



Molten salt reactors (MSRs) offer a promising alternative for sustainable nuclear energy production, thanks to their intrinsic safety and their ability to close the nuclear fuel cycle, notably through the use of a fast neutron spectrum. This type of reactor can use liquid chloride salts containing plutonium and other actinides as fuel. As part of the development of this nuclear pathway, the CEA supports the development of a PuCl3 production process. The synthesis of this chloride has already been carried out at small scale at the CEA and elsewhere in the world. Several starting materials can be used for the synthesis of the trichloride, notably plutonium metal, plutonium oxide and plutonium oxalate. The most industrially promising synthesis route is the oxalate route, because it can be transferred to the equipment already present at the La Hague site. This process consists of converting the oxalate into plutonium chloride via a gas–solid reaction with a chlorinating agent, such as HCl for example. However, the reaction mechanism and the decomposition of the oxalate in a chlorinated environment are still poorly understood. A detailed understanding of this transformation would make it possible to optimize operating conditions and facilitate the scale-up of this synthesis. The topic will initially focus on determining the reaction mechanism of Ce oxalate (a surrogate for Pu) to the chloride. Small-scale studies will be performed to identify the various reaction intermediates using analytical techniques such as X-ray diffraction (XRD), thermogravimetric analysis / differential thermal analysis (TGA/DTA) and analysis of the gases produced during the reaction. The kinetics as well as the enthalpy changes will also be studied in order to obtain key data for modelling a large-scale process. Subsequently, an optimization of the PuCl3 synthesis at the scale of a few tens of grams will be carried out. These studies will first be conducted under non-radioactive conditions on a surrogate to validate the experimental approach, before being transposed to radioactive conditions.

