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Abstract The paper investigated the possibility of extractive separation of palladium from platinum and rhodium with ionic liquid Cyphos IL 101. A technological solution obtained by dissolving waste materials was used as the test material. Based on the experiments performed, it was found that a 10% (v/v) solution of the Cyphos IL 101 ionic liquid in toluene allows the extraction of both Pd and Pt with an efficiency of 99% from the initial solution when extraction is carried out at the pH 0.5, vorg:vaq phase ratio 1:1 and contact time of 15 min. Moreover, the research proved that it is possible to separate Pd from Pt at the stripping stage using a 0.1 mol/dm3 thiourea solution while maintaining a high selectivity coefficient.

Abstract The objective of this study was to assess the potential for recovering precious metals from technological solutions using an ion-exchange dynamic method. Precious metals like platinum, palladium, rhodium, and gold are essential materials in various industries such as: automotive, electronics, pharmaceuticals, and jewellery. Due to their limited occurrence in primary sources, there is a growing trend in the market to extract these metals from secondary sources. The research involved conducting sorption and elution tests under different parameters to investigate their impact on the process in dynamic conditions. Additionally, an attempt was made to calculate the operational and total capacity of the resins, which has not been done previously for industrial solutions. The results showed that using Puromet MTS9200, Puromet MTS9850, and Lewatit MonoPlus MP600 resins, the sorption process could be effectively carried out in dynamic conditions with a contact time of 5 min between the technological solution and the resin bed. For optimal elution, the contact time between the eluent solution and the bed should range between 10 and 30 min. To improve rhodium sorption efficiency, it was found that neutralizing the technological solution to a pH of approximately 7 and using Lewatit MonoPlus MP600 resin could be beneficial.

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.

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.

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.

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.

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 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.

The article presents a new method of producing anhydrous nickel(II) perrhenate of high purity, entirely from waste from the national Cu industry. This method consists mainly of the reaction of water-washed nickel(II) oxide (obtained by purification in a mixture of alcohols, and subsequent roasting of the Ni-containing sulfate semi-finished products (NSP) at 1200 °C) with perrhenic acid (obtained using the ion exchange method). After the dissolution of nickel(II) oxide in the acid (at a temperature in the range of 60–80 °C) and obtaining a pH of 5–8, the solution is sent to evaporate to dryness, also at a temperature not exceeding 80 °C. The obtained crude nickel(II) perrhenate is washed with methanol and subsequently dried at 160 °C to obtain its anhydrous form, with the following composition: 10.5% of Ni; 66.6% of Re;

Rhenium is an element that exhibits a broad range of oxidation states. Synthesis paths of selected rhenium compounds in its seventh oxidation state, which are common precursors for organic reaction catalysts, were presented in this paper. Production technologies for copper perrhenate, aluminum perrhenate as well as the ammonia complex of cobalt perrhenate, are thoroughly described. An ion exchange method, based on Al or Cu metal ion sorption and subsequent elution by aqueous perrhenic acid solutions, was used to obtain perrhenates. The produced solutions were neutralized to afford the targeted aluminum perrhenate and copper perrhenate products in high purity. The developed technologies allow one to manage the wastes from the production of these perrhenates as most streams were recycled. Hexaamminecobalt(III) perrhenate was produced by a newly developed method enabling us to produce a high purity compound in a reaction of spent hexaamminecobalt(III) chloride solution with a perrhenic acid. All prepared compounds are the basis for precursor preparation in organic catalysis.

The precipitation of tannin complex of germanium from sulfuric solutions obtained after dross leaching was investigated. The tested solutions contained mainly zinc, germanium, indium, and tin. The influence of temperature, time, amount of added tannic acid and its purity was determined. The application of pure tannic acid allowed the precipitation of >99% of germanium and decreased its concentration in a solution 99% Sn and reduced its concentration in the solution below 0.025 g/dm3.

Methods for the preparation of selected metal perrhenates and their mixtures are presented in this paper. These materials are suitable for reduction, and therefore for production of alloy powders containing rhenium and other superalloy components, i.e., Cr, Ni and Co. Prepared compounds may be also used as substrates for electrowinning of binary and ternary rhenium alloys. All developed methods are based on an ion exchange technique. This technique allows management of waste solutions, limitation of valuable metals losses, and, importantly, production of high-purity components.

Leaching of the dross containing 28.7% Sn, 18.0 Pb, 10.6% Cu, 8.9% Ge, 8.1% Zn, and 2.7% In in sulphuric and oxalic acid solution was investigated. The dross was obtained from thermal oxidation of by-product alloy generated during a New Jersey (NJ) zinc rectification process. The influence of different process conditions (temperature, time, acid concentration, and solid to liquid ratio) on leaching yield of the main components was determined. Additionally, the impact of oxidant (hydrogen peroxide, sodium hypochlorite, manganese (IV) oxide) addition on leachabilities was investigated. Germanium leaching yields exceeding 80% were observed for both sulphuric and oxalic acid solutions. Indium leachability in H2C2O4(aq) was found at the level of 20%, while in H2SO4(aq), it strongly depends on process temperature, and reached 80% at 80 °C.

This paper is devoted to the preparation of high-purity anhydrous nanocrystalline cesium perrhenate, which is applied in catalyst preparation. It was found that anhydrous cesium perrhenate with a crystal size