years). The first question that must be asked is what will be the neutron balance of such a facility. Let us suppose that an asymptotic state has been reached, where fuel of stable isotopic composition is added to the reactor and only fission products with short half-life and stable isotopes are extracted. It is not evident for the moment, if MSDT can work under these conditions as a critical reactor, or if it must be built as a subcritical reactor with external neutron source. Preliminary results from RRC Kurchatov institute indicate that the additional neutron source may not be necessary - at least if one through cycle VVER fuel is burned, but for example for the spent MOX fuel the situation is not obvious at all. The study of a neutron balance of the MSDT is a complex task, because it depends not only on the core geometry, but also on the fuel composition, which evolves during the transmutation process. An advantage of a molten salt fuel concept over the traditional solid fuel is that the decreasing level of the fissile material in the salt can be continuously compensated. Nevertheless as a concentration of fission products increases during the time, a simple addition of fissile material is not sufficient for an unlimited functioning of the reactor. In fact certain isotopes among the fission products (b7Gd, 149Sm, l48Pm etc.) have an important cross section for neutron absorption and thus it will be necessary to extract them from the salt. Previous considerations show, that the asymptotic fuel composition and hence also the neutron balance of the reactor depends on available technology for fuel preparation and a molten salt reprocessing. For the moment two stage preparation of MSDT fuel (Pu+MA) from the spent VVER fuel is considered: First U is stripped out by the florid volatility method, then PU and MA are separated from the fission products using pyrochemical methods, namely elecrorefining. Electrorefining is considered as well for the reprocessing of molten salt fuel. Principal advantage of electrorefining is its presumed universality for extraction of any element and the compactness of the reprocessing device. Nevertheless as these pyrochemical methods are still in the stage of research it is not clear for the moment if their application will allow an efficient reprocessing of the fuel. That is why, after a brief description of an electrorefiner, we try here bellow to gather some of the open problems of pyrochemical reprocessing. An answer to these questions, obtained by mutual effort of physicists and chemists, would be a major step forward in the preparation of MSDT.

II. Reprocessing by pyrochemical methods: open problems

Basic electrorefining apparatus consist of two electrodes, called anode and cathode, which are immersed in the electrolyte. In our case the electrolyte is formed by the carrier salt - mixture of LiF, BeF2, NaF and KF, in which could be potentially

608 Page 2 of 8 dissolved uranium (UF3+UF4), plutonium (PuFj), minor actinides and fission products (depending on the type of the reactor). Some of these elements do not form stable molecules, but they are instead decomposed in the form of ions. If a potential difference is applied between cathode and anode, ions start to migrate towards electrodes. If a potential difference between an electrode and ion is equal or bigger than a reduction potential of a given ion. ion is reduced on the electrode. It is the difference between the reduction potentials of different elements, which enables their separation. Preceding qualitative description of the electrorefining process leads to following observations:

1. If the carrier salt, which forms a major part of the electrolyte, is decomposed into a ionic form under the working conditions of a electrolyzer, the reduction potential of carrier salt cations should be higher than the reduction potential if ions we want to extract from the electrolyte.

2. A solubility of fission products in the carrier salt must be checked to avoid their sedimentation in the reactor. Results of this study will furnish constraints for extraction of fission products from the carrier salt. Fission products with a high solubility and small cross section for absorption of neutrons may be left in the reactor, which can lead to a significant simplification of reprocessing.

3. For the moment, most of experimental (see for example [1-4]) and theoretical [ 1,5-9] work was done on pyrochemical reprocessing in chloride salts environment. The question of the transfer of this experience into the fluoride salts environment arises naturally. The first step should be a development of a thermodynamic model for the molten fluoride salts environment. As shown in the case of chloride salts [1,6], these models can furnish a valuable information about the evolution of a process of electrorefining for given initial conditions. Equilibrium distributions of elements of interest between the molten salt and electrodes can be evaluated, as well as atom mol fractions of elements extracted on an electrode. Principal unknowns for these calculations are the activities of different elements in the solution (carrier salt, electrode), which must be measured experimentally. Their approximate values for a given solution can be also deduced from the experimental values obtained for solutions of similar composition.

4. A theory of pyrochemical processes-is far from being complete and a deeper understanding is desirable. The main shortcoming of current models resides in fact that the electrotransport is treated as an equilibrium process. The time scale needed to attain the equilibrium is not known, while the speed of the process is one of principal criteria for a successful industrial application. The speed is limited by two main factors: by the time necessary for the transport between the electrodes, and by the characteristic time of exchange of ions between electrolyte and electrode. The mixing of the electrolyte can enhance the speed of the transport between electrodes. Hence the principal unknown remains the time scale of

609 Page 3 of 8 transport of ions from the steady layer in the vicinity of an electrode, where mixing is no more effective, to an electrode. The difficulty with the molten salt mixtures is that several types of ions with different reduction potentials are generally present in an electrolyte. Hence actual transfer from an electrolyte to an electrode is not limited only by the reduction potential of a given element, but also by the organization of ions of different types in the vicinity of an electrode. The presence of an ion with higher reduction potential in the vicinity of an electrode might inhibit the other ions with lower reduction potential from being reduced. This process could be at least partially understood by studying the concentration profile of a mixture of different ions in the double layer of ideally polarized electrode. Recent progress in the double layer theory ( see [10-18] and figs. 1,2) seems to enable such calculations.

5. Elements are reduced on an electrode by an electrochemical reaction, at which electrons are transferred from the metal electrode to electron orbitals of ions in the vicinity of the electrode. The rate of the reaction depends on the difference of the Fermi level in metal and energy of the lowest unoccupied orbital of ions in the solution. While the Fermi level is controlled by the potential imposed on the electrode, the energy of electronic orbitals of ions depends on the potential in the solution, hence on the ion distribution in the vicinity of the electrode. Because of the possible fluctuations (caused for example by the thermal movement of ions) this potential might be ill defined, which could lead to the difficulties to separate elements with close reduction potentials. This is one more argument to study the ionic concentration profiles in the vicinity of an electrode.

6. It is well known that due to surface growth instability [19], the sediment at the electrode does not growth in one layer but forms rather complicated structures [4]. Ions are not reduced along the whole interface, but only at its tips where the gradient of the electrostatic potential is the most important [20,21]. Influence of this phenomenon on the efficiency of electrolysis is not evident and precise control of the potential difference between the electrode and electrolyte, needed for a good separation of certain elements, might become difficult. Moreover the surface growth in the form of "hairy " is not convenient from the practical point of view. Hairs are easily broken and an important quantity of electrolyte remains on the electrode if it is took out from the electrolyzer. For these reasons experimental conditions must be looked for which would allow a control of the growth geometry.

7. In a first order approximation the reduction potential increases with the decreasing atomic number. Hence it is likely that extraction of embarassing fission products by means of electrolysis will not be a straightforward task, because U, Pu and MA must be extracted first. This point is crucial for the implementation of reprocessing plant in MSDT. In projects for molten salt reactors a bypass in flow sheet diagram for a continuous fuel reprocessing is often considered. In view of the above remark this approach seems to be problematic, at least at the current stage of progress in pyrochemical reprocessing. Other alternatives should be therefore

610 Page 4 of 8 HI*- \KR Symposium tin VVlUt RvachK Vhwki *td S*f«v. Sc|MM

considered as cleaning up of. whole batch when the reactor is shut down, or reprocessing of smaller amounts of motten salt which would be withdrawn and then reentered during the reactor operation. The second possibility allows continuous operation of the reactor but it must be verified if the concentration of fission products could be held at acceptable level.

The chemical reprocessing technology is an integral part of any facility for transmutation of nuclear waste. Hence the technical possibilities of a given way of reprocessing must be known before a detailed flow sheet diagram and reactor design are prepared. Here, we tried to summarize some open questions related to electrorefining, which is a promising technology for both the reprocessing and fuel preparation. We believe that a mutual effort of physicists and chemists can lead to satisfactory answer to these questions. At least a qualitative theoretical answer would simplify the experimental work and permit a quicker progress on the MSDT preparation.

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Figures

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Fig. 1. A simple diagram of electrical double-layer.. Helmholtz double layer (left), where the negative charge of the electrode is compensated by a layer of cations next to the interface, and diffuse Gouy-Chapman double layer (right), where the cations form a diffuse layer in the solution. From [22].

Concentration profiles for RPM MC siniuliiion

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.** *°*8o»e»88888888888888888888888888888888; 0 • 0 2 4 6 z/d Fig. 2 : Anion (with charge q=-2e and q=-le) and cation concentration profiles obtained from Monte-Carlo simulations using the Restricted primitive model (RPM): ions are represented as charged hard spheres of a given diameter (diameters of all spheres are equal), solvent is a isotropic dielectric continuum characterized by a dielectric constant e.

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References

[I] Z.Tomczuk, J.P. Ackerman. R.D. Wolson, and W.E. Miller. Uranium transport to solid electrodes in pyrochemical reprocessing of nuclear fuel. J. Electrochem. Soc, 139:3523. 1992.

[2] M.Iizuka. T.Koyama. N.Kondo. R.Fujita, and H.Tanaka. Actinides recovery from molten salt/liquid metal system by electrochemical methods. J. Nucl. Mat.. 247:183. 1997.

[3] T.Koyama, M.Iizuka, N.Kondo, R.Fujita, and H.Tanake. Electrodepositiopn of uranium in stirred liquid cadmium cathode. J. Nucl. Mat., 247:227, 1997.

[4] T.C. Totemeier and R.D. Mariani Morphologies of uranium and uranium- zirconium electrodeposits. J. Nuc!. Mat., 250:131,1997.

[5] I.Johnson. The thermodynamics of pyrochemical process for liquid metal reactor fuel cycles. J. Nucl. Mat., 154:169. 1988.

[6] J.P. Ackerman. Chemical basis for pyrochemical reprocessing of nuclear fuel. Ind. Eng.Chem. Res.. 30:141, 1991.

[7] H.P. Navvada and N.P. Bhat. Thermochemical modelling of electrotransport of uranium andplutonium in an electrorefiner. Nucl Eng. Des., 179:75, 1998.

[8] T.Koyama, M.Iizuka, and H.Tanaka. Process evaluation of semi-commercial pyrometallurgical reprocessing facility. In International conference on nuclear ingeneering ASME, volume4, page 259, 1996.

[9] T.Kobayashi and M.Tokivvai. Developement of trail, a simulation code for the molten salt electrodefming of spent nuclear fuel, J. Alloys and Comp., 197:7, 1993.

[10] C.N. Patra. Structure of electric double layers: A simple weighted density functional approach. J. Chem. Phys., 111:9832, 1999.

[II] N.Goto, T.Kakitani, T.Yamamoto, and Y.Hatano. Monte Carlo simulation study- on the structure and reaction at metal-electrolyte interface.//. Mechanism of nonlinear electrode reactions. J. Phys. Soc. Japan, 68:3729, 1999.

[12] A.Chandra. Dynamics of electrical double layer formation at a charger solid surface. Theochem, 430:105, 1998.

[13] P.Attard. Asymptotic analysis of primitive model electrolytes and the electrical double layer. Phys. Rev. E. 48:3604. 1993.

613 Page 7 of 8 [14] Z.Tang, L.E. Scriven, and H.T. Davis. A three component model of the electrical double layer. J. Chem. Phys., 97:494, 1992.

[15] D.Boda. C.K.wong-Yu, and D.Henderson. Monte carlo simulation of an ion-dipole mixture as a model os an electrical double layer. J. Chem. Phys., 109:7362, 1998.

[16] C.N. Patra and S.K.. Ghosh. Electric double layer at a metal/electrolyte interface: a density functional approach. J. Chem. Phys., 102:2556, 1995.

[ 17 ] M.Plischke and D.Henderson. The primitive model of the electric double layer: nonsymmetric electrolytes. J. Chem. Phys., 90:5738, 1989.

[18] B.Svenson, B.Jonsson, and C.ER. Woodward. Monte carlo simulation of an electric double layer. J. Phys. Chem., 94:2105, 1990.

[19] R.Aogaki, K.Kitazawa, Y.Kose, and K.Fueki. Theory of powdered crystal formation in electrocrystallization - occurence of morphological instability at the electrode interface. Electroch. Acta, 25:965, 1980.

[20] J.-N. Chazalvtel. Electrochemical aspects of the generation of ramified metallic electrodeposits. J. Phys. A, 42:7355, 1990.

[21] G.Marshall and P.Mocskos. Growth model for ramified electrochemical deposition in the presence of diffusion, migration, and electrocenvection. Phys. rev. E, 55:549, 1997.

[22] A. Regner. Technickd elektrochemie I. Academia, Praha 1967

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