Engineering topics

Newell, J

Publications and source records attributed to Newell, J.

4 records

DOE OSTI2011

CHARACTERIZATION OF DWPF MELTER OFF-GAS QUENCHER SAMPLE

The Savannah River National Laboratory (SRNL) recently received a deposit sample from the Melter Primary Off Gas System (POG) of the Defense Waste Processing Facility (DWPF). This sample was composed of material that had been collected while the quencher was in operation January 27, 2011 through March 31, 2011. DWPF requested, through a technical assistance request, characterization of the melter off-gas deposits by x-ray diffraction (XRD), scanning electron microscopy (SEM), and chemical analysis. The purpose of the Melter Off-Gas System is to reduce the amount of radioactive particles and mercury in the gases vented to the atmosphere. Gases emitted from the melter pass through the primary film cooler, quencher, Off-Gas Condensate Tank (OGCT), Steam Atomized Scrubbers (SAS), a condenser, a high efficiency mist eliminator, and a high efficiency particulate air filter, before being vented to the Process Vessel Vent System. The film coolers cool the gases leaving the melter vapor space from {approx}750 C to {approx}375 C, by introducing air and steam to the flow. In the next step, the quencher cools the gas to about 60 C by bringing the condensate from the OGCT in contact with the effluent (Figure 1). Most of the steam in the effluent is then condensed and the melter vapor space pressure is reduced. The purpose of the OGCT is to collect and store the condensate formed during the melter operation. Condensate from the OGCT is circulated to the SAS and atomized with steam. This atomized condensate is mixed with the off-gas to wet and join the particulate which is then removed in the cyclone. The next stage incorporates a chilled water condenser which separates the vapors and elemental mercury from the off-gas steam. Primary off-gas deposit samples from the DWPF melter have previously been analyzed. In 2003, samples from just past the film cooler, from the inlet of the quencher and inside the quencher were analyzed at SRNL. It was determined that the samples were a mixture of sludge and glass frit. The major component was Si along with Fe, Al, and other elements in the radioactive waste being processed. The deposits analyzed also contained U-235 fission products and actinide elements. Prior to that, deposits in the off-gas system in the DWPF nonradioactive half scale melter and the one-tenth scale integrated DWPF melter system were analyzed and determined to be mixtures of alkali rich chlorides, sulfates, borates, and fluorides entrained with iron oxides, spinels and frit particles formed by vapor-phase transport and condensation. Additional work was performed in 2007 in which researchers similarly found the deposits to be a combination of sludge and frit particles.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2011

DWPF FLOWSHEET STUDIES WITH SIMULANT TO DETERMINE THE IMPACT OF NEXT GENERATION SOLVENT ON THE CPC PROCESS AND GLASS FORMULATION

As a part of the Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) Life Extension Project, a next generation solvent (NGS), a new strip acid, and modified monosodium titanate (mMST) will be deployed. The NGS is comprised of four components: 0.050 M MaxCalix (extractant), 0.50 M Cs-7SB (modifier), 0.003 M guanidine-LIX-79, with the balance ({approx}74 wt%) being Isopar{reg_sign} L. The strip acid will be changed from dilute nitric acid to dilute boric acid (0.01 M). Because of these changes, experimental testing with the next generation solvent and mMST was required to determine the impact of these changes in 512-S and Defense Waste Processing Facility (DWPF) operations, as well as Chemical Process Cell (CPC), glass formulation activities, and melter operations. Because of these changes, experimental testing with the next generation solvent and mMST is required to determine the impact of these changes. A Technical Task Request (TTR) was issued to support the assessments of the impact of the next generation solvent and mMST on the downstream DWPF flowsheet unit. The TTR identified five tasks to be investigated: (1) CPC Flowsheet Demonstration for NGS; (2) Solvent Stability for DWPF CPC Conditions; (3) Glass Formulation Studies; (4) Boron Volatility and Melt Rate; and (5) CPC Flowsheet Demonstration for mMST.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2011

GLYCOLIC-FORMIC ACID FLOWSHEET FINAL REPORT FOR DOWNSELECTION DECISION

Flowsheet testing was performed to develop the nitric-glycolic-formic acid flowsheet (referred to as the glycolic-formic flowsheet throughout the rest of the report) as an alternative to the nitric/formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be removed in the Sludge Receipt and Adjustment Tank (SRAT) with minimal hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Forty-six runs were performed in total, including the baseline run and the melter feed preparation runs. Significant results are summarized. The baseline nitric/formic flowsheet run, using the SB6 simulant produced by Harrell was extremely difficult to process successfully under existing DWPF acceptance criteria with this simulant at the HM levels of noble metals. While nitrite was destroyed and mercury was removed to near the DWPF limit, the rheology of the SRAT and SME products were well above design basis and hydrogen generation far exceeded the DWPF SRAT limit. In addition, mixing during the SME cycle was very poor. In this sense, the nitric/glycolic/formic acid flowsheet represents a significant upgrade over the current flowsheet. Mercury was successfully removed with almost no hydrogen generation and the SRAT and SME products yield stresses were within process limits or previously processed ranges. The glycolic-formic flowsheet has a very wide processing window. Testing was completed from 100% to 200% of acid stoichiometry and using a glycolic-formic mixture from 40% to 100% glycolic acid. The testing met all processing requirements throughout these processing windows. This should allow processing at an acid stoichiometry of 100% and a glycolic-formic mixture of 80% glycolic acid with minimal hydrogen generation. It should also allow processing endpoints in the SRAT and SME at significantly higher total solids content and may be effective at acid stoichiometries below 100%, although no testing was performed below 100% acid stoichiometry. There are several issues related to the development of the glycolic-formic flowsheet. First, the measurement of anions using the new glycolate anion procedure likely needs to be optimized to improve the accuracy of the anions important to DWPF processing and REDOX prediction. Second, the existing REDOX equation with an added term for glycolate did not accurately predict the glass REDOX for the glycolic-formic flowsheet. Improvement of the anion measurement or modification of the REDOX methodology or equation may be necessary to improve the REDOX prediction. Last, the glycolic-formic flowsheet dissolves a number of metals, including iron. This leads to a thinner slurries but also dissolves up a portion of the iron, which is currently used for criticality control. It is recommended that DWPF continue to support development of the glycolic-formic flowsheet. This flowsheet meets or outperforms the baseline flowsheet in off-gas generation, mercury removal, product rheology and general ease of processing. Additional testing is in progress to demonstrate the effectiveness of the nitric-glycolic-formic flowsheet in processing a wide sludge processing window using the matrix sludge simulants.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2010

GLYCOLIC - FORMIC ACID FLOWSHEET DEVELOPMENT

Flowsheet testing was performed to further develop the nitric/glycolic/formic acid flowsheet as an alternative to the nitric/formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be removed in the Sludge Receipt and Adjustment Tank (SRAT) with minimal hydrogen generation. All other processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Eight runs were performed in total, including the baseline run. The baseline nitric/formic flowsheet run was extremely difficult to process under existing DWPF acceptance criteria with this simulant at the HM levels of noble metals. While nitrite was destroyed and mercury was removed to near the DWPF limit, the rheology of the SRAT and SME products were well above design basis and hydrogen generation far exceeded the DWPF limit. In addition, mixing during the SME cycle was very poor. In this sense, the nitric/glycolic/formic acid flowsheet represents a significant upgrade over the current flowsheet. In the nitric/glycolic/formic flowsheet runs, mercury was successfully removed with almost no hydrogen generation and the SRAT and SME products yield stresses were within process limits or previously processed ranges. It is recommended that DWPF continue to support development of the nitric/glycolic/formic flowsheet. Although experience is limited at this time, this flowsheet meets or outperforms the current flowsheet in many regards, including off-gas generation, mercury removal, product rheology and general ease of processing. Additional flowsheet testing will allow for a more thorough understanding of the chemistry and effectiveness of the flowsheet over a range of sludge compositions and formic/glycolic ratios. This testing will also show whether the REDOX and metal solubility concerns with this change in the flowsheet can be addressed by just adjusting the volumes of glycolic acid added. The outstanding issues regarding the glycolic/formic flowsheet include increasing understanding of the impact on glass REDOX control and increased metal solubility, particularly iron, during processing. Additionally, evaluations of the utility of the flowsheet over varying sludge compositions should be completed to ensure flowsheet robustness. Work has already been initiated to further understand the REDOX and iron solubility areas.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗