DESIGN AND PERFORMANCE OBJECTIVES OF THE SINGLE CELL TEST SYSTEM FOR SO2 DEPOLARIZED ELECTROLYZER DEVELOPMENT

The single cell test system development for the SRNL sulfur dioxide-depolarized electrolyzer has been completed. Operating experience and improved operating procedures were developed during test operations in FY06 and the first quarter of FY07. Eight different cell configurations, using various MEA designs, have been tested. The single cell test electrolyzer has been modified to overcome difficulties experienced during testing, including modifications to the inlet connection to eliminate minute acid leaks that caused short circuits. The test facility was modified by adding a water bath for cell heating, thus permitting operation over a wider range of flowrates and cell temperatures. Modifications were also identified to permit continuous water flushing of the cathode to remove sulfur, thus extending operating time between required shutdowns. This is also expected to permit a means of independently measuring the rate of sulfur formation, and the corresponding SO{sub 2} flux through the membrane. This report contains a discussion of the design issues being addressed by the single cell test program, a test matrix being conducted to address these issues, and a summary of the performance objectives for the single cell test system. The current primary objective of single cell test system is to characterize and qualify electrolyzer configurations for the following 100-hour longevity tests. Although the single cell test system development is considered complete, SRNL will continue to utilize the test facility and the single cell electrolyzer to measure the operability and performance of various cell design configurations, including new MEA's produced by the component development tasks

Glass Frit Clumping And Dusting

DWPF mixes a slurry of glass frit (Frit 418) and dilute (1.5 wt%) formic acid solution with high level waste in the Slurry Mix Evaporator (SME). There would be advantages to introducing the frit in a non-slurry form to minimize water addition to the SME, however, adding completely dry frit has the potential to generate dust which could clog filters or condensers. Prior testing with another type of frit, Frit 320, and using a minimal amount of water reduced dust generation, however, the formation of hard clumps was observed. To examine options and behavior, a TTQAP [McCabe and Stone, 2013] was written to initiate tests that would address these concerns. Tests were conducted with four types of glass frit; Frit 320, DWPF Frit 418, Bekeson Frit 418 and Multi-Aspirator Frit 418. The last two frits are chemically identical to DWPF Frit 418 but smaller particles were removed by the respective vendors. Test results on Frit Clumping and Dusting are provided in this report. This report addresses the following seven questions. Short answers are provided below with more detailed answers to follow. 1. Will the addition of a small amount of water, 1.5 wt%, to dry DWPF Frit 418 greatly reduce the dust generation during handling at DWPF? a. Yes, a small scale test showed that adding a little water to the frit greatly reduced dust generation during handling. 2. Will the addition of small amounts of water to the frit cause clumping that will impair frit handling at DWPF? a. No, not with Frit 418. Although clumps were observed to form when 1.5 wt% water was mixed with DWPF Frit 418, then compressed and air-dried overnight, the clumps were easily crushed and did not form the hardened material noted when Frit 320 was tested. 3. What is the measured size distribution of dust generated when dry frit is handled? (This affects the feasibility and choice of processing equipment for removing the dust generating fraction of the frit before it is added to the SME.) a. The size distribution for the dust removed from fresh DWPF Frit 418 while it was being shaken in a small scale LabRAM test was measured. The median size on a volume basis was 7.6 μm and 90% of the frit particles were between 1.6 and 28 μm. The mass of dust collected using this test protocol was much less than 1% of the original frit. 4. Can the dust be removed in a small number of processing steps and without the larger frit particles continuing to spall additional dust sized particles? a. Test results using a LabRAM were inconclusive. The LaRAM performs less efficient particle size separation than the equipment used by Bekeson and Multi-Aspirator. 5. What particle size of frit is expected to create a dust problem? a. The original criterion for creating a dusting problem was those particle sizes that were readily suspended when being shaken. For that criterion calculations and Microtrac size analyses indicated that particles smaller than 37 μm are likely dust generators. Subsequently a more sophisticated criterion for dust problem was considered, particle sizes that would become suspended in the air flow patterns inside the SME and possibly plug the condenser. That size may be larger than 37 μm but has not yet been determined. 6. If particles smaller than 37 μm are removed will bulk dust generation be eliminated? a. Video-taped tests were performed using three gallons each of three types of frit 418, DWPF frit, Bekeson frit and Multi-Aspirator frit. Frit was poured through air from a height of approximately eight feet into a container half filled with water. Pouring Bekeson frit or Multi-Aspirator frit generated markedly less visible dust, but there was still a significant amount, which still has the potential of causing a dust problem. 7. Can completely dry frit be poured into the SME without having dust plug the condenser at the top of the vessel? a. Because of the complexity of air currents inside the SME and the difficulty of defensible size scaling a more prototypical test will be required to answer this question. We recommend construction of a full scale mockup of the top half of the SME with a shallow basin of water at the bottom and a simulated condenser at the top. It could be made from simple materials such as PVC pipe, cardboard and clear plastic and tested with dry frit. Depending on results, this may need to be coupled with the proposed pneumatic transfer system

NITRATE DESTRUCTION LITERATURE SURVEY AND EVALUATION CRITERIA

This report satisfies the initial phase of Task WP-2.3.4 Alternative Sodium Recovery Technology, Subtask 1; Develop Near-Tank Nitrate/Nitrite Destruction Technology. Some of the more common anions in carbon steel waste tanks at SRS and Hanford Site are nitrate which is corrosive, and nitrite and hydroxide which are corrosion inhibitors. At present it is necessary to periodically add large quantities of 50 wt% caustic to waste tanks. There are three primary reasons for this addition. First, when the contents of salt tanks are dissolved, sodium hydroxide preferentially dissolves and is removed. During the dissolution process the concentration of free hydroxide in the tank liquid can decrease from 9 M to less than 0.2 M. As a result, roughly half way through the dissolution process large quantities of sodium hydroxide must be added to the tank to comply with requirements for corrosion control. Second, hydroxide is continuously consumed by reaction with carbon dioxide which occurs naturally in purge air used to prevent buildup of hydrogen gas inside the tanks. The hydrogen is generated by radiolysis of water. Third, increasing the concentration of hydroxide increases solubility of some aluminum compounds, which is desirable in processing waste. A process that converts nitrate and nitrite to hydroxide would reduce certain costs. (1) Less caustic would be purchased. (2) Some of the aluminum solid compounds in the waste tanks would become more soluble so less mass of solids would be sent to High Level Vitrification and therefore it would be not be necessary to make as much expensive high level vitrified product. (3) Less mass of sodium would be fed to Saltstone at SRS or Low Level Vitrification at Hanford Site so it would not be necessary to make as much low level product. (4) At SRS less nitrite and nitrate would be sent to Defense Waste Processing Facility (DWPF) so less formic acid would be consumed there and less hydrogen gas would be generated. This task involves literature survey of technologies to perform the nitrate to hydroxide conversion, selection of the most promising technologies, preparation of a flowsheet and design of a system. The most promising technologies are electrochemical reduction of nitrates and chemical reduction with hydrogen or ammonia. The primary reviewed technologies are listed and they aredescribed in more detail later in the report: (1) Electrochemical destruction; (2) Chemical reduction with agents such as ammonia, hydrazine or hydrogen; (3) Hydrothermal reduction process; and (4) Calcination. Only three of the technologies on the list have been demonstrated to generate usable amounts of caustic; electrochemical reduction and chemical reduction with ammonia, hydrazine or hydrogen and hydrothermal reduction. Chemical reduction with an organic reactant such as formic acid generates carbon dioxide which reacts with caustic and is thus counterproductive. Treatment of nitrate with aluminum or other active metals generates a solid product. High temperature calcination has the potential to generate sodium oxide which may be hydrated to sodium hydroxide, but this is unproven. The following criteria were developed to evaluate the most suitable option. The numbers in brackets after the criteria are relative weighting factors to account for importance: (1) Personnel exposure to radiation for installation, routine operation and maintenance; (2) Non-radioactive safety issues; (3) Whether the technology generates caustic and how many moles of caustic are generated per mole of nitrate plus nitrite decomposed; (4) Whether the technology can handle nitrate and nitrite at the concentrations encountered in waste; (5) Maturity of technology; (6) Estimated annual cost of operation (labor, depreciation, materials, utilities); (7) Capital cost; (8) Selectivity to nitrogen as decomposition product (other products are flammable and/or toxic); (9) Impact of introduced species; (10) Selectivity for destruction of nitrate vs. nitrite; and (11) Cost of deactivation and demolition. Each technology was given a score from one to five, five being most desirable, in each criterion. The results for the evaluation, in order from most to least promising was, Electrochemical, Chemical Reduction, Hydrothermal and Calcining. Another report [Steimke and Steeper, 2011] contains a flowsheet and design of an in-tank Electrochemical unit

Solids Accumulation Scouting Studies

The objective of Solids Accumulation activities was to perform scaled testing to understand the behavior of remaining solids in a Double Shell Tank (DST), specifically AW-105, at Hanford during multiple fill, mix, and transfer operations. It is important to know if fissionable materials can concentrate when waste is transferred from staging tanks prior to feeding waste treatment plants. Specifically, there is a concern that large, dense particles containing plutonium could accumulate in poorly mixed regions of a blend tank heel for tanks that employ mixing jet pumps. At the request of the DOE Hanford Tank Operations Contractor, Washington River Protection Solutions, the Engineering Development Laboratory of the Savannah River National Laboratory performed a scouting study in a 1/22-scale model of a waste staging tank to investigate this concern and to develop measurement techniques that could be applied in a more extensive study at a larger scale. Simulated waste tank solids: Gibbsite, Zirconia, Sand, and Stainless Steel, with stainless steel particles representing the heavier particles, e.g., plutonium, and supernatant were charged to the test tank and rotating liquid jets were used to mix most of the solids while the simulant was pumped out. Subsequently, the volume and shape of the mounds of residual solids and the spatial concentration profiles for the surrogate for heavier particles were measured. Several techniques were developed and equipment designed to accomplish the measurements needed and they included: 1. Magnetic particle separator to remove simulant stainless steel solids. A device was designed and built to capture these solids, which represent the heavier solids during a waste transfer from a staging tank. 2. Photographic equipment to determine the volume of the solids mounds. The mounds were photographed as they were exposed at different tank waste levels to develop a composite of topographical areas. 3. Laser rangefinders to determine the volume of the solids mounds. The mounds were scanned after tank supernatant was removed. 4. Core sampler to determine the stainless steel solids distribution within the solids mounds. This sampler was designed and built to remove small sections of the mounds to evaluate concentrations of the stainless steel solids at different special locations. 5. Computer driven positioner that placed the laser rangefinders and the core sampler in appropriate locations over solids mounds that accumulated on the bottom of a scaled staging tank where mixing is poor. These devices and techniques were effective to estimate the movement, location, and concentrations of the solids representing heavier particles and could perform well at a larger scale The experiment contained two campaigns with each comprised of ten cycles to fill and empty the scaled staging tank. The tank was filled without mixing, but emptied, while mixing, in seven batches; the first six were of equal volumes of 13.1 gallons each to represent the planned fullscale batches of 145,000 gallons, and the last, partial, batch of 6.9 gallons represented a full-scale partial batch of 76,000 gallons that will leave a 72-inch heel in the staging tank for the next cycle. The sole difference between the two campaigns was the energy to mix the scaled staging tank, i.e., the nozzle velocity and jet rotational speed of the two jet pumps. Campaign 1 used 22.9 ft/s, at 1.54 rpm based on past testing and Campaign 2 used 23.9 ft/s at 1.75 rpm, based on visual observation of minimum velocity that allowed fast settling solids, i.e., sand and stainless steel, to accumulate on the scaled tank bottom

Use of an Eductor to Reliably Dilute a Plutonium Solution

Savannah River Site (SRS) in South Carolina is dissolving Pu239 scrap, which is a legacy from the production of nuclear weapons materials, and will later convert it into oxide form to stabilize it. An eductor has been used to both dilute and transfer a plutonium containing solution between tanks. Eductors have the advantages of simplicity and no moving parts. Reliable control of dilution is important because the geometry of the receiving tank could potentially allow a nuclear criticality. Dilution factor was to have been controlled by the appropriate choice of flow restrictor in the line between the plutonium solution tank and the eductor. However, dilution factors measured for liquid transfers with different flow restrictors showed unexpected trends, causing concern that the process was not well understood. As a result, the performance of the eductor and associated piping were analyzed using a mathematical model. The one dimensional, two phase model accounted for eductor performance and for air and vapor coming out of solution at low pressures. The unexpected trends were shown to be the result of variations in viscosities and densities of both the plutonium solution and the nitric acid solution used as both the motive fluid and diluent. The model agreed well with existing data and was then used to make pre-test predictions of flows for four solution transfers with good agreement. This provided confidence that the eductor system was a reliable method for obtaining specified dilution factors. Based on model results, recommendations were made and implemented for the operation of the eductor transfer system. One unexpected result of the analysis was the observation that slow corrosion inside the eductor is increasing the dilution factor, which is a conservative trend

Transient Heat Transfer in TCAP Coils

The Thermal Cycling Absorption Process (TCAP) is used to separate isotopes of hydrogen. TCAP involves passing a stream of mixed hydrogen isotopes through palladium deposited on kieselguhr (Pd/k) while cycling the temperature of the Pd/k. Kieselguhr is a silica mineral also called diatomite. To aid in the design of a full scale facility, the Thermal Fluids Laboratory was used by the Chemical and Hydrogen Technology Section to compare the heat transfer properties of three different configurations of stainless steel coils containing kieselguhr and helium. Testing of coils containing Pd/k and hydrogen isotopes would have been more prototypical but would have been too expensive. Three stainless steel coils filled with kieselguhr were tested; one made from 2.0 inch diameter tubing, one made from 2.0 inch diameter tubing with foam copper embedded in the kieselguhr and one made from 1.25 inch diameter tubing. It was known prior to testing that increasing the tubing diameter from 1.25 inch to 2.0 inch would slow the rate of temperature change. The primary purpose of the testing was to measure to what extent the presence of copper foam in a 2.0" tubing coil would compensate for the effect of larger diameter. Each coil was connected to a pressure gage and the coil was evacuated and backfilled with helium gas. Helium was used instead of a mixture of hydrogen isotopes for reasons of safety. Each coil was quickly immersed in a stirred bath of ethylene glycol at a temperature of approximately 100 degrees Celsius. The coil pressure increased, reflecting the increase in average temperature of its contents. The pressure transient was recored as a function of time after immersion. Because of the actual process will use Pd/k instead of kieselguhr, additional tests were run to determine the differences in thermal properties between the two materials. The method was to position a thermocouple at the center of a hollow sphere and pack the sphere with Pd/k. The sphere was sealed, quickly submerged in a bath of boiling water and the temperature transient was recorded. There sphere was then opened, the Pd/k was replaced with kieselguhr and the transient was repeated. The response was a factor of 1.4 faster for Pd/k than for kieselguhr, implying a thermal diffusivity approximately 40 percent higher than for kieselguhr. Another implication is that the transient tests with the coils would have proceeded faster if the coils had been filled with Pd/k rather than kieselguhr

Glass Frit Clumping And Dusting

DWPF mixes a slurry of glass frit (Frit 418) and dilute (1.5 wt%) formic acid solution with high level waste in the Slurry Mix Evaporator (SME). There would be advantages to introducing the frit in a non-slurry form to minimize water addition to the SME, however, adding completely dry frit has the potential to generate dust which could clog filters or condensers. Prior testing with another type of frit, Frit 320, and using a minimal amount of water reduced dust generation, however, the formation of hard clumps was observed. To examine options and behavior, a TTQAP [McCabe and Stone, 2013] was written to initiate tests that would address these concerns. Tests were conducted with four types of glass frit; Frit 320, DWPF Frit 418, Bekeson Frit 418 and Multi-Aspirator Frit 418. The last two frits are chemically identical to DWPF Frit 418 but smaller particles were removed by the respective vendors. Test results on Frit Clumping and Dusting are provided in this report. This report addresses the following seven questions. Short answers are provided below with more detailed answers to follow. 1. Will the addition of a small amount of water, 1.5 wt%, to dry DWPF Frit 418 greatly reduce the dust generation during handling at DWPF? a. Yes, a small scale test showed that adding a little water to the frit greatly reduced dust generation during handling. 2. Will the addition of small amounts of water to the frit cause clumping that will impair frit handling at DWPF? a. No, not with Frit 418. Although clumps were observed to form when 1.5 wt% water was mixed with DWPF Frit 418, then compressed and air-dried overnight, the clumps were easily crushed and did not form the hardened material noted when Frit 320 was tested. 3. What is the measured size distribution of dust generated when dry frit is handled? (This affects the feasibility and choice of processing equipment for removing the dust generating fraction of the frit before it is added to the SME.) a. The size distribution for the dust removed from fresh DWPF Frit 418 while it was being shaken in a small scale LabRAM test was measured. The median size on a volume basis was 7.6 μm and 90% of the frit particles were between 1.6 and 28 μm. The mass of dust collected using this test protocol was much less than 1% of the original frit. 4. Can the dust be removed in a small number of processing steps and without the larger frit particles continuing to spall additional dust sized particles? a. Test results using a LabRAM were inconclusive. The LaRAM performs less efficient particle size separation than the equipment used by Bekeson and Multi-Aspirator. 5. What particle size of frit is expected to create a dust problem? a. The original criterion for creating a dusting problem was those particle sizes that were readily suspended when being shaken. For that criterion calculations and Microtrac size analyses indicated that particles smaller than 37 μm are likely dust generators. Subsequently a more sophisticated criterion for dust problem was considered, particle sizes that would become suspended in the air flow patterns inside the SME and possibly plug the condenser. That size may be larger than 37 μm but has not yet been determined. 6. If particles smaller than 37 μm are removed will bulk dust generation be eliminated? a. Video-taped tests were performed using three gallons each of three types of frit 418, DWPF frit, Bekeson frit and Multi-Aspirator frit. Frit was poured through air from a height of approximately eight feet into a container half filled with water. Pouring Bekeson frit or Multi-Aspirator frit generated markedly less visible dust, but there was still a significant amount, which still has the potential of causing a dust problem. 7. Can completely dry frit be poured into the SME without having dust plug the condenser at the top of the vessel? a. Because of the complexity of air currents inside the SME and the difficulty of defensible size scaling a more prototypical test will be required to answer this question. We recommend construction of a full scale mockup of the top half of the SME with a shallow basin of water at the bottom and a simulated condenser at the top. It could be made from simple materials such as PVC pipe, cardboard and clear plastic and tested with dry frit. Depending on results, this may need to be coupled with the proposed pneumatic transfer system

Test Plan for Characterization Testing of SO2-depolarized Electrolyzer Cell Designs

SRNL received funding in FY 2005 to test the Hybrid Sulfur (HyS) Process for generating hydrogen. This technology employs an electrolyzer that uses a sulfur dioxide depolarized anode to greatly reduce the electrical energy requirement. The required current is the same as for conventional electrolysis of water, but the required cell voltage is reduced. The electrolyzer is a key part of HyS technology. Completing the material loop for HyS requires a high temperature decomposition of sulfuric acid to regenerate the sulfur dioxide gas needed for the anode reaction. Oxygen is also produced and could be sold. The decomposition of sulfuric acid is being studied by others in a separately funded task. It is not included in this SRNL task

Design and Experimental Test Plan for Hybrid Sulfur Single Cell Pressurized Electrolyzer

The Hybrid Sulfur (HyS) process is one of the leading thermochemical cycles being studied as part of the DOE Nuclear Hydrogen Initiative (NHI). SRNL is conducting analyses and research and development for the Department of Energy on the HyS process. A conceptual design report and development plan for the HyS process was issued on April 1, 2005 [Buckner, et. al., 2005] , and a report on atmospheric testing of a sulfur dioxide depolarized electrolyzer (SDE), a major component of the HyS process, was issued on August 1, 2005 [Steimke, 2005]. The purpose of this report is to document work related to the design and experimental test plan for a pressurized SDE. Pressurized operation of the SDE is a key requirement for development of an efficient and cost-effective HyS process. The HyS process, a hybrid thermochemical cycle proposed and investigated in the 1970s and early 1980s by Westinghouse Electric Corporation, is a high priority candidate for NHI due to the potential for high efficiency and its relatively high level of technical maturity. It was demonstrated in laboratory experiments by Westinghouse in 1978. Process improvements and component advancements that build on that work are being pursued. One of the objectives of the current work is to develop the SDE in order to permit the demonstration of a closed-loop laboratory model of the HyS process. The heart of the HyS process for generating hydrogen is a bank of electrolyzers incorporating sulfur dioxide depolarized anodes. SRNL planned, designed, built and operated a facility for testing single cell electrolyzers at ambient temperature and near atmospheric pressure during the spring and summer of 2005. The major contribution of the SRNL work was the establishment of the proof-of-concept for utilizing the proton-exchange-membrane (PEM) cell design for the SDE operation. Since PEM cells are being extensively developed for automotive fuel cell use, they offer significant potential for cost-effective application for the HyS Process. This report discusses the modifications necessary to the existing SRNL sulfur dioxide depolarized electrolyzer test facility to allow testing at up to 80 C and 90 psig. Because of the need for significant additional equipment and the ability to infer performance results to higher pressures, it recommends delaying further modifications to support testing at up to 300 psig (the commercial goal) until other, higher priority technical issues are addressed. These issues include membrane material selection, component designs, catalyst type and loading, etc. The factors and rationale that should be considered in developing and executing a detailed test matrix for pressurized operation are also discussed. In addition, an electrolyzer assembly design has been developed to allow the testing of different Membrane Electrode Assemblies (MEA's) as part of the planned FY06 HyS Development Program to complete selection of component design specifications for the HyS electrolyzer. MEA's are used in PEM cells to allow intimate contact and minimal resistance between the electrodes and the electrolyte layer. The pressurized electrolyzer assembly presented in this report will facilitate rapid change-out and testing of various MEA designs as part of the electrolyzer development effort

PHASE I SINGLE CELL ELECTROLYZER TEST RESULTS

This document reports the results of Phase I Single Cell testing of an SO{sub 2}-Depolarized Water Electrolyzer. Testing was performed primarily during the first quarter of FY 2008 at the Savannah River National Laboratory (SRNL) using an electrolyzer cell designed and built at SRNL. Other facility hardware were also designed and built at SRNL. This test further advances this technology for which work began at SRNL in 2005. This research is valuable in achieving the ultimate goal of an economical hydrogen production process based on the Hybrid Sulfur (HyS) Cycle. The focus of this work was to conduct single cell electrolyzer tests to further develop the technology of SO{sub 2}-depolarized electrolysis as part of the HyS Cycle. The HyS Cycle is a hybrid thermochemical cycle that may be used in conjunction with advanced nuclear reactors or centralized solar receivers to produce hydrogen by water-splitting. Like all other sulfur-based cycles, HyS utilizes the high temperature thermal decomposition of sulfuric acid to produce oxygen and regenerate sulfur dioxide. The unique aspect of HyS is the generation of hydrogen in a water electrolyzer that is operated under conditions where dissolved sulfur dioxide depolarizes the anodic reaction, resulting in substantial voltage reduction. Low cell voltage is essential for both thermodynamic efficiency and hydrogen cost. Sulfur dioxide is oxidized at the anode, producing sulfuric acid that is sent to the high temperature acid decomposition portion of the cycle. The electrolyzer cell uses the membrane electrode assembly (MEA) concept. The anode and cathode are formed by spraying platinum containing catalyst on both sides of a Proton Exchange Membrane (PEM). In most testing the material of the PEM was NafionR. The electrolyzer cell active area can be as large as 54.8 cm{sup 2}. Feed to the anode of the electrolyzer is a sulfuric acid solution containing sulfur dioxide. The partial pressure of sulfur dioxide could be varied in the range of 1 to 6 atm (15 to 90 psia). Temperatures could be controlled in the range from ambient to 80 C. Hydrogen generated at the cathode of the cell was collected for the purpose of flow measurement and composition analysis. The test facility proved to be easy to operate, versatile, and reliable