Sustainable recovery of critical elements from seawater saltworks bitterns by integration of high selective sorbents and reactive precipitation and crystallisation: Developing the probe of concept with on-site produced chemicals and energy

The availability of raw mineral resources containing elements included in the Critical Raw Materials (CRMs) list is a growing concern for the European Union. Sea mining has been identified as a promising secondary source. In particular, brines obtained in solar saltworks (bitterns) contain relevant amounts of valuable CRMs such as Mg(II), B(III), other alkaline/alkaline earth metals (Rb(I), Cs(I), Sr(II)) and transition/post-transition elements (Co(II), Ga(III), Ge(IV)). However, the low concentration of some of these elements (µg/L) requires an effort to develop recovery routes that are sustainable and economically feasible where the required chemicals and energy are produced on-site from the saltworks bitterns (i.e. HCl and NaOH). Even the conventional recovery processes such as ion exchange, sorption and precipitation, which have proved to be competitive for metals recovery, are challenged in the case of Trace Elements (TEs). This work studies the recovery of TEs included in the CRMs list from saltworks bitterns after ion exchange processes. First, batch crystallisation and reactive precipitation were tested for some target elements in single-component solutions: Sr(II), Co(II), Ga(III), Ge(IV) and B(III). Then, the experiments were carried out with multi-component synthetic solutions assuming different scenarios of bittern streams coming out a selective extraction stage using sorption and ion exchange processes. The targeted elements were recovered except for Ge(IV), where alternative routes need to be evaluated, as its precipitation involves the use of tannic acid or sulphide solutions that could not be produced from the bitterns. However, a further concentration step would be necessary to achieve element concentrations closer to the mineral phases saturation. Moreover, model simulations were performed using the PHREEQC program, which provided a good prediction of the experimental trends obtained in most cases.