Chromatographic Purification of Lithium, Vanadium, and Uranium from Seawater Using Organic Composite Adsorbents Composed of Benzo-18-Crown-6 and Benzo-15-Crown-5 Embedded in Highly Porous Silica Beads

The use of the composite adsorbents composed of benzo-15-crown5 (abbreviated as BC15) and benzo-18-crown-6 (BC18) for the simultaneous recovery of vanadium (V), uranium (U), and lithium (Li) from seawater has been proposed for industrial applications. The adsorption and desorption behavior of these elements on BC15 and BC18 has been examined in various types of aqueous solutions over a wide temperature range. As a result, it was shown that BC15 and BC18 have sufficient adsorption ability for the simultaneous recovery of V, U, and Li from seawater. Moreover, it was seen that the distribution coefficients (K-d) of V decrease with an increase in [HCl](T) (subscript T: total concentration), indicating that the anionic V species such as H2V4O134- are exponentially changed into the cationic V species such as V3+, VO2+, and VO2+ under the condition [HCl](T) = 1.0 M, and the complexation reactions between BC15 (or BC18) and the initial V structures are inhibited. Besides, it was reasonably shown that the adsorption mechanism is the path through the electrostatic interaction between the anionic V species such as H2V4O134-, and the-C-O-C- single bond that the electron density is eccentrically located in ether functional groups in crown ether rings in BC15 and BC18 (or the -C-OH single bond that the electron density is eccentrically located in bisphenol A in BC15 and BC18). Then, the chromatography experiment of V, U, and Li on BC15 (or BC18) at 298 K was carried out by flowing seawater, 1.0 x 10(-2) M HCl, and 1.0 M HCl in sequence. The first peak of V can be separated from the plateau of Li and the first and second peaks of U in the case of the BC15 system. The recovery ratios of V and U were more than 80%. On the other hand, entirely overlapping chromatograms were obtained in the case of the BC18 system, and accordingly, the recovery ratios of V and U were much lower. In short, the separation efficiency of V with BC15 is more pre-eminent than that with BC18. Judging from these results, the durability of BC15 was finally assessed for industrial applications, that is, the aforementioned chromatography experiment was repeatedly carried out to check whether V, U, and Li were stably and mutually separated from seawater or not. The evidence that the recovery performances of V, U, and Li from seawater do not decrease at all after at least five cycle tests was provided. This indicates that this information will be valuable for the development of a practical chromatographic technology to simultaneously recover V, U, and Li from seawater.