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A sodium (Na) Super Ion Conductor (NaSICON), has been studied at Pacific Northwest National Laboratory (PNNL) to investigate its ability to separate sodium from radioactively contaminated sodium salt solutions for treating U.S. Department of Energy (DOE) tank wastes. Ceramatec Inc. developed and fabricated a membrane disk containing a proprietary NAS-GY material formulation that was electrochemically tested in a bench-scale apparatus with both a simulant and a radioactive tank-waste solution to determine the membrane performance when removing sodium from DOE tank wastes. Implementing this sodium separation process can result in significant cost savings by reducing the disposal volume of low-activity wastes and by producing a 19 M NaOH feedstock product for recycle into waste treatment processes such as sludge leaching, regenerating ion exchange resins, inhibiting corrosion in carbon-steel tanks, or retrieving tank wastes. In actual waste tests, average sodium transport rates of 10.3 kg/day/m2 wer...

The rheology of a single coarse granular powder has been studied with shear vane rotational viscometry. The torque required to maintain constant rotation of a vane tool in a loose bed of glass beads (with a mean particle size of 203 μm) is measured as a function of vane immersion depth and rotational speed. The resulting torque profiles exhibit both Coulombic behavior at low rotational rates and fluid-like, collisional behavior at high rotational rates. Analyzing vane shaft and end effects allows the flow dynamics at the cylindrical and top and bottom disk surfaces of vane rotation to be determined. Disk surfaces show a uniform torque profile consistent with Coulombic friction over most of the rotational rates studied. In contrast, cylindrical surfaces show both frictional and collisional torque contributions, with significant dynamic torque increases at deep immersion depths and fast vane rotation.

The U.S. Department of Energy plans to vitrify approximately 60,000 metric tons of high-level waste (HLW) sludge from underground storage tanks at the Hanford Site in Southwest Washington State. To reduce the volume of HLW requiring treatment, a goal has been set to remove a significant quantity of the aluminum, which comprises nearly 70 percent of the sludge. Aluminum is found in the form of gibbsite and sodium aluminate, which can be easily dissolved by washing the waste stream with caustic, and boehmite, which comprises nearly half of the total aluminum, but is more resistant to caustic dissolution and requires higher treatment temperatures and hydroxide concentrations. Chromium, which makes up a much smaller amount (~3%) of the sludge, must also be removed because there is a low tolerance for chromium in the HLW immobilization process. In this work, the coupled dissolution kinetics of aluminum and chromium species during caustic leaching of actual Hanford HLW samples is examined. The experimental results are used to develop a model that provides a basis for predicting dissolution dynamics from known process temperature and hydroxide concentration.

A constitutive model is developed to represent shear granular flows of cohesionless solids. The model is based on the postulate that the friction coefficient and the solids fraction in a moving granular material are exclusive functions of the inertial number, which represents the ratio of inertial to normal stress forces. The constitutive equation obtained has the same form as a multidimensional Bingham fluid model, albeit with apparent viscosity and yield stress that depend on the vertical normal stress. The model is applied to previously published experimental results dealing with shear flows of granular beds made up of cohesionless spherical particles. The first case analyzed corresponds to a granular bed moving on top of a rotating disk. The model captures the main trends of the velocity profiles with a single adjustable parameter. The second case is a conventional Couette flow, for which the model is capable of representing the velocity and solids fraction profiles measured experimentally.

This paper investigates the use of the shear vane technique as a means of determining frictional and cohesive interparticle force contributions to the shear strength of coarse glass bead powders and slurries. To this end, the shear strength of 203-μm glass beads in air and slurried in water and kaolinite suspensions was determined as a function of vane immersion depth, vane geometry, and container size. Both vane immersion depth and container diameter are found to significantly impact the shear strength measured using the vane technique. An equation describing interparticle frictional and cohesive contributions to shear vane measurements was derived in an effort to describe the experimental results. A Janssen stress distribution model for granular materials forms the basis for this equation and appears to explain the behavior of shear strength measurements at varying immersion depths. The presence of the Janssen stress distribution can affect the interpretation of shear vane results. Rather than shear strength being a material property, as is the case with flocculated colloid slurries and polymer solutions, shear strength becomes a process property where vane depth, container size, and container material can result in significant measurement variations. Such parameters should be considered before using the shear vane results on applications involving granular material components.

Model predictive control is applied to batch recipe synthesis scheduling problems. Due to the complexity of this class of problems, a state explosion situation exists where an exponential number of possible combinations of tasks exist in the solution set. In order to overcome this situation the batch processes are modeled discretely with Petri nets. This discrete model can be used to create a coverability tree. The coverability tree can be used to eliminate combinations of tasks, which are not safe or not useful to the process. As a result, the number of possible combinations of batch tasks is reduced to the point that the model predictive control algorithm can be used as a batch recipe synthesis package. This technique is applied to a batch process and compared with another technique. These two techniques yield similar results.

Most correlations/models for minimum transport or critical velocity of slurry were developed for slurries composed of particles greater than ∼100–200 µm diameter with narrow particle-size distributions which is typical of the minerals industry. Many other process industries handle smaller particles. In particular waste slurries at the U.S. Department of Energy's Hanford Site have broad size distributions and significant fractions of smaller particles. Despite the size of these wastes, recent studies at Pacific Northwest National Laboratory indicate that the small particles might be of sufficient density to pose a significant risk for pipeline deposition and plugging. To allow predictive assessment of deposition of fine dense particles for waste slurry transport at the U.S. DOE Hanford site, a pipeline-transport correlation for critical velocity was developed using a simple power-law between two dimensionless numbers important for slurry transport, the deposition Froude and Archimedes numbers. The correlation accords well with experimental data for slurries with Archimedes numbers

Controlling the stability and rheological properties of colloidal slurries has been an important but challenging issue for various industries such as cosmetics, ceramic processing, and nuclear waste treatment. For example, at the US Department of Energy Hanford and Savannah River sites, operation of the waste treatment facilities with increased solids loading increases waste processing rates but negatively impacts the rheological properties. We investigated various rheological modifiers on a Fe(2)O(3)/Al(OH)(3)-rich nuclear waste simulant, characterized by high ionic strength and pH, to reduce yield stress of the colloidal slurry. Rheological modifiers change particle interactions in colloidal slurries; they mainly alter the electrostatic and steric interactions, leading to a change in rheological properties. Weak acid-type rheological modifiers strengthen electrostatic repulsion whereas nonionic/polymer surfactant-type rheological modifiers introduce a steric repulsion. Using rheological analysis, it was found that citric acid and polyacrylic acid are good rheological modifiers for the simulant tested, effectively reducing yield stresses by as much as 70%. Further analysis supports the idea that adding these rheological modifiers increases the stability of the slurry. A likely mechanism for the observed effects of citric acid and polyacrylic acid on slurry behavior is identified as both binding cations in bulk solution and adsorption on the surface of the particles.

One of the concerns expressed by the External Flowsheet Review Team (EFRT) is about the potential for pipe plugging at the Waste Treatment and Immobilization Plant (WTP). Per the review’s executive summary, “Piping that transports slurries will plug unless it is properly designed to minimize this risk. This design approach has not been followed consistently, which will lead to frequent shutdowns due to line plugging.” To evaluate the potential for plugging, deposition-velocity tests were performed on several physical simulants to determine whether the design approach is conservative. Deposition velocity is defined as the velocity below which particles begin to deposit to form a moving bed of particles on the bottom of a straight horizontal pipe during slurry-transport operations. The deposition velocity depends on the system geometry and the physical properties of the particles and fluid. An experimental program was implemented to test the stability-map concepts presented in WTP-RPT-175 Rev. 01. Two types of simulant were tested. The first type of simulant was similar to the glass-bead simulants discussed in WTP-RPT-175 Rev. 0 ; it consists of glass beads with a nominal particle size of 150 µm in a kaolin/water slurry. The initial simulant was prepared at a target yield stressmore » of approximately 30 Pa. The yield stress was then reduced, stepwise, via dilution or rheological modifiers, ultimately to a level of

The WTP pipe plugging issue, as stated by the External Flowsheet Review Team (EFRT) Executive Summary, is as follows: “Piping that transports slurries will plug unless it is properly designed to minimize this risk. This design approach has not been followed consistently, which will lead to frequent shutdowns due to line plugging.” A strategy was employed to perform critical-velocity tests on several physical simulants. Critical velocity is defined as the point where a stationary bed of particles deposits on the bottom of a straight horizontal pipe during slurry transport operations. Results from the critical velocity testing provide an indication of slurry stability as a function of fluid rheological properties and transport conditions. The experimental results are compared to the WTP design guide on slurry transport velocity in an effort to confirm minimum waste velocity and flushing velocity requirements as established by calculations and critical line velocity correlations in the design guide. The major findings of this testing is discussed below. Experimental results indicate that the use of the Oroskar and Turian (1980) correlation in the design guide is conservative—Slurry viscosity has a greater affect on particles with a large surface area to mass ratio. The increased viscous forces on these particles result in a decrease in predicted critical velocities from this traditional industry derived equations that focus on particles large than 100 m in size. Since the Hanford slurry particles generally have large surface area to mass ratios, the reliance on such equations in the Hall (2006) design guide is conservative. Additionally, the use of the 95% percentile particle size as an input to this equation is conservative. However, test results indicate that the use of an average particle density as an input to the equation is not conservative. Particle density has a large influence on the overall result returned by the correlation. Lastly, the viscosity correlation used in the WTP design guide has been shown to be inaccurate for Hanford waste feed materials. The use of the Thomas (1979) correlation in the design guide is not conservative—In cases where 100% of the particles are smaller than 74 m or particles are considered to be homogeneous due to yield stress forces suspending the particles the homogeneous fraction of the slurry can be set to 100%. In such cases, the predicted critical velocity based on the conservative Oroskar and Turian (1980) correlation is reduced to zero and the design guide returns a value from the Thomas (1979) correlation. The measured data in this report show that the Thomas (1979) correlation predictions often fall below that measured experimental values. A non-Newtonian deposition velocity design guide should be developed for the WTP— Since the WTP design guide is limited to Newtonian fluids and the WTP expects to process large quantities of such materials, the existing design guide should be modified address such systems. A central experimental finding of this testing is that the flow velocity required to reach turbulent flow increases with slurry rheological properties due to viscous forces dampening the formation of turbulent eddies. The flow becomes dominated by viscous forces rather than turbulent eddies. Since the turbulent eddies necessary for particle transport are not present, the particles will settle when crossing this boundary called the transitional deposition boundary. This deposition mechanism should be expected and designed for in the WTP.

This report contains a review of potential cost benefits of NaSICON Ceramic membranes for the separation of sodium from Hanford tank waste. The primary application is for caustic recycle to the Waste Treatment and Immobilization Plant (WTP) pretreatment leaching operation. The report includes a description of the waste, the benefits and costs for a caustic-recycle facility, and Monte Carlo results obtained from a model of these costs and benefits. The use of existing cost information has been limited to publicly available sources. This study is intended to be an initial evaluation of the economic feasibility of a caustic recycle facility based on NaSICON technology. The current pretreatment flowsheet indicates that approximately 6,500 metric tons (MT) of Na will be added to the tank waste, primarily for removing Al from the high-level waste (HLW) sludge (Kirkbride et al. 2007). An assessment (Alexander et al. 2004) of the pretreatment flowsheet, equilibrium chemistry, and laboratory results indicates that the quantity of Na required for sludge leaching will increase by 6,000 to 12,000 MT in order to dissolve sufficient Al from the tank-waste sludge material to maintain the number of HLW canisters produced at 9,400 canisters as defined in the Office of River Protectionmore » (ORP) System Plan (Certa 2003). This additional Na will significantly increase the volume of LAW glass and extend the processing time of the Waste Treatment and Immobilization Plant (WTP). Future estimates on sodium requirements for caustic leaching are expected to significantly exceed the 12,000-MT value and approach 40,000-MT of total sodium addition for leaching (Gilbert, 2007). The cost benefit for caustic recycling is assumed to consist of four major contributions: 1) the cost savings realized by not producing additional immobilized low-activity waste (ILAW) glass, 2) caustic recycle capital investment, 3) caustic recycle operating and maintenance costs, and 4) research and technology costs needed to deploy the technology. In estimating costs for each of these components, several parameters are used as inputs. Due to uncertainty in assuming a singular value for each of these parameters, a range of possible values is assumed. A Monte Carlo simulation is then performed where the range of these parameters is exercised, and the resulting range of cost benefits is determined.« less

A family of inorganic ceramic materials, called sodium (Na) Super Ion Conductors (NaSICON), has been studied at Pacific Northwest National Laboratory (PNNL) to investigate their ability to separate sodium from radioactively contaminated sodium salt solutions for treating U.S. Department of Energy (DOE) tank wastes. Ceramatec Inc. developed and fabricated a membrane containing a proprietary NAS-GY material formulation that was electrochemically tested in a bench-scale apparatus with both a simulant and a radioactive tank-waste solution to determine the membrane performance when removing sodium from DOE tank wastes. Implementing this sodium separation process can result in significant cost savings by reducing the disposal volume of low-activity wastes and by producing a NaOH feedstock product for recycle into waste treatment processes such as sludge leaching, regenerating ion exchange resins, inhibiting corrosion in carbon-steel tanks, or retrieving tank wastes.

This report presents the results of preparation and characterization of chemical plugs based on selected Hanford Site waste simulants. Included are the results of chemical plug bench testing conducted in support of the M1/M6 Flow Loop Chemical Plugging/Unplugging Test (TP-RPP-WTP-495 Rev A). These results support the proposed plug simulants for the chemical plugging/ unplugging tests. Based on the available simulant data, a set of simulants was identified that would likely result in chemical plugs. The three types of chemical plugs that were generated and tested in this task consisted of: 1. Aluminum hydroxide (NAH), 2. Sodium aluminosilicate (NAS), and 3. Sodium aluminum phosphate (NAP). While both solvents, namely 2 molar (2 M) nitric acid (HNO3) and 2 M sodium hydroxide (NaOH) at 60°C, used in these tests were effective in dissolving the chemical plugs, the 2 M nitric acid was significantly more effective in dissolving the NAH and NAS plugs. The caustic was only slightly more effecting at dissolving the NAP plug. In the bench-scale dissolution tests, hot (60°C) 2 M nitric acid was the most effective solvent in that it completely dissolved both NAH and NAS chemical plugs much faster (1.5 – 2 x) than 2 M sodium hydroxide.more » So unless there are operational benefits for the use of caustic verses nitric acid, 2 M nitric acid heated to 60°C C should be the solvent of choice for dissolving these chemical plugs. Flow-loop testing was planned to identify a combination of parameters such as pressure, flush solution, composition, and temperature that would effectively dissolve and flush each type of chemical plug from preformed chemical plugs in 3-inch-diameter and 4-feet-long pipe sections. However, based on a review of the results of the bench-top tests and technical discussions, the Waste Treatment Plant (WTP) Research and Technology (R&T), Engineering and Mechanical Systems (EMS), and Operations concluded that flow-loop testing of the chemically plugged pipe sections would not provide any additional information or useful data. The decision was communicated through a Sub Contract Change Notice (SCN-070) that included a revised scope as follows: • Photographing the chemical plugs in the pipes before extrusion to compare the morphology of aged gels with that of fresh gels. • Setting up an extrusion apparatus and extruding the chemical plugs. • Documenting the qualitative observations on the efforts to remove the chemical plug materials from the pipe sections. • Performing X-ray diffraction (XRD) analysis of extruded gel samples to detect any crystallization of gel during storage. • Disposing of the extruded gel as a waste. • Documenting the analytical results in a test report. There were no significant morphological differences between the fresh and aged plugs except for an overgrowth of small transparent crystals on the surface of the aged NAS gel plug. An initial pressure of 15 KPa for the NAS plug and from ~2 to 6 KPa for the NAH plug. Following extrusion, the NAP plug sections were thixotropic. The bulk of all the aged gel plugs consisted of amorphous material with nitratine constituting the crystalline phase. A separate question about the whether the current in-tank waste conditions will bound the future multi-tank blended feed conditions for the Waste Treatment Plant is outside the scope of this study.« less

Cleaning up the nation’s nuclear weapons complex remains as one of the most technologically challenging and financially costly problems facing the U.S. Department of Energy (DOE). Safety, cost, and technological challenges have often delayed progress in retrieval, processing, and final disposition of high-level waste, spent nuclear fuel, and challenging materials. Some of the issues result from the difficulty and complexity of the technological issues; others have programmatic bases, such as contracting strategies that may provide undue focus on near-term, specific clean-up goals or difficulty in developing and maintaining stakeholder confidence in the proposed solutions. We propose that independent basic fundamental science research focused on the full cleanup life-cycle offers an opportunity to help address these challenges by providing 1) scientific insight into the fundamental mechanisms involved in currently selected processing and disposal options, 2) a rational path to the development of alternative technologies should the primary options fail, 3) confidence that models that predict long-term performance of different disposal options are based upon the best available science, 4) fundamental science discovery that enables transformational solutions to revolutionize the current baseline processes.

The U.S. Department of Energy plans to vitrify both high-level and low-activity waste at the Hanford Site in southeastern Washington State. One aspect of the planning includes a need for a caustic recycle process to separate sodium hydroxide for recycle. Sodium is already a major limitation to the waste-oxide loading in the low-activity waste glass to be vitrified at the Waste Treatment Plant, and additional sodium hydroxide will be added to remove aluminum and to control precipitation in the process equipment. Aluminum is being removed from the high level sludge to reduce the number of high level waste canisters produced. A sodium recycle process would reduce the volume of low-activity waste glass produced and minimize the need to purchase new sodium hydroxide, so there is a renewed interest in investigating sodium recycle. This document describes an electrochemical facility for recycling sodium for the WTP.

The U.S. Department of Energy (DOE) Office of River Protection’s Waste Treatment and Immobilization Plant (WTP) will process and treat radioactive waste that is stored in tanks at the Hanford Site. Piping, pumps, and mixing vessels have been selected to transport, store, and mix the high-level waste slurries in the WTP. This report addresses the analyses performed by the Rheology Working Group (RWG) and Risk Assessment Working Group composed of Pacific Northwest National Laboratory (PNNL), Bechtel National Inc. (BNI), CH2M HILL, DOE Office of River Protection (ORP) and Yasuo Onishi Consulting, LLC staff on data obtained from documented Hanford waste analyses to determine a best-estimate of the rheology of the Hanford tank wastes and their settling behavior. The actual testing activities were performed and reported separately in referenced documentation. Because of this, many of the required topics below do not apply and are so noted.

This test plan was prepared by the Pacific Northwest National Laboratory (PNNL) under contract with Fluor Hanford (FH). The test plan describes the scope and conditions to be used to perform laboratory-scale testing of the Sludge Treatment Project (STP) hydrothermal treatment of K Basin sludge. The STP, managed for the U. S. Department of Energy (DOE) by FH, was created to design and operate a process to eliminate uranium metal from the sludge prior to packaging for Waste Isolation Pilot Plant (WIPP) by using high temperature liquid water to accelerate the reaction, produce uranium dioxide from the uranium metal, and safely discharge the hydrogen. The proposed testing builds on the approach and laboratory test findings for both K Basin sludge and simulated sludge garnered during prior testing from September 2006 to March 2007. The outlined testing in this plan is designed to yield further understanding of the nature of the chemical reactions, the effects of compositional and process variations and the effectiveness of various strategies to mitigate the observed high shear strength phenomenon observed during the prior testing. These tests are designed to provide process validation and refinement vs. process development and design input. The expected outcome is to establish more » a level of understanding of the chemistry such that successful operating strategies and parameters can be implemented within the confines of the existing STP corrosion vessel design. In July 2007, the DOE provided direction to FH regarding significant changes to the scope of the overall STP. As a result of the changes, FH directed PNNL to stop work on most of the planned activities covered in this test plan. Therefore, it is unlikely the testing described here will be performed. However, to preserve the test strategy and details developed to date, the test plan has been published. « less

Pulse jet mixer technology has been selected for implementation in the Hanford Waste Treatment Plant. However, processing non-Newtonian fluids using this technology is not mature. Experiments were conducted at several scales to develop an understanding of the scaling mechanisms that govern this type of mixer performance.Copyright © 2007 by ASME

This project had two primary objectives. The first was to understand the physical properties and behavior of select Hanford tank sludges under conditions that might exist during retrieval, treatment, packaging, and transportation for disposal at the Waste Isolation Pilot Plant (WIPP). The second objective was to develop a fundamental understanding of these sludge suspensions by correlating the macroscopic properties with particle interactions occurring at the colloidal scale. The specific tank wastes considered herein are contained in thirteen Hanford tanks including three double-shell tanks (DSTs) (AW-103, AW-105, and SY-102) and ten single-shell tanks (SSTs) (B-201 through B-204, T-201 through T-204, T-110, and T-111). At the outset of the project, these tanks were designated as potentially containing transuranic (TRU) process wastes that would be treated and disposed of in a manner different from the majority of the tank wastes.

The long-term behavior of Hanford Site K Basin sludge with respect to loss of supernatant water and solids compaction is important in designing sludge storage and handling systems. This report describes the results of laboratory tests performed to understand and predict K Basin sludge drying and compaction rates under extended (28-month) {approx}34 C hot cell storage. Tests were conducted with six K Basin sludge materials, a control sample of simulated K Basin sludge, and a control sample containing only K Basin supernatant liquid. All samples were held in graduated cylinders fitted with threaded plastic caps. Quantitative data were gathered on how the mass and volume of K Basin sludge, and its associated supernatant liquid, changed with respect to storage time. The tests showed that the K Basin sludge samples lost water unpredictably, depending on cap seal tightness, with projected dryout times for a 1-cm cover water depth ranging from 5 to 216 months. Though the ambient radiation field ({approx}5 Rad/hour) likely contributed to cap seal degradation, water evaporation rates were found to be independent of the contained material (water vs. sludge; radioactive vs. non-radioactive sludge). Although water was lost at variable rates from sludge samples during storage in the hot more » cell (and, presumably, in long-term containerized storage), the sludge itself had no intrinsic propensity to enhance or diminish the rate of water evaporation compared with that exhibited by water stored in the same environment. Most of the compaction of the six KE Basin sludges and the simulated sludge occurred in the first week. Subsequent compaction to 28-months time provided little additional increase in settled sludge density. Agitating the settled sludge likewise had little to no effect on the density. However, one tested sludge contained unreacted uranium metal that began to generate corrosion product hydrogen gas after 78 days of settling and strongly altered the apparent sludge density. T he lengthy induction time shows again that uranium metal-bearing sludge may lie quiescent for long periods, even at comparatively warm temperatures, before initiating gas generation. When the testing was completed, the sludge samples were removed from the graduated cylinders. Most sludge re-suspended readily but a canister sludge sample that had previously been allowed to dry out during storage self-cemented into a hard-cake monolith and could not be re-suspended. Settled sludge density and the concentrations of 154Eu, 241Am, and the plutonium isotopes were found to follow the dry basis uranium concentration in the sludge solids. These findings amplify observations made in prior characterization studies that showed that sludge density and radiolytic, fissile material, and TRU (primarily 241Am and 238,239,240Pu) concentrations are proportional to uranium concentration. The sludge pH, found to decrease from {approx}8 to {approx}5 with a dry basis uranium concentration increase from {approx}2.5 to 82 wt% , provides data useful in designing sludge storage and process equipment. « less

Hanford K Basin sludge contains metallic uranium and uranium oxides that will corrode, hydrate, and, consequently, generate heat and hydrogen gas during storage. Heat is generated within the K Basin sludge by radiolytic decay and the reaction of uranium metal with water. To maintain thermal stability, the sludge must be retrieved, staged, transported, and stored in systems designed to provide a rate of heat removal that prevents the temperature in the sludge from increasing beyond acceptable limits. To support the dispositioning of the sludge to T Plant, modeling and testing and analyses are being performed to predict the behavior of sludge when placed into the storage containers. Two physical properties of the sludge that are critical to the modeling and analyses efforts are thermal conductivity and the sludge shear strength (yield stress). This report provides the results of thermal conductivity and shear strength measurements performed on representative sludge samples from the K East Basin.