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

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

DEMONSTRATION OF SIMULATED WASTE TRANSFERS FROM TANK AY-102 TO THE HANFORD WASTE TREATMENT FACILITY

In support of Hanford's AY-102 Tank waste certification and delivery of the waste to the Waste Treatment and Immobilization Plant (WTP), Savannah River National Laboratory (SRNL) was tasked by the Washington River Protection Solutions (WRPS) to evaluate the effectiveness of mixing and transferring the waste in the Double Shell Tank (DST) to the WTP Receipt Tank. This work is a follow-on to the previous 'Demonstration of Internal Structures Impacts on Double Shell Tank Mixing Effectiveness' task conducted at SRNL 1. The objective of these transfers was to qualitatively demonstrate how well waste can be transferred out of a mixed DST tank and to provide insights into the consistency between the batches being transferred. Twelve (12) different transfer demonstrations were performed, varying one parameter at a time, in the Batch Transfer Demonstration System. The work focused on visual comparisons of the results from transferring six batches of slurry from a 1/22nd scale (geometric by diameter) Mixing Demonstration Tank (MDT) to six Receipt Tanks, where the consistency of solids in each batch could be compared. The simulant used in this demonstration was composed of simulated Hanford Tank AZ-101 supernate, gibbsite particles, and silicon carbide particles, the same simulant/solid particles used in the previous mixing demonstration. Changing a test parameter may have had a small impact on total solids transferred from the MDT on a given test, but the data indicates that there is essentially no impact on the consistency of solids transferred batch to batch. Of the multiple parameters varied during testing, it was found that changing the nozzle velocity of the Mixer Jet Pumps (MJPs) had the biggest impact on the amount of solids transferred. When the MJPs were operating at 8.0 gpm (22.4 ft/s nozzle velocity, U{sub o}D=0.504 ft{sup 2}/s), the solid particles were more effectively suspended, thus producing a higher volume of solids transferred. When the MJP flow rate was reduced to 5 gpm (14 ft/s nozzle velocity, U{sub o}D = 0.315 ft{sup 2}/s) to each pump, dead zones formed in the tank, resulting in fewer solids being transferred in each batch to the Receipt Tanks. The larger, denser particles were displaced (preferentially to the smaller particles) to one of the two dead zones and not re-suspended for the duration of the test. As the liquid level dropped in the MDT, re-suspending the particles became less effective (6th batch). The poor consistency of the solids transferred in the 6th batch was due to low liquid level in the MDT, thus poor mixing by the MJPs. Of the twelve tests conducted the best transfer of solids occurred during Test 6 and 8 where the MJP rotation was reduced to 1.0 rpm

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

NITRATE CONVERSION OF HB-LINE REILLEXTM HPQ RESIN

Reillex{trademark} HPQ ion exchange resin is used by HB Line to remove plutonium from aqueous streams. Reillex{trademark} HPQ resin currently available from Vertellus Specialties LLC is a chloride ionic form, which can cause stress corrosion cracking in stainless steels. Therefore, HB Line Engineering requested that Savannah River National Laboratory (SRNL) convert resin from chloride form to nitrate form in the Engineering Development Laboratory (EDL). To perform this task, SRNL treated two batches of resin in 2012. The first batch of resin from Reilly Industries Batch 80302MA was initially treated at SRNL in 2001 to remove chloride. This batch of resin, nominally 30 liters, has been stored wet in carboys since that time until being retreated in 2012. The second batch of resin from Batch 23408 consisted of 50 kg of new resin purchased from Vertellus Specialties in 2012. Both batches were treated in a column designed to convert resin using downflow of 1.0 M sodium nitrate solution through the resin bed followed by rinsing with deionized water. Both batches were analyzed for chloride concentration, before and after treatment, using Neutron Activation Analysis (NAA). The resin specification [Werling, 2003] states the total chlorine and chloride concentration shall be less than 250 ppm. The resin condition for measuring this concentration is not specified; however, in service the resin would always be fully wet. Measurements in SRNL showed that changing from oven dry resin to fully wet resin, with liquid in the particle interstices but no supernatant, increases the total weight by a factor of at least three. Therefore, concentration of chlorine or chloride expressed as parts per million (ppm) decreases by a factor of three. Therefore, SRNL recommends measuring chlorine concentration on an oven dry basis, then dividing by three to estimate chloride concentration in the fully wet condition. Chloride concentration in the first batch (No.80302MA) was nearly the same before the current treatment (759 ppm dry) and after treatment (745 ppm dry or {approx}248 ppm wet). Treatment of the second batch of resin (No.23408) was very successful. Chloride concentration decreased from 120,000 ppm dry to an average of 44 ppm dry or {approx}15ppm wet, which easily passes the 250 ppm wet criterion. Per guidance from HB Line Engineering, SRNL blended Batch 80302 resin with Batch P9059 resin which had been treated previously by ResinTech to remove chloride. The chloride concentrations for the two drums of Batch P9059 were 248 ppm dry ({approx}83 ppm wet) {+-}22.8% and 583 ppm dry ({approx}194 ppm wet) {+-} 11.8%. The blended resin was packaged in five gallon buckets

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

METHOD TO PREVENT SULFUR ACCUMULATION INSIDE MEMBRANE ELECTRODE ASSEMBLY

HyS is conceptually the simplest of the thermochemical cycles and involves only sulfur chemistry. In the HyS Cycle hydrogen gas (H{sub 2}) is produced at the cathode of the electrochemical cell (or electrolyzer). Sulfur dioxide (SO{sub 2}) is oxidized at the anode to form sulfuric acid (H{sub 2}SO{sub 4}) and protons (H{sup +}) as illustrated below. A separate high temperature reaction decomposes the sulfuric acid to water and sulfur dioxide which are recycled to the electrolyzers, and oxygen which is separated out as a secondary product. The electrolyzer includes a membrane that will allow hydrogen ions to pass through but block the flow of hydrogen gas. The membrane is also intended to prevent other chemical species from migrating between electrodes and undergoing undesired reactions that could poison the cathode or reduce overall process efficiency. In conventional water electrolysis, water is oxidized at the anode to produce protons and oxygen. The standard cell potential for conventional water electrolysis is 1.23 volts at 25 C. However, commercial electrolyzers typically require higher voltages ranging from 1.8 V to 2.6 V [Kirk-Othmer, 1991]. The oxidation of sulfur dioxide instead of water in the HyS electrolyzer occurs at a much lower potential. For example, the standard cell potential for sulfur dioxide oxidation at 25 C in 50 wt % sulfuric acid is 0.29 V [Westinghouse, 1980]. Since power consumption by the electrolyzers is equal to voltage times current, and current is proportional to hydrogen production, a large reduction in voltage results in a large reduction in electrical power cost per unit of hydrogen generated

PILOT-SCALE TESTING OF THE SUSPENSION OF MST, CST, AND SIMULATED SLUDGE SLURRIES IN A SLUDGE TANK

The Small Column Ion Exchange (SCIX) process is being developed to remove cesium, strontium, and actinides from Savannah River Site (SRS) Liquid Waste using an existing waste tank (i.e., Tank 41H) to house the process. Following strontium, actinide, and cesium removal, the concentrated solids will be transported to a sludge tank (i.e., monosodium titanate (MST)/sludge solids to Tank 42H or Tank 51H and crystalline silicotitanate (CST) to Tank 40H) for eventual transfer to the Defense Waste Processing Facility (DWPF). Savannah River National Laboratory (SRNL) is conducting pilot-scale mixing tests to determine the pump requirements for mixing MST, CST, and simulated sludge. The purpose of this pilot scale testing is to determine the pump requirements for mixing MST and CST with sludge in a sludge tank and to determine whether segregation of particles occurs during settling. Tank 40H and Tank 51H have four Quad Volute pumps; Tank 42H has four standard pumps. The pilot-scale tank is a 1/10.85 linear scaled model of Tank 40H. The tank diameter, tank liquid level, pump nozzle diameter, pump elevation, and cooling coil diameter are all 1/10.85 of their dimensions in Tank 40H. The pump locations correspond to the current locations in Tank 40H (Risers B2, H, B6, and G). The pumps are pilot-scale Quad Volute pumps. Additional settling tests were conducted in a 30 foot tall, 4 inch inner diameter clear column to investigate segregation of MST, CST, and simulated sludge particles during settling

SAVANNAH RIVER SITE TANK 18 AND TANK 19 WALL SAMPLER PERFORMANCE

A sampling tool was required to evaluate residual activity ({mu}Curies per square foot) on the inner wall surfaces of underground nuclear waste storage tanks. The tool was required to collect a small sample from the 3/8 inch thick tank walls. This paper documents the design, testing, and deployment of the remotely operated sampling device. The sampler provides material from a known surface area to estimate the overall surface contamination in the tank prior to closure. The sampler consisted of a sampler and mast assembly mast assembly, control system, and the sampler, or end effector, which is defined as the operating component of a robotic arm. The mast assembly consisted of a vertical 30 feet long, 3 inch by 3 inch, vertical steel mast and a cantilevered arm hinged at the bottom of the mast and lowered by cable to align the attached sampler to the wall. The sampler and mast assembly were raised and lowered through an opening in the tank tops, called a riser. The sampler is constructed of a mounting plate, a drill, springs to provide a drive force to the drill, a removable sampler head to collect the sample, a vacuum pump to draw the sample from the drill to a filter, and controls to operate the system. Once the sampler was positioned near the wall, electromagnets attached it to the wall, and the control system was operated to turn on the drill and vacuum to remove and collect a sample from the wall. Samples were collected on filters in removable sampler heads, which were readily transported for further laboratory testing