Caustic-Side Solvent-Extraction Modeling for Hanford Interim Pretreatment System

The purpose of this work is to examine the applicability of the Caustic-Side Solvent Extraction (CSSX) process for the removal of cesium from Hanford tank-waste supernatant solutions in support of the Hanford Interim Pretreatment System (IPS). The Hanford waste types are more challenging than those at the Savannah River Site (SRS) in that they contain significantly higher levels of potassium, the chief competing ion in the extraction of cesium. It was confirmed by use of the CSSX model that the higher levels of potassium depress the cesium distribution ratio (DCs), as validated by measurement of DCs values for four of eight specified Hanford waste-simulant compositions. The model predictions were good to an apparent standard error of ±11%. It is concluded from batch distribution experiments, physical-property measurements, equilibrium modeling, flowsheet calculations, and contactor sizing that the CSSX process as currently employed for cesium removal from alkaline salt waste at the SRS is capable of treating similar Hanford tank feeds. For the most challenging waste composition, 41 stages would be required to provide a cesium decontamination factor (DF) of 5000 and a concentration factor (CF) of 5. Commercial contacting equipment with rotor diameters of 10 in. for extraction and 5 in. for stripping should have the capacity to meet throughput requirements, but testing will be required to confirm that the needed efficiency and hydraulic performance are actually obtainable. Markedly improved flowsheet performance was calculated for a new solvent formulation employing the more soluble cesium extractant BEHBCalixC6 used with alternative scrub and strip solutions, respectively 0.1 M NaOH and 10 mM boric acid. The improved system can meet minimum requirements (DF = 5000 and CF = 5) with 17 stages or more ambitious goals (DF = 40,000 and CF = 15) with 19 stages. Potential benefits of further research and development are identified that would lead to reduced costs, greater adaptability of the process to DOE alkaline salt wastes, and greater readiness for implementation. Such benefits accrue from optimal sizing of centrifugal contactors for application of the CSSX process for the IPS; more accurate modeling of cesium extraction with greater flexibility and applicability to a variety of feeds and flowsheet conditions; and further improving and optimizing the alternative CSSX solvent and scrub/strip system

Alkaline-Side Extraction of Cesium from Savannah River Tank Waste Using a Calixarene-Crown Ether Extractant

Results are presented supporting the viability of the alkaline-side CSEX process as a potential replacement for the In-Tank Precipitation process for removal of cesium from aqueous high-level waste (HLW) at the Savannah River Site (SRS). Under funding from the USDOE Efficient Separations and Crosscutting program, a flowsheet was suggested in early June of 1998, and in the following four months, this flowsheet underwent extensive testing, both in batch tests at ORNL and ANL and in two centrifugal-contactor tests at ANL. To carry out these tests, the initial ESP funding was augmented by direct funds from Westinghouse Savannah River Corporation. The flowsheet employed a solvent containing a calixarene-crown hybrid compound called BoBCalixC6 that was invented at ORNL and can now be obtained commercially for government use from IBC Advanced Technologies. This special extractant is so powerful and selective that it can be used at only 0.01 M, compensating for its expense, but a modifier is required for use in an aliphatic diluent, primarily to increase the cesium distribution ratio D{sub Cs} in extraction. The modifier selected is a relatively economical fluorinated alcohol called Cs3, invented at ORNL and so far available. only from ORNL. For the flowsheet, the modifier is used at 0.2 M in the branched aliphatic kerosene Isopar{reg_sign} L. Testing at ORNL and ANL involved simulants of the SRS HLW. After extraction of the Cs from the waste simulant, the solvent is scrubbed with 0.05 M HNO{sub 3} and stripped with a solution comprised of 0.0005 M HNO{sub 3} and 0.0001 M CsNO{sub 3}. The selection of these conditions is justified in this report, both on the basis of experimental data and underlying theory

Caustic-Side Solvent Extraction: Prediction of Cesium Extraction for Actual Wastes and Actual Waste Simulants

This report presents the work that followed the CSSX model development completed in FY2002. The developed cesium and potassium extraction model was based on extraction data obtained from simple aqueous media. It was tested to ensure the validity of the prediction for the cesium extraction from actual waste. Compositions of the actual tank waste were obtained from the Savannah River Site personnel and were used to prepare defined simulants and to predict cesium distribution ratios using the model. It was therefore possible to compare the cesium distribution ratios obtained from the actual waste, the simulant, and the predicted values. It was determined that the predicted values agree with the measured values for the simulants. Predicted values also agreed, with three exceptions, with measured values for the tank wastes. Discrepancies were attributed in part to the uncertainty in the cation/anion balance in the actual waste composition, but likely more so to the uncertainty in the potassium concentration in the waste, given the demonstrated large competing effect of this metal on cesium extraction. It was demonstrated that the upper limit for the potassium concentration in the feed ought to not exceed 0.05 M in order to maintain suitable cesium distribution ratios

Cord blood-circulating endothelial progenitors for treatment of vascular diseases

Abstract Adult peripheral blood (PB) endothelial progenitor cells (EPC) are produced in the bone marrow and are able to integrate vascular structures in sites of neoangiogenesis. EPCs thus represent a potential therapeutic tool for ischaemic diseases. However, use of autologous EPCs in cell therapy is limited by their rarity in adult PB. Cord blood (CB) contains more EPCs than PB, and they are functional after expansion. They form primary colonies that give rise to secondary colonies, each yielding more than 10 7 cells after few passages. The number of endothelial cells obtained from one unit of CB is compatible with potential clinical application. EPC colonies can be securely produced, expanded and cryopreserved in close culture devices and endothelial cells produced in these conditions are functional as shown in different in vitro and in vivo assays. As CB EPCderived endothelial cells would be allogeneic to patients, it would be of interest to prepare them from ready-existing CB banks. We show that not all frozen CB units from a CB bank are able to generate EPC colonies in culture, and when they do so, number of colonies is lower than that obtained with fresh CB units. However, endothelial cells derived from frozen CB have the same phenotypical and functional properties than those derived from fresh CB. This indicates that CB cryopreservation should be improved to preserve integrity of stem cells other than haematopoietic ones. Feasibility of using CB for clinical applications will be validated in porcine models of ischaemia. Origin and role of EP

Recommended Guanidine Suppressor for the Next-Generation Caustic-Side Solvent Extraction Process

The guanidine recommended for the Next-Generation Caustic-Side is N,N ,N -tris(3,7-dimethyloctyl)guanidine (TiDG). Systematic testing has shown that it is significantly more lipophilic than the previously recommended guanidine DCiTG, the active extractant in the commercial guanidine product LIX -79, while not otherwise changing the solvent performance. Previous testing indicated that the extent of partitioning of the DCiTG suppressor to the aqueous strip solution is significantly greater than expected, potentially leading to rapid depletion of the suppressor from the solvent and unwanted organic concentrations in process effluents. Five candidate guanidines were tested as potential replacements for DCiTG. The tests included batch extraction with simulated waste and flowsheet solutions, third-phase formation, emulsion formation, and partition ratios of the guanidine between the solvent and aqueous strip solution. Preliminary results of a thermal stability test of the TiDG solvent at one month duration indicated performance approximately equivalent to DCiTG. Two of the guanidines proved adequate in all respects, and the choice of TiDG was deemed slightly preferable vs the next best guanidine BiTABG

Next Generation Solvent Development for Caustic-Side Solvent Extraction of Cesium

This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modular Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University developed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Inter Laboratory efforts were coordinated in complementary fashion with engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation

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

Next Generation Extractants for Cesium Separation from High-Level Waste: From Fundamental Concepts to Site Implementation

This project unites expertise at Oak Ridge National Laboratory (ORNL) and Texas Tech University (TTU, Prof. Richard A. Bartsch) to answer fundamental questions addressing the problem of cesium removal from high-level tank waste. Efforts focus on novel solvent-extraction systems containing calixcrown extractants designed for enhanced cesium binding and release. Exciting results are being obtained in three areas: (1) a new lipophilic cesium extractant with a high solubility in the solvent; (2) new proton-ionizable calixcrowns that both strongly extract cesium and "switch off" when protonated; and (3) an improved solvent system that may be stripped with more than 100-fold greater efficiency. Scientific questions primarily concern how to more effectively reverse extraction, focusing on the use of amino groups and proton-ionizable groups to enable pH-switching. Synthesis is being performed at ORNL (amino calixcrowns) and TTU (proton-ionizable calixcrowns). At ORNL, the extraction behavior is being surveyed to assess the effectiveness of candidate solvent systems, and systematic distribution measurements are under way to obtain a thermodynamic understanding of partitioning and complexation equilibria. Crystal structures obtained at ORNL are revealing the structural details of cesium binding. The overall objective is a significant advance in the predictability and efficiency of cesium extraction from high-level waste in support of potential implementation at U. S. Department of Energy (USDOE) sites

Evaluation of Factors Affecting Cesium Extraction Performance by Calix[4]Arene Derivatives

Novel aza-crown derivatives of dioctyloxy-calix[4]arene crown-6 were examined for their cesium extraction performance at different pH levels. These studies are of interest in addressing high-level waste tank remediation and the removal of 137Cs, a major contributor to heat and radiation generation. Preliminary studies were done to assess the performance of these calixarene compounds under varying conditions. Results showed an increase of cesium extraction with pH as well as expected trends in diluent effects and anion selectivity. Poor extraction performance of some aza-crown derivatives raised questions regarding the possibility of intramolecular hydrogen-bonding. A novel methylated derivative was used to address these questions. Additional experiments were conducted to determine the extraction effect on pH. Results indicate an increase in cesium extraction with pH, as shown in preliminary studies. Mono-aza derivatives were shown to exhibit better cesium extraction performance than their di-aza counterparts. The methylated derivative showed poorer extraction performance than the non-methylated derivative, indicating that completely removing the possibility of intramolecular hydrogen-bonding has negative effects on extraction performance. This suggests that the hydrogen-bonding facilitates anion co-extraction, which would lead to better overall extraction. Mono-aza derivatives were shown to cause unexpected changes in pH. This could possibly be attributed to protonation of the calix crown