Adam P. Poloski

Modeling of Boehmite Leaching from Actual Hanford High‐Level Waste Samples

Abstract The Department of Energy plans to vitrify approximately 60,000 metric tons of high level waste sludge from underground storage tanks at the Hanford Nuclear Reservation. To reduce the volume of high level waste requiring treatment, a goal has been set to remove about 90 percent of the aluminum, which comprises nearly 70 percent of the sludge. Aluminum in the form of gibbsite and sodium aluminate can be easily dissolved by washing the waste stream with caustic, but boehmite, which comprises nearly half of the total aluminum, is more resistant to caustic dissolution, and requires higher treatment temperatures and hydroxide concentrations. In this work, the dissolution kinetics of aluminum species during caustic leaching of actual Hanford high level waste samples is examined. The experimental results are used to develop a shrinking platelet model that provides a basis for the prediction of dissolution dynamics from a known process temperature and hydroxide concentration. This model is further developed to include the effects of particle size polydispersity, which is found to strongly influence the rate of dissolution. Two identical parameters for this model are used to describe leaching data from two sets of leaching results. When compared to other common monodisperse shrinking particle models, this result suggests a more physically meaningful model.

Deposition Velocities of Newtonian and Non-Newtonian Slurries in Pipelines

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.

Caustic Recycle from Hanford Tank Waste Using NaSICON Ceramic Membranes

Abstract 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 were achieved at average sodium transport efficiencies of 99%. The membrane was found to be highly selective to sodium ions resulting in no detectable cation transport except Na and a small quantity (0.04% to 0.06%) of 137Cs. An average decontamination factor of 2000 was observed with respect to 137Cs. As expected, Gibbsite precipitation was observed as OH− ions were depleted from the tank waste.

Stabilization and control of rheological properties of Fe2O3/Al(OH)3-rich colloidal slurries under high ionic strength and pH.

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.

Caustic Recycle from Hanford Tank Waste Using NaSICON Ceramic Membrane Salt Splitting Process

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.

Preconceptual Design Description for Caustic Recycle Facility

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.

Characterization and Correlation of Particle-Level Interactions to the Macroscopic Rheology of Powders, Granular Slurries, and Colloidal Suspensions

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.

Scientific Opportunities to Reduce Risk in Nuclear Process Science

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.