Synthesis, Development, and Testing of High-Surface-Area Polymer-Based Adsorbents for the Selective Recovery of Uranium from Seawater

The ocean contains uranium with an approximate concentration of 3.34 ppb, which can serve as an incredible supply source to sustain nuclear energy in the United States. Unfortunately, technology currently available to recover uranium from seawater is not efficient enough and mining uranium on land is still more economical. We have developed polymer-based adsorbents with high uranium adsorption capacities by grafting amidoxime onto high-surface-area polyethylene (PE) fibers. Various process conditions have been screened, in combination with developing a rapid testing protocol (<24 h), to optimize the process. These adsorbents are synthesized through radiation-induced grafting of acrylonitrile (AN) and methacrylic acid (MAA) onto PE fibers, followed by the conversion of nitriles to amidoximes and basic conditioning. In addition, the uranium adsorption capacity, measured in units of g_U/kg_ads, is greatly increased by reducing the diameter of the PE fiber or changing its morphology. An increase in the surface area of the PE polymer fiber allows for more grafting sites that are positioned in more-accessible locations, thereby increasing access to grafted molecules that would normally be located in the interior of a fiber with a larger diameter. Polymer fibers with hollow morphologies are able to adsorb beyond 1 order of magnitude more uranium from simulated seawater than current commercially available adsorbents. Several high-surface-area fibers were tested in natural seawater and were able to extract 5–7 times more uranium than any adsorbent reported to date

Elution of Uranium and Transition Metals from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater

High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na₂CO₃–H₂O₂ and hydrochloric acid elution methods can remove ∼95% of the uranium sequestered by the adsorbent after 42 days of exposure in real seawater. The Na₂CO₃–H₂O₂ elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium­(V) and amidoxime is also discussed based on our ⁵¹V NMR data