This work presents the research results on the development of an innovative, hydrometallurgical technology for the production of manganese(II) perrhenate dihydrate from recycled waste. These wastes are scraps of Ni-based superalloys containing Re and scraps of Li–ion batteries containing Mn—specifically, solutions from the leaching of black mass. This work presents the conditions for the production of Mn(ReO₄)₂·2H₂O. Thus, to obtain Mn(ReO₄)₂·2H₂O, manganese(II) oxide was used, precipitated from the solutions obtained after the leaching of black mass from Li–ion batteries scrap and purified from Cu, Fe and Al (pH = 5.2). MnO₂ precipitation was carried out at a temperature < 50 °C for 30 min using a stoichiometric amount of KMnO₄ in the presence of H₂O₂. MnO₂ precipitated in this way was purified using a 20% H₂SO₄ solution and then H₂O. Purified MnO₂ was then added alternately with a 30% H₂O₂ solution to an aqueous HReO₄ solution. The reaction was conducted at room temperature for 30 min to obtain a pH of 6–7. Mn(ReO₄)₂·2H₂O precipitated by evaporating the solution to dryness was purified by recrystallization from H₂O with the addition of H₂O₂ at least twice. Purified Mn(ReO₄)₂·2H₂O was dried at a temperature of 100–110 °C. Using the described procedure, Mn(ReO₄)₂·2H₂O was obtained with a purity of >99.0%. This technology is an example of the green transformation method, taking into account the 6R principles.

This paper presents comparative experimental results for the single-stage and two-stage counter-current acid leaching of battery masses, with the addition of a booster, from different types of LIB waste. Three different types of battery masses were used in this research: Material I, module car; Material II, tablets and laptops; and Material III, mobile phones. These materials were obtained during the mechanical processing of Li-ion battery waste, which were dried at a temperature in the range of 80–180 °C. Leaching studies of these materials were carried out using the single-stage acid leaching method with the addition of hydrogen peroxide, and the innovative two-stage counter-current acid leaching method, also with the addition of hydrogen peroxide. The single-stage leaching of the battery mass (regardless of the composition of the material) in a 15% or 20% sulfuric acid solution with the addition of 30% H₂O₂ aqueous solution, for 2 h, with a solid-to-liquid-phase ratio of 1:5 or 1:4 at a temperature of 60 °C ensures the leaching of cobalt, nickel, copper and lithium with efficiencies above 95%. On the other hand, the use of an innovative method of two-stage counter-current leaching of the battery mass ensures the leaching of cobalt, nickel, copper and lithium at a level significantly greater than 95%, while obtaining a concentration of cobalt in the leaching solution at a level of nearly 50 g/dm³. It also reduces the leaching time of a single stage to 1 h and, importantly, reduces the amount of waste solutions and the consumption of H₂O₂ and sulfuric acid. The developed method of the two-stage counter-current leaching of battery masses is therefore characterized by high efficiency and low environmental impact, thanks to which it can be used in commercial processes for the recycling of lithium-ion batteries.

This study outlines findings from an investigation into the development of a hydrometallurgical process for manufacturing various forms of zinc perrhenate, entirely from waste from recycling and from the Zn–Pb industry. Scraps of Re-bearing Ni-based superalloys and acidic waste, circulating zinc solutions generated during the production of Zn by the electrolytic method and which contain >45 g/dm³ of Zn, Na, Mn, and Mg, were used in the research. In the publication, the conditions for the production of three types of zinc perrhenate, i.e., Zn(ReO₄)₂·4H₂O, Zn(ReO₄)_2, and Zn(ReO₄)₂·2H₂O, are presented. As a result of the analysis of the obtained results, it was concluded that to obtain the above-mentioned forms of zinc perrhenate, zinc carbonate can be used, precipitated from acidic, waste, and multi-component solutions after their prior neutralization to pH 4.0 and partial purification from Mn, Mg, and Na using metallurgical zinc oxide. Zinc carbonate should be precipitated using Na₂CO₃ at pH 6.3 and subsequently purified from other impurities, i.e., Mg, Na, and Mn, using aqueous ammonia solutions. As a result, zinc carbonate was obtained, which was used in a reaction with an aqueous solution of HReO₄ to produce zinc perrhenate. The precipitated forms of Zn(ReO₄)₂ were obtained by appropriately drying the crude and hydrated Zn(ReO₄)₂ to obtain its tetrahydrate, dihydrate, and anhydrous forms, respectively, using drying temperatures of 55, 135, and 185 °C. The developed technology has been submitted for a patent and is an example of a technology founded on the principles of sustainable development, with a particular emphasis on the minimalization of loss of rhenium and zinc at all stages of its realization.

The work presents the research results regarding the development of an innovative technology for the production of lithium perrhenate. The new technology is based entirely on hydrometallurgical processes. The source of lithium was solutions created during the processing of Li-ion battery masses, and the source of rhenium was perrhenic acid, produced from the scraps of Ni-based superalloys. The research showed that with the use of lithium carbonate, obtained from post-leaching solutions of Li-ion battery waste and properly purified (by washing with water, alcohol, and cyclic purification with CO₂), and perrhenic acid, lithium perrhenate can be obtained. The following conditions: room temperature, time 1 h, 30% excess of lithium carbonate, and rhenium concentration in the acid from 20 g/dm³ to 300 g/dm³, allowed to produce a compound containing a total of 1000 ppm of metal impurities. The developed technology is characterized by the management of all aqueous waste solutions and solid waste and the lack of loss of valuable metals such as rhenium and lithium after the initial precipitation step of lithium carbonate.