[en] The primary purpose of the present investigation was to examine the effects of amine size and structure on phase disengagement. Nine commercial tertiary amines were tested together with four laboratory-quality amines for uranium extraction and both organic-continuous (OC) and aqueous-continuous (AC) phase disengagement under Amex-type conditions. Synthetic acid sulfate solutions with and without added colloidal silica and actual ore leach solutions were used as the aqueous phases. Phase disengagement results were correlated with amine size and branching and solution wetting behavior on a silicate (glass) surface. The results suggest that the performance of some Amex systems may be improved by using branched chain tertiary amine extractants of higher molecular weight than are now normally used

[en] The crown ether bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 can be utilized in a solvent-extraction process for the removal of technetium as pertechnetate ion, TcO₄^- from solutions simulating highly radioactive alkaline defense wastes (''tank wastes'') stored at several sites in the United States. The process employs non-halogenated and non-volatile diluents and modifiers and includes an efficient stripping procedure using only water. More than 95% of the pertechnetate present at 6 x 10^-5 M in Melton Valley (Oak Ridge, TN) and Hanford (Washington) tank-waste simulants was removed following two cross-current extraction contacts using 0.02 M bis-4,4'(5')[(tertbutyl)cyclohexano]- 18-crown-6 in 2:1 vol/vol TBP/Isopar reg-sign M diluent at 25 C. Similarly, for both simulants, more than 98% of the pertechnetate contained in the solvent was back-extracted following two cross-current stripping contacts using deionized water

[en] The purpose of this task is to develop an efficient solvent-extraction and stripping process for the removal of the fission products Tc-99, Sr-90, and Cs-137 from alkaline tank wastes, such as those stored at Hanford and Oak Ridge. As such, this task expands upon FY 1995's successful development of a solvent-extraction and stripping process for technetium separation from at sign e tank-waste solutions. This process has in fact already been extended to include the capability of removing both Tc and Sr simultaneously. In this form, the process has been given the name SRTALK and will be developed further in this program as a prelude to developing a system capable of removing Tc, Sr, and Cs together. Such a system could potentially simplify and improve fission-product removal from tank waste. In addition, it would possess the advantages already inherent in our Tc solvent-extraction process: No required feed adjustment, economical water stripping, low consumption of materials, and low waste volume

[en] Weapons production and research and development operations at various U.S. Department of Energy (DOE) sites have left a huge legacy of environmental contamination and risk. The most glaring of these problems is the 3.4 x 10⁵ m³ of high-level wastes stored in tanks at the Savannah River, Hanford, Idaho National Engineering and Environmental Laboratory, and Oak Ridge sites. The conversion of these tank wastes into stable waste forms for permanent disposition is arguably the largest environmental remediation effort ever undertaken. The management of anions in the wastes plays a critical role in processing these wastes. Anions can be hazardous in themselves, or they can complicate the waste-management process. The role of the following key anions in processing and immobilizing the DOE tank wastes will be discussed: phosphate, sulfate, chromate, and pertechnetate. This paper will also review work that has been done with actual wastes relevant to separating these anions

[en] The extraction of alkali metal nitrates by 18-crown-6, 21-crown-7, and 24-crown-8 ethers, bearing cyclohexano, benzo-, t-alkylbenzo, and furano- substituents, in 1,2-dichloroethane has been surveyed. Introduction of a furano substituent onto the macrocyclic ring of 18-crown-6 or 21 crown-7 ethers causes a significant reduction in both extraction efficiency and selectivity. Addition of an additional benzo group to dibenzo-21 -crown-7, to give tribenzo-21 -crown-7, decreases both extraction efficiency and selectivity, whereas addition of one or two additional benzo groups to dibenzo-24-crown-8 increases the extraction efficiency and selectivity for the larger ions Rb+ and Cs⁺ Detailed equilibrium modeling of the extraction by lipophilic 21 -crown-7 ethers indicates that the addition of t-alkyl substituents onto the benzo groups has only a minor effect on the extraction of cesium nitrate by dibenzo-21 -crown-7 ethers

[en] The goal of this project is the development of highly selective extractants for anions targeting important and timely problems of critical interest to the EMSP mission. In particular, sulfate poses a special problem in cleaning up the Hanford waste tanks in that it interferes with vitrification, but available technologies for sulfate removal are limited. The basic chemical aspects of anion receptor design of functional pH independent systems as well as design of separations strategies for selective and efficient removal of targeted anions have been probed. Key findings include: (1) some of the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate from acidic, nitrate-containing aqueous media. Receptor design, structural influences on anion binding affinities, and findings from liquid-liquid extraction studies will be discussed

[en] 'The purpose of this task is to undertake the design, synthesis, and characterization of the next generation of crown ethers for metal-ion separations applicable to the US Department of Energy''s (DOE''s) environmental needs. The general target problem is the removal of alkali and alkaline-earth metal contaminants from certain environmental and waste streams. Although not a radioactivity hazard, Li⁺ ions leaching from burial sites containing more than 12 metric tons of lithium compounds contaminate the groundwater at the Oak Ridge Y-12 Plant and have raised noncompliance concerns because of the resultant toxicity to aquatic biota. A more highly visible problem has been treatment of high-level wastes stored in underground tanks at Oak Ridge National Laboratory (ORNL), Idaho National Engineering and Environmental Laboratory, and especially the Hanford Site. The fission products ⁹⁰Sr and ¹³⁷Cs have been explicitly targeted for removal by the following DOE programs: the Office of Environmental Management, the Office of Science and Technology, the Tank Waste Remediation System, the Tanks Focus Area, and the Efficient Separations and Processing Cross-Cutting Program. These seemingly ubiquitous fission products also appear in soil and groundwater at numerous DOE sites. In addition, radium has recently been named as a target contaminant at the Niagara Falls Storage Site. Unfortunately, the separations technologies needed to address these problems either do not exist or exhibit substantial deficiencies. Established techniques such as solvent extraction and ion exchange certainly have a strong role to play, especially as enhanced with the use of the new highly selective metal-ion hosts such as crown ethers and calixarenes. Recently applied results in the United States, France, Russia, and elsewhere have demonstrated the effective performance of crown ethers under realistic or actual process conditions for the removal of alkali and alkaline-earth metal ions from waste, including high-levelnuclear waste. From these results, one can readily appreciate how improvements in selectivity and extraction strength can immediately translate to improvements and cost savings in existing technologies. One can also envision extending crown-ether-based chemistry to solve other problems, such as groundwater remediation. Achieving these ends will require the design and synthesis of new crown compounds with next-generation capabilities, which will in turn require efforts to build upon the current base of fundamental knowledge pertaining to host-guest chemistry, solvent extraction, and ion exchange.'

[en] Disclosed herein are a class of anion exchange resins containing two different exchange sites with improved selectivity and sorptive capability for chemical species in solution, such as heptavalent technetium as pertechnetate anion, TcO₄^-. The resins are prepared by first reacting haloalkylated crosslinked copolymer beads with a large tertiary amine in a solvent in which the resin beads can swell, followed by reaction with a second, smaller, tertiary amine to more fully complete the functionalization of the resin. The resins have enhanced selectivity, capacity, and exchange kinetics

[en] Two main objectives concerning removal of fission products from high-level tank wastes will be accomplished in this project. The first objective entails the development of an acid-side Cs solvent-extraction (SX) process applicable to remediation of the sodium-bearing waste (SBW) and dissolved calcine waste (DCW) at INEEL. The second objective is to develop alkaline-side SX processes for the combined removal of Tc, Cs, and possibly Sr and for individual separation of Tc (alone or together with Sr) and Cs. These alkaline-side processes apply to tank wastes stored at Hanford, Savannah River, and Oak Ridge. This work exploits the useful properties of crown ethers and calixarenes and has shown that such compounds may be economically adapted to practical processing conditions. Potential benefits for both acid- and alkaline-side processing include order-of-magnitude concentration factors, high rejection of bulk sodium and potassium salts, and stripping with dilute (typically 10 mM) nitric acid. These benefits minimize the subsequent burden on the very expensive vitrification and storage of the high-activity waste. In the case of the SRTALK process for Tc extraction as pertechnetate anion from alkaline waste, such benefits have now been proven at the scale of a 12-stage flowsheet tested in 2-cm centrifugal contactors with a Hanford supernatant waste simulant. SRTALK employs a crown ether in a TBP-modified aliphatic kerosene diluent, is economically competitive with other applicable separation processes being considered, and has been successfully tested in batch extraction of actual Hanford double-shell slurry feed (DSSF)

[en] Improved understanding and performance of the alkaline-side CSEX process has been obtained through the characterization of impurity effects that hinder complete stripping of cesium from the solvent. It is shown in this report that tests of the alkaline-side CSEX process conducted in the summer and fall of 1998 were complicated by the presence of common surfactant anions, undecyl- and dodecylsulfonate, as trace impurities in the two simulants tested. This conclusion was drawn from the results of a series of systematic extraction tests followed by a definitive identification by electrospray mass spectrometry (ES-MS). Based on this understanding, a straightforward preventative measure involving the addition of a lipophilic tertiary amine extractant at a small concentration to the solvent is proposed and demonstrated