Patent Application
20250002654
This application is based upon and claims priority to Turkish Patent Application No. 2023/007409, filed on Jun. 22, 2023, the entire contents of which are incorporated herein by reference.
The invention pertains to the technical fields of synthetic organic chemistry, polymer chemistry, and hydrometallurgy. The polymer mentioned in the invention is synthesized through a single-step synthetic organic chemistry reaction and belongs to the class of porous hyper-covalent polymers. Furthermore, the separation of specific metals from electronic waste at different levels of acidity and the subsequent adsorption and recovery of valuable metals in the metal mixture solution prepared with the polymer described in the invention are related to the technical field of hydrometallurgy.
The unstoppable advancement in technology seen in mobile phones, computers, and various electronic devices has continually triggered the desire for newer, more advanced, and affordable devices, leading to a significant increase in societal consumption. This surge has resulted in a decrease in the usage lifespan and lifecycle of electronic products, leaving behind a massive electronic waste (e-waste). It is officially documented that in 2019, the e-waste amounted to 53.6 million metric tons (Mt), with only 17.4% being properly collected and recycled. Despite a 1.8 Mt increase in recycled e-waste since 2014, the total e-waste production has risen by 9.2 Mt, indicating that recycling efforts are struggling to keep up with global e-waste growth. Due to slow adoption of collection and recycling, many countries face significant environmental and public health risks, including resource depletion, greenhouse gas emissions, and the release of toxic substances into the environment during informal recycling procedures. Despite 71% of the world's population being covered by e-waste policies, legislation, or regulations with various parameters, even countries with formal e-waste management systems have relatively low collection and recycling rates. Given the available data, it is evident that recycling rates cannot keep up with the rapid increase in the production-consumption cycle of high-tech products. Moreover, the scarcity or limited quantities of valuable metals used in technological products necessitate the recovery of these metals from e-waste using environmentally friendly and cost-effective systems and techniques, achieving the highest possible efficiency. Urban mining is known as the recovery and recycling of valuable metals from electronic waste and is practiced in many countries using various methods. The application of separating and purifying to obtain pure metal is referred to as refining. The recycling of metals from electronic waste is carried out using three different techniques under the main headings of pyrometallurgy and hydrometallurgy: dry refining, wet refining, and biological refining. In the dry refining method conducted within pyrometallurgical processes, the metal and slag mixture formed after the direct incineration of electronic waste at a temperature of 1000° C. or higher is separated based on density differences. Valuable metals targeted to be captured by this method are obtained in solid solutions, while the direct incineration leads to the formation of plastic-derived secondary pollutants and other hazardous substances, causing air pollution. Additionally, the main disadvantages of the dry refining process include the high cost of equipment, substantial energy consumption for reaching high temperatures, and the inability to separate certain metals such as aluminum using this method. On the other hand, wet and biological refining applications under hydrometallurgy are more environmentally friendly and cost-effective compared to pyrometallurgical applications. However, especially in wet refining applications, a major disadvantage of this method is the numerous recycling steps for valuable metals and the leaving of toxic waste solutions by some of the solvents and materials used. The primary drawback in biological refining applications is the difficulty in controlling microbial behavior during the application due to the complexity of the microbial behavior despite theoretically calculable limitless uses, making them usable only under very limited conditions. In wet refining applications, methods such as solid phase extraction, filtration, co-precipitation, cyanide leaching, ion exchange resins, electrochemical treatment, and reverse osmosis are employed for the recovery of gold and other valuable metals from aqueous solutions. Among these refining methods, the adsorption method, which allows the capture of gold even at very low concentrations and is particularly interesting, is becoming more appealing day by day. E-waste contains various metals such as copper, iron, and tin in high quantities, as well as valuable metals like gold, silver, platinum, and palladium, constituting less than 1% by weight. Particularly due to its excellent physical and chemical properties, gold, among these valuable metals, finds widespread use in computers, phones, medical equipment, electronics industry, robotics, aerospace, jewelry, pharmaceuticals, and other industrial fields (HUTCHINGS, Graham. A golden future. Nature Chemistry, 2009, 1.7:584-584.). Gold embedded in e-waste has garnered significant interest in urban mining due to its high market price, being a rare element, and its high economic value. Hence, the development of low-cost, environmentally friendly, and highly efficient recycling methods for gold from e-waste holds great importance. Jadhav and Hocheng have determined the experimental conditions where the highest metal dissolution occurs by altering parameters such as prepared acid and base mixtures, temperature, and stirring speed for metal elements' dissolution in e-wastes (Jadhav, U.; Hocheng, H. Hydrometallurgical recovery of metals from large printed circuit board pieces. Scientific Reports, 2015, 5.1:1-10). In a study conducted by Yavuz and colleagues, a multi-step method was employed to synthesize a porphyrin based porous polymer, which showed high selectivity in the adsorption of precious metal elements, particularly gold (YAVUZ, Cafer Tayyar, et al. Porous porphyrin polymer and method of recovering precious metal elements using the same. U.S. Pat. No. 10,961,343, 2021.). In the same study, the synthesized polymer, with modifications on the solvent systems developed by Jadhav and Hocheng, was successfully utilized in the recovery of gold and valuable metals from electronic waste leachates or river and seawater (JADHAV, U.; HOCHENG, H. Hydrometallurgical recovery of metals from large printed circuit board pieces. Scientific Reports, 2015, 5.1:1-10). In a study conducted in 2023 by Sadak and colleagues, a microporous hyper-crosslinked conjugated polymer named EBE-06 was synthesized by modifying cyclotriphosphazene and tricarbazole, and the structural and gas storage properties of the polymer were investigated for Carbon Capture, Utilization, and Storage (CCUS) (Sadak, A. E., Cucu, E., Hamur, B., Ün, İ., & Altundas, R. (2023). Cyclotriphosphazene and tricarbazole based microporous hyper-crosslinked conjugated polymer for carbon capture, utilization and storage (CCUS): Exceptional CO2 selectivity and high capacity CO2, CH4, and H2 capture. Journal of CO2 Utilization, 67, 102304). This publication, not directly related to the topic discussed in this study, involves the examination of entirely different features as it aims to prevent carbon dioxide produced by major factories and power plants from reaching the atmosphere and contributing to global warming. Upon reviewing the literature, the metal leaching process is typically achieved by mixing specific concentrations of one or two acid systems and immersing electronic waste into these prepared solution systems in a single-step process to uptake valuable metals into these solutions (JADHAV, U.; HOCHENG, H. Hydrometallurgical recovery of metals from large printed circuit board pieces. Scientific Reports, 2015, 5.1:1-10). When the same solution systems were tested, it was observed that the majority of gold and other valuable elements on electronic waste either were not absorbed into these solution systems or could be absorbed in very low amounts.
What differentiates the subject matter of this patent from previous patents in the related field is primarily the two-step metal leaching process utilizing solutions with different levels of acidity. In the first-stage leaching process, tin-like metals, which are abundant in electronic waste and could adversely affect the adsorption stage, are removed from the electronic waste in the first solution, while the majority of valuable elements, including gold, remain undissolved on the electronic waste. In the second leaching process, almost all of the undissolved valuable elements from the first leaching process are absorbed into the solution. Another point that distinguishes the invention from previous patents and studies is that the synthesized polymer is the first polymer made using carbazole and phosphazene molecules and possesses the ability to selectively capture gold and other valuable metal elements from the metal leachate solutions of electronic waste. Additionally, unlike similar materials in the literature, the synthesized polymer can be synthesized in a single step and with high efficiency, and it can be easily purified. Moreover, the cost of the synthesized polymer is lower than similar materials in the literature, providing an additional advantage for the material.
During the leaching process of metals from electronic waste using hydrometallurgical techniques, the current acid mixture systems used often result in a significant portion of valuable metal elements, especially gold, either remaining on the electronic waste or remaining undissolved in the acidic solution. The valuable metals absorbed into the solution are much less than their actual amounts on electronic waste, and due to the high presence of metals like tin and copper compared to the valuable metals in the solution, selectively separating the valuable metals from these metal leachates is a challenging task. Furthermore, polymers developed to selectively capture valuable metals tend to either have high costs or require synthesis in multiple steps. Another crucial aspect from a cost perspective is the high stability of the synthesized polymers for repeated use. One of the aims of the present invention is to provide a method for the selective separation of certain metals on electronic waste through a two-step leaching application on electronic waste to solve the problems mentioned above. Additionally, it describes the synthesis and application of carbazole hexachlorocyclotriphosphazene based porous polymers and derivatives that enable the high selectivity capture and recovery of valuable metals, especially gold, from the solution obtained after the second-stage leaching. Moreover, the obtained polymer can be synthesized in a single step at low cost and high efficiency. Another advantage of the synthesized polymer material is its ability to be used in at least three repeated cycles, enhancing its cost-effectiveness.
In this section, the present invention will be described in more detail with reference to examples provided. These examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The purpose of providing these examples is to make the invention understandable and clear to a person with general knowledge in the art based on the known state of the art.
The carbazole phosphazene based polymer was prepared in a single-step reaction following the method mentioned in the literature (Sadak, A. E., Cucu, E., Hamur, B., Ün, İ., & Altundas, R. (2023), Cyclotriphosphazene and tricarbazole based microporous hyper-crosslinked conjugated polymer for CCUS: Exceptional CO2 selectivity and high capacity CO2, CH4, and H2 capture. Journal of CO2 Utilization, 67, 102304.)
Here, n and m are integers representing the numbers of repeating units, where n is an integer between 1000 and 50000, and m is an integer between 1000 and 50000.
A, as the linking molecule, can connect carbazoles to each other from any carbon of the benzene groups, positioned among the carbazoles.
R can be any derivative derived from the following cyclic molecules of benzene derivatives containing a varying number of carbazoles, bonded by hydrogen atoms or nitrogen atoms of carbazole:
The carbazole phosphazene based polymer represented by Formula 1 can be represented by the following Formula 2:
Here, e can be an integer between 1000 and 50000, representing the number of repeating units.
The synthesis of the carbazole phosphazene based polymer involves dissolving 1,3,5-tri(9H-carbazol-9-yl)benzene monomer and hexachlorocyclotriphosphazene monomer in dichlorobenzene, followed by a mixing process. This is further accompanied by a polymerization reaction catalyzed by AlCl3 or FeCl3.
The synthesis of the carbazole phosphazene based polymer may involve the following steps:
In the mentioned synthesis steps, magnetic stirring can preferably be used for mixing processes.
The obtained polymer structure has a BET specific surface area preferably in the range of 250-2200 m2/g and a pore size preferably in the range of 0-30 nm. The characteristic feature of the obtained carbazole phosphazene based polymer is its adsorbent property. When added to solutions containing valuable metal elements, the valuable metal elements adhere to the polymer and can be recovered by desorption from the polymer. The carbazole phosphazene based polymer can be used for the recovery of valuable metal elements from solutions containing valuable metal elements in another application. The method for recycling valuable metal elements from metal solutions containing valuable metal elements comprises the following steps:
The metal solution containing valuable metal elements can be wastewater from a plating factory or metal solution leaches from electronic waste. The valuable metal elements can be one or more of Au, Pd, Ag, Zr, Pt, Mo, Sc, Re, and Ti, and are not limited to this list. pH values can be adjusted according to the valuable metal elements during the method application. The pH values of the solutions containing valuable metal elements (gold, platinum, silver, and palladium, etc.) to which the carbazole phosphazene based polymer is added can be in the range of 1-10 and preferably 2, 4, 7, or 9. When the valuable metal element is palladium (Pd), the pH of the solution containing the valuable metal element is preferably 2-9, more preferably 7; when the valuable metal element is platinum (Pt), the pH of the solution is preferably 2-9, more preferably 4; when the valuable metal element is gold (Au), the pH of the solution is preferably 2-9, more preferably 2; and when the valuable metal element is silver (Ag), the pH of the solution is preferably 2-9, more preferably 2.
A method for calculating the adsorption efficiency of the carbazole phosphazene based polymer for valuable metal element adsorption can be applied, involving the following steps:
The method for recovering valuable metal elements adsorbed by the carbazole phosphazene based polymer may include the following steps:
The mixing process is preferably performed by adding 1 mL of the solution per 1 milligram of the polymer, and more preferably at 40-80° C., more preferably at 50-70° C., even more preferably at 60° C., for 1-86 hours, preferably for 1, 3, 6, 12, 24, 36, 48, 54, 72, and 86 hours, more preferably at 80-150 rpm, even more preferably at 120 rpm.
The carbazole phosphazene based polymer used for the recovery of valuable metal elements from solutions containing valuable metal elements can be reused multiple times. To enable the reuse of the used polymer, a method containing the following steps can be applied:
In another application of the invention, the carbazole phosphazene based polymer containing valuable metal elements can be used for the recovery of valuable metal elements from electronic waste materials such as random access memory (RAM), graphics card, and smart card, which contain valuable metal elements. The method for recovering valuable metal elements from electronic waste materials comprises the following steps:
The method for recovering precious metal elements from the mentioned electronic waste materials in step (b) of the method preferably has a molar concentration of the acid solution lower than the molar concentration of the acid solution used in step (c).
The method for recovering precious metal elements from the mentioned electronic waste materials may include the following steps:
The aforementioned precious metal elements may be selected from the group consisting of Au, Pd, Ag, Zr, Pt, Mo, Sc, Re, and Ti, among others, and are not limited to this list. During the steps where pH adjustments are made in the method for recovering precious metal elements from electronic waste materials, the pH can be adjusted based on the precious metal elements intended for recovery, preferably to pH 2-9, more preferably to pH 2. For high-efficiency recovery of the precious metal element palladium (Pd), the pH of the solution can be preferably adjusted to pH 2-9, more preferably to pH 7. For the precious metal element platinum (Pt), the pH of the solution can be preferably adjusted to pH 2-9, more preferably to pH 4. For the precious metal element gold (Au), the pH of the solution can be preferably adjusted to pH 2-9, more preferably to pH 2. For the precious metal element silver (Ag), the pH of the solution can be preferably adjusted to pH 2-9, more preferably to pH 2.
40 mL of anhydrous 1,2-dichlorobenzene was placed in a flask, to which 2.79 g of AlCl3 (20.92 mmol, 12 equivalents) was added at room temperature. The mixture was stirred for 15 minutes. Then, 606 mg of hexachlorocyclotriphosphazene (1.74 mmol, 1 equivalent) was dissolved in a 15 mL solution of 1,2-dichlorobenzene and added to the mixture. Subsequently, 1.00 g of 1,3,5-tri(9H-carbazol-9-yl)benzene (1.74 mmol, 1 equivalent), dissolved in 20 mL of 1,2-dichlorobenzene, was added to the reaction mixture. The mixture was stirred with a magnetic stirrer at room temperature for 6 hours. After 6 hours, the mixture was heated to 190° C. and stirred with a magnetic stirrer for 18 hours at this temperature. Upon completion of the reaction time, the reaction mixture was cooled to room temperature and filtered through a No. 3 glass filter to remove the solvent. The resulting black solid was successively washed with 200 mL of 2 N HCl, 200 mL of distilled water, and 100 mL of methanol. The solid polymer was transferred to a beaker and subjected to 30 minutes of ultrasonication in 100 mL of methanol. It was then filtered through a No. 3 glass filter. Subsequently, it was purified through successive 24 hour soxhlet extractions with 100 mL of methanol, tetrahydrofuran, and acetone. The final product was dried in a vacuum oven at 120° C. for 24 hours. The carbazole phosphazene based porous polymer was obtained as a light brown solid with a yield of 1.198 g (98%). IR (powder, cm−1): 1590, 1454, 1311, 1214, 1056, 867, 803, 589, 541.
Structural analysis was performed through the comparison of the spectra obtained from Fourier Transform Infrared Spectroscopy (FTIR) measurements of 1,3,5-tri(9H-carbazol-9-yl)benzene, hexachlorocyclotriphosphazene, and the carbazole-phosphazene based polymer obtained from these reagents (Formula 2). The analysis results are shown in
From the conducted elemental analysis results, it can be inferred that the carbon, nitrogen, and hydrogen content of the obtained polymer (Formula 2) closely align with the theoretically calculated values, further confirming the accuracy of the structure.
Additionally, nitrogen adsorption and desorption measurements conducted at 77 K are presented in
The thermal stability of Formula 2 was measured in air and nitrogen environments using thermogravimetric analysis (TGA) method. The graph shown in
To calculate metal ion selectivity, adsorption experiments were conducted using synthesized Formula 2 with three different standard solutions containing various metal ions. Certified reference solutions containing various metals were used as the inductively coupled plasma-mass spectrometry (ICP-MS) standard solutions. These solutions, containing metals that do not interact and cause precipitation when combined, were diluted from the first standard solution containing 7 elements with a concentration of 10 ppm to the second standard solution containing 48 elements and the third standard solution containing 13 elements. Dilutions were made using deionized water to obtain a calibration curve for ICP analysis. These solutions were further diluted up to 100 fold using deionized water to obtain a 10 point calibration curve. The diluted solutions were divided into three portions for parallel measurements, and each portion was completed to 10 mL with deionized water. To each experimental sample, 10 mg of Formula 2 was added, and the mixture was magnetically stirred at 120 rpm at room temperature for 24 hours. After 24 hours, each sample was filtered using a 0.45 μm hydrophobic membrane polytetrafluoroethylene (PTFE) filter using a 3 mL plastic syringe. The metal concentrations in the filtered samples were measured using the ICP-MS device, and the results shown in
To determine the effect of pH variation on the adsorption rate of Formula 2 in gold, platinum, silver, and palladium ion solutions, aqueous solutions were prepared, each containing approximately 50 ppb of gold, platinum, silver, and palladium ions, with pH values of 2, 4, 7, and 9. Additionally, for calibration purposes, 8 point mixture metal ion solutions ranging from 0.5 ppb to 60 ppb were prepared. Formula 2 (5 mg) was added to each solution with varying pH, each containing 10 mL of metal ion mixture. The concentration of metal ions in each solution was measured using ICP-MS at 1, 2, 3, 6, 12, and 24 hours after the start, and the adsorption efficiency was calculated by comparing it with the initial concentrations.
To determine the maximum amount of gold ions that Formula 2 can adsorb per gram, the following experiment was conducted. A 10,000 ppm stock solution of gold (III) chloride trihydrate was prepared using deionized water and kept at +4° C. for 7 days for the solution to stabilize. After 7 days, the real concentration of the solution was determined using ICP-MS after filtration using a 0.45 μm PTFE filter. The prepared gold (III) chloride trihydrate stock solution was diluted to 20, 100, 250, 500, 750, 1000, 3000, 5000, and 7500 ppm solutions, and for each concentration, the solution was divided into portions with 3 parallel measurements for each concentration. Approximately 10 mg of Formula 2 was added to each sample, and the prepared samples were mixed at 120 rpm for 48 hours at 20° C. After 48 hours, each sample was centrifuged at 4500 rpm and then filtered with a 45 μm PTFE filter. The remaining gold ion concentration in the solutions was determined using ICP-MS. The adsorbed gold ion amounts from the obtained measurement results are shown in
To determine the desorption and recovery conditions of gold adsorbed by the polymer, Formula 2 was added to a saturated gold solution of 735 ppm and mixed at 120 rpm for 48 hours at 20° C. After 48 hours, the polymer, washed with distilled water and filtered through 11 μm filter paper, was left to dry for 24 hours at 100° C. in a vacuum oven. The amount of gold ions adsorbed by the polymer was determined by ICP-MS analysis of the filtered solution. For optimization of the desorption conditions, a three-stage (consisting of three separate experiments) desorption determination method was followed, different from the desorption studies in the literature, for the determination of desorption conditions after gold adsorption by the polymer (YAVUZ, Cafer Tayyar, et al. Porous porphyrin polymer and method of recovering precious metal elements using the same. U.S. Pat. No. 10,961,343, 2021.). Since the desorption experiments in the literature were completed in a total of 48 hours by taking samples at increasing time intervals, all acid mixture combinations for comparison of desorption experiment efficiencies were moved to the second stage based on the 48-hour results. For the first stage of the desorption efficiency determination experiment, for the 8 different solution systems consisting of; % 5 HNO3; % 10 HNO3; % 30 HNO3; 0.05 M thiourea/0.05 M H2SO4; % 18 HNO3/% 2 HCl; % 3 HNO3/% 9 HCl; 0.1 M thiourea/0.1 M H2SO4; 0.1 M thiourea/1.0 M HCl/1.0 M HNO3, approximately 1-10 mg of gold adsorbed polymer was taken for each experiment, preferably approximately 3 mg, and 3 parallels were taken; for each 1 milligram of the polymer, 1 mL of the solution was added, and the mixtures were mixed at 60° C. for 48 hours at 120 rpm. After 48 hours, the concentration of gold ions desorbed in each experimental sample was determined by ICP-MS. The 48-hour initial desorption experiment results shown in
To determine the change in efficiency in repeated adsorption and desorption experiments of the carbazole phosphazene based polymer shown as Formula 2, Formula 2 was added to a 735 ppm gold solution and stirred at 120 rpm for 48 hours at 20° C. At the end of the duration, the remaining gold amount in the solution was measured by ICP-MS, and the amount of gold adsorbed by the polymer was calculated. For the desorption experiment, 1 mL of 0.1 M thiourea/1.0 M HCl/1.0 M HNO3 solution was added for each 1 mg of gold adsorbed by Formula 2, and the mixture was stirred at 60° C. for 72 hours at 120 rpm. After 72 hours, Formula 2 was separated by filtration through an 11 μm filter paper. The sample taken from the solution was filtered using a 0.45 μm PTFE filter, and the amount of desorbed gold ions in the solution was measured by ICP-MS. Before reusing Formula 2, it was boiled in a Formula 2 solution for 6 hours with 1 mL of 2% NaOH solution for each 1 mg of the polymer. Then, it was washed with 5 mL of deionized water for each 1 mg of the polymer and left to dry at 100° C. in a vacuum oven. According to the results of the cyclic adsorption-desorption experiments repeated three times, shown in
To demonstrate the applicability of Formula 2 in the real adsorption and recycling of gold ions from electronic waste products, three practical experiments were conducted on printed circuit boards with different amounts of metal content: random-access memory (RAM), graphics card, and motherboard. Although the selected three circuit boards had different amounts of metal content, ICP-MS measurements carried out on the graphics card showed significantly higher amounts of copper (Cu) and tin (Sn) compared to other metals (Table 2). In the selective leaching measurements, the results indicated that the use of a low molar concentration solution in the first stage of leaching may result in many of the gold and other valuable elements remaining in the printed circuit components without dissolving in the solution. After the first leaching process, the remaining parts were separated by filtration, and gold and the remaining valuable metal elements were transferred to the second solution using a more concentrated acidic solution. For the second leaching, acidic solutions with molar concentrations ranging from 5.0 to 12.0 M, composed of HCl, HNO3, or a mixture of both, can be used.
In the experiment details provided in the tables, a 12.0 M HCl solution was used for the second leaching. After the second leaching, the obtained metal leach mixture was adjusted to the optimal pH of 2 (as shown in
The printed circuit boards were soaked in 1.0 M HCl for 48 hours in the initial leaching process. The acidic solution, after filtration, was diluted to a volume of 1000 mL with a 10 M NaOH solution and deionized water to achieve a pH of 2. It was observed that tin metal precipitated in a white color during this dilution. To determine which metal ions were present in the initial leaching solution and the total metal content, a sample was taken from the solution for measurement by ICP-MS. The types and amounts of metal ions in the initial leaching solution for RAM, graphics card, and motherboard are shown in Table 4.
The portions of the printed circuit boards taken from the initial leaching solution were immersed in 12 M HCl solution at a rate of 2 mL per gram for 24 hours, using an incubator shaker at 20° C. and 150 rpm. After 24 hours, the printed circuit boards were removed from the solution, and the solution was filtered through an 11 μm cellulose filter paper. Images 1-6 display the printed circuit boards after being kept in 12 M HCl for 24 hours in the second leaching process. The filtered acidic solution was diluted to a volume of 1000 mL with a 10 M NaOH solution and deionized water to achieve a pH of 2. A sample was taken from the solution for measurement by ICP-MS to determine which metal ions were present in the solution and the total metal content. The types and amounts of metal ions in the solution for RAM, graphics card, and motherboard are presented in Table 5.
A 250 mL portion of the prepared solution was taken, and 62.5 mg of the porous polymer, denoted as Formula 2, a carbazole phosphazene based polymer, was added to the solution to achieve a ratio of 1 mg of polymer per 4 mL of the solution. The mixture was then stirred at 20° C. and 120 rpm for 48 hours using an incubator shaker. After completion of the duration, the solution was filtered through an 11 μm cellulose filter paper to separate the polymers. The remaining metal ion concentrations in the solution were measured using ICP-MS.
The separation and recycling method performed in the laboratory using the disclosed method and polymer has the potential to be utilized in recycling facilities established for electronic waste. While the present invention has been described in detail based on certain features, it will be understood by those skilled in the art that this specification is merely a preferred arrangement and does not limit the scope of the present invention. Therefore, the scope of the present invention is defined by the claims and their equivalents provided herewith.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2023/007409 | Jun 2023 | TR | national |
