Engineering topics

Pickenheim, B

Publications and source records attributed to Pickenheim, B.

5 records

DOE OSTI2011

ELAWD GROUT HOPPER MOCK-UP TESTING

A 10-inch READCO mixer is used for mixing the premix (45 (wt%) fly ash, 45 wt% slag, and 10 wt% portland cement) with salt solution in the Saltstone Production Facility (SPF). The Saltstone grout free falls into the grout hopper which feeds the suction line leading to the Watson SPX 100 duplex hose pump. The Watson SPX 100 pumps the grout through approximately 1500 feet of piping prior to being discharged into the Saltstone Disposal Facility (SDF) vaults. The existing grout hopper has been identified by the Saltstone Enhanced Low Activity Waste Disposal (ELAWD) project for re-design. The current nominal working volume of this hopper is 12 gallons and does not permit handling an inadvertent addition of excess dry feeds. Saltstone Engineering has proposed a new hopper tank that will have a nominal working volume of 300 gallons and is agitated with a mechanical agitator. The larger volume hopper is designed to handle variability in the output of the READCO mixer and process upsets without entering set back during processing. The objectives of this task involve scaling the proposed hopper design and testing the scaled hopper for the following processing issues: (1) The effect of agitation on radar measurement. Formation of a vortex may affect the ability to accurately measure the tank level. The agitator was run at varying speeds and with varying grout viscosities to determine what parameters cause vortex formation and whether measurement accuracy is affected. (2) A dry feeds over addition. Engineering Calculating X-ESR-Z-00017 1 showed that an additional 300 pounds of dry premix added to a 300 gallon working volume would lower the water to premix ratio (W/P) from the nominal 0.60 to 0.53 based on a Salt Waste Processing Facility (SWPF) salt simulant. A grout with a W/P of 0.53 represents the upper bound of grout rheology that could be processed at the facility. A scaled amount of dry feeds will be added into the hopper to verify that this is a recoverable situation. (3) The necessity of baffles in the hopper. The preference of the facility is not to have baffles in the hopper; however, if the initial testing indicates inadequate agitation or difficulties with the radar measurement, baffles will be tested.

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DOE OSTI2011

GLYCOLIC ACID PHYSICAL PROPERTIES, IMPURITIES, AND RADIATION EFFECTS ASSESSMENT

The Defense Waste Processing Facility (DWPF) is pursuing alternative reductants/flowsheets to increase attainment to meet closure commitment dates. In fiscal year 2009, SRNL evaluated several options and recommended the further assessment of the nitric/formic/glycolic acid flowsheet. SRNL is currently performing testing with this flowsheet to support the DWPF down-select of alternate reductants. As part of the evaluation, SRNL was requested to determine the physical properties of formic and glycolic acid blends. Blends of formic acid in glycolic acid were prepared and their physical properties tested. Increasing amounts of glycolic acid led to increases in blend density, viscosity and surface tension as compared to the 90 wt% formic acid that is currently used at DWPF. These increases are small, however, and are not expected to present any difficulties in terms of processing. The effect of sulfur impurities in technical grade glycolic acid was studied for its impact on DWPF glass quality. While the glycolic acid specification allows for more sulfate than the current formic acid specification, the ultimate impact is expected to be on the order of 0.03 wt% sulfur in glass. Note that lower sulfur content glycolic acid could likely be procured at some increased cost if deemed necessary. A paper study on the effects of radiation on glycolic acid was performed. The analysis indicates that substitution of glycolic acid for formic acid would not increase the radiolytic production rate of H{sub 2} and cause an adverse effect in the SRAT or SME process. It has been cited that glycolic acid solutions that are depleted of O{sub 2} when subjected to large radiation doses produced considerable quantities of a non-diffusive polymeric material. Considering a constant air purge is maintained in the SRAT and the solution is continuously mixed, oxygen depletion seems unlikely, however, if this polymer is formed in the SRAT solution, the rheology of the solution may be affected and pumping of the solution may be hindered. However, an irradiation test with a simulated SRAT product supernate containing glycolic acid in an oxygen depleted atmosphere found no evidence of polymerization.

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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.

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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.

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DOE OSTI2010

SLUDGE WASHING AND DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS FOR SLUDGE BATCH 6 QUALIFICATION

Prior to initiating a new sludge batch in the Defense Waste Processing Facility (DWPF), Savannah River National Laboratory (SRNL) is required to simulate this processing, including Chemical Process Cell (CPC) simulation, waste glass fabrication, and chemical durability testing. This report documents this simulation for the next sludge batch, Sludge Batch 6 (SB6). SB6 consists of Tank 12 material that has been transferred to Tank 51 and subjected to Low Temperature Aluminum Dissolution (LTAD), Tank 4 sludge, and H-Canyon Pu solutions. Following LTAD and the Tank 4 addition, Liquid Waste Operations (LWO) provided SRNL a 3 L sample of Tank 51 sludge for SB6 qualification. Pu solution from H Canyon was also received. SB6 qualification included washing the sample per LWO plans/projections (including the addition of Pu from H Canyon), DWPF CPC simulations, waste glass fabrication (vitrification), and waste glass characterization and chemical durability evaluation. The following are significant observations from this demonstration. Sludge settling improved slightly as the sludge was washed. SRNL recommended (and the Tank Farm implemented) one less wash based on evaluations of Tank 40 heel projections and projections of the glass composition following transfer of Tank 51 to Tank 40. Thorium was detected in significant quantities (>0.1 wt % of total solids) in the sludge. In past sludge batches, thorium has been determined by Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS), seen in small quantities, and reported with the radionuclides. As a result of the high thorium, SRNL-AD has added thorium to their suite of Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) elements. The acid stoichiometry for the DWPF Sludge Receipt and Adjustment Tank (SRAT) processing of 115%, or 1.3 mol acid per liter of SRAT receipt slurry, was adequate to accomplish some of the goals of SRAT processing: nitrite was destroyed to below 1,000 mg/kg and mercury was removed to below the DWPF target with 750 g of steam per g of mercury. However, rheological properties did not improve and were above the design basis. Hydrogen generation rates did not exceed DWPF limits during the SRAT and Slurry Mix Evaporator (SME) cycles. However, hydrogen generation during the SRAT cycle approached the DWPF limit. The glass fabricated with the Tank 51 SB6 SME product and Frit 418 was acceptable with respect to chemical durability as measured by the Product Consistency Test (PCT). The PCT response was also predictable by the current durability models of the DWPF Product Composition Control System (PCCS). It should be noted, however, that in the first attempt to make glass from the SME product, the contents of the fabrication crucible foamed over. This may be a result of the SME product's REDOX (Reduction/Oxidation - Fe{sup 2+}/{Sigma}Fe) of 0.08 (calculated from SME product analytical results). The following are recommendations drawn from this demonstration. In this demonstration, at the request of DWPF, SRNL caustic boiled the SRAT contents prior to acid addition to remove water (to increase solids concentration). During the nearly five hours of caustic boiling, 700 ppm of antifoam was required to control foaming. SRNL recommends that DWPF not caustic boil/concentrate SRAT receipt prior to acid addition until further studies can be performed to provide a better foaming control strategy or a new antifoam is developed for caustic boiling. Based on this set of runs and a recently completed demonstration with the SB6 Waste Acceptance Product Specifications (WAPS) sample, it is recommended that DWPF not add formic acid at the design addition rate of two gallons per minute for this sludge batch. A longer acid addition time appears to be helpful in allowing slower reaction of formic acid with the sludge and possibly decreases the chance of a foam over during acid addition.

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