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Uranium from Seawater Program Review; Fuel Resources Uranium from Seawater Program DOE Office of Nuclear Energy

Uranium from Seawater Program Review; Fuel Resources Uranium from Seawater Program DOE Office of Nuclear Energy
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Release: 2013
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For nuclear energy to remain sustainable in the United States, economically viable sources of uranium beyond terrestrial ores must be developed. The goal of this program is to develop advanced adsorbents that can extract uranium from seawater at twice the capacity of the best adsorbent developed by researchers at the Japan Atomic Energy Agency (JAEA), 1.5 mg U/g adsorbent. A multidisciplinary team from Oak Ridge National Laboratory, Lawrence Berkeley National Laboratory, Pacific Northwest National Laboratory, and the University of Texas at Austin was assembled to address this challenging problem. Polymeric adsorbents, based on the radiation grafting of acrylonitrile and methacrylic acid onto high surface-area polyethylene fibers followed by conversion of the nitriles to amidoximes, have been developed. These poly(acrylamidoxime-co-methacrylic acid) fibers showed uranium adsorption capacities for the extraction of uranium from seawater that exceed 3 mg U/g adsorbent in testing at the Pacific Northwest National Laboratory Marine Sciences Laboratory. The essence of this novel technology lies in the unique high surface-area trunk material that considerably increases the grafting yield of functional groups without compromising its mechanical properties. This technology received an R & D100 Award in 2012. In addition, high surface area nanomaterial adsorbents are under development with the goal of increasing uranium adsorption capacity by taking advantage of the high surface areas and tunable porosity of carbon-based nanomaterials. Simultaneously, de novo structure-based computational design methods are being used to design more selective and stable ligands and the most promising candidates are being synthesized, tested and evaluated for incorporation onto a support matrix. Fundamental thermodynamic and kinetic studies are being carried out to improve the adsorption efficiency, the selectivity of uranium over other metals, and the stability of the adsorbents. Understanding the rate-limiting step of uranium uptake from seawater is also essential in designing an effective uranium recovery system. Finally, economic analyses have been used to guide these studies and highlight what parameters, such as capacity, recyclability, and stability, have the largest impact on the cost of extraction of uranium from seawater. Initially, the cost estimates by the JAEA for extraction of uranium from seawater with braided polymeric fibers functionalized with amidoxime ligands were evaluated and updated. The economic analyses were subsequently updated to reflect the results of this project while providing insight for cost reductions in the adsorbent development through "cradle-to-grave" case studies for the extraction process. This report highlights the progress made over the last three years on the design, synthesis, and testing of new materials to extract uranium for seawater. This report is organized into sections that highlight the major research activities in this project: (1) Chelate Design and Modeling, (2) Thermodynamics, Kinetics and Structure, (3) Advanced Polymeric Adsorbents by Radiation Induced Grafting, (4) Advanced Nanomaterial Adsorbents, (5) Adsorbent Screening and Modeling, (6) Marine Testing, and (7) Cost and Energy Assessment. At the end of each section, future research directions are briefly discussed to highlight the challenges that still remain to reduce the cost of extractions of uranium for seawater. Finally, contributions from the Nuclear Energy University Programs (NEUP), which complement this research program, are included at the end of this report.


Recovery of Uranium from Seawater

Recovery of Uranium from Seawater
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Release: 2013
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A new series of polymer-supported extractants is proposed for the removal and recovery of uranium from seawater. The objective is to produce polymers with improved stability, load ing capacity, and sorption kinetics compared to what is found w ith amidoximes. The target ligands are diphosphonates and aminomethyldiphosphonates. Small molecule analogues, especially of aminomethyld iphos-phonates, have exceptionally high stability constants for the uranyl ion. The polymeric diphosphonates will have high affinities due to their ability to form six-membered rings with the uranyl ion while the aminomethyldiphosphonates may have yet higher affin ities due to possible tridentate coordination and their greater acidity. A representative set of the polymers to be prepared are indicated below. The preparations to be developed will be from readily availab le starting materials in a minimum number of steps. The structures will be analyzed through FTIR and XPS spectra, supplementing zero point charge determinations and elemental analyses. The uranyl distribution coefficients will be determined from synthetic seawater containing 5 ppm UO2{sup 2+} to allow for accurate analysis by ICP. With solutions having higher concentrations of the uranyl ion, adsorption isotherms and loading capacities will be determined. Polymers w ith high distribution coefficients will be evaluated with authentic seawater samples and uranyl levels of 3 ppb using radiotracer techniques. Rate studies will measure the sorption kinetics. Regeneration of the polymers after loading w ith the uranyl ion will be studied w ith a series of regenerants, including sodium carbonate, 1-hydroxyethyl-1,1-diphosphonic acid, and oxalic acid. The optimum ligand w ill be immobilized onto polypropylene, thus allow ing for its application to uranium recovery from seaw ater. The approach taken w ill be the formation of polypropylene fibers grafted with vinylbenzyl chloride using supercritical CO2 technology. The scCO2 allows the monomer and free radical initiator (benzoyl peroxide) to enter deep within the polymer to give high grafting yields. The aromatic groups can then be functionalized in exactly the same w ay that the beads were modified. Uniform functionalization is expected because the porosity of the fiber permits accessibility of the reagents. Removal of the scCO2 solvent is obviously implemented simply by reducing the pressure. Conditions that minimize homopolymer formation and any degradation of the polypropylene have been defined with maleic anhydride as the monomer and should extend to vinylbenzyl chloride.


Systems Studies on the Extraction of Uranium from Seawater

Systems Studies on the Extraction of Uranium from Seawater
Author: Michael J. Driscoll
Publisher:
Total Pages: 131
Release: 1981
Genre: Marine mineral resources
ISBN:

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This report summarizes the work done at MIT during FY 1981 on the overall system design of a uranium-from-seawater facility. It consists of a sequence of seven major chapters, each of which was originally prepared as a stand-alone internal progress report. These chapters trace the historical progression of the MIT effort, from an early concern with scoping calculations to define the practical boundaries of a design envelope, as constrained by elementary economic and energy balance considerations, through a parallel evaluation of actively-pumped and passive current-driven concepts, and thence to quantification of the features of a second generation system based on a shipboard-mounted, actively-pumped concept designed around the use of thin beds of powdered ion exchange resin supported by cloth fiber cylinders (similar to the baghouse flyash filters used on power station offgas). An assessment of the apparently inherent limitations of even thin settled-bed sorber media then led to selection of an expanded bed (in the form of an ion exchange "wool"), which would permit an order of magnitude increase in flow loading, as a desirable advance. Thus the final two chapters evaluate ways in which this approach could be implemented, and the resulting performance levels which could be attained. Overall, U 308 production costs under 200 $/lb appear to be within reach if a high capacity (several thousand ppm U) ion exchange wool can be developed.