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

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

Warm Water Oxidation Verification - Scoping and Stirred Reactor Tests

Scoping tests to evaluate the effects of agitation and pH adjustment on simulant sludge agglomeration and uranium metal oxidation at {approx}95 C were performed under Test Instructions(a,b) and as per sections 5.1 and 5.2 of this Test Plan prepared by AREVA. (c) The thermal testing occurred during the week of October 4-9, 2010. The results are reported here. For this testing, two uranium-containing simulant sludge types were evaluated: (1) a full uranium-containing K West (KW) container sludge simulant consisting of nine predominant sludge components; (2) a 50:50 uranium-mole basis mixture of uraninite [U(IV)] and metaschoepite [U(VI)]. This scoping study was conducted in support of the Sludge Treatment Project (STP) Phase 2 technology evaluation for the treatment and packaging of K-Basin sludge. The STP is managed by CH2M Hill Plateau Remediation Company (CHPRC) for the U.S. Department of Energy. Warm water ({approx}95 C) oxidation of sludge, followed by immobilization, has been proposed by AREVA and is one of the alternative flowsheets being considered to convert uranium metal to UO{sub 2} and eliminate H{sub 2} generation during final sludge disposition. Preliminary assessments of warm water oxidation have been conducted, and several issues have been identified that can best be evaluated through laboratory testing. The scoping evaluation documented here was specifically focused on the issue of the potential formation of high strength sludge agglomerates at the proposed 95 C process operating temperature. Prior hydrothermal tests conducted at 185 C produced significant physiochemical changes to genuine sludge, including the formation of monolithic concretions/agglomerates that exhibited shear strengths in excess of 100 kPa (Delegard et al. 2007)

Warm Water Oxidation Verification - Scoping and Stirred Reactor Tests

Scoping tests to evaluate the effects of agitation and pH adjustment on simulant sludge agglomeration and uranium metal oxidation at {approx}95 C were performed under Test Instructions(a,b) and as per sections 5.1 and 5.2 of this Test Plan prepared by AREVA. (c) The thermal testing occurred during the week of October 4-9, 2010. The results are reported here. For this testing, two uranium-containing simulant sludge types were evaluated: (1) a full uranium-containing K West (KW) container sludge simulant consisting of nine predominant sludge components; (2) a 50:50 uranium-mole basis mixture of uraninite [U(IV)] and metaschoepite [U(VI)]. This scoping study was conducted in support of the Sludge Treatment Project (STP) Phase 2 technology evaluation for the treatment and packaging of K-Basin sludge. The STP is managed by CH2M Hill Plateau Remediation Company (CHPRC) for the U.S. Department of Energy. Warm water ({approx}95 C) oxidation of sludge, followed by immobilization, has been proposed by AREVA and is one of the alternative flowsheets being considered to convert uranium metal to UO{sub 2} and eliminate H{sub 2} generation during final sludge disposition. Preliminary assessments of warm water oxidation have been conducted, and several issues have been identified that can best be evaluated through laboratory testing. The scoping evaluation documented here was specifically focused on the issue of the potential formation of high strength sludge agglomerates at the proposed 95 C process operating temperature. Prior hydrothermal tests conducted at 185 C produced significant physiochemical changes to genuine sludge, including the formation of monolithic concretions/agglomerates that exhibited shear strengths in excess of 100 kPa (Delegard et al. 2007)

Distribution of Fission Products into Tributyl Phosphate under Applied Nuclear Fuel Recycling Conditions

Tributyl phosphate (TBP) is an important industrial extractant used in the Plutonium Uranium Redox Extraction (PUREX) process for recovering uranium and plutonium from used nuclear fuel. Distribution data have been assessed for a variety of fission and corrosion product trace metals at varying uranium concentrations under representative PUREX extraction (3 M HNO₃) and stripping (0.1 M HNO₃) conditions. As might have been anticipated, the extraction of most trace metals was found to decrease or remain constant with increasing uranium concentration. In contrast, the extraction of some low valence transition metals was found to increase with increasing uranium concentration. The increase in extraction of low valence transition metals may be related to TBP forming reverse micelles instead of recovering uranium as a classical UO₂(NO₃)₂(TBP)₂ coordination complex. The low valence transition metals may be being recovered into the cores of the reverse micelles. Also unanticipated was the lack of impact the TBP degradation product, dibutyl phosphate (DBP), had on the recovery of metals in batch distribution studies. This is possibly related to the batch contacts completed in these experiments not adequately recreating the multistage aspects of industrial-scale uranium extraction done using mixer settlers or centrifugal contactors

Hexavalent Americium Recovery Using Copper(III) Periodate

Separation of americium from the lanthanides is considered one of the most difficult separation steps in closing the nuclear fuel cycle. One approach to this separation could involve oxidizing americium to the hexavalent state to form a linear dioxo cation while the lanthanides remain as trivalent ions. This work considers aqueous soluble Cu³⁺ periodate as an oxidant under molar nitric acid conditions to separate hexavalent Am with diamyl amylphosphonate (DAAP) in <i>n</i>-dodecane. Initial studies assessed the kinetics of Cu³⁺ periodate autoreduction in acidic media to aid in development of the solvent extraction system. Following characterization of the Cu³⁺ periodate oxidant, solvent extraction studies optimized the recovery of Am from varied nitric acid media and in the presence of other fission product, or fission product surrogate, species. Short aqueous/organic contact times encouraged successful recovery of Am (distribution values as high as 2) from nitric acid media in the absence of redox active fission products. In the presence of a post-plutonium uranium redox extraction (post-PUREX) simulant aqueous feed, precipitation of tetravalent species (Ce, Ru, Zr) occurred and the distribution values of ²⁴¹Am were suppressed, suggesting some oxidizing capacity of the Cu³⁺ periodate is significantly consumed by other redox active metals in the simulant. The manuscript demonstrates Cu³⁺ periodate as a potentially viable oxidant for Am oxidation and recovery and notes the consumption of oxidizing capacity observed in the presence of the post-PUREX simulant feed will need to be addressed for any approach seeking to oxidize Am for separations relevant to the nuclear fuel cycle

Removing Phosphate from Hanford High-Phosphate Tank Wastes: FY 2010 Results

The U.S. Department of Energy (DOE) is responsible for environmental remediation at the Hanford Site in Washington State, a former nuclear weapons production site. Retrieving, processing, immobilizing, and disposing of the 2.2 × 105 m3 of radioactive wastes stored in the Hanford underground storage tanks dominates the overall environmental remediation effort at Hanford. The cornerstone of the tank waste remediation effort is the Hanford Tank Waste Treatment and Immobilization Plant (WTP). As currently designed, the capability of the WTP to treat and immobilize the Hanford tank wastes in the expected lifetime of the plant is questionable. For this reason, DOE has been pursuing supplemental treatment options for selected wastes. If implemented, these supplemental treatments will route certain waste components to processing and disposition pathways outside of WTP and thus will accelerate the overall Hanford tank waste remediation mission

Sigma Team for Minor Actinide Separation: PNNL FY 2011 Status Report

This report summarizes work conducted in FY 2011 at PNNL to investigate new methods of separating the minor actinide elements (Am and Cm) from the trivalent lanthanide elements, and separation of Am from Cm. For the former, work focused on a solvent extraction system combining an acidic extractant (HDEHP) with a neutral extractant (CMPO) to form a hybrid solvent extraction system referred to as TRUSPEAK (combining the TRUEX and TALSPEAK processes). For the latter, ligands that strongly bing uranyl ion were investigated for stabilizing corresponding americyl ion

Separating and Stabilizing Phosphate from High-Level Radioactive Waste: Process Development and Spectroscopic Monitoring

Removing phosphate from alkaline high-level waste sludges at the Department of Energy’s Hanford Site in Washington State is necessary to increase the waste loading in the borosilicate glass waste form that will be used to immobilize the highly radioactive fraction of these wastes. We are developing a process which first leaches phosphate from the high-level waste solids with aqueous sodium hydroxide, and then isolates the phosphate by precipitation with calcium oxide. Tests with actual tank waste confirmed that this process is an effective method of phosphate removal from the sludge and offers an additional option for managing the phosphorus in the Hanford tank waste solids. The presence of vibrationally active species, such as nitrate and phosphate ions, in the tank waste processing streams makes the phosphate removal process an ideal candidate for monitoring by Raman or infrared spectroscopic means. As a proof-of-principle demonstration, Raman and Fourier transform infrared (FTIR) spectra were acquired for all phases during a test of the process with actual tank waste. Quantitative determination of phosphate, nitrate, and sulfate in the liquid phases was achieved by Raman spectroscopy, demonstrating the applicability of Raman spectroscopy for the monitoring of these species in the tank waste process streams