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

Spectroscopic Characterization of Aqua [ fac-Tc(CO)3]+ Complexes at High Ionic Strength.

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I-VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac-Tc(CO)3(OH2)3- n(OH) n]1- n (where n = 0-3) were examined by a range of spectroscopic techniques including 99Tc/13C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc-C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac-Tc(CO)3(OH2)3]+ > [ fac-Tc(CO)3(OH2)2(OH)] > [ fac-Tc(CO)3(OH2)(OH)2]-. These results correlate with established trends of the 99Tc upfield chemical shift and carbonyl 13C downfield chemical shift. The lone exception is [ fac-Tc(CO)3(OH)]4 which exhibits a comparatively low electron density at the metal center attributed to the μ3-bridging nature of the -OH ligands causing less σ-donation and no π-donation. This work also reports the first observations of these compounds by XPS and [ fac-Tc(CO)3Cl3]2- by XAS. The unique and distinguishable spectral features of the aqua [ fac-Tc(CO)3]+ complexes lay the foundation for their identification in the complex aqueous matrixes

Iodine (I- and IO3-) Sequestration and Removal by CoAl and NiAl Layered Double Hydroxides

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Sodium Hydroxide Extraction From Caustic Leaching Solutions

This report describes experiments conducted to demonstrate the proof-of-principle of a method to recover NaOH from Hanford tank sludge leaching solutions. Aqueous solutions generated from leaching actual Hanford tank waste solids were used. The process involves neutralization of a lipophilic weak acid (t-octylphenol was used in these experiments) by reaction with NaOH in the aqueous phase. This results in the transfer of Na into the organic phase. Contacting with water reverses this process, reprotonating the lipophilic weak acid and transferring Na back into the aqueous phase as NaOH. The work described here confirms the potential application of solvent extraction to recover and recycle NaOH from solutions generated by leaching Hanford tank sludges. Solutions obtained by leaching sludges from tanks S-110 and T-110 were used in this work. It was demonstrated that Na+ is transferred from caustic leaching solution to the organic phase when contacted with t-octylphenol solutions. This was accompanied by a concomitant decrease in the aqueous-phase hydroxide ion concentration. Seventy to 80 % of the extracted Na was recovered by 3 to 4 sequential contacts of the organic phase with water. Cesium was co-extracted by the procedure, but Al and Cr remained in the feed stream

Water O–H Stretching Raman Signature for Strong Acid Monitoring via Multivariate Analysis

A distinct need exists for real time information on an acid concentration of industrial aqueous streams. Acid strength affects efficiency and selectivity of many separation processes, including nuclear fuel reprocessing. Despite the seeming simplicity of the problem, no practical solution has been offered yet, particularly for the large-scale schemes involving toxic streams such as highly radioactive nuclear wastes. The classic potentiometric technique is not amiable for online measurements due to the requirements of frequent calibration/maintenance and poor long-term stability in aggressive chemical and radiation environments. Therefore, an alternative analytical method is needed. In this work, the potential of using Raman spectroscopic measurements for online monitoring of strong acid concentration in solutions relevant to dissolved used nuclear fuel was investigated. The Raman water signature was monitored for solution systems containing nitric and hydrochloric acids and their sodium salts of systematically varied composition, ionic strength, and temperature. The trivalent neodymium ion simulated the presence of multivalent f metals. The Gaussian deconvolution analysis was used to interpret observed effects of the solution nature on the Raman water O–H stretching spectrum. The generated Raman spectroscopic database was used to develop predictive multivariate regression models for the quantification of the acid and other solution components, as well as selected physicochemical properties. This method was validated using independent experiments conducted in a flow solvent extraction system

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