DESs are fluids generally composed of two or three cheap and safe components that are capable of self-association, often through hydrogen bond interactions, to form eutectic mixtures with a melting point lower than that of each individual component. DESs are generally liquid at temperatures lower than 100 °C, and they exhibit similar physico-chemical properties to traditional ILs, while being much cheaper and environmentally friendlier. Most of them are mixtures of choline chloride and a hydrogen-bond donor (e.g., urea, ethylene glycol, malonic acid) or mixtures of choline chloride with a hydrated metal salt. Other choline salts (e.g. acetate, citrate, nitrate) have a much higher costs or need to be synthesised,[3] and the DES formulated from these anions are typically much more viscous and can have higher conductivities than for choline chloride.[4] This results in lower plating rates and poorer throwing power and for this reason chloride-based DES systems are still favoured. For instance, Reline (a 1:2 mixture of choline chloride and urea) has been used to selectively recover Zn and Pb from a mixed metal oxide matrix.[5] Similarly, Ethaline (a 1: 2 mixture of choline chloride and ethylene glycol) facilitates metal dissolution in electropolishing of steels.[6] DESs have also demonstrated promising results to recover metals from complex mixtures such Cu/Zn and Ga/As,[7] and precious metals from minerals.[8] It has also been demonstrated that metals can be recovered from complex mixtures by electrocatalysis using a combination of DESs as lixiviants and an oxidising agent,[9] while metal ions can be simultaneously separated from the solution by electrowinning.[10]
Precious metals are rare, naturally occurring metallic chemical elements of high economic value. Chemically, the precious metals tend to be less reactive than most elements. They include gold and silver, but also the so-called platinum group metals: ruthenium, rhodium, palladium, osmium, iridium, and platinum (see precious metals). Extraction of these metals from their corresponding hosting minerals would typically require pyrometallurgy (e.g., roasting), hydrometallurgy (cyanidation), or both as processing routes.
Early studies have demonstrated that gold dissolution rate in Ethaline compares very favourably to the cyanidation method, which is further enhanced by the addition of iodine as an oxidising agent. In an industrial process the iodine has the potential to be employed as an electrocatalyst, whereby it is continuously recovered in situ from the reduced iodide by electrochemical oxidation at the anode of an electrochemical cell. Dissolved metals can be selectively deposited at the cathode by adjusting the electrode potential. The method also allows better selectivity as part of the gangue (e.g., pyrite) tend to be dissolved more slowly.[11]
Sperrylite (PtAs2) and moncheite (PtTe2), which are typically the more abundant platinum minerals in many orthomagmatic deposits, do not react under the same conditions in Ethaline because they are disulphide (pyrite), diarsenide (sperrylite) or ditellurides (calaverite and moncheite) minerals, which are particularly resistant to iodine oxidation. The reaction mechanism by which dissolution of platinum minerals is taking place is still under investigation.
Metal sulfides (e.g., pyrite FeS2, arsenopyrite FeAsS, chalcopyrite CuFeS2) are normally processed by chemical oxidation either in aqueous media or at high temperatures. In fact, most base metals, e.g., aluminium, chromium, must be (electro)chemically reduced at high temperatures by which the process entails a high energy demand, and sometimes large volumes of aqueous waste is generated. In aqueous media chalcopyrite, for instance, is more difficult to dissolve chemically than covellite and chalcocite due to surface effects (formation of polysulfide species,[12][13]). The presence of Cl− ions has been suggested to alter the morphology of any sulfide surface formed, allowing the sulfide mineral to leach more easily by preventing passivation.[14] DESs provide a high Cl− ion concentration and low water content, whilst reducing the need for either high additional salt or acid concentrations, circumventing most oxide chemistry. Thus, the electrodissolution of sulfide minerals has demonstrated promising results in DES media in absence of passivation layers, with the release into the solution of metal ions which could be recovered from solution.
During extraction of copper from copper sulfide minerals with Ethaline, chalcocite (Cu2S) and covellite (CuS) produce a yellow solution, indicating that [CuCl4]2− complex are formed. Meanwhile, in the solution formed from chalcopyrite, Cu2+ and Cu+ species co-exist in solution due to the generation of reducing Fe2+ species at the cathode. The best selective recovery of copper (>97 %) from chalcopyrite can be obtained with a mixed DES of 20 wt.% ChCl-oxalic acid and 80 wt.% Ethaline.[15]
Recovery of metals from oxide matrixes is generally carried out using mineral acids. However, electrochemical dissolution of metal oxides in DES can allow to enhance the dissolution up to more than 10 000 times in pH neutral solutions.[16]
Studies have shown that ionic oxides such as ZnO tend to have high solubility in ChCl:malonic acid, ChCl:urea and Ethaline, which can resemble the solubilities in aqueous acidic solutions, e.g., HCl. Covalent oxides such as TiO2, however, exhibits almost no solubility. The electrochemical dissolution of metal oxides is strongly dependent on the proton activity from the HBD, i.e. capability of the protons to act as oxygen acceptors, and on the temperature. It has been reported that eutectic ionic fluids of lower pH-values, such as ChCl:oxalic acid and ChCl:lactic acid, allow a better solubility than that of higher pH (e.g., ChCl:acetic acid).[17] Hence, different solubilities can be obtained by using, for instance, different carboxylic acids as HBD.[18]