Dorota Kopyto

This paper presents the research results on the synthesis of rhenium catalysts MTO, Re₂O₇/Al₂O₃, and M-Re₂O₇/Al₂O₃ (where M = Ni, Ag, Co, Cu) from rhenium compounds (ammonium perrhenate, perrhenic acid, nickel(II) perrhenate, cobalt(II) perrhenate, zinc perrhenate, silver perrhenate, and copper(II) perrhenate) derived from waste materials. Methyltrioxorhenium (MTO) was obtained from silver perrhenate with a yield of over 80%, whereas when using nickel(II), cobalt(II), and zinc perrhenates, the product was contaminated with tin compounds and the yield did not exceed 17%. The Re₂O₇/Al₂O₃ and M-Re₂O₇/Al₂O₃ catalysts were obtained from the above-mentioned rhenium compounds. Alumina obtained in a calcination process of aluminum nitrate nonahydrate was used as a support. The catalysts were characterized in terms of their chemical and phase composition and physicochemical properties. Catalytic activity in model reactions, such as cyclohexene epoxidation and hex-1-ene homometathesis, was also studied. MTO obtained from silver perrhenate showed >70% activity in the epoxidation reaction, thus surpassing commercial MTO (1.0 mol% MTO, room temperature, and reaction time—2 h). Ag-Re₂O₇/Al₂O₃, Cu-Re₂O₇/Al₂O₃, and H-Re₂O₇/Al₂O₃ catalysts were inactive, while Co-Re₂O₇/Al₂O₃ and Ni-Re₂O₇/Al₂O₃ showed low activity (70% activity in this reaction (2.5 wt% Re, room temperature, and reaction time—2 h). The results indicate the potential of using rhenium compounds derived from waste materials to synthesize active catalysts for chemical processes.

This paper presents a method for obtaining cobalt(II) perrhenate from waste derived from two types of materials, i.e., Li-ion battery scrap, or more precisely, battery mass, and superalloy scrap. Both of the above-mentioned materials are a source of Co. However, a source of rhenium is perrhenic acid produced from ammonium perrhenate (recycled) by the ion exchange method using resins. Co(OH)₂ can be precipitated from solutions resulting from the leaching of Li-ion battery mass, sludge from the Zn-Pb industry and superalloy scrap. The compound, after proper purification, can be used in a reaction with perrhenic acid to form Co(ReO₄)₂. The reaction should be conducted under the following conditions: time 1 h, room temperature, 30% excess of cobalt(II) hydroxide, and rhenium concentration in HReO₄ from about 20 g/dm³ to 300 g/dm³. This work shows that with the use of Co(OH)_2, obtained from waste, an anhydrous form of cobalt(II) perrhenate can be obtained, containing < 1000 ppm of the cumulative metal impurities.

Laboratory tests were conducted for the production of high-purity perrhenic acid using a membrane technique—electrodialysis. Four solutions were used in the tests: diluate, concentrate, anolyte, and catholyte. The experiments were carried out in a two-stream system. The influence of basic process parameters, including the flow rate of process streams or current density, on the purity of the obtained perrhenic acid were examined. Electrodialysis was also carried out as part of this research, aiming to concentrate the perrhenic acid >100 g/dm³. The concentrate solution obtained in the concentration tests, with a concentration of 148.7 g/dm³ HReO₄ and 530 mg/dm³ NH₄⁺, was then sent to the purification process using the electrodialysis method. The purification process was carried out until the concentration of NH₄⁺ ions was 3 in the concentrate. Finally, perrhenic acid was obtained with the following composition: 169.7 g/dm³ HReO₄ and 70 mg/dm³ NH₄⁺. Based on this research, a technological scheme for producing high-purity HReO₄ by electrodialysis was developed.

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.

Methods for obtaining high-purity perrhenic acid (with metallic impurities content below 100 ppm) of a high concentration > 200 g/dm³ and entirely from secondary raw materials were compared. Comparative analyses of three methods were performed: electrodialysis, solvent extraction (research carried out directly as part of the Small Grant project acronym RenMet), and ion-exchange (developed as part of previous projects implemented by Łukasiewicz-IMN). The basic process parameters were selected as comparative indicators: efficiency and selectivity of the process, purity of the obtained product, availability and consumption of raw materials and reagents, equipment necessary to carry out the process, the profitability of the technology, and the ecological aspects, i.e., the possibility of managing the generated solid waste and post-production solutions. Analysis of the verified indicators allowed us to select the most economically and ecologically advantageous method of obtaining high-purity perrhenic acid from secondary raw materials. Its preparation using the ion-exchange method emphasizes the product’s purity and the process’s simplicity, using readily available waste materials and renewable ion-exchange resin, and is based on a sustainable circular economy.

The aim of this work was to develop an effective method for obtaining perrhenic acid from available ammonia waste solutions using the solvent extraction method. An ammonia waste solution was used as the test material, with Re and NH₄⁺ concentrations of 13.5 and 43.7 g/dm³, respectively. The scope of this study includes the following: the selection of an appropriate extractant for testing, and the examination of the impact of individual parameters on the efficiency and selectivity of extraction and stripping. The obtained results made it possible to determine the conditions for the production of perrhenic acid via the extraction method using organic solutions of trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101). The outcome of this study was the development of a method for obtaining perrhenic acid and the production of the acid sample with an efficiency of >90% and a Re concentration of >100 g/dm³.

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.

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.

This research aimed to evaluate the effectiveness of new organic substances, including a novel ionic liquid based on polyhexamethylenebiguanidine, polyhexamethyleneguanidine, and safranin in the copper electrorefining process. Experiments were conducted on a small laboratory scale using industrial copper anodes. Single doses of new additives did not improve process indicators (current efficiency, average cell voltage, specific energy consumption) or the quality of copper cathode deposits. However, a combination of a new ionic liquid based on polyhexamethylenebiguanidine and thiourea resulted in a satisfactory current efficiency of 97%, an average cell voltage of 0.110 V, a low specific energy consumption index of approximately 100 kWh/t_Cu, and smooth cathode surfaces. These results were superior to those obtained with industrial additives (bone glue and thiourea). The findings enhance our understanding of how these substances influence the electrorefining process and suggest the potential for more efficient and sustainable methods. Further research is recommended to validate these findings and explore their industrial applications.

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.