Radioactive Waste Processing at the Savannah River Site Bill Holtzscheiter April 2014

Outline Background A look at the facilities and materials Overview of the radioactive waste process A look at the facilities and materials Highly Radioactive Sludge Highly Radioactive Glass Key Chemistry Neutralization Reactions Oxidation-Reduction Reactions Combustion Reactions Processing Objectives Maximize Waste Loading into the Glass Increase Waste Throughput Summary

SRS High Level Waste System

Vitrification Process Diagram Nitric Acid, Formic Glycolic Acid, and Antifoam Additions Antifoam Additions, Decon Frit Water Additions, and Frit Additions – Eliminate 1.5 wt.% formic acid in frit addition Actinides-U, Np, Pu PRFT 221-S Pump Tank Used for Transfer Sludge Receipt Tank Glass Mix Tank Melter Feed Tank Melter SAMPLE ANALYSIS HOLD POINT-GLASS ACCEPTABLE? Waste Acceptance Items/Activities SRAT Sample Analyses WASTE FORM COMPLIANCE PLAN (WCP) AND WASTE FORM QUALIFICATION REPORTS (WQR) Tank 40 Radioactive Waste Aqueous Cs-137 stream Cesium Tank Actnide Tank Glass Sample Denotes Changes

Defense Waste Processing Facility

Sludge Processing Steps - Two to three transfers from Tank 40 (7200 to 8500 gallons) - Caustic Boiling to concentrate contents - Addition of U, Pu-238, Np Cool Down and Sample Analysis Determine the amount of acid and the blend of formic and nitric - Concentration/Reflux (Hg Removal) to 6000 gallons Add the mildly acidic Cs stream) Sample to confirm composition Transfer ~4500 gallons to SME for further processing Transfer Pump Mercury Sump Diameter 12’ Height 18’ Volume 11,000 Gal. Prime Water Line Salt Stream 90 % Formic Acid Air Purge Antifoam Agent 50 WT% Nitric Acid Sludge (from LPPP) Sample Pump Agitator Three Foil Blade 4 Paddle Flat Blade Heating Coils Cooling Coils

Glass Mixing Steps Steps Add glass former frit Concentrate mixture (as necessary) Concentrate mixture Cool down SME Sample SME product Run final Product Confirmation Calculations (PCCS Model) for quality control, and MOG calculations Transfer ~4500 gallons to MFT for feeding of the melter Diameter 12’ Height 18’ Volume 11,000 Gal. Prime Water Line Transfer Pump to MFT Mercury Sump Formic Acid for Redox Canister Decon Frit Antifoam Agent Process Frit Sample Pump Agitator Three Foil Blades 4 Paddle Flat Blades Heating Coils Cooling Coils Slurry from SRAT Air Purge

Melter Feed Tank Steps Typically no adjustments are made to the Melter Feed Tank qualified feed. 4-5 cans poured per batch processed Diameter 12’ Height 18’ Volume 11,000 Gal. Prime Water Line Transfer Pump to Melter Mercury Sump Formic/Nitric Acid Canister Decon Frit Sample Pump Agitator Three Foil Blades 4 Paddle Flat Blades Heating Coils Cooling Coils Slurry from SME Air Purge

Melter -Joule heated melter. Pours by vacuum -Receives Feed from the Melter Feed Tank at ~1.2 gpm -Glass Pool Temperature ranges 1120°C – 1145 ° C -Equipped with 4 bubblers each capable of bubbling Argon at rate of 1.5 scfm -Have recently achieved 225 – 230 lbs/hr. -Nameplate 228 lbs/hr. -Each canister holds ~ 4000 lbs of glass

Picture of Melter Top

Actual Radioactive Glass-Crucible

Radioactive Glass Canisters Waste Form-Borosilicate Glass

Waste Description The radioactive waste contains most of the Periodic Table in one form or another. Major components include Fe(OH)3, Al (OH)3, Na(NO3), other metals such as Mg, Mn, Ca, Cs, in various forms. Carbonates, nitrogen oxides, sulfur oxides, and Hg. There is a sludge component and a salt/supernate component The sludge is fed to the process at a pH~ 12 At about 18 weight percent solids (fairly dilute)

Simulated Radioactive Waste

Same Waste-High Viscosity

Measured Radionuclides

Process Chemistry Nitric acid is added to the sludge to neutralize the hydroxide and lower the pH to about 6. Formic acid (HCOOH) is added to reduce Hg from either the oxide or nitrate states to metallic Hg Once in the metallic state, the vessel is boiled and the Hg is removed by a process called steam stripping. The steam literally carries the Hg to another vessel where it is removed from the process.

Selected Reactions Neutralization Reactions M= Mg, Fe, Ca, Al, Mn M++ (OH)2 + HNO3  M++O + NOx + H2O M++CO3 + HNO3  M++(NO3)2 + CO2 + H2O Nitrite Destruction Reactions Reductions Reactions Reductions Reactions

Problematic Chemistry Formic acid also produces hydrogen in the presence of Rh, Pt, and Ru HCOOH  H2 + CO2 2H2 + O2  2H2O What kind of reaction is the above reaction? Why would it be an issue? Why is hydrogen thought to be important to future green energy in the US? Hindenberg

BMW 7 Series Hydrogen Car

Small Scale Process Development

Balance Performed for Each Batch of Feed Processed through DWPF Maintain H2 generation below safety limits for SRAT/SME cycles while trying to minimize CO2 and N2O production Hg reduction and stripping Adjustment of rheological properties that allow a maximum wt.% solids target (viscosity) REDOX Balancing (prevent foaming or metal deposition in the melter) Balancing carbon and nitrogen sources to ensure Melter Off Gas Flammability is met Ensuring waste and glass former blending is correct Ensuring waste loading commitment is met (have to allow 3-4 WL points based on equipment and analytical uncertainty) Ensuring mass per unit volume moved through the facility meets canister production goals

Summary Waste process and how it is different from a manufacturing process A very important combustion reaction Resulted in the explosion for the Hindenberg Provides the basis for the hydrogen economy Has to be carefully managed when it appears in any chemical process. Reviewed terms that you have had in your chemistry course Combustion reactions Viscosity Radioactivity, curies, types of radiation You have had a glimpse of a complex chemical process that helps clean up the highly radioactive waste generated during the production of nuclear weapons materials

Where are the Curies?