Crown Ether-Grafted Graphene Oxide-Based Materials—Synthesis, Characterization and Study of Lithium Adsorption from Complex Brine

Direct lithium extraction from unconventional resources requires the development of effective adsorbents. Crown ether-containing materials have been reported as promising structures in terms of lithium selectivity, but data on adsorption in real, highly saline brines are scarce. Crown ether-grafted graphene oxides were synthesized using 2-hydroxymethyl-12-crown-4, hydroxy-dibenzo-14-crown-4 and epichlorohydrin as a source of anchoring groups. The obtained carbonaceous materials were used to prepare chitosan-polyvinyl alcohol composites. The prepared materials (and intermediate products) were characterized using FTIR, XRD, Raman spectroscopy and SEM-EDS methods. Adsorption tests were performed in a pure diluted LiCl solution ([Li] = 200 mg/kg) as well as in a real, highly saline oilfield brine ([Li] ≈ 220 mg/kg), and the distribution coefficients (K_d) were determined. The obtained results show that K_d in pure LiCl solution was in the range of 0.9-75.6, while in brine it was in the range of 0.2-2.3. The study indicates that the high affinity for lithium in pure LiCl solution is mostly associated with the non-selective interaction of lithium ions with the graphene oxide matrix (COOH groups). It was also shown that the application of dibenzo-14-crown-4 moiety to graphene oxide modification groups increases the affinity of the composite material for lithium ions compared to an analogous material containing 12-crown-4-ether groups.