Dehalogenation reactions between halide salts and phosphate compounds
Reactions between phosphoric acid [H 3 PO 4 ] or ammonium hydrogen phosphates [i.e., NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 ] and halide salts can be used to dehalogenate (remove halides from) salt-based waste streams, where the process of removing halides yields products that have more efficient disposal pathways for repository storage. In this context, the term efficiency is defined as higher waste loadings and simplified immobilization processes with potential for recycle of certain salt components (e.g., 37 Cl as H 37 Cl or NH 4 37 Cl). The main streams identified for these processes are nuclear wastes generated during electrochemical reprocessing of used nuclear fuel as well as used halide salts from molten salt reactor operation. The potential byproducts of these reactions are fairly consistent across the range of halide species (i.e., F, Cl, Br, I) where the most common are hydrogen halides [e.g., HCl (g) ] or ammonium halides (e.g., NH 4 Cl). However, trihalide compounds (e.g., NCl 3 ), nitrogen triiodide ammine adducts [NI 3 ·(NH 3 ) x ], and ammonium triiodide (NH 4 I 3 ) are also possible. Several of these byproducts (i.e., NCl 3 , NBr 3 , NI 3 , and NH 4 I 3 ) are shock-sensitive contact explosives so their production in these processes must be tracked and carefully controlled, which includes methods of immediate neutralization upon production such as direct transport to a caustic scrubber for dissolution. Several benefits arise from utilizing H 3 PO 4 as the phosphate additive during dehalogenation reactions for making iron phosphate waste forms including more oxidized iron (higher Fe 3+ :Fe 2+ ratios), higher chemical durabilities, and the avoidance of trihalides, but the byproducts are hydrogen halides, which are corrosive and require special handling.