Processing of Zinnwaldite Wastes to Obtain Lithium and Rubidium Compounds

"Gypsum and limestone methods were examined in this study to process zinnwaldite wastes originating from dressing Sn-W ores mined in the Czech Republic. These wastes containing 0.20-0.30% Li and 0.10-0.20% Rb were subjected to magnetic separation to obtain a zinnwaldite concentrate with 1.36% Li and 0.94% Rb. It was observed that processing of the zinnwaldite concentrate with gypsum resulted in almost 96% recovery of Li into aqueous liquors, whilst rubidium extraction was only 25%. At the same time, it is possible to extract almost 92% Li and Rb from the identical zinnwaldite concentrate if the concentrate is processed by limestone method. Lithium carbonate, a final product of both methods was recovered from the refined sulphate solution using K2CO3 as a precipitation agent and/or from unrefined hydroxide solution using gaseous CO2. In the continuation of this study, rubidium will be separated from carbonate solutions after Li2CO3 precipitation as RbAl(SO4)2, an intermediate for Rb2CO3 production. IntroductionLithium is used as an alloying constituent in lightweight alloys, as a heat transfer medium in nuclear reactors and as a component in primary and secondary batteries. With the development of a new generation of electric vehicles, the lithium demand will dramatically grow. Lithium chemicals find extensive application in many industrial branches such as metallurgical, glass, ceramic and pharmaceutical industries. Rubidium compounds are predominantly used in psychiatry and medicine, in magneto-optic modulators, solid-state lasers, phosphors and components of electrolytes for fuel cells. The four most important lithium minerals are amblygonite, spodumene, petalite, and lepidolite. Spodumene LiAlSi2O6 (6.0-7.5% Li2O) and petalite LiAlSi4O10 (3.5-4.5% Li2O) belong to aluminosilcate minerals. Lepidolite (Li.Al)3(Al.Si)4O10(F.OH)2 (3.30-7.74% Li2O), lithium mica, is the most important representative of the mica minerals, a subgroup of the aluminosilicates. It frequently contains 3–5% Rb2O and eventually caesium. Zinnwaldite, which has the general formula K(Li.Al.Fe)3(Al.Si)4O10(F.OH)2 (2-5% Li2O), is regarded as a variety of lepidolite with a high iron content. Commercial amblygonite is a complex phosphate (Li.Na)Al(F.OH)PO4 (up to 9.88% Li2O), however, its deposits have not been commercially exploited because of their small size. Natural brines with a high lithium chloride content are important in the industrial production of lithium [l]"