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WO2025009455A1 - Procédé de récupération de métal - Google Patents

Procédé de récupération de métal Download PDF

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Publication number
WO2025009455A1
WO2025009455A1 PCT/JP2024/023245 JP2024023245W WO2025009455A1 WO 2025009455 A1 WO2025009455 A1 WO 2025009455A1 JP 2024023245 W JP2024023245 W JP 2024023245W WO 2025009455 A1 WO2025009455 A1 WO 2025009455A1
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WIPO (PCT)
Prior art keywords
lithium
leaching
residue
alkaline
recovery method
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English (en)
Japanese (ja)
Inventor
裕次郎 時田
康文 芳賀
洋 宮永
慧 鹿田
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Jx Metals Circular Solutions Co Ltd
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Jx Metals Circular Solutions Co Ltd
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Priority to JP2025531513A priority Critical patent/JPWO2025009455A1/ja
Publication of WO2025009455A1 publication Critical patent/WO2025009455A1/fr
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • metals such as cobalt, nickel, manganese, lithium, aluminum, and iron in the battery powder are leached with acid to obtain a metal-containing solution in which the metals are dissolved.
  • metal-containing solution in which the metals are dissolved.
  • aluminum ions, iron ions, manganese ions, and the like are removed from the metal-containing solution sequentially or simultaneously by neutralization or solvent extraction.
  • the cobalt ions and nickel ions in the metal-containing solution are separated by solvent extraction.
  • the nickel ions are separated by extraction, a metal-containing solution in which lithium ions remain is obtained.
  • This specification provides a metal recovery method that can effectively remove aluminum.
  • the above metal recovery method allows aluminum to be effectively removed.
  • One embodiment of the metal recovery method is a method for recovering metals from lithium ion battery waste.
  • This method includes a pretreatment step of subjecting lithium ion battery waste to a pretreatment including a heat treatment to obtain an Al-containing intermediate containing aluminum and lithium, a lithium leaching step of contacting the Al-containing intermediate with a liquid to leach lithium in the Al-containing intermediate into the liquid, adjusting the pH of the liquid at the end of the lithium leaching to 7 to 13, and obtaining a residue and a lithium-containing solution, and an alkaline leaching step of contacting the residue from the lithium leaching step with an alkaline solution to leach aluminum in the residue into the alkaline solution.
  • a lithium leaching process is carried out before the alkaline leaching process, and lithium is separated and recovered to a certain extent from the Al-containing intermediate in advance in the lithium leaching process.
  • the amount of lithium leached into the alkaline solution can be reduced compared to when the alkaline leaching process is carried out without going through the lithium leaching process.
  • the metal recovery method of the embodiment described here can be carried out in the process illustrated in FIG. 1 or 2.
  • lithium ion battery waste is subjected to pretreatment including heat treatment, crushing, and sieving, and the sieved material obtained thereby is treated as an Al-containing intermediate, and the above-mentioned lithium leaching process and alkaline leaching process are carried out as wet treatment.
  • the pretreatment process includes heat treatment, crushing, and sieving as in FIG. 1, but differs from FIG.
  • the medium-diameter sieved material may be subjected to the lithium leaching process and alkaline leaching process as it is, but the lithium leaching process and alkaline leaching process may also be carried out on the magnetic material obtained by eddy current sorting.
  • the large-diameter sieved material is subjected to magnetic separation, re-crushing and re-sieving, and the sieved material obtained by re-sieving is subjected to the lithium leaching process and the alkali leaching process. In this way, battery powder is obtained.
  • an acid leaching process can be carried out in which the battery powder is leached with acid to obtain a metal-containing solution containing various metal ions, and a metal separation process can be carried out in which the metal ions are separated from the metal-containing solution.
  • a metal separation process can be carried out in which the metal ions are separated from the metal-containing solution.
  • Lithium-ion battery waste can be various in-vehicle lithium-ion batteries that can be installed in vehicles such as hybrid cars, fuel cell cars, and electric cars, and that are discarded due to the scrapping of the vehicle, battery replacement, manufacturing defects, or other reasons. However, it is not limited to in-vehicle lithium-ion battery waste, and can include various lithium-ion battery waste for other purposes. Lithium-ion battery waste refers to lithium-ion batteries that are subject to recycling, and it does not matter whether the lithium-ion batteries are traded for a value, or traded free of charge or as industrial waste.
  • the lithium ion batteries contained in such lithium ion battery waste include a positive electrode material, a negative electrode material, an electrolyte, and an aluminum case around them.
  • the positive electrode material and the negative electrode material can be respectively formed by fixing a positive electrode active material or a negative electrode active material to a positive electrode current collector such as aluminum foil or a negative electrode current collector such as copper foil, for example, with polyvinylidene fluoride (PVDF) or other organic binders.
  • PVDF polyvinylidene fluoride
  • the positive electrode active material is, for example, a single metal oxide of lithium, nickel, cobalt, and manganese, or a composite metal oxide of two or more of them.
  • positive electrode active materials examples include LiCoO 2 , LiNiO 2 , Li-Co-Ni-O 2 , and Li-Co-Ni-Mn-O. It is desirable to recover the metal contained in the positive electrode active material as a valuable metal in terms of effective utilization of resources.
  • the metals contained in the positive electrode active material may change form from the oxides described above by heat treatment or the like described below, but regardless of the form, the metals derived from the positive electrode active material, such as cobalt, nickel, and lithium (hereinafter also referred to as "positive electrode-derived metals”), are the subject of recovery here.
  • waste lithium-ion batteries for vehicles may contain terminals containing copper and/or iron, iron cases, stainless steel cases, etc.
  • Waste lithium-ion batteries for vehicles have a metal frame such as iron as the exterior skeleton, and lithium-ion battery cells are housed inside the frame.
  • This type of lithium-ion battery waste often contains multiple battery cells, which are bundled together to form a battery module, and are further configured by connecting multiple battery modules together.
  • lithium-ion battery waste may also include a BMS (Battery Management System) that monitors each battery cell, a cooling device that cools the battery, and wires that connect them.
  • the wires are made of a metal containing copper, such as copper (Cu wire), and are connected to each battery cell and the BMS to transmit information (temperature, voltage, etc.) related to the temperature and voltage of each battery cell to the BMS.
  • resin members may be provided between and around the battery cells.
  • the casing of lithium-ion battery waste usually contains an electrolyte solution in which an electrolyte such as lithium hexafluorophosphate is dissolved in an organic solvent.
  • an electrolyte such as lithium hexafluorophosphate
  • organic solvent for example, ethylene carbonate, diethyl carbonate, etc. may be used as the organic solvent.
  • the positive electrode active material is difficult to separate from the aluminum foil.
  • an alkaline leaching process is performed, which can reduce the amount of aluminum ions mixed into the metal-containing solution obtained after the acid leaching process.
  • a pretreatment process as described below is performed, such aluminum can be removed more effectively.
  • the pretreatment step At least a heat treatment is performed on the lithium ion battery waste.
  • the pretreatment step includes heat treatment, crushing, and sieving in this order or in random order.
  • FIG. 2 after heat treatment, crushing, and sieving are performed in order, small-diameter sieved matter, medium-diameter sieved matter, and large-diameter sieved matter with different particle sizes are obtained by sieving, and the medium-diameter sieved matter and the large-diameter sieved matter are further processed.
  • the sieved matter that falls on the sieve has a particle size equal to or larger than the predetermined side length of the sieve hole, or the sieved matter that falls on the sieve has a particle size less than the predetermined side length of the sieve hole.
  • the steps are performed in the order of heat treatment, crushing, and sieving.
  • the order may be crushing, heat treatment, and sieving, although not shown.
  • treatment other than heat treatment, crushing, and sieving may be included in the pretreatment process, such as when the lithium ion battery waste is disassembled and then heat treatment, crushing, and sieving are performed.
  • heat treatment, crushing, and sieving are performed in the order shown in Figures 1 and 2.
  • battery powder refers to a powder in which the positive electrode material components are separated and concentrated by performing some kind of processing on lithium ion battery waste.
  • Battery powder can be obtained as a powder in which the positive electrode material components are concentrated by performing heat treatment on lithium ion battery waste and, if necessary, further crushing and sieving.
  • the residue obtained after the alkaline leaching process described below also becomes battery powder.
  • the heat treatment is performed for the purpose of removing the electrolyte in the lithium ion battery waste.
  • the temperature is not particularly important as long as the lithium ion battery waste is heated.
  • the lithium ion battery waste may be heated to a temperature at which the electrolyte can be removed, for example, a relatively low temperature of about 100°C or 200°C (for example, 100°C or higher, typically 100°C to 185°C or 185°C to 350°C).
  • the electrolyte evaporates, and lithium hexafluorophosphate, lithium fluoride generated by decomposition of lithium hexafluorophosphate, etc. may remain.
  • the lithium ion battery waste may be heated at a relatively high temperature of 300°C or higher, for example, 350°C to 650°C, particularly 400°C to 600°C, for 1 hour to 8 hours.
  • LiCoO2 in the positive electrode active material may be decomposed to produce cobalt oxide, metallic cobalt, lithium carbonate, etc.
  • the composition of the positive electrode active material changes due to heat treatment, but here, even if it has been subjected to heat treatment, it may be called a positive electrode active material.
  • heating may be performed in an air atmosphere or an inert atmosphere, but is not limited thereto and various atmospheres can be used.
  • the heat treatment may be performed in a reduced pressure atmosphere such as a vacuum. Heating in an air atmosphere and heating in an inert atmosphere may both be performed in any order. Preferably, after heating in an inert atmosphere, the atmosphere is switched and heating is further performed in an air atmosphere.
  • the heat treatment furnace is not particularly limited, but for example, an atmospheric and vacuum electric furnace or an atmospheric muffle furnace can be used for a batch type, or a roller hearth kiln or mesh belt kiln can be used for a continuous type.
  • a variety of known crushers can be used here, but specific examples include impact crushers that apply impact while cutting the case and battery, such as a sample mill, hammer mill, pin mill, wing mill, tornado mill, and hammer crusher.
  • a screen can be installed at the outlet of the crusher, so that the batteries are discharged from the crusher through the screen when they have been crushed to a size that can pass through the screen.
  • the crushed material obtained by the above crushing is subjected to sieving, whereby it is sieved according to its size and separated into multiple types of sieved material with different particle sizes.
  • the sieved material obtained by sieving is an Al-containing intermediate material, which is subjected to a lithium leaching process and an alkaline leaching process, and the residue from the alkaline leaching process is battery powder B.
  • the under-sieved material may contain almost no aluminum but metals derived from the positive electrode, in which case the under-sieved material can be battery powder A. Battery powders A and B are subjected to an acid leaching process, from which metals can be recovered.
  • the crushed material is sieved to obtain at least small, medium and large sieved matter with different particle sizes.
  • the crushed material is divided into three types, but it is also possible to divide it into four or more types of sieved matter including the small, medium and large sieved matter.
  • the small sieved matter which has a relatively small particle size, may contain positive electrode-derived metals without substantially containing aluminum, and can be subjected to the acid leaching process as battery powder A.
  • the medium-sized sieved material may contain aluminum as well as metals derived from the positive electrode, and as described below, eddy current sorting may be performed as necessary to extract the magnetized material (Al-containing intermediate), after which the lithium leaching process and alkaline leaching process may be performed. However, this eddy current sorting may be omitted, in which case the medium-sized sieved material is subjected to the lithium leaching process and alkaline leaching process as an Al-containing intermediate. The residue after this alkaline leaching process becomes battery powder B. Alternatively, the lithium leaching process and alkaline leaching process may be omitted, and the medium-sized sieved material or the magnetized material after eddy current sorting may be used as battery powder B.
  • the large-diameter sieved material which often contains aluminum and metals derived from the positive electrode, it is preferable to further perform magnetic separation, re-crushing, and re-sieving to obtain an under-sieved material from which as much aluminum as possible has been separated.
  • the under-sieved material obtained by re-sieving can be fed into the acid leaching process as battery powder C. Meanwhile, the over-sieved material obtained by re-sieving is subjected to the lithium leaching process and the alkaline leaching process. The residue after the alkaline leaching process becomes battery powder D. If the lithium-ion battery waste contains a certain amount of copper or aluminum, most of that copper and aluminum will be distributed in the over-sieved material obtained by re-sieving.
  • the mesh size of each sieve can be appropriately set, taking into consideration the following points:
  • the small-diameter sieved material is used as battery powder A as is, it is desirable that it contains few impurities other than the metals to be recovered (iron, aluminum, copper, etc.).
  • the crushed material is classified by particle size, the crushed material containing these impurities is distributed mostly on the large particle size side. For this reason, if the mesh size of the sieve that separates the small-diameter sieved material from the medium-diameter sieved material is made small to a certain extent, it is possible to prevent the quality of the impurities contained in battery powder A from increasing.
  • the impurities contained in the medium-sized sieved material can be removed by such treatments or processes.
  • the mesh size separating the small-sized sieved material from the medium-sized sieved material can be set based on the quality of impurities contained in the small-sized sieved material (battery powder A).
  • the mesh size of the sieve that separates the medium-sized and large-sized sieved materials can be set based on the iron content of the medium-sized sieved materials.
  • low-force magnetic separation that can remove iron may be performed as described below, whereas low-force magnetic separation is not performed for the medium-sized sieved materials.
  • the medium-sized sieved materials contain a certain amount of iron, when eddy current separation is performed on the medium-sized sieved materials, the ferromagnetic iron will be included in the magnetized materials to be recovered.
  • the iron contained in the crushed materials originates from the terminals and casings, and is therefore distributed on the large particle size side. For this reason, it is desirable to appropriately set the mesh size of the sieve that separates the medium-sized and large-sized sieved materials so that the medium-sized sieved materials do not contain more than the allowable amount of iron.
  • a known eddy current sorting machine for eddy current sorting, which includes a belt conveyor having a belt for transporting the objects (medium-sized objects in this case) and a pulley around which the belt is wound and driven to rotate. Inside the pulley is a built-in rotor that rotates at high speed to generate a high-frequency alternating magnetic field. The rotor has alternating north and south poles arranged in the circumferential direction, and when it rotates at high speed, an alternating magnetic field is generated.
  • the above surface magnetic flux density refers to the magnetic flux density at the surface of the position where the medium-diameter or large-diameter sieved material is subjected to magnetic force in the magnetic separator.
  • a pulley-type magnetic separator in which a belt conveyor is wrapped around a magnet pulley, it is the surface magnetic flux density on the magnet pulley when the large-diameter sieved material on the belt conveyor passes through the magnet pulley.
  • the liquid to be contacted with the Al-containing intermediate in the lithium leaching step is not particularly limited as long as it has a pH of 7 to 13 at the end of lithium leaching, and the pH before contacting with the Al-containing intermediate may be less than 7.
  • the pH of the liquid before contacting with the Al-containing intermediate may be 2 to 10.
  • the pH here means a value measured at room temperature (typically 20°C), and if the temperature of the liquid is higher, the pH is the pH when it is lowered to room temperature.
  • the liquid is typically water, and specifically, tap water, industrial water, distilled water, purified water, ion-exchanged water, pure water, ultrapure water, etc. can be used.
  • the liquid temperature when the Al-containing intermediate is contacted with the liquid can be 10°C to 80°C.
  • the pulp concentration can be 25 g/L to 450 g/L. This pulp concentration means the ratio of the dry weight (g) of the Al-containing intermediate to the amount (L) of the liquid to be contacted with the Al-containing intermediate.
  • the time for lithium leaching can be 0.1 hours to 5 hours. If the lithium leaching time is short, lithium is not sufficiently leached, and if the lithium leaching time is long, a large amount of LiAl 2 (OH) 7 hydrate is produced, which is difficult to leach in the subsequent alkaline leaching. For this reason, the lithium leaching time is preferably 0.5 to 3 hours.
  • the pH may rise to about 11-12 due to the leaching of lithium carbonate and the like in the Al-containing intermediate.
  • an acid such as sulfuric acid may be added as necessary to adjust the pH.
  • the amount of acid added can be adjusted so that the pH is 7-13, preferably 7-12, at the end of lithium leaching. If the pH is less than 7, there is a risk that cobalt and the like will dissolve, and if it exceeds 12, there is a concern that aluminum and the like will dissolve.
  • the lithium ion concentration of the lithium-containing solution is preferably 1.0 g/L to 2.5 g/L.
  • the lithium leaching rate in the lithium leaching process may be, for example, 40% to 60%.
  • the lithium leaching rate can be calculated by mass from the lithium content of the Al-containing intermediate before the lithium leaching process and the lithium content of the residue obtained in the lithium leaching process.
  • the lithium carbonate is purified by performing repulp washing on the lithium carbonate and blowing in carbon dioxide gas to dissolve the carbonic acid in the liquid, removing solid impurities by solid-liquid separation, followed by deoxidization and concentration, and isolating and recovering high-quality lithium carbonate by solid-liquid separation.
  • Alkaline leaching process The residue obtained from the lithium leaching step is subjected to an alkali leaching step in which aluminum is separated and removed from the residue.
  • the residue after the lithium leaching process is immersed in an alkaline solution and stirred, etc., to bring it into contact with the alkaline solution, and the aluminum in the residue is leached into the alkaline solution.
  • the residue after the lithium leaching process has a relatively low lithium content. Therefore, even if a small amount of lithium is leached from the residue along with the aluminum in the alkaline leaching process, the amount of lithium leached is reduced. This makes it possible to suppress lithium loss.
  • the alkaline solution used in the alkaline leaching step can have a pH of 13.0 or more and an OH - concentration of 8 mol/L or less before contact with the residue.
  • the pH of the alkaline solution after contact with the residue is preferably maintained at 12.0 or more, and further preferably at 13.0 or more.
  • the OH - concentration of the alkaline solution after contact with the residue may be 8 mol/L or less.
  • the OH - concentration of the alkaline solution after contact with the residue is preferably 5 mol/L or less.
  • components such as sodium derived from the alkaline solution can be easily removed during washing after solid-liquid separation, and there is also an advantage that an increase in the amount of acid consumed in the acid leaching step due to the components when the acid leaching step is performed thereafter is suppressed.
  • the alkaline solution for example, a sodium hydroxide solution, a potassium hydroxide solution, etc. can be used.
  • the above pH refers to a value measured at room temperature (typically 20° C.), and when the temperature of the alkaline solution is higher, the pH is the value measured when the temperature is lowered to room temperature.
  • the temperature of the alkaline solution used to leach aluminum from the residue in the alkaline leaching process is preferably maintained within the range of 10°C to 80°C, and more preferably within the range of 10°C to 50°C. If the liquid temperature is too high, there is a concern that the reactivity will be high, causing sudden generation of hydrogen or a sudden rise in the liquid temperature that will become uncontrollable. If the liquid temperature is too low, the reactivity will decrease and the alkaline separation process may take a long time.
  • the pulp concentration can be, for example, 20 g/L to 500 g/L. This pulp concentration refers to the ratio of the dry weight (g) of the residue to the amount (L) of alkaline solution brought into contact with the residue.
  • the time for leaching aluminum may be, for example, 0.5 hours to 3.0 hours.
  • the alkaline solution after alkaline leaching (aluminum leaching solution) may be used for alkaline leaching again, allowing the alkaline solution to be used repeatedly for alkaline leaching. This can reduce costs and the amount of liquid.
  • the aluminum leaching After the aluminum leaching is complete, solid-liquid separation is performed to obtain an aluminum leachate containing aluminum ions and a residue containing cobalt, nickel, etc.
  • the aluminum ion concentration in the aluminum leachate may be, for example, 2 g/L to 60 g/L, or may be 2 g/L to 40 g/L.
  • the lithium content of the residue obtained in the alkaline leaching process is 0.5% to 8% by mass
  • the cobalt content is 1% to 30% by mass
  • the nickel content is 1% to 30% by mass
  • the manganese content is 1% to 30% by mass
  • the aluminum content is 0.5% to 40% by mass.
  • aluminum may be contained in the form of Al (metal) or a trace amount of LiAlO2 . It is considered that LiAlO2 is generated by the heat treatment described above.
  • the residue after the lithium leaching process may contain Al (metal), a trace amount of LiAlO2 , a hydrate of LiAl2 (OH) 7 , etc.
  • the hydrate of LiAl2 (OH) 7 is often not dissolved. For this reason, a small amount of aluminum may remain in the residue after the alkali leaching process.
  • the residue obtained in the alkaline leaching process is battery powder (battery powders B and D in the example in Figure 2).
  • This battery powder can be subjected to the acid leaching process described below.
  • the metal-containing solution obtained from the acid leaching process may have a cobalt ion concentration of 10 g/L to 50 g/L, a nickel ion concentration of 10 g/L to 50 g/L, a manganese ion concentration of 0 g/L to 50 g/L, an aluminum ion concentration of 1.0 g/L to 20 g/L, an iron ion concentration of 0.1 g/L to 5.0 g/L, a copper ion concentration of 0.005 g/L to 0.2 g/L, and a fluoride ion concentration of 0.01 g/L to 20 g/L.
  • Metal separation process In the metal separation step, metals such as cobalt and nickel can be separated from the metal-containing solution by various known techniques, and the necessary metals can be recovered. Specifically, the metal-containing solution can be neutralized and/or subjected to solvent extraction, etc., to separate and recover each metal in the metal-containing solution.
  • Example 1 As shown in FIG. 2, the lithium ion battery waste was subjected to heat treatment, crushing and sieving, and the large diameter sieved matter obtained by the sieving was further subjected to magnetic separation, re-crushing and re-sieving, and the Al-containing intermediate with the quality (mass%) shown in Table 1 was obtained as the sieved matter of the re-sieving.
  • the small diameter sieved matter obtained by the sieving was designated as battery powder A.
  • the medium diameter sieved matter obtained by the sieving was subjected to eddy current separation, and the magnetic material separated by the eddy current separation was designated as battery powder B.
  • the under-sieved matter obtained by the above re-sieving was designated as battery powder C.
  • Table 2 shows that battery powders A to C have a relatively high distribution rate of cobalt and nickel, but as shown in Table 1, the Al-containing intermediate also contained a certain amount of cobalt, etc. In order to remove aluminum from the Al-containing intermediate and recover cobalt, etc., the following process was carried out.
  • the Al-containing intermediate was subjected to lithium leaching for 5 hours at a pulp concentration of 100 g/L and room temperature (20°C). Distilled water with a pH of 5.8 was used for lithium leaching.
  • Figure 4 shows the change in the leaching rate of aluminum and lithium over time. In lithium leaching, a high lithium leaching rate is desirable from the viewpoint of suppressing lithium loss during the subsequent alkaline leaching, and a low aluminum leaching rate is desirable from the viewpoint of recovering high-purity lithium.
  • the pH at the end of leaching was 12.7. All of the cobalt and nickel were transferred to the residue and were not leached.
  • the residue after lithium leaching was immersed in an alkaline solution to perform alkali leaching of aluminum.
  • a sodium hydroxide aqueous solution with a concentration of 50 g/L was used as the alkaline solution, the pulp concentration was 50 g/L, the liquid temperature was room temperature (20°C), and the leaching time was 5 hours.
  • the graph shown in Figure 5 was obtained. Note that the leaching rate was calculated assuming that the mass of each metal in the Al-containing intermediate before lithium leaching was 100%. Figure 5 also shows the change in pH over time. In alkaline leaching, a higher aluminum leaching rate is desirable because it reduces the amount of aluminum distributed in the alkaline leaching residue (battery powder D) (and the amount of aluminum carried over to the subsequent acid leaching).
  • Example 2 Alkaline leaching of aluminum was carried out in the same manner as in Example 1 using the same residue after lithium leaching as in Example 1, except that the liquid temperature was 50° C. As a result, one hour after the start of alkaline leaching, the leaching rate of aluminum was 62%, and the leaching rate of lithium was about 13%.
  • Table 5 shows the purity and distribution rate of the sum of battery powders A to C shown in Table 2 and the residue (battery powder D) obtained after one hour of alkaline leaching
  • Table 6 shows the purity and distribution rate of the sum of these and the lithium in the lithium-containing solution obtained by lithium leaching.
  • Example 3 The same procedure as in Example 1 was followed except that the lithium leaching was completed after 1 hour, followed by the alkaline leaching. The pH at the end of the lithium leaching was 12.8.
  • the leaching rate of aluminum was 55% and the leaching rate of lithium was 9%.
  • the leaching rate of aluminum increased by about 5% compared to Example 1. This is considered to be due to the fact that the lithium leaching time was shortened to the minimum time required for lithium leaching, thereby suppressing the formation of LiAl2 (OH) 7 hydrate, which is difficult to leach by alkaline leaching, during lithium leaching.
  • Table 7 shows the purity and distribution rate of the sum of battery powders A to C shown in Table 2 and the residue (battery powder D) obtained after one hour of alkaline leaching
  • Table 8 shows the purity and distribution rate of the sum of these and the lithium in the lithium-containing solution obtained by lithium leaching.

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  • Processing Of Solid Wastes (AREA)

Abstract

Le procédé de récupération d'un métal à partir de déchets de batterie au lithium-ion selon la présente invention comprend : une étape de prétraitement consistant à soumettre les déchets de batterie au lithium-ion à un prétraitement comprenant un traitement thermique pour obtenir un intermédiaire contenant de l'Al contenant de l'aluminium et du lithium ; une étape de lixiviation de lithium consistant à amener l'intermédiaire contenant de l'Al en contact avec un liquide pour lixivier le lithium contenu dans l'intermédiaire contenant de l'Al dans le liquide, régler le pH du liquide à la fin de la lixiviation du lithium à 7-13, et obtenir un résidu et une solution contenant du lithium ; et une étape de lixiviation alcaline consistant à amener le résidu de l'étape de lixiviation du lithium en contact avec une solution alcaline et lixivier l'aluminium contenu dans le résidu dans la solution alcaline.
PCT/JP2024/023245 2023-07-04 2024-06-26 Procédé de récupération de métal Pending WO2025009455A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
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