Electrodialysis with Bipolar Membranes to valorise saline waste streams: Analysing the fate of valuable minor elements

Brine mining can represent a valuable non-conventional resource for the extraction of Mg, Li, B, Sr and other Trace Elements (TEs) such as Rb, Cs, whose recoveries require chemical reagents such as alkaline and acidic solutions. In a circular strategy, these required chemicals can be produced in-situ through Electrodialysis with Bipolar Membranes (EDBM). In this work, a laboratory EDBM unit was operated using real brines from Trapani saltworks to investigate, for the first time, the migration of minor and trace ions, as Li, B, Sr, Cs and Rb through ion-exchange membranes (IEMs). Two different operating configurations were tested by feeding real brines: i) only in the salt channel or ii) in both salt and alkaline compartments. Trace ions migration was assessed by determining their apparent transport number in IEMs to better understanding their "fate" within the EDBM process. The use of real solutions in the base channel resulted in a 50 % reduction in the process water demand, while achieving similar overall Current Efficiencies (75-78 %) and Specific Energy Consumptions (1.50-1.80 kWh/kg_NaOH) compared to the reference layout, where real brine was only fed in the salt compartment. Li, Rb, Sr and Cs were mostly transported across the cation-exchange membrane and concentrated in the alkaline channel. Such results lay the ground for the use of complex (multi-ionic) solutions and new designs of the EDBM process that can be operated in integrated chains to valorise saline wastes, reducing water consumption and avoiding the dilution of trace elements before their selective recovery.