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Article

Recovery of Zinc and Rhenium for the Production of Zinc Perrhenates

by
Katarzyna Leszczyńska-Sejda
*,
Joanna Malarz
,
Dorota Kopyto
,
Karolina Goc
,
Alicja Grzybek
,
Mateusz Ciszewski
,
Arkadiusz Palmowski
,
Grzegorz Benke
and
Karolina Pianowska
Łukasiewicz Research Network—Institute of Non-Ferrous Metals, Sowińskiego 5, 44-100 Gliwice, Poland
*
Author to whom correspondence should be addressed.
Crystals 2024, 14(8), 725; https://doi.org/10.3390/cryst14080725
Submission received: 27 June 2024 / Revised: 3 August 2024 / Accepted: 11 August 2024 / Published: 14 August 2024
(This article belongs to the Topic Advances in Inorganic Synthesis)
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Versions Notes

Abstract

:
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.

Graphical Abstract

1. Introduction

Zinc is a widely known and used metal. It is not included in the group of critical raw materials for the EU [1,2,3]. However, it is certainly a valuable metal with many applications, the resources of which are decreasing significantly from year to year [4,5,6]. Zinc is a transition metal known primarily for its high corrosion resistance [7,8,9]. This metal is essential for life, playing a key role in many biological processes [10,11,12]. It is used in many areas, such as steel and paint production (as a white pigment), as well as in the cosmetic industry [13,14,15]. Zn is also a component of a lot of alloys, such as brass, which increases its use in the industry [16,17,18]. In medicine, zinc is often used in dietary supplements due to its role in the functioning of the immune system [10,19,20]. The chemical properties of zinc determine its uses. Thus, zinc has a density of 7.14 g/cm3, a melting point of 419.5 °C, and, at the same time, a boiling point of 907 °C. It conducts electricity, has magnetic properties, is diamagnetic, and has a Mohs hardness of 2.5 [21,22,23]. Due to its wide range of applications and distinctive properties, this metal continues to be a focal point of research for numerous scientists across various disciplines.
On the other hand, rhenium is a specific metal, mainly due to the fact that it occurs extremely rarely in nature but also because of its price and niche applications. Rhenium application possibilities are determined by its chemical properties. It is mainly used in the production of superalloys and catalysis [24,25,26]. Rhenium shows exceptional physical properties, including an extremely elevated melting temperature exceeding 3180 °C, considerable density (21.0 g/cm3), substantial hardness (7 on the Mohs scale), and resistance to both heat and chemical reactions [24,27,28]. It can be produced from raw materials, as it is often found alongside copper in its ores. However, in recent years, the focus has shifted towards obtaining this metal through recycling, such as from superalloys [24].
Global rhenium production reaches approximately 56-75 metric tons annually. Most of the production stems from primary sources, with Chile being the leading manufacturer, followed by the United States and Poland. In contrast, recycling processes contribute 8 tons to the annual production of this element [24,29,30]. The main players in the area of Re-recycling are the USA, Germany, Czechia, Canada, and Poland [30,31,32]. Meanwhile, the world’s annual production of zinc is 10–13 million tons. One-third of the zinc production comes from China, although other countries also play an important role, like Peru (1.4 million tons), Australia (1.3 million tons), India (0.8 million tons), and the USA (780 thousand tons) [33,34,35].
Both rhenium and zinc are produced in Poland. Rhenium is produced from primary raw materials by KGHM Polska Miedź S.A. [36,37,38] and from secondary raw materials by Innovator Sp. z o. o. [39,40]. Zinc in Poland is produced by ZGH “Bolesław” S.A. using an electrochemical method (80 thousand tons/year) and by HCM “Miasteczko Śląskie” S.A. using a metallurgical method (80 thousand tons/year). During electrolytic zinc production in Poland, many sulfate solutions are created containing significant amounts of Zn and other impurities such as Mg, Na, and Mn. These solutions constitute waste for zinc recovery in this technology [41,42,43].
This work describes the preparation of three forms of zinc perrhenate, which is a stable rhenium salt in the seventh oxidation state [44,45,46]. This compound, like other perrhenates: ammonium, rubidium, nickel, cobalt, cesium, chromium, aluminum, manganese, and lithium, can be used for the production of alloys and catalysts or in medicine [24,47,48]. The objective of this study was to synthesize a compound that would integrate the distinctive properties of both rhenium and zinc, thereby expanding its potential applications in fields such as catalysis, alloy production, and even medicine [24].
Existing publications offer limited information on zinc perrhenate. There are only several publications on the preparation, properties, and use of Zn(ReO4)2.
The first mention of the preparation of zinc perrhenate dates back to 1933 and was described in Z. Anorg. Allg. Ch. by E. Wilke-Dörfurt and T. Gunzert. The authors of this publication conducted research on the production of rhenium salts and showed that zinc perrhenate can be obtained in a reaction between HReO4 and ZnCO3 [49].
At the beginning of the second half of the 20th century, W.T. Smith and G.E. Maxwell researched the production of zinc perrhenate tetrahydrate in a reaction between zinc hydroxide, zinc oxide or zinc carbonate, and perrhenic acid [50].
Meanwhile, H. G. Mayfield, Jr., and W. E. Bull in 1969 detailed the process of forming zinc perrhenate complexes with pyridine [51].
In 1978, K. Skudlarski, J. Kapała, and M. Kowalska determined the vapor pressure of thermal decomposition products and the enthalpy of the decomposition reaction of zinc perrhenate. As part of these studies, they found that zinc perrhenate decomposes into zinc oxide in the solid phase and rhenium(VII) oxide in the gaseous form [52].
In 1982, Russian scientists L.L. Zajtseva, A.V. Velichko, A.V. Demin, A.I. Sukhikh, and N.V. Morgunov described the production of zinc perrhenate tetrahydrate as a result of the reaction of zinc oxide or zinc carbonate (IV) with perrhenic acid. This publication also describes the results of the chemical and thermal analysis, infrared spectroscopy, and X-ray phase analysis. The investigation was conducted to ascertain the composition and examine the physicochemical properties of zinc perrhenate [53].
In 1982, an article was published in Transition Met. Chem. described a reaction of zinc perrhenate with an aqueous ammonia solution, in which the [Zn(NH3)4](ReO4)2 complex was formed [54].
In turn, A. Butz, I. Svoboda, H. Paulus, and H. Fuess researched the preparation of zinc perrhenate tetrahydrate in the reaction between ZnCO3 and HReO4. The reaction was carried out at 50–60 °C in a CO2 atmosphere. After the reaction was completed, the excess carbonate was filtered off, and the solution was left in a water bath at 56 °C until crystals of zinc perrhenate tetrahydrate precipitated. The authors also presented the crystallographic structure of zinc perrhenate tetrahydrate, which showed that the compound had an octahedral structure. The diamagnetic properties of Zn(ReO4)2∙4H2O were also demonstrated. It was determined that the compound undergoes two-stage dehydration below 200 °C. The publication also focused on the physicochemical properties of this compound, describing that the melting point of zinc perrhenate is 748 °C and the complete decomposition of the hydrate occurs in the temperature range of 740–1130 °C [55].
However, in an article written by J. Wang, L. Zhang, T. Li, and K. Zhang, the influence of the addition of zinc perrhenate to lubricants was described, where it acted as a friction-reducing agent [56].
In 1998, in Jour. Salt. St. Chem., the dehydration process results of zinc perrhenate dihydrate and tetrahydrate were published [57].
In 2020, a crystallographic analysis of zinc perrhenate was presented. It showed that Zn(ReO4)2 crystallizes in the trigonal space group. The structure was established as two-dimensional [58].
In 1968, K. Ulbricht and H. Kriegsmann conducted Ramman and IR spectroscopy analyses. The researchers scrutinized how the crystalline structure and cationic characteristics impact the internal molecular vibrations of zinc perrhenate. Zinc perrhenate was obtained in the reaction between zinc oxide and perrhenic acid [59].
In an American patent, no. US 4027004A, a method for producing zinc perrhenate from zinc oxide and rhenium(VI) oxide was described. This process was conducted at a pressure of 58 kbar and a temperature of 1300 °C for an hour. Zinc perrhenate produced in this way could be used in electronic components, e.g., resistors [60].
Most of the above-mentioned publications and research focus on synthesizing the compound from commercially available materials and not from waste. Such an approach is in accordance with the principles of sustainable development, helping to save the natural reserves of those metals. However, that is not the only advantage. By utilizing existing waste from specific industries and companies, recycling efforts can be enhanced, and product portfolios can be diversified through the creation of a new compound. This innovation can potentially open up new revenue streams. Moreover, production costs are minimized in this scenario, as no new materials need to be purchased, and manufacturers can often repurpose existing equipment for this production process.
In summary, this study outlines a comprehensive hydrometallurgical process for the production of zinc perrhenate, in which both Re and Zn were recovered from waste materials. The developed technology is distinguished by no losses of rhenium and zinc via the management of all waste generated during the process [61,62,63].

2. Materials and Methods

Perrhenic acid utilized in this study was produced through the leaching of superalloy scrap with a granulation of less than 1 mm. The leaching agent in this process was sulfuric acid with oxidizing agents (hydrogen peroxide and/or nitric acid). The diverse compositions of the superalloy scraps are presented in Table 1. In addition to rhenium, these materials also contained substantial amounts of nickel (43–53%), cobalt (7–22%), chromium (4–10%), aluminum (13–15%), and iron (up to 1.3%). This leaching process yielded a solution containing 1.5 g/dm3 of rhenium but also nickel, as well as cobalt, iron, chromium, and aluminum. This solution was directed to the recovery of rhenium as ammonium perrhenate (catalytic purity, Innovator, Gliwice, Poland), using a technology developed at the Łukasiewicz Research Network—Institute of Non-Ferrous Metals (Łukasiewicz-IMN). Then, using this technology, perrhenic acid was obtained, containing 15–500 g/dm3 of Re, <0.0001% of Ca, <0.0001% of K, <0.0001% of Mg, <0.0001% of Cu, <0.0001% of Na, <0.0001% of Mo, <0.0001% of Ni, <0.0001% of Pb, <0.0001% of Fe, <0.0001% of NH4+, <0.0001% of Bi, <0.0001% of Zn, <0.0001% of W, <0.0001% of As, and <0.0001% of Al (Innovator; Gliwice; Polska) [64,65].
Solutions obtained during the electrolytic production of Zn, which constitute an acidic, waste, multi-component material, were used as a source of zinc. In addition to zinc, the solutions used in the experiments also contained significant amounts of Mg (14–17%), Mn (~5.2%), Na (6–8%), and a large amount of free acid (even up to 185 g/dm3). The compositions of the solutions used in the tests are summarized in Table 2.
One zinc solution was used in the tests, obtained by combining the solutions whose compositions are presented in Table 2. The solution obtained after the combination contained 53.4 g/dm3 of Zn, 16.2 g/dm3 of Mg, 5.2 g/dm3 of Mn, 7.1 g/dm3 of Na, and 178.4 g/dm3 of H2SO4.
The following materials were utilized in the research: metallurgical ZnO (>90%, ZGH Bolesław, Bukowno, Poland), CaCO3 (p.a., Chempur, Piekary Śląskie, Poland), Na2CO3 (p.a., Chempur, Piekary Śląskie, Poland), NH4HCO3 (p.a., Chempur, Piekary Śląskie, Poland), NH3 (25%, p.a., Chempur, Piekary Śląskie, Poland).

3. Methods

3.1. Methodology for the Neutralization of Free Sulfuric Acid in Zn Solutions

A total of 3 dm3 of acidic, waste, multi-component zinc solution was poured into a beaker equipped with a mechanical stirrer. This solution was continuously stirred while maintaining a temperature of ~40 °C. Calcium carbonate or metallurgical zinc oxide were added to the solution in portions until the pH was in the range of 3.5–4.5. The mixture was mixed for 1 h and then, after that, filtered. The obtained precipitate was washed with hot water on a filter. In this way, a solution was obtained, which was sent to the stage of zinc carbonate precipitation. The reactions can occur as follows:
H2SO4 + CaCO3 → CaSO4 + H2O + CO2
H2SO4 + ZnO → ZnSO4 +H2O

3.2. Methodology for the Precipitation of Zinc Carbonate

A total of 1 dm3 of the solution obtained after the neutralization of free acid (pH = 4.0) using metallurgical ZnO was poured into a beaker equipped with a mechanical stirrer. During continuous stirring at room temperature, sodium carbonate or ammonium bicarbonate were added in their solid form until the pH of the solution reached 5.1–5.4, and then as solutions with concentrations of 300 g/dm3 and 250 g/dm3, respectively, to the pH of 6.0–7.2. In the experiments, the excess of the precipitating agent, ranging from 0 to 50%, was tested. Carbonate solutions were dosed in portions due to the rapid formation of foam. The mixture was stirred for 2 h and then filtered. The precipitate was washed with a small amount of water, and then a part of it was dried at 110 °C until a stable mass was achieved in order to perform chemical analysis.
The reaction can occur as follows:
ZnSO4 + CaCO3 → ZnCO3 + CaSO4

3.3. Methodology for the Purification of Zinc Carbonate

A total of 200 g of wet zinc carbonate obtained during the precipitation tests was put in a glass beaker equipped with a magnetic stirrer and a heating plate. An aqueous ammonia solution with a concentration of 25% was added in the amount of 0.2–0.6 dm3 for each 100 g of the precipitate. The mixture was then stirred at room temperature for an hour. The undissolved residue was separated by filtration. The clear post-filtration solution was heated to ~100 °C with constant stirring in order to remove ammonia and re-precipitate purified zinc carbonate. Purified zinc carbonate was filtered, and a part of it was dried at 110 °C until a stable mass was achieved in order to perform chemical analyses.

3.4. Methodology for Obtaining Various Forms of Zinc Perrhenate

Zinc carbonate obtained after ammonia purification was used for research on the production of zinc perrhenate. Investigations into the production of zinc perrhenate were conducted to check the impact of rhenium concentration in perrhenic acid and the resulting pH, influenced by the excess of zinc carbonate, on the efficiency of zinc perrhenate precipitation. This study also considered the purity of the obtained compounds. Four concentrations of perrhenic acid were examined: 15, 50, 295, and 500 g/dm3. To assess the effect of perrhenic acid concentration, an excess of zinc carbonate was applied, resulting in pH values ranging from 6.0 to 8.0. These tests were performed at room temperature for 1 h. Due to the significant differences in rhenium concentrations, samples of varying volumes were used: 1 dm3 for 15 g/dm3 Re acid and 0.5 and 0.05 dm3 for higher rhenium concentrations, respectively. Following neutralization, the residue was filtered, and the solution was concentrated to dryness at a temperature not exceeding 80 °C. A portion of the precipitate was dried at 180 °C for analytical purposes. The remaining samples of zinc perrhenate were dried using a WPS 210S moisture analyzer from Mettler Tolledo in a temperature range of 40 to 200 °C to determine the temperature values at which three forms of zinc perrhenate identified in the literature can be obtained. The reaction occurs as follows:
ZnCO3 + 2HReO4 → Zn(ReO4)2 + H2O + CO2

4. Chemical Analysis

All analyses were conducted at the Analytical Chemistry Centre and Functional Materials Centre (Łukasiewicz Research Network—Institute of Non-Ferrous Metals, Gliwice, Poland).
The rhenium content in Zn(ReO4)2 and HReO4 was quantified using a thin-layer X-ray fluorescence spectrometer (ZSX Primus, Rigaku, Tokyo, Japan). Additionally, the ammonium ions present in the aqueous perrhenic acid solution were determined through distillation, followed by titration using the Nessler method.
The concentrations of Zn, Pb, Bi, Cu, Mo, W, As, Al, Mn, Cr, Ca, K, Mg, Na, Fe, Co, and Ni were determined using the following instrumental techniques: graphite furnace atomic absorption spectroscopy (Z-2000, HITACHI, Tokyo, Japan), inductively coupled plasma—mass spectroscopy (Nexion, PerkinElmer, Waltham, MA, USA), inductively coupled plasma—optical emission spectroscopy (ULTIMA 2, HORIBA Jobin-Ivon, Kyoto, Japan; and Optima 5300 V, PerkinElmer, Waltham, MA, USA), and flame atomic absorption spectrometry (THERMO SOLAAR S4, Thermo Fisher Scientific, Waltham, MA, USA, with a flame module and deuterium background correction).
XRD analyses were performed using a Rigaku MiniFlex 600 XRD diffractometer, supplied with an X-ray tube with a wavelength of 1.5406 Å and a stripe detector, silicon D/TeX, and a high-resolution 2.5” Soller slit on the primary and scattered beam.
SEM-EDS analyses were performed using a Zeiss Gemini 1525 scanning electron microscope (Zeiss, Oberkochen, Germany) of high resolution, supplied with a Quantax xFlash®6 Bruker Nano X-ray spectrometer.
The temperature effect on the zinc carbonate structure was determined using differential thermal analysis (DTA). Measurements were made using an STA (DTA/TG) Netzsch F3 Jupiter device in an argon atmosphere. A total of 3 DTA/TG measurements were performed, ranging from room temperature to 1200 °C for zinc carbonate at a heating rate of 10 °C/min and a cooling rate of 30 °C/min. Al2O3 crucibles were used for measurements. The source data were read using the software OriginLab included with the device and presented in the form of graphs of the DTA (heat flow) and TG (percentage of mass) signals as a function of temperature. Based on them, characteristic transformation and degradation temperatures were determined.

5. Results and Discussion

5.1. Test Results on the Neutralization of Free Sulfuric Acid

The first stage of the research was the neutralization of the free sulfuric acid contained in the test solution. Two materials were used for neutralization: finely ground chalk (CaCO3) and metallurgical zinc oxide, purified from chlorides and fluorides containing 63.5% Zn. In both cases, the neutralization of the solution was carried out until the assumed pH values were achieved: 3.5, 4.0, and 4.5. Table 3 shows the compositions of the solutions obtained as a result of the neutralization with CaCO3, and Table 4 shows the compositions of solutions after the neutralization with ZnO.
Tests have shown that both materials effectively eliminated free sulfuric acid. When neutralized with chalk, a gypsum deposit was formed, which can be used as an additive in the production of cement. Zinc losses while using CaCO3 were low, and the highest loss was 2.6% after reaching the pH of 4.5. The data in Table 3 also show that there was no change in the concentration of Mg, Mn, and Na in the solutions.
The use of zinc oxide for neutralization obviously caused an increase in the zinc concentration in the solution, proportional to the initial acid content. In both cases, changes in Mg, Mn, and Na concentrations were insignificant, as shown in Table 4.

5.2. Test Results on the Precipitation of ZnCO3 from Neutralized Solutions

Zinc carbonate precipitation tests were carried out for two precipitating agents (sodium carbonate and ammonium bicarbonate). The excess precipitating agent was tested in the range of 0 to 50%. Table 4 and Table 5 summarize the results of the tests on the precipitation of zinc carbonate using sodium carbonate, and Table 6 and Table 7—use ammonium bicarbonate. The comparison of the precipitation efficiencies is also shown in Figure 1, Figure 2 and Figure 3.
Based on the results included in Table 5 and Table 6, it can be concluded that the excess of the precipitating agent did not influence the precipitation efficiency, as it stayed above 97% throughout the entire process. The lowest efficiency of 97.23% was obtained after using 50% excess precipitating agent. In all cases, similar amounts of the compound were obtained (121.4–122.2 g), which contained around 60% moisture each time. The biggest impurities in ZnCO3 were Mg (up to 3.2%) and Na (up to 3.6%). ZnCO3, obtained without the use of excess precipitating agents, was the most impure one.
The results obtained using ammonium bicarbonate as the precipitating agent were very similar to the ones obtained using calcium carbonate, mostly in relation to the amount of compound obtained, its moisture content, and purity. In this case, the precipitation efficiency was above 95% no matter the excess of the precipitating agent, as is shown in Table 7 and Table 8. However, similar to using CaCO3, the lowest one (95.9%) was obtained while using 50% excess of the precipitating agent.
The analysis of the results of the conducted experiments allowed us to conclude that the precipitation of zinc carbonate should be carried out in two stages: by adding solid Na2CO3 to the pH in the range of 5.1–5.4 and then by adding Na2CO3 solution (300 g/dm3) until the pH of 6.3 is obtained. As can be seen, with the increase in the excess of both precipitating agents, the efficiency of Zn precipitation decreased slightly, and the content of other impurities also decreased. Using both precipitating agents in the entire tested range, high precipitation efficiencies of >95% were obtained. Therefore, it was decided that the 10% excess of the precipitating agent (sodium carbonate) should be used to precipitate zinc carbonate. In each case, significant amounts of magnesium, manganese, and sodium were observed in the obtained products (zinc carbonates), amounting to 2.0–3.4%, 0.9–1.3%, and 2.1–3.6%, respectively. Therefore, these carbonates were purified using aqueous ammonia solutions.

5.3. Test Results on the Purification of Zinc Carbonate

Various amounts of a 25% aqueous ammonia solution were used to study the purification of zinc carbonate. Table 9 summarizes the results of the tests conducted.
It was decided that to completely purify zinc carbonate precipitated from acidic, waste, and multi-component solutions generated during the production of electrolytic zinc, a minimum of 0.4 dm3 of aqueous ammonia solution should be used for each 100 g of crude, wet precipitate. In those conditions, it was possible to remove the impurities to the corresponding levels: <0.01 of Mg, <0.01 of Mn, and 0.10 of Na.
The solution obtained after the purification step had significant amounts of Mg, Mn, and Na, which should be sent to the recovery step of those metals using known methods. The purified ammonia solution could be recirculated to the HReO4 production step.
SEM-EDS (Figure 3 and Figure 4), as well as DTA and TG (Figure 5) analyses, were performed for the purified zinc carbonate.
All the performed analyses confirmed that, as a result of the proposed method, high-purity zinc carbonate could be obtained from the acidic, waste, multi-component solution generated during the production of electrolytic zinc in the Polish steelworks.

5.4. Test Results on Obtaining Various Forms of Zinc Perrhenate

Zinc carbonate, after purification with ammonia solution, was used for the research on the production of zinc perrhenate (the composition of ZnCO3 is presented in Table 9—samples 3–5). The outcomes of the experiments examining the impact of Re concentration in perrhenic acid on the precipitation efficiency of zinc perrhenate are presented in Table 10 and Figure 6.
A pronounced impact of rhenium concentration (ranging from 15 to 500 g/dm3) on the zinc perrhenate precipitation efficiency is apparent. The precipitation efficiency increased with the increasing Re concentration in HReO4 (from 59.7% for 15 g/dm3 of Re to 99.1% for 295 g/dm3 of Re). For this reason, it was concluded that the precipitation of the above-mentioned compound should be carried out using higher acid concentrations, i.e., >295 g/dm3 of Re. The precipitation of zinc perrhenate using higher concentrations of rhenium in perrhenic acid is consistent with the principle of sustainable development, as the utilization of more concentrated mixtures reduces the volume of generated waste.
The effect of pH on the efficiency of zinc perrhenate precipitation was also researched. The tests were conducted at the resultant pH in the range of 6.0 to 7.8 for 1 h at room temperature for the acid with a rhenium concentration of 295 g/dm3. Following neutralization, the solution underwent filtration to remove residue and was then successively concentrated to dryness at a temperature not surpassing 80 °C, after which it was dried at 180 °C. The results of the tests on the influence of pH on the efficiency of the obtained compound are presented in Table 11 and Figure 7.
The investigation revealed that the efficiency of zinc perrhenate precipitation was not significantly impacted by the pH values in the tested range, as can be seen in the results included in Table 11. For the pH range of 6.5–8.0, very similar efficiencies of precipitation of the target compound were obtained, above 90%. The lowest efficiency was obtained while conducting the experiments at pH 6, and it reached 79.4%. Therefore, it can certainly be said that in order to obtain zinc perrhenate, the process should be conducted at a pH of 6.5–8.0. However, it should be emphasized that an increasingly higher pH is associated with unnecessary technological problems as a larger mass of produced solid waste has to be recycled; therefore, the pH of the process should be 6.5.
For the selected zinc perrhenate precipitated at pH 6.5 and dried at 180 °C, analyses of its composition were performed; the test results are presented in Table 12. Additionally, an XRD analysis was performed (Figure 8). For the precipitated zinc perrhenate, drying tests were carried out to obtain various forms of zinc perrhenate (Figure 9). The scheme of the zinc perrhenate production method is shown in Figure 10.
Using a drying temperature of 55 °C, we were able to obtain a compound corresponding to the tetrahydrate form of zinc perrhenate, while 135 °C allowed us to obtain a compound corresponding to the dihydrate form of zinc perrhenate. The composition of the compound obtained when dried at 185 °C corresponds to the anhydrous form of zinc perrhenate. XRD analysis was performed for zinc perrhenate dried at 180 °C. XRD analysis showed that the vast majority of the compound was the anhydrous form of zinc perrhenate, and there was only a minimal amount of the tetrahydrate form.
In our study, we successfully synthesized zinc perrhenate in various hydrated forms using waste materials. Specifically, we used rhenium from the leaching solution of superalloy scrap and zinc from acidic, waste-circulating solutions generated during electrolytic zinc production. This approach distinguishes our work from previous publications, which primarily focused on obtaining high-purity Zn(ReO4)2 from commercial products. Our manuscript details a novel method for producing different forms of Zn(ReO4)2 entirely from waste materials. The next phase of our research will explore the potential applications of this high-purity product in catalysis and alloy production. This investigation is crucial for the potential implementation of this technology in industrial processes. By demonstrating practical applications, we aim to bridge the gap between laboratory research and real-world implementation, potentially opening new avenues for sustainable material production and waste utilization.

6. Conclusions

The conducted research showed that while using properly purified zinc carbonate, produced from acidic waste solutions originating from the production of electrolytic Zn, and perrhenic acid with a rhenium concentration of >295 g/dm3, various forms of zinc perrhenate can be obtained—tetrahydrate, dihydrate, and anhydrous ones—containing 1000 ppm of the total amount of metallic impurities. To accomplish this, the process should be conducted under the following conditions: time 1 h, room temperature, pH = 6.5, rhenium concentration >295 g/dm3.
The novel hydrometallurgical process for the production of three distinct forms of zinc perrhenate was developed based on the described research. Waste materials were used as sources of zinc and rhenium. The method is made up of 7 stages, i.e., neutralization, precipitation of zinc carbonate, purification of crude zinc carbonate using ammonia solution, preparation of zinc–rhenium solution, evaporation, and precipitation and drying of zinc perrhenate (depending on the form at temperatures of 55, 135, and 185 °C).
The created technology is distinguished by its comprehensive management of all aqueous waste solutions and solid waste, ensuring the conservation of valuable metals such as rhenium and zinc. The comprehensive diagram of the developed method, illustrating its entirety, including all recirculation, is presented in Figure 10.

7. Patents

A part of the findings from this study has been submitted to the Patent Office of the Republic of Poland for potential patenting on 5 April 2024, entitled Sposób otrzymywania renianów(VII) cynku z odpadowych, obiegowych, kwaśnych roztworów cynkowych powstających przy produkcji Zn metodą elektrolityczną (English title: Method of obtaining zinc perrhenates from acidic, waste, circulating zinc solutions, generated during the production of Zn by the electrolytic method).

Author Contributions

Conceptualization, K.L.-S. and G.B.; methodology, K.L.-S., G.B. and M.C.; validation, K.P., K.L.-S. and D.K.; investigation, K.P., J.M. and A.P.; resources, K.L.-S., G.B., D.K. and A.P.; data curation, K.L.-S., A.G., G.B., A.P. and D.K.; writing—original draft preparation, K.L.-S. and A.G.; writing—review and editing, K.L.-S., K.G. and A.G.; visualization, K.L.-S., J.M. and K.G.; supervision, G.B., D.K., M.C. and K.L.-S.; project administration, K.L.-S.; funding acquisition, K.L.-S. All authors have read and agreed to the published version of the manuscript.

Funding

The work was co-funded by the Norwegian Financial Mechanism 2014–2021—Small Grant 2020 NOR/SGS//RenMet/0049/2020-00 (11/PE/0146/21), entitled: Innovative hydrometallurgical technologies for the production of rhenium compounds from recycled waste materials for catalysis, electromobility, aviation, and defense industry.

Data Availability Statement

Data are available on request due to restrictions of privacy. The data presented in this study are available on request from the corresponding author. The data are not publicly available due to patent applications and project contracts.

Acknowledgments

The authors would like to extend their gratitude for the quantitative chemical analyses performed at the Centre of Analytical Chemistry, for the qualitative XRD analyses conducted at the Centre of Functional Materials (particularly Łukasz Hawełek and Tymon Warski), and for SEM-EDS analyses conducted at the Centre of Advanced Materials Technologies (Grzegorz Muzia). All centers belong to the Łukasiewicz Research Network—Institute of Non-Ferrous Metals.

Conflicts of Interest

The authors declare no conflicts of interest. The funders had no role in the design of the study, in the collection, analysis, or interpretation of data, in the writing of the manuscript, or in the decision to publish the results.

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Crystals 14 00725 g001
Figure 1. The influence of the excess precipitating agent (sodium carbonate) on the Zn precipitation efficiency.
Figure 1. The influence of the excess precipitating agent (sodium carbonate) on the Zn precipitation efficiency.
Crystals 14 00725 g001
Crystals 14 00725 g002
Figure 2. The influence of the excess precipitating agent (ammonium bicarbonate) on the Zn precipitation efficiency.
Figure 2. The influence of the excess precipitating agent (ammonium bicarbonate) on the Zn precipitation efficiency.
Crystals 14 00725 g002
Crystals 14 00725 g003
Figure 3. SEM analysis of ZnCO3.
Figure 3. SEM analysis of ZnCO3.
Crystals 14 00725 g003
Crystals 14 00725 g004
Figure 4. EDS analysis of ZnCO3.
Figure 4. EDS analysis of ZnCO3.
Crystals 14 00725 g004
Crystals 14 00725 g005
Figure 5. DTA and TG analyses of ZnCO3 with heating to 1200 °C. *: temperature at which TGA analysis was performed.
Figure 5. DTA and TG analyses of ZnCO3 with heating to 1200 °C. *: temperature at which TGA analysis was performed.
Crystals 14 00725 g005
Crystals 14 00725 g006
Figure 6. The influence of Re concentration in HReO4 on the Zn(ReO4)2 precipitation efficiency.
Figure 6. The influence of Re concentration in HReO4 on the Zn(ReO4)2 precipitation efficiency.
Crystals 14 00725 g006
Crystals 14 00725 g007
Figure 7. The influence of the pH on the Zn(ReO4)2 precipitation efficiency.
Figure 7. The influence of the pH on the Zn(ReO4)2 precipitation efficiency.
Crystals 14 00725 g007
Crystals 14 00725 g008
Figure 8. XRD patterns of zinc perrhenate produced entirely from waste, dried at 180 °C.
Figure 8. XRD patterns of zinc perrhenate produced entirely from waste, dried at 180 °C.
Crystals 14 00725 g008
Crystals 14 00725 g009
Figure 9. Drying graphs for zinc perrhenate.
Figure 9. Drying graphs for zinc perrhenate.
Crystals 14 00725 g009
Crystals 14 00725 g010
Figure 10. Scheme of producing zinc perrhenate from zinc carbonate obtained from waste solutions from the Zn–Pb industry.
Figure 10. Scheme of producing zinc perrhenate from zinc carbonate obtained from waste solutions from the Zn–Pb industry.
Crystals 14 00725 g010
Table 1. Superalloy scrap compositions.
Table 1. Superalloy scrap compositions.
No.Composition, %
ReNiCoCrAlFe
11.7843.326.504.7014.501.30
21.1037.9019.509.1013.900.08
32.5052.307.544.3014.01.01
45.2035.5021.215.2013.200.56
Table 2. Compositions of the multi-component waste solutions generated during the production of Zn by the electrolytic method.
Table 2. Compositions of the multi-component waste solutions generated during the production of Zn by the electrolytic method.
No.Concentration, g/dm3
ZnMgNaMn Free Acid
145.016.77.15.2185
255.516.56.75.2180
360.214.57.75.3160
Table 3. Compositions of the solutions resulting from the neutralization using calcium carbonate.
Table 3. Compositions of the solutions resulting from the neutralization using calcium carbonate.
pHVolume after Neutralization, dm3Concentration after Neutralization, g/dm3Losses of Zn,
%
ZnMgMnNa
3.53.151.016.05.07.01.3
4.03.052.615.95.06.9 1.5
4.53.052.015.95.06.92.6
Table 4. Compositions of the solutions resulting from the neutralization using metallurgical ZnO.
Table 4. Compositions of the solutions resulting from the neutralization using metallurgical ZnO.
pHVolume after Neutralization, dm3Concentration after Neutralization, g/dm3
ZnMgMnNa
3.53.0170.116.05.07.3
4.03.0172.015.55.07.4
4.53.0172.215.45.07.3
Table 5. Results of the tests on the precipitation of zinc carbonate using sodium carbonate.
Table 5. Results of the tests on the precipitation of zinc carbonate using sodium carbonate.
Excess of Precipitating Agent, %pHVolume, dm3Concentration of Zn in the Solution after Precipitation, g/dm3ZnCO3 Precipitation Efficiency, %
06.01.0<0.0199.98
106.31.10.1099.79
306.51.10.4599.05
507.21.21.2097.23
Table 6. Composition of the obtained zinc carbonate using sodium carbonate.
Table 6. Composition of the obtained zinc carbonate using sodium carbonate.
Excess of Precipitating Agent, %Mass of Dry ZnCO3, gMoisture Content in ZnCO3, %Composition, %
ZnMgMnNa
0122.360.551.83.21.23.6
10121.561.552.12.21.02.5
30121.460.851.62.11.02.5
50122.260.751.22.00.92.4
Table 7. Results of the tests on the precipitation of zinc carbonate using ammonium bicarbonate.
Table 7. Results of the tests on the precipitation of zinc carbonate using ammonium bicarbonate.
Excess of Precipitating Agent, %pHVolume, dm3Concentration of Zn in the Solution after Precipitation, g/dm3ZnCO3 Precipitation Efficiency, %
06.01.2<0.0199.9
106.41.20.2099.5
306.51.30.6098.5
507.01.41.5095.9
Table 8. Composition of the obtained zinc carbonate using ammonium bicarbonate.
Table 8. Composition of the obtained zinc carbonate using ammonium bicarbonate.
Excess of Precipitating Agent, %Mass of Dry ZnCO3, gMoisture Content in ZnCO3, %Content, %
ZnMgMnNa
0122.260.452.03.41.32.1
10121.462.552.12.51.12.2
30121.461.851.42.41.22.4
50120.064.751.62.31.02.4
Table 9. Composition of zinc carbonate after purification with ammonia solution.
Table 9. Composition of zinc carbonate after purification with ammonia solution.
No.Amount of Purifying Agent, dm3Mass of Dry, Crude ZnCO3, gMoisture Content in ZnCO3, %Composition, %
ZnMgMnNa
10.420060.551.80.230.101.20
20.620061.552.10.10<0.010.50
30.410060.852.0<0.01<0.010.10
40.510060.751.7<0.01<0.010.10
50.610063.751.8<0.01<0.010.10
Table 10. Results of the tests of the influence of Re concentration in HReO4 on the Zn(ReO4)2 precipitation efficiency.
Table 10. Results of the tests of the influence of Re concentration in HReO4 on the Zn(ReO4)2 precipitation efficiency.
Concentration of Re in HReO4,
g/dm3		Volume of
HReO4,
cm3		Final pHMass of
Zn(ReO4)2,
g		Mass of Precipitate after Neutralization, gPrecipitation Efficiency of
Zn(ReO4)2,
%
15.010007.813.61.5559.7
50.05007.224.10.9063.4
295.0506.520.50.2399.1
500.0256.718.80.1098.9
Table 11. Results of the tests of the influence of the pH on the Zn(ReO4)2 precipitation efficiency.
Table 11. Results of the tests of the influence of the pH on the Zn(ReO4)2 precipitation efficiency.
pHMass of
Zn(ReO4)2, g		Mass of Precipitate after Neutralization, gPrecipitation Efficiency of Zn(ReO4)2, %
6.017.80.1579.4
6.520.50.2391.4
7.020.60.6091.9
7.520.71.2092.3
7.820.81.7092.8
Table 12. Compositions of zinc perrhenates dried at different temperatures.
Table 12. Compositions of zinc perrhenates dried at different temperatures.
Drying Temperature, °CComposition, %
ReZnNiCo
Na		Cu
Ca		FePb
Mn		Mo
Mg
5558.410.3<0.01<0.01<0.001<0.001<0.001<0.001
13561.910.9<0.01<0.01<0.001<0.001<0.001<0.001
18063.211.2<0.01<0.01<0.001<0.001<0.001<0.001
18565.811.6<0.01<0.01<0.001<0.001<0.001<0.001
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Leszczyńska-Sejda, K.; Malarz, J.; Kopyto, D.; Goc, K.; Grzybek, A.; Ciszewski, M.; Palmowski, A.; Benke, G.; Pianowska, K. Recovery of Zinc and Rhenium for the Production of Zinc Perrhenates. Crystals 2024, 14, 725. https://doi.org/10.3390/cryst14080725

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Leszczyńska-Sejda K, Malarz J, Kopyto D, Goc K, Grzybek A, Ciszewski M, Palmowski A, Benke G, Pianowska K. Recovery of Zinc and Rhenium for the Production of Zinc Perrhenates. Crystals. 2024; 14(8):725. https://doi.org/10.3390/cryst14080725

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Leszczyńska-Sejda, Katarzyna, Joanna Malarz, Dorota Kopyto, Karolina Goc, Alicja Grzybek, Mateusz Ciszewski, Arkadiusz Palmowski, Grzegorz Benke, and Karolina Pianowska. 2024. "Recovery of Zinc and Rhenium for the Production of Zinc Perrhenates" Crystals 14, no. 8: 725. https://doi.org/10.3390/cryst14080725

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