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

Abstract

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 (Kd) were determined. The obtained results show that Kd 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.