Patent Application
20250043382
This specification discloses a method for leaching metals.
In recent years, the recovery of valuable metals from lithium ion battery waste discarded due to product life, manufacturing defects, or other reasons has been widely studied from the viewpoint of effective utilization of resources.
In order to recover valuable metals from lithium ion battery waste, for example, battery powder obtained through a heat treatment or other treatments is brought into contact with an acidic leaching solution to leach in the acidic leaching solution metals such as nickel, cobalt, manganese, aluminum and iron in the battery powder. This can provide a leached solution in which the metals are dissolved.
Subsequently, as described in Patent Literatures 1 to 3, solvent extraction or neutralization, or the like, is carried out to remove sequentially or simultaneously aluminum, iron, manganese and the like, among the metals dissolved in the leached solution. Valuable metals such as nickel and cobalt are then separated by solvent extraction and concentrated to recover them.
In the treatment of lithium ion battery waste as described above, relatively large amounts of froth may be generated from the acidic leaching solution when battery powder is brought into contact with the acidic leaching solution. Such a foaming phenomenon can interfere with the smooth operation of the step of leaching the metals in the battery powder into the acidic leaching solution.
This specification discloses a method for leaching metals that can effectively suppress foaming of an acidic leaching solution when leaching the metals in battery powder into the acidic leaching solution.
The method for leaching metals disclosed in this specification is a method for bringing battery powder resulting from lithium ion battery waste into contact with an acidic leaching solution inside a leaching vessel to leach metals contained in the battery powder into the acidic leach solution, wherein the leaching vessel comprises a movable member operably disposed at a position above a liquid surface of the acidic leaching solution stored therein, and the method comprises destroying froth generated in the acidic leaching solution by operation of the movable member.
According to the method for leaching metals as described above, it is possible to effectively suppress foaming of an acidic leaching solution when leaching metals in battery powder into the acidic leaching solution.
Embodiments of the method for leaching metals as described above will be described below in detail.
The method for leaching metals according to an embodiment is a method for bringing battery powder resulting from lithium ion battery waste into contact with an acidic leaching solution inside a leaching vessel to leach the metals contained in the battery powder into the acidic leaching solution.
The leaching vessel used has a movable member operably disposed at a position on a liquid surface of the acidic leaching solution stored therein. When the metals in the battery powder are leached inside the leaching vessel, the movable member is operated, and froth generated in the acidic leaching solution are destroyed by the operation of the movable member. This allows the froth generated in the acidic leaching solution to be effectively eliminated during leaching of the metals.
Such a method for leaching metals can be used in the process of recovering certain metals such as valuable metals, from lithium ion battery waste. Here, the method for leaching metals is described as an example where it is applied to a metal leaching step in a metal recovery process for lithium ion battery waste as illustrated in
Lithium ion battery waste of interest is vehicle lithium ion batteries or consumer electronics lithium ion batteries, which have been discarded due to battery product life, manufacturing failure, or other reasons. The vehicle lithium ion batteries include those contained in vehicle battery packs mounted on vehicles such as hybrid vehicles and electric vehicles. The consumer electronics lithium ion batteries include those used in various electronic devices such as mobile phones. Recovery of valuable metals such as cobalt, nickel and other valuable metals from such lithium ion battery waste is required from the viewpoint of effective utilization of resources.
The vehicle battery pack containing the vehicle lithium ion batteries generally includes metal cases forming housings around the cases, batteries housed inside the cases, each having a plurality of battery cells such as lithium ion batteries and other components. There are vehicle battery packs having various shapes, depending on the space constraints of the vehicles on which they are mounted. For example, there is a vehicle battery pack having a vertically long outer shape which is longer in one direction, such as a rectangular parallelepiped shape that is substantially rectangular in a plane view.
The lithium ion battery waste typically includes: a cathode material in which a cathode active material comprised of single metal oxides of one or more of lithium, nickel, cobalt and manganese or composite metal oxides two or more of them is applied and fixed onto an aluminum foil (a cathode substrate) via, for example, an organic binder such as polyvinylidene fluoride (PVDF); an anode material made of a carbon-based material; and an organic electrolytic solution such as ethylene carbonate or diethyl carbonate or other electrolytes. In addition, the lithium ion battery waste may contain copper, iron, and the like.
The pretreatment step may include a heat treatment, a crushing treatment and a sieving treatment in this order or in random order, but at least one of them may be omitted. The lithium ion battery waste is subjected to the pretreatment step to obtain the battery powder. As used herein, the battery powder refers to powder obtained by subjecting the lithium ion battery waste to any pretreatment step to separate and concentrate cathode material components. The battery powder may be obtained as powder by subjecting the lithium ion battery waste to the crushing treatment and the sieving treatment, with or without the heat treatment, thereby concentrating the cathode material components.
Here, an example of a case where the heat treatment is performed will be described below in detail. As an example of a case where the heat treatment is not performed, there is the following technique or the like as an example: the residual electricity of the lithium ion battery waste is first discharged, and then crushed and sieved, and the resulting cathode material with the aluminum foil is then treated with a solvent to dissolve the binder, and the cathode electrode material components are separated from the aluminum foil and recovered.
When the heat treatment is performed, the heat treatment involves heating the lithium ion battery waste. It should be noted that, in the case of lithium ion battery waste from the vehicle battery packs, it is difficult to disassemble them because they have robust structures protected by metal cases, and disassembling them may have a risk of causing electric shock due to residual voltage. Therefore, the lithium ion battery waste may be subjected to the heat treatment without disassembling it, while maintaining the structure in which the batteries and the like are surrounded by the cases.
The heat treatment of the lithium ion battery waste may be performed in an inert atmosphere or an air atmosphere. A part of the heat treatment may be performed in one of the inert atmosphere and the air atmosphere, and the remaining of the heat treatment may be performed in the other of the inert atmosphere and the air atmosphere. For example, the heat treatment may be first performed in an inert atmosphere, and the atmosphere may be then changed to perform the heat treatment in the air atmosphere. The atmosphere for this heat treatment can be appropriately selected in view of various factors such as characteristics of each atmosphere and working efficiency, which will be described later.
The heat treatment in the inert atmosphere suppresses explosive combustion of organic electrolytes and other substances that may be contained in the lithium ion battery waste, leading to easy control of a temperature inside a heat treatment furnace, and also suppresses the formation of nickel oxide and cobalt oxide and promotes the formation of cobalt and nickel which are metals easily dissolved in an acid, leading to increased recovery rates of valuable metals. If the temperature control of the heat treatment furnace becomes difficult, aluminum foil and other aluminum materials may melt, and valuable metals such as cobalt and nickel may be incorporated into the molten aluminum, leading to solidification. In this case, there is concern that the valuable metals will be removed together with the aluminum in a sieving treatment described below, resulting in decreased recovery rates of the valuable metals.
If the temperature in the heat treatment furnace can be controlled, the formation of powdered lithium aluminate due to the reaction of aluminum with lithium oxide can be suppressed. It should be noted that the formation of lithium aluminate promoted at high temperature and under high oxygen partial pressure leads to a decrease in the lithium leaching rate when lithium is leached in the metal leaching step as described below, because lithium aluminate has lower solubility in water than lithium carbonate. Further, aluminum foil that has not reacted into lithium aluminate can be easily separated by a sieving treatment. On the other hand, if lithium aluminate is formed, the aluminum foil becomes brittle and is easily mixed into the battery powder in the sieving treatment.
Specifically, the heat treatment in the inert atmosphere can be performed in an atmosphere containing at least one selected from the group consisting of nitrogen, carbon dioxide and water vapor. Among them, an atmosphere mainly containing nitrogen is preferable. The heat treatment may be performed while allowing such an inert gas to flow. Oxygen may be contained in a trace amount to some extent, and an oxygen partial pressure during heat treatment can be maintained in a range of 0 atm to 4×10−2 atm as measured by a zirconia-type oxygen concentration meter. When the inert gas is introduced into a heat treatment furnace, it is preferable that the oxygen concentration of the inert gas may be 0.05% by volume to 4.00% by volume, and the flow rate in the heat treatment furnace may be 6 m3/hr to 60 m3/hr. Also here, the lithium ion battery waste can be heated to reach a temperature of 400° C. to 800° C. and maintain it at this temperature.
The heat treatment in the air atmosphere can suppress a foaming phenomenon in acid leaching in the metal leaching step. Substances resulting from incomplete thermal decomposition of the heat treatment in the inert atmosphere can cause the foaming during acid leaching.
The heat treatment in the air atmosphere is preferable because any adjustment of the atmosphere becomes unnecessary to lead to a simple process. At this time, the lithium ion battery waste can be heated to reach a temperature of 400° C. to 800° C. and maintain it at this temperature.
For the heat treatment, for example, an atmospheric electric furnace or atmospheric muffle furnace can be used in the case of a batch type, or a roller hearth kiln, mesh belt kiln, pusher kiln or the like can be used in the case of a continuous type. Among them, the roller hearth kiln and pusher kiln are preferred because they are suitable for large-scale processing.
The crushing treatment is carried out, for example, in order to remove the batteries from the cases of the vehicle battery packs in the lithium ion battery waste and destroy the housings of the batteries, and also selectively separate the cathode active materials from the aluminum foils coated with the cathode active materials. Here, various known devices or equipment can be used, and specific examples thereof include an impact-type crusher capable of crushing the cases and the batteries by applying an impact while cutting them, such as a sample mill, a hammer mill, a pin mill, a wing mill, a tornado mill, a hammer crusher and the like. A screen can be installed at the outlet of the crusher, so that the batteries are discharged from the crusher through the screen when the batteries are crushed to have a size that can pass through the screen.
After the crushing, if necessary, the crushed batteries are roughly pulverized or powdered into powder, and then sieved using a sieve having an appropriate mesh size. As a result, aluminum, copper and the like can remain on the sieve, for example, and battery powder containing lithium, cobalt, nickel and the like from which aluminum, copper, and the like have been removed to some extent can be obtained under the sieve.
As described below, when carbon is contained in the battery powder, for example in the form of relatively fine carbon powder derived from anode materials, the foaming during the acid leaching in the metal leaching step tends to be more remarkable. This tendency does not depend on the details of the pretreatment step, such as the presence or absence of the heat treatment, as long as carbon is present in the battery powder. In this embodiment, any battery powder that does not contain carbon and any battery powder that does contain carbon can be targeted, and in both cases, the foaming during the acid leaching can be effectively suppressed.
To leach the metals in the battery powder as described above, the battery powder can optionally be brought into contact with a liquid such as water to leach lithium, and the resulting residue can be then brought into contact with an acidic leaching solution to leach other metals into the acidic leaching solution. The leaching of lithium provides a lithium dissolved solution, and the acid leaching provides a leached solution in which metals such as cobalt, nickel, manganese, aluminum, copper, and iron are dissolved.
When the lithium is leached prior to the leaching with the acidic leaching solution, water may be brought into contact with the battery powder, and specifically, tap water, industrial water, distilled water, purified water, ion-exchanged water, pure water, ultrapure water, and the like can be used. In addition, a liquid temperature at the time of contact of the battery powder with the liquid can be 10° C. to 60° C.
The lithium dissolved solution obtained by the leaching of lithium can be subjected to treatments such as solvent extraction, neutralization, and carbonation, thereby recovering lithium in the lithium-dissolved solution as lithium carbonate. The lithium carbonate thus obtained may optionally be purified to reduce impurity grade.
The battery powder as the residue or the like after the above lithium leaching is brought into contact with the acidic leaching solution to leach metals such as cobalt and nickel contained therein into the acidic leaching solution. During the acid leaching using the acidic leaching solution, the froth may be generated from the acidic leaching solution, and such froth inhibit any smooth acid leaching. To address this, a leaching vessel 1 having a cylindrical shape with a bottom as illustrated in
In the illustrated leaching vessel 1, as an example of the movable member, a rotating member 2 having a plate shape such as a flat plate shape or other shapes, movable above a liquid surface 22, is disposed above a position where the liquid surface 22 would exist if an acidic leaching solution 21 was stored therein. As a result, when the battery powder is brought into contact with the acidic leaching solution 21, as illustrated, froth Ba that are generated in the acidic leaching solution 21 and float on the liquid surface 22 are destroyed by the rotation of the rotating member 2. Consequently, the froth Ba are prevented from leaking out of an opening 3 on an upper side of the leaching vessel 1, thus allowing the acid leaching to be performed smoothly.
The specific structure and shape of the rotating member 2 is not limited as long as it can be rotated above the liquid surface 22 to destroy the froth Ba. In the illustrated example, the leaching vessel 1 further includes a rotating shaft 2a which extends in the depth direction of the acidic leaching solution 21, and to which a rotational driving force is applied from a drive source not shown. The rotating member 2 is attached to this rotating shaft 2a in an orientation that extends parallel to a direction orthogonal to the depth direction (horizontal direction), and can be rotated around the rotating shaft 2a in a horizontal plane parallel to the liquid surface 22 upon the rotation of the rotating shaft 2a. The rotating shaft 2a may be positioned in the substantially center of the leaching vessel 1 in a cross section orthogonal to the depth direction of the leaching vessel 1. Here, a single plate-shaped rotating member 2 having a rectangle in a side view is provided around the rotating shaft 2a, but two or more rotating members 2 may be provided, for example, equally spaced in the circumferential direction.
The rotating member 2 in the height direction (the up-down direction in
The leaching vessel 1 shown in
In this case, as shown in
The rotational speed of the rotating member 2 during acid leaching is, for example, 50 to 500 rpm. If the rotational speed is too slow, the rotation of the rotating member 2 cannot keep up with the generation of the froth, so that the foaming may not be sufficiently suppressed. On the other hand, an excessively high rotational speed is unnecessary from the viewpoint of the suppression of the foaming, as well as if the rotational speed is too fast, there is a risk that the froth Ba may be scattered. In the case where the rotating shaft 2a is shared by the rotating member 2 and the agitating blade 2b as shown in
In
In the leaching vessel 1 having the baffle plate 5, the radial length of the rotating member 2 (the distance from the rotating shaft 2a to the outer end of the rotating member 2) may not be so long in terms of preventing interference of the rotating member 2 with the baffle plates 5. In the leaching vessel 1 shown in
The embodiment where the rotating member 2 is used has been described above in detail as an example of the movable member. However, the movable member is not limited to the rotating member 2 as long as it can move above the liquid surface 22 of the acidic leaching solution 21 and can destroy the froth Ba. Other examples of the movable members, which are not shown in the figure, include, for example, rod-shaped or plate-shaped or other shaped reciprocating members that are driven to repeatedly reciprocate above the liquid surface 22 of the acidic leaching solution 21 in a direction orthogonal to the height direction. Such a reciprocating member can be brought into contact with the froth Ba generated on the liquid surface 22 of the acidic leaching solution 21 in the outward direction to suppress the rising of the froth Ba, and then brought in to contact with the froth Ba again in the return direction during a period of time until the froth Ba rise to an allowable height. This enables the reciprocating member to suppress the froth Ba below the allowable height.
By the way, the acidic leaching solution 21 may contain, for example, 50 g/L or more, typically 60 g/L to 400 g/L, of sulfuric acid, although other acids may be used. When the acidic leaching solution 21 containing sulfuric acid, especially at a relatively high concentration as described above, is brought into contact with the battery powder, the generation of froth Ba becomes more remarkable, so that it is effective to use the leaching vessel 1 having the rotating member such as the rotating member 2 as described above.
In addition, the methods of bringing the battery powder into contact with the acidic leaching solution 21 containing sulfuric acid include bringing the battery powder into contact with a sulfuric acid solution of concentrated or dilute sulfuric acid, and adding concentrated sulfuric acid to a slurry in which the battery powder is dispersed in water or other liquid, and the like. The generation of the froth Ba as described above is thought to be mainly caused by a hydrogen gas produced in the leaching reaction. Therefore, it is assumed that when the battery powder is brought into contact with the sulfuric acid solution of dilute sulfuric acid, the generation rate of the hydrogen gas is relatively slow and the degree of foaming is lower. On the other hand, a lower sulfuric acid concentration slows the leaching rate and reduces an efficiency of the metal leaching step. Therefore, from the perspective of improving the efficiency of the metal leaching step, it is desirable to add the battery powder to the sulfuric acid solution having the higher concentration (e.g., a sulfuric acid concentration of 50 g/L or higher) as described above, or to add concentrated sulfuric acid (a sulfuric acid concentration of 90% by mass or higher (e.g., 98% by mass)) to the slurry containing the battery powder. In this embodiment, since the foaming can be suppressed by the movable member such as the rotating member 2, the battery powder can be added to the sulfuric acid solution of concentrated sulfuric acid, or sulfuric acid can be added to the slurry containing the battery powder to increase the efficiency of the metal leaching step.
It was newly found that when the carbon content in the battery powder is higher than 17% by mass, e.g., 17 to 50% by mass, larger number of froth Ba are generated when the battery powder is in contact with the acidic leaching solution 21. Therefore, when the battery powder having such a higher carbon content is brought into contact with the acidic leaching solution 21, the defoaming by the movable member (the rotating member 2 and the like) provided in the leaching vessel 1 functions even more effectively.
Also, it was newly found that the particle size distribution of the battery powder affects the generation of the froth Ba during the acid leaching. Specifically, when the particle size of the battery powder is measured with a laser diffraction and scattering particle size distribution measuring device (such as MT3000II manufactured by MicrotracBEL Corp.) to obtain a particle size distribution graph on a volume basis, if multiple peaks appear on the particle size distribution graph, the Ba froth during acid leaching will increase when the area ratio of the peak located on the smallest diameter side is relatively high, such as 15% or more, for example 15% to 40%. Therefore, it is effective to apply this embodiment to the battery powder having such a larger percentage of small particles. The area ratio of the peak located on the smallest diameter side can be determined by doubling the cumulative frequency at the peak position on the particle size distribution graph. Here, the cumulative frequency at the peak position as described above means the cumulative value of the frequency from the smallest diameter side of the peak located on the smallest diameter side to that peak on the particle size distribution graph as shown in
The pH of the acidic leaching solution is preferably 0.0 to 4.0 during the acid leaching, and it may be 0.5 to 2.0 after the acid leaching is completed. The oxidation-reduction potential (ORP value, based on silver/silver chloride potential) may be, for example,-250 mV to 0 mV immediately after the acid leaching, and it may be about 300 mV in the leached solution after solid-liquid separation. During the acid leaching, the acidic leaching solution can be agitated at, for example, 50 rpm to 500 rpm using an agitator having the agitating shaft 2b and the like if necessary. The liquid temperature during the acid leaching may be 60° C. to 80° C., for example.
In the acid leaching of the metal leaching step, only one leaching stage may be performed, or multiple leaching stages may be repeated multiple times. When the multiple leaching stages are performed, each leaching stage includes a first leaching stage of leaching the battery powder with the acidic leaching solution and separating the leached residue to obtain a leached solution, and a second leaching stage of leaching the leached residue from the first leaching stage with the acidic leaching solution to obtain a leached solution. The leached solution obtained in the final leaching stage (the second leaching stage if there are two leaching stages: the first leaching stage and the second leaching stage), among those leaching stages, is used by containing it in the acidic leaching solution of the next first leaching stage. Also, the leached solution obtained in each leaching stage other than the final leaching stage (the first leaching stage if there are two leaching stages: first leaching stage and second leaching stage) is sent to the next step (impurity removal and metal recovery step). When the multiple leaching stages are repeated in such a way, many of the metals (such as copper) for which the leaching is desired to be suppressed can be separated as a leached residue without leaching those metals, while increasing the leaching rates of the metals to be leached (such as cobalt and/or nickel) in the battery powder.
The leached solution as described above may be subjected to a step of recovering metals such as cobalt and nickel after impurities are removed. For example, the removal of impurities includes removal of some of aluminum and iron by neutralization, and removal of the remaining aluminum and manganese by solvent extraction, and the like. In the recovery of the metals, cobalt and nickel can be recovered by sequentially extracting cobalt and nickel by solvent extraction and stripping them.
Next, the method for leaching metals as described above was experimentally carried out and the effects thereof were confirmed, as described below. However, the descriptions herein are merely for illustrative and are not intended to be limited.
The lithium ion battery waste was subjected to a heat treatment to obtain battery powder. The battery powder was subjected to acid leached using a leaching vessel (2 L beaker) having the rotating member, the agitating blade, and the baffle plates as shown in
In the acid leaching, sulfuric acid was added while rotating the rotating member and the agitating blade at the rotational speeds shown in Table 1, and at this time, the foaming height VT, expressed by the equation: VT=(VF+VL)/VL, was measured from the volume VL of the acidic leaching solution and the volume VF of the froth on the liquid surface. The results are shown in
In Example 1, the foaming height VT increased to 1.6 after 50 minutes from the start of the addition of sulfuric acid, but it did not increase thereafter. In Example 1, the rotational speed of the rotating member was switched to 150 rpm at the elapsed time of 70-75 minutes, 360 rpm at the elapsed time of 75-80 minutes, and 300 rpm at other times, but the foaming height VT could be suppressed to 1.6 or less at any rotation speed. As shown in
In Example 2, the foaming height VT increased to 1.4 after 40 minutes from the start of the addition of sulfuric acid, but it did not increase thereafter. As shown in
In Example 3, the foaming height VT increased to 1.4 after 50 minutes from the start of the addition of sulfuric acid, but it did not increase thereafter. As shown in FIG. 7, the froth on the liquid surface were in the form of mountain around the rotational shaft in the foaming height VT range of 1.0 to 1.2. After that, the froth remained at the edge portion of the rotating member in the region where they were in contact with the rotating member (VT=1.2) and rose to the position of VT=1.4 in the region on the upper side of the baffle plate around the rotating member, but they were suppressed without rising to a position higher than that.
The lithium ion battery waste was subjected to the heat treatment under the predetermined conditions to prepare several types of battery powder, which had different percentages of small particles as measured by the method as described above. Each battery powder was subjected to acid leaching. The VT was calculated from the volume VL of the acidic leaching solution and the volume VF of the froth generated in the acidic leaching solution based on the equation: VT=(VF+VL)/VL. The results are graphically shown in
It is found from
Several types of battery powder having different carbon contents obtained from the lithium ion battery waste were prepared. Each of these battery powders was subjected to the acid leaching. In this case, the VT was calculated from the volume VL of the acidic leaching solution and the volume VF of the froth generated in the acidic leaching solution based on the equation: VT=(VF+VL)/VL. The results are graphically shown in
It is found from
As described above, it was found that the method for leaching metals as described above could effectively suppress the foaming of the acidic leaching solution.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-200262 | Dec 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/037332 | 10/5/2022 | WO |
