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Boehmite dissolution experiments were conducted at NaOH concentrations of 10 and 12 M to determine whether the increased aluminum solubility at high hydroxide concentration would offset the increase in added sodium, causing a decrease in the amount of sodium added during boehmite dissolution. A shrinking-core dissolution rate model with a reversible reaction was fitted to the test data. The resulting model included the effects of temperature, hydroxide concentration, and dissolved aluminum concentration. The rate was found to depend on the ∼1.5 power of hydroxide molarity. When the rate model was used to simulate batch boehmite dissolution, a concentration range of 7–9 M NaOH was found to minimize the mass of sodium needed to dissolve a given mass of aluminum, potentially reducing it by as much as two-thirds. The time required to dissolve the boehmite could be decreased by using hydroxide concentrations greater than ∼10 M.

This paper examines the electrochemical and direct internal steam–methane reforming performance of the solid oxide fuel cell when subjected to pressurization. Pressurized operation boosts the Nernst potential and decreases the activation polarization, both of which serve to increase cell voltage and power while lowering the heat load and operating temperature. A model considering the activation polarization in both the fuel and the air electrodes was adopted to address this effect on the electrochemical performance. The pressurized methane conversion kinetics and the increase in equilibrium methane concentration are considered in a new rate expression. The models were then applied in simulations to predict how the distributions of direct internal reforming rate, temperature, and current density are effected within stacks operating at elevated pressure. A generic 10 cm counter-flow stack model was created and used for the simulations of pressurized operation. The predictions showed improved thermal and electrical performance with increased operating pressure. The average and maximum cell temperatures decreased by 3% (20 °C) while the cell voltage increased by 9% as the operating pressure was increased from 1 to 10 atm.

Boehmite leaching tests were carried out at NaOH concentrations of 10 M and 12 M, temperatures of 85°C and 60°C, and a range of initial aluminate concentrations. These data, and data obtained during earlier 100°C tests using 1 M and 5 M NaOH, were used to establish the dependence of the boehmite dissolution rate on hydroxide concentration, temperature, and initial aluminate concentration. A semi-empirical kinetic model for boehmite leaching was fitted to the data and used to calculate the NaOH additions required for leaching at different hydroxide concentrations. The optimal NaOH concentration for boehmite leaching at 85°C was estimated, based on minimizing the amount of Na that had to be added in NaOH to produce a given boehmite conversion.

Testing Summary Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and is to be operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.” The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP; vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct injection of steam to accelerate the leaching process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP-1, the 19-M NaOH is added to un-concentrated waste slurry (3 to 8 wt% solids), while for leaching in UFP-2, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before adding caustic. The work described in this report addresses the kinetics of caustic leach under WTP conditions, based on tests performed with a Hanford waste simulant. The tests were completed at the lab-scale and in the PEP, which is a 1/4.5-scale mock-up of key PTF process equipment. The purpose of this report is to summarize the results from both scales that are related to caustic leach chemistry to support a scale-up factor for the submodels to be used in the G2 model, which predicts WTP operating performance. The scale-up factor will take the form of an adjustment factor for the rate constant in the boehmite leach kinetic equation in the G2 model.

CH2M HILL Hanford Group, Inc. is identifying and developing supplemental process technologies to accelerate the Hanford tank waste cleanup mission. Bulk vitrification, containerized grout, and steam reforming are three technologies under consideration for treatment of the radioactive saltcake wastes in 68 single-shell tanks. To support development and testing of these technologies, Pacific Northwest National Laboratory (PNNL) was tasked with developing a cold dissolved saltcake simulant formulation to be representative of an actual saltcake waste stream, preparing 25- and 100-L batches of the simulant, and analyzing the composition of the batches to ensure conformance to formulation targets. Lacking a defined composition for dissolved actual saltcake waste, PNNL used available tank waste composition information and an equilibrium chemistry model (Environmental Simulation Program [ESP{trademark}]) to predict the concentrations of analytes in solution. Observations of insoluble solids in initial laboratory preparations for the model-predicted formulation prompted reductions in the concentration of phosphate and silicon in the final simulant formulation. The analytical results for the 25- and 100-L simulant batches, prepared by an outside vendor to PNNL specifications, agree within the expected measurement accuracy ({approx}10%) of the target concentrations and are highly consistent for replicate measurements, with a few minor exceptions. In parallel with themore » production of the 2nd simulant batch (100-L), a 1-L laboratory control sample of the same formulation was carefully prepared at PNNL to serve as an analytical standard. The instrumental analyses indicate that the vendor prepared batches of solution adequately reflect the as-formulated simulant composition. In parallel with the simulant development effort, a nominal 5-M (molar) sodium actual waste solution was prepared at the Hanford Site from a limited number of tank waste samples. Because this actual waste solution w as also to be used for testing the supplemental treatment technologies, the modeled simulant formulation was predicated on the composite of waste samples used to prepare it. Subsequently, the actual waste solution was filtered and pretreated to remove radioactive cesium at PNNL and then analyzed using the same instrumentation and procedures applied to the simulant samples. The overall agreement of measured simulant and actual waste solution compositions is better than {+-}10% for the most concentrated species including sodium, nitrate, hydroxide, carbonate, and nitrite. While the magnitude of the relative difference in the simulant and actual waste composition is large (>20% difference) for a few analytes (aluminum, chromium, fluoride, potassium, and total organic carbon), the absolute differences in concentration are in general not appreciable. Our evaluation is that these differences in simulant and actual waste solutions should have a negligible impact on bulk vitrification and containerized grout process testing, while the impact of the low aluminum concentration on steam reforming is yet to be determined.« less

The waste in Hanford tanks generates a mixture of flammable gases and releases it into the tank headspace. The potential hazard resulting from flammable gas generation requires that controls be established to prevent ignition and halt operations if gas concentrations reach levels of concern. In cases where only hydrogen is monitored, a control limit of 6,250 ppm hydrogen has been in use at Hanford for several years. The hydrogen-based control limit is intended to conservatively represent 25% of the lower flammability limit of a gas mixture, accounting for the presence of flammable gases other than hydrogen, with ammonia being the primary concern. This report reviews the technical basis of the current control limit based on observed and projected concentrations of hydrogen and ammonia representing a range of gas release scenarios. The conclusion supports the continued use of the current 6,250 ppm hydrogen control limit

This report was prepared as part of a task supporting the deployment of the retained gas sampler (RGS) system in Flammable Gas Watch List Tanks. The emphasis of this report is on presenting supplemental information about the ammonia measurements resulting from retained gas sampling of Tanks 241-AW-101, A-101, AN-105, AN-104, AN-103, U-103, S-106, BY-101, BY-109, SX-106, AX-101, S-102, S-111, U-109, and SY-101. This information provides a better understanding of the accuracy of past RGS ammonia measurements, which will assist in determining flammable and toxicological hazards.

This report presents an overview of what is known about the flammability of the gases generated and retained in Hanford waste tanks in terms of the gas composition, the flammability and detonability limits of the gas constituents, and the availability of ignition sources. The intrinsic flammability (or nonflammability) of waste gas mixtures is one major determinant of whether a flammable region develops in the tank headspace; other factors are the rate, surface area, volume of the release, and the tank ventilation rate, which are not covered in this report.

The flammable gas hazard in Hanford waste tanks was made an issue by the behavior of double-shell Tank (DST) 241-SY-101 (SY-101). Shortly after SY-101 was filled in 1980, the waste level began rising periodically, due to the generation and retention of gases within the slurry, and then suddenly dropping as the gases were released. An intensive study of the tank's behavior revealed that these episodic releases posed a safety hazard because the released gas was flammable, and, in some cases, the volume of gas released was sufficient to exceed the lower flammability limit (LFL) in the tank headspace (Allemann et al. 1993). A mixer pump was installed in SY-101 in late 1993 to prevent gases from building up in the settled solids layer, and the large episodic gas releases have since ceased (Allemann et al. 1994; Stewart et al. 1994; Brewster et al. 1995). However, the surface level of SY-101 has been increasing since at least 1995, and in recent months the level growth has shown significant and unexpected acceleration. Based on a number of observations and measurements, including data from the void fraction instrument (VFI), we have concluded that the level growth is caused largely by increased gas retention in the floating crust. In September 1998, the crust contained between about 21 and 43% void based on VFI measurements (Stewart et al. 1998). Accordingly, it is important to understand the dominant mechanisms of gas retention, why the gas retention is increasing, and whether the accelerating level increase will continue, diminish or even reverse. It is expected that the retained gas in the crust is flammable, with hydrogen as a major constituent. This gas inventory would pose a flammable gas hazard if it were to release suddenly. In May 1997, the mechanisms of bubble retention and release from crust material were the subject of a workshop. The evaluation of the crust and potential hazards assumed a more typical void of roughly 15% gas. It could be similar to percolati on in single-shell tank (SST) waste forms. The much higher void being currently observed in SY-101 represents essentially a new crust configuration, and the mechanisms for sudden gas release need to be evaluated. The purpose of this study is to evaluate the situation of gas bubbles in crust based on the previous work on gas bubble retention, migration, and release in simulants and actual waste. We have also conducted some visual observations of bubble migration through simulated crusts to help understand the interaction of the various mechanisms.

Four double-contained receiver tanks (DCRTs) at Hanford will be used to store salt-well pumped liquids from tanks on the Flammable Gas Watch List. This document was created to serve as a reference document describing the current knowledge of flammable gas issues in DCRTs. The document identifies, describes, evaluates, and attempts to quantify potential gas carryover and release mechanisms. It estimates several key parameters needed for these calculations, such as initial aqueous concentrations and ventilation rate, and evaluates the uncertainty in those estimates. It justifies the use of the Schumpe model for estimating vapor-liquid equilibrium constants. It identifies several potential waste compatibility issues (such as mixing and pH or temperature changes) that could lead to gas release and provides a basis for calculating their effects. It evaluates the potential for gas retention in precipitated solids within a DCRT and whether retention could lead to a buoyant displacement instability (rollover) event. It discusses rates of radiolytic, thermal, and corrosive hydrogen generation within the DCRT. It also describes in detail the accepted method of calculating the lower flammability limit (LFL) for mixtures of flammable gases. The report incorporates these analyses into two models for calculating headspace flammability, one based on instantaneous equilibrium between dissolved gases and the headspace and one incorporating limited release rates based on mass-transfer considerations. Finally, it demonstrates the use of both models to estimate headspace flammable gas concentrations and minimum ventilation rates required to maintain concentrations below 25% of the LFL.

Four double-contained receiver tanks (DCRTs) at Hanford will be used to store salt-well pumped liquids from tanks on the Flammable Gas Watch List. This document was created to serve as a technical basis or reference document for flammable gas issues in DCRTs. The document identifies, describes, evaluates, and attempts to quantify potential gas carryover and release mechanisms. It estimates several key parameters needed for these calculations, such as initial aqueous concentrations and ventilation rate, and evaluates the uncertainty in those estimates. It justifies the use of the Schumpe model for estimating vapor-liquid equilibrium constants. It identifies several potential waste compatibility issues (such as mixing and pH or temperature changes) that could lead to gas release and provides a basis for calculating their effects. It evaluates the potential for gas retention in precipitated solids within a DCRT and whether retention could lead to a buoyant displacement instability (rollover) event. It discusses rates of radiolytic, thermal, and corrosive hydrogen generation within the DCRT. It also describes in detail the accepted method of calculating the lower flammability limit (LFL) for mixtures of flammable gases.