skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF)

Abstract

Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe +2/ΣFe ratios of between 0.09 and 0.33, retains radionuclides in the melt and thus the final glass. Specifically, long-lived radioactive 99Tc species are less volatile in the reduced Tc 4+ state as TcO 2 than as NaTcO 4 or Tc 2O 7, and ruthenium radionuclides in the reduced Ru 4+ state are insoluble RuO 2 in the melt which are not as volatile as NaRuO 4 where the Ru is in the +7 oxidation state. Similarly, hazardous volatile Cr 6+ occurs in oxidized melt pools as Na 2CrO 4 or Na 2Cr 2O 7, while the Cr +3 state is less volatile and remains in the melt as NaCrO 2 or precipitates as chrome rich spinels. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1373537
Report Number(s):
SRNL-STI-2017-00005
TRN: US1800532
DOE Contract Number:
AC09-08SR22470; AC09-76SR00001; AC09-96SR18500
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; HIGH-LEVEL RADIOACTIVE WASTES; WASTE PROCESSING; OXIDATION; REDUCTION

Citation Formats

Jantzen, C. M., Williams, M. S., Edwards, T. B., Trivelpiece, C. L., and Ramsey, W. G. Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF). United States: N. p., 2017. Web. doi:10.2172/1373537.
Jantzen, C. M., Williams, M. S., Edwards, T. B., Trivelpiece, C. L., & Ramsey, W. G. Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF). United States. doi:10.2172/1373537.
Jantzen, C. M., Williams, M. S., Edwards, T. B., Trivelpiece, C. L., and Ramsey, W. G. Wed . "Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF)". United States. doi:10.2172/1373537. https://www.osti.gov/servlets/purl/1373537.
@article{osti_1373537,
title = {Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF)},
author = {Jantzen, C. M. and Williams, M. S. and Edwards, T. B. and Trivelpiece, C. L. and Ramsey, W. G.},
abstractNote = {Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe+2/ΣFe ratios of between 0.09 and 0.33, retains radionuclides in the melt and thus the final glass. Specifically, long-lived radioactive 99Tc species are less volatile in the reduced Tc4+ state as TcO2 than as NaTcO4 or Tc2O7, and ruthenium radionuclides in the reduced Ru4+ state are insoluble RuO2 in the melt which are not as volatile as NaRuO4 where the Ru is in the +7 oxidation state. Similarly, hazardous volatile Cr6+ occurs in oxidized melt pools as Na2CrO4 or Na2Cr2O7, while the Cr+3 state is less volatile and remains in the melt as NaCrO2 or precipitates as chrome rich spinels. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam.},
doi = {10.2172/1373537},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Jun 14 00:00:00 EDT 2017},
month = {Wed Jun 14 00:00:00 EDT 2017}
}

Technical Report:

Save / Share:
  • Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe +2/ΣFe ratios of between 0.09 and 0.33, a range which is not overly oxidizing or overly reducing, helps retain radionuclides in the melt, i.e. long-lived radioactive 99Tc species in the less volatile reduced Tc 4+ state, 104Ru in the melt as reduced Ru +4 state as insoluble RuO 2, and hazardous volatile Cr 6+ in themore » less soluble and less volatile Cr +3 state in the glass. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam. Currently, the Defense Waste Processing Facility (DWPF) is running a formic acid-nitric acid (FN) flowsheet where formic acid is the main reductant and nitric acid is the main oxidant. During decomposition formate and formic acid releases H 2 gas which requires close control of the melter vapor space flammability. A switch to a nitric acid-glycolic acid (GN) flowsheet is desired as the glycolic acid flowsheet releases considerably less H 2 gas upon decomposition. This would greatly simplify DWPF processing. Development of an EE term for glycolic acid in the GN flowsheet is documented in this study.« less
  • The conversions of nitrite to nitrate, the destruction of glycolate, and the conversion of glycolate to formate and oxalate were modeled for the Nitric-Glycolic flowsheet using data from Chemical Process Cell (CPC) simulant runs conducted by Savannah River National Laboratory (SRNL) from 2011 to 2016. The goal of this work was to develop empirical correlation models to predict these values from measureable variables from the chemical process so that these quantities could be predicted a-priori from the sludge or simulant composition and measurable processing variables. The need for these predictions arises from the need to predict the REDuction/OXidation (REDOX) statemore » of the glass from the Defense Waste Processing Facility (DWPF) melter. This report summarizes the work on these correlations based on the aforementioned data. Previous work on these correlations was documented in a technical report covering data from 2011-2015. This current report supersedes this previous report. Further refinement of the models as additional data are collected is recommended.« less
  • An evaluation of the previous Chemical Processing Cell (CPC) testing was performed to determine whether the planned concurrent operation, or “coupled” operations, of the Defense Waste Processing Facility (DWPF) with the Salt Waste Processing Facility (SWPF) has been adequately covered. Tests with the nitricglycolic acid flowsheet, which were both coupled and uncoupled with salt waste streams, included several tests that required extended boiling times. This report provides the evaluation of previous testing and the testing recommendation requested by Savannah River Remediation. The focus of the evaluation was impact on flammability in CPC vessels (i.e., hydrogen generation rate, SWPF solvent components,more » antifoam degradation products) and processing impacts (i.e., acid window, melter feed target, rheological properties, antifoam requirements, and chemical composition).« less
  • Ion Chromatography (IC) is the principal analytical method used to support studies of Sludge Reciept and Adjustment Tank (SRAT) chemistry at DWPF. A series of prior analytical ''Round Robin'' (RR) studies included both supernate and sludge samples from SRAT simulant, previously reported as memos, are tabulated in this report.2,3 From these studies it was determined to standardize IC column size to 4 mm diameter, eliminating the capillary column from use. As a follow on test, the DWPF laboratory, the PSAL laboratory, and the AD laboratory participated in the current analytical RR to determine a suite of anions in SRAT simulantmore » by IC, results also are tabulated in this report. The particular goal was to confirm the laboratories ability to measure and quantitate glycolate ion. The target was + or - 20% inter-lab agreement of the analyte averages for the RR. Each of the three laboratories analyzed a batch of 12 samples. For each laboratory, the percent relative standard deviation (%RSD) of the averages on nitrate, glycolate, and oxalate, was 10% or less. The three laboratories all met the goal of 20% relative agreement for nitrate and glycolate. For oxalate, the PSAL laboratory reported an average value that was 20% higher than the average values reported by the DWPF laboratory and the AD laboratory. Because of this wider window of agreement, it was concluded to continue the practice of an additional acid digestion for total oxalate measurement. It should also be noted that large amounts of glycolate in the SRAT samples will have an impact on detection limits of near eluting peaks, namely Fluoride and Formate. A suite of scoping experiments are presented in the report to identify and isolate other potential interlaboratory disceprancies. Specific ion chromatography inter-laboratory method conditions and differences are tabulated. Most differences were minor but there are some temperature control equipment differences that are significant leading to a recommendation of a heated jacket for analytical columns that are remoted for use in radiohoods. A suggested method improvement would be to implement column temperture control at a temperature slightly above ambient to avoid peak shifting due to temperature fluctuations. Temperature control in this manner would improve short and longer term peak retention time stability. An unknown peak was observed during the analysis of glycolic acid and SRAT simulant. The unknown peak was determined to best match diglycolic acid. The development of a method for acetate is summaraized, and no significant amount of acetate was observed in the SRAT products tested. In addition, an alternative Gas Chromatograph (GC) method for glycolate is summarized.« less
  • Savannah River Remediation (SRR) is evaluating changes to its current DWPF flowsheet to improve processing cycle times. This will enable the facility to support higher canister production while maximizing waste loading. Higher throughput is needed in the CPC since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the DWPF gas chromatographs (GC) and the potential for production of flammable quantities of hydrogen, reducing or eliminating the amount of formic acid used in the CPC is being developed. Earlier work at Savannah River National Laboratory has shown that replacing formicmore » acid with an 80:20 molar blend of glycolic and formic acids has the potential to remove mercury in the SRAT without any significant catalytic hydrogen generation. This report summarizes the research completed to determine the feasibility of processing without formic acid. In earlier development of the glycolic-formic acid flowsheet, one run (GF8) was completed without formic acid. It is of particular interest that mercury was successfully removed in GF8, no formic acid at 125% stoichiometry. Glycolic acid did not show the ability to reduce mercury to elemental mercury in initial screening studies, which is why previous testing focused on using the formic/glycolic blend. The objective of the testing detailed in this document is to determine the viability of the nitric-glycolic acid flowsheet in processing sludge over a wide compositional range as requested by DWPF. This work was performed under the guidance of Task Technical and Quality Assurance Plan (TT and QAP). The details regarding the simulant preparation and analysis have been documented previously.« less