Hanford Waste Vitrification Plant hydrogen generation study: Formation of ammonia from nitrate and nitrate in hydrogen generating systems

The Hanford Waste Vitrification Plant (HWVP) is being designed for the Departrnent of Energy (DOE) to immobilize pretreated highly radioactive wastes in glass for permanent disposal in the HWVP, formic acid is added to the waste before vitrification to adjust glass redox and melter feed rheology. The operation of the glass melter and durability of the glass are affected by the glass oxidation state. Formation of a conductive metallic sludge in an over-reduced melt can result in a shortened melter lifetime. An over-oxidized melt may lead to foaming and loss of ruthenium as volatile RuO{sub 4}. Historically, foaming in the joule heated ceramic melter has been attributed to gas generation in the melt which is controlled by instruction of a reductant such as formic acid into the melter feed. Formic acid is also found to decrease the melter feed viscosity thereby facilitating pumping. This technical report discusses the noble metal catalyzed formic acid reduction of nitrite and/or nitrate to ammonia, a problem of considerable concern because of the generation of a potential ammonium nitrate explosion hazard in the plant ventilation system