Permanganate Oxidation of Defense Waste Processing Facility (DWPF) Recycle Collection Tank (RCT) Simulants – Protocol Runs for Nominal and Chemical Process Cell (CPC) Foamover Conditions

Savannah River National Laboratory (SRNL) has completed a work scope in support of the Savannah River Remediation (SRR) Nitric-Glycolic flowsheet. Glycolic acid will replace formic acid as a reducing agent in the pre-processing of High-Level Waste sludge performed at the Defense Waste Processing Facility (DWPF). Glycolic acid will perform the same function as formic acid, namely reduction of mercury and adjustment of feed rheology and melter oxidation/reduction potential, while significantly reducing the potential for hydrogen generation in DWPF processing. Development testing has demonstrated glycolic acid virtually eliminates hydrogen production in the pre-processing steps. The Nitric-Glycolic flowsheet significantly improves DWPF's ability to address one of the Savannah River Site's key challenges - the incorporation of effluent received from the Salt Waste Processing Facility (SWPF). SWPF will deliver significant effluent volume to DWPF, resulting in a concurrent increase in DWPF effluent returned to the Concentration, Storage and Transfer Facilities (CSTF). This work scope demonstrates that glycolate can be destroyed under the Nitric-Glycolic flowsheet prior to returning the DWPF recycle stream to CSTF. To avoid potential flammability issues due to thermolysis of glycolate in CSTF, SRR tasked SRNL to quantify and mitigate glycolate returns via DWPF's recycle stream. The development of a strategy for glycolic mitigation was initiated with a system's engineering workshop. Various chemical and/or physical solutions for how and where to destroy glycolate were considered – consistent with DWPF's operational capabilities and process requirements. The workshop identified chemical oxidation of glycolate within the DWPF Recycle Collection Tank (RCT) as the most promising option. (The RCT collects offgas condensate from pre-processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF.) A series of down-select experimental tests were performed that showed sodium permanganate was the most effective oxidant. This work was performed to identify an appropriate operational protocol for DWPF implementation. Building upon the downselect experiments, the work targeted an improved description of suitable RCT conditions prior to the strike (pH, etc.), permanganate addition rate, and destruction reaction kinetics. Data collected were also used to determine the best expression of reaction stoichiometry and the effective minimum permanganate addition required.