Mechanism of Phosphorus Removal from Hanford Tank Sludge by Caustic Leaching

Two experiments were conducted to explore the mechanism by which phosphorus is removed from Hanford tank sludge by caustic leaching. In the first experiment, a series of phosphate salts were treated with 3 M NaOH under conditions prototypic of the actual leaching process to be performed in the Waste Treatment and Immobilization Plant (WTP). The phosphates used were aluminum phosphate, bismuth phosphate, chromium(III) phosphate, and -tri-calcium phosphate; all of these phases have previously been determined to exist in Hanford tank sludge. The leachate solution was sampled at selected time intervals and analyzed for the specific metal ion involved (Al, Bi, Ca, or Cr) and for P (total and as phosphate). The solids remaining after completion of the caustic leaching step were analyzed to determine the reaction product. In the second experiment, the dependence of P removal from bismuth phosphate was examined as a function of the hydroxide ion concentration. It was anticipated that a plot of log[phosphate] versus log[hydroxide] would provide insight into the phosphorus-removal mechanism. This report describes the test activities outlined in Section 6.3.2.1, Preliminary Investigation of Phosphate Dissolution, in Test Plan TP-RPP-WTP-467, Rev.1. The objectives, success criteria, and test conditions of Section 6.3.2.1 are summarized here

The SX Solver: A New Computer Program for Analyzing Solvent-Extraction Equilibria.

A new computer program, the SX Solver, has been developed to analyze solvent-extraction equilibria. The program operates out of Microsoft Excel{reg_sign} and uses the built-in ''Solver'' function to minimize the sum of the square of the residuals between measured and calculated distribution coefficients. The extraction of nitric acid by tributyl phosphate has been modeled to illustrate the program's use

Separating the Minor Actinides Through Advances in Selective Coordination Chemistry

This report describes work conducted at the Pacific Northwest National Laboratory (PNNL) in Fiscal Year (FY) 2012 under the auspices of the Sigma Team for Minor Actinide Separation, funded by the U.S. Department of Energy Office of Nuclear Energy. Researchers at PNNL and Argonne National Laboratory (ANL) are investigating a simplified solvent extraction system for providing a single-step process to separate the minor actinide elements from acidic high-level liquid waste (HLW), including separating the minor actinides from the lanthanide fission products

Closing the Nuclear Fuel Cycle with a Simplified Minor Actinide Lanthanide Separation Process (ALSEP) and Additive Manufacturing

Expanded low-carbon baseload power production through the use of nuclear fission can be enabled by recycling long-lived actinide isotopes within the nuclear fuel cycle. This approach provides the benefits of (a) more completely utilizing the energy potential of mined uranium, (b) reducing the footprint of nuclear geological repositories, and (c) reducing the time required for the radiotoxicity of the disposed waste to decrease to the level of uranium ore from one hundred thousand years to a few hundred years. A key step in achieving this goal is the separation of long-lived isotopes of americium (Am) and curium (Cm) for recycle into fast reactors. To achieve this goal, a novel process was successfully demonstrated on a laboratory scale using a bank of 1.25-cm centrifugal contactors, fabricated by additive manufacturing, and a simulant containing the major fission product elements. Americium and Cm were separated from the lanthanides with over 99.9% completion. The sum of the impurities of the Am/Cm product stream using the simulated raffinate was found to be 3.2 × 10−3 g/L. The process performance was validated using a genuine high burnup used nuclear fuel raffinate in a batch regime. Separation factors of nearly 100 for 154Eu over 241Am were achieved. All these results indicate the process scalability to an engineering scale

Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties

Process Development for Permanganate Addition During Oxidative Leaching of Hanford Tanks Sludges

Previous Bechtel National, Incorporated (BNI)-sponsored studies have targeted optimizing sodium permanganate for the selective oxidation of chromium from washed Hanford tank sludges (Rapko et al. 2004; Rapko et al. 2005). The recommendation from previous work was that contact with sodium permanganate in a minimally caustic solution, i.e., 0.1 to 0.25 M [OH-] initially, provided maximum Cr dissolution while minimizing concomitant Pu dissolution. At the request of BNI, further work on oxidative alkaline leaching was performed

Countercurrent Actinide Lanthanide Separation Process (ALSEP) Demonstration Test with a Simulated PUREX Raffinate in Centrifugal Contactors on the Laboratory Scale

An Actinide Lanthanide Separation Process (ALSEP) for the separation of trivalent actinides (An(III)) from simulated raffinate solution was successfully demonstrated using a 32-stage 1 cm annular centrifugal contactor setup. The ALSEP solvent was composed of a mixture of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N′,N′-tetra-(2-ethylhexyl)-diglycolamide (T2EHDGA) in n-dodecane. Flowsheet calculations and evaluation of the results were done using the Argonne’s Model for Universal Solvent Extraction (AMUSE) code using single-stage distribution data. The co-extraction of Zr(IV) and Pd(II) was prevented using CDTA (trans-1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid) as a masking agent in the feed. For the scrubbing of co-extracted Mo; citrate-buffered acetohydroxamic acid was used. The separation of An(III) from the trivalent lanthanides (Ln(III)) was achieved using citrate-buffered diethylene-triamine-N,N,N′,N″,N″-pentaacetic acid (DTPA), and Ln(III) were efficiently back extracted using N,N,N′,N′-tetraethyl-diglycolamide (TEDGA). A clean An(III) product was obtained with a recovery of 95% americium and curium. The Ln(III) were efficiently stripped; but the Ln(III) product contained 5% of the co-stripped An(III). The carryover of Am and Cm into the Ln(III) product is attributed to too few actinide stripping stages, which was constrained by the number of centrifugal contactors available. Improved separation would be achieved by increasing the number of An strip stages. The heavier lanthanides (Pr, Nd, Sm, Eu, and Gd) and yttrium were mainly routed to the Ln product, whereas the lighter lanthanides (La and Ce) were mostly routed to the raffinate

Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?= C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO3] > 0.3 M. Preliminary results suggest that the Kl?ui resins can separate Pu(IV) from sample solutions containing high concentrations of competing ions. Conceptual protocols for recovery of the Pu from the resin for subsequent analysis have been proposed, but further work is needed to perfect these techniques. Work on this subject will be continued in FY 2007. Automated laboratory equipment (in conjunction with Task 3 of the NA-22 Automation Project) will be used in FY 2007 to improve the efficiency of these experiments. The sorption of actinide ions on self-assembled monolayer on mesoporous supports materials containing diphosphonate groups was also investigated. These materials also showed a very high affinity for tetravalent actinides, and they also sorbed U(VI) fairly strongly. Computational Ligand Design An extended MM3 molecular mechanics model was developed for calculating the structures of Kl?ui ligand complexes. This laid the groundwork necessary to perform the computer-aided design of bis-Kl?ui architectures tailored for Pu(IV) complexation. Calculated structures of the Kl?ui ligand complexes [Pu(Kl?ui)2(OH2)2]2+ and [Fe(Kl?ui)2]+ indicate a ''bent'' sandwich arrangement of the Kl?ui ligands in the Pu(IV) complex, whereas the Fe(III) complex prefers a ''linear'' octahedral arrangement of the two Kl?ui ligands. This offers the possibility that two Kl?ui ligands can be tethered together to form a material with very high binding affinity for Pu(IV) over Fe(III). The next step in the design process is to use de novo molecule building software (HostDesigner) to identify potential candidate architectures

Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of vitrification. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudo hydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties

Status Report on Phase Identification in Hanford Tank Sludges

The U.S. Department of Energy plans to vitrify Hanford's underground storage tank wastes. The vitrified wastes will be divided into low-activity and high-level fractions. There is an effort to reduce the quantity of high-activity wastes by removing nonradioactive components because of the high costs involved in treating high-level waste. Pretreatment options, such as caustic leaching, to selectively remove nonradioactive components are being investigated. The effectiveness of these proposed processes for removing nonradioactive components depends on the chemical phases in the tank sludges. This review summarizes the chemical phases identified to date in Hanford tank sludges