The evaluation of the pyrochemistry for the treatment of Gen IV nuclear fuels - Inert matrix chlorination studies in the gas phase or molten chloride salts

The structure of the fuels for the future Gen IV nuclear reactors will be totally different from those of PWR, especially for the GFR concept including a closed cycle. In these reactors, fissile materials (carbides or nitrides of actinides) should be surrounded by an inert matrix. In order to build a reprocessing process scheme, the behavior of the potential inert matrices (silicon carbide, titanium nitride, and zirconium carbide and nitride) was studied by hydro- and pyrometallurgy. This paper deals with the chlorination results at high temperature by pyrometallurgy. For the first time, the reactivity of the matrix towards chlorine gas was assessed in the gas phase. TiN, ZrN and ZrC are very reactive from 400 °C whereas it is necessary to be over 900 °C for SiC to be as fast. In molten chloride melts, the bubbling of chlorine gas is less efficient than in gas phase but it is possible to attack the matrices. Electrochemical methods were also used to dissolve the refractory materials, leading to promising results with TiN, ZrN and ZrC. The massive SiC samples used were not conductive enough to be studied and in this case specific SiC-coated carbon electrodes were used. The key point of these studies was to find a method to separate the matrix compounds from the fissile material in order to link the head to the core of the process (electrochemical separation or liquid-liquid reductive extraction in the case of a pyrochemical reprocessing).