No abstract

Uranium recovery from seawater has been investigated for several decades for the purpose of securing nuclear fuel for energy production. In this study, field column experiments have been performed at the Marine Sciences Laboratory of the Pacific Northwest National Laboratory (PNNL) using a laboratory-proven, amidoxime-based polymeric adsorbent developed at the Oak Ridge National Laboratory (ORNL). The adsorbent was packed either in in-line filters or in flow-through columns. The maximum amount of uranium uptake from seawater was 3.3 mg of U/g of adsorbent after 8 weeks of contact between the adsorbent and seawater. This uranium adsorption amount was about 3 times higher than the maximum amount achieved in this study by a leading adsorbent developed at the Japan Atomic Energy Agency (JAEA). Both adsorbents were tested under similar conditions. The results were used to update an assessment of the cost of large-scale recovery of uranium from seawater using the ORNL adsorbent. The updated uranium production cost was estimated to be reduced to $610/kg of U, approximately half the cost estimated for the JAEA technology.

The worlds oceans, where uranium is found quite uniformly at a concentration of 3.3 mg L À1 , present an alternative source of uranium to terrestrial mining for nuclear fuel. Environmental concerns associated with mining will undoubtedly increase as reserves are depleted, thus increasing the utility of more environmentally friendly feedstocks. [1][2][3][4] Hence, before terrestrial resources become scarce, the development of sorbents designed for seawater extraction is of strategic importance to guarantee future uranium resources. From the first inorganic adsorbents, which showed poor selectivity and mechanical resistance, to the most recent polyethylene-fiberbased sorbents containing amidoxime-carboxylic acid copolymers, and more recently layered metal sulfides and metalorganic frameworks, interest in uranium seawater extractions has continuously increased among governments worldwide. [5][6][7][8][9][10] Because the concentration of uranium in the oceans is relatively low, maximization of the adsorption properties of sorbents, for example, through changes in their surface area and pore structure, can greatly improve the kinetics of uranium extraction and the adsorption capacity simultaneously. [11] To facilitate the uptake of uranyl ions with fast kinetics, various sorbents containing the amidoxime group, such as hydrogels, [12] particles and beads, [13] membranes, [14] macroporous fibers, [15] and composites, [16] have been prepared by suspension polymerization, radiation-induced grafting, and even sonochemical functionalization. However, silica beads and most carbon materials have a relatively small accessible surface area for the growth of large polymers or a low number of surface sites available for the grafting of functional groups. Thus, the design of substrates with large numbers of accessible reactive sites for the grafting of polymeric surface groups is necessary for the development of materials with improved uranium-adsorption capacity.Recently, porous polymers based on divinylbenzene (DVB) have been developed for applications in separations and catalysis. [17] For example, the copolymerization of p-styrene sulfonate with divinylbenzene led to a catalytically active porous polymer. This method has the additional advantage that polymers can be obtained with controlled porosity and high surface areas without porogens. It is thus time-and cost-effective, as well as more environmentally friendly than the templated synthesis of carbonaceous materials. [18] Motivated by these findings, we report herein nanoporous polymers based on the vinylbenzyl chloride (VBC) monomer and the DVB cross-linking agent. As well as a well-developed nanoporous structure of micro-and mesopores, the obtained polymers contain large numbers of accessible chlorine species, which can be used as initiators for atom-transfer radical polymerization (ATRP). These materials are the first examples of ATRP initiators in which the initiator species is located within the framework of the mesoporous support. The accessible framework and surface...

Fiber adsorbents synthesizedviaATRP.