JP7333098B2 - Valuable metal recovery method from waste batteries - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act 1) Presented at a research meeting of an academic organization Social Promotion Organization [Date] March 15, 2021

TECHNICAL FIELD The present invention relates to a method for recovering valuable metals such as cobalt, nickel, and lithium from used waste batteries such as lithium ion batteries, for which collection and recycling efforts are required.

Patent Document 1 describes a roasting process of roasting waste batteries, a crushing process of putting the roasted products in a crushing container and crushing them using a chain mill, and sieving the crushed products to separate the sieved products and the unsieved products. A method for recovering valuable metals from waste batteries is disclosed, comprising a sieving step to separate the

In Patent Document 2, a used lithium battery incorporated in an iron case is roasted together with the iron case, the resulting roasted product is crushed, primary magnetic separation is performed to separate magnetic substances and non-magnetic substances, and further A method for recovering valuables from used lithium batteries is disclosed in which the non-magnetic materials are subjected to secondary magnetic separation.

Japanese Patent Application Laid-Open No. 2021-139019 JP-A-11-185833

The invention of Patent Document 1 describes that the roasting temperature is preferably 700° C. or higher and 1200° C. or lower. Some of the iron, etc. attached to the inner wall of the main body of the roasting furnace such as the kiln may interfere with smooth operation or may lead to deterioration of the kiln itself, which is not preferable. Therefore, it is suggested that the waste batteries are put directly into the main body of the roasting furnace. Then, since the melting point of the aluminum contained in the waste battery is 660.3° C., the aluminum melts in the roasting furnace and solidifies and adheres to the bottom wall of the furnace, for example, in lumps of about 5 cm in height. Therefore, there is a problem that it is extremely difficult to recover the aluminum adhering to the bottom wall of the furnace and mixed with members that are not melted at the roasting temperature of the waste battery. Furthermore, the aluminum melted at the roasting temperature contains waste battery materials that do not melt at the roasting temperature, and there is a problem that the recovery rate of the waste battery materials that do not melt at the roasting temperature is low. Ta.

According to the invention of Patent Document 2, if the roasting temperature is too high, the roasted product will melt and solidify, making it difficult to crush the roasted product, and the copper will melt and damage the furnace. Since the description and the description of the drum before roasting and the drum after roasting are shown in FIG. 1, it is suggested that the roasted product is stored in a drum and roasted. Then, since the melting point of the aluminum contained in the waste battery is 660.3° C., the aluminum melts inside the drum and solidifies and adheres to the bottom wall of the peripheral wall, etc., in clumps of about 5 cm in height. There is a problem that it is extremely difficult to separate and recover the aluminum adhering to the bottom wall of the waste battery, which is mixed with members that are not melted at the roasting temperature of the waste battery. Furthermore, the aluminum melted at the roasting temperature contains waste battery materials that do not melt at the roasting temperature, and there is a problem that the recovery rate of the waste battery materials that do not melt at the roasting temperature is low. Ta.

The present invention has been devised in view of these problems, and it is possible to prevent unmelted metal from being mixed with the molten metal that is melted in the roasting process, and to easily recover the molten metal that is not mixed with unmelted metal. An object of the present invention is to provide a method for recovering valuable metals from waste batteries.

In the method for recovering valuable metals from waste batteries according to claim 1, the waste batteries are stored in an iron container having a plurality of air holes in the peripheral wall including the vicinity of the bottom wall, and a plurality of the iron containers are placed. a roasting step of roasting the waste battery with the tray -shaped iron saucer placed in a roasting furnace; It is characterized by comprising a crushing step of crushing with an impact load, and a magnetic separation/sieving step of carrying out magnetic separation and sieving simultaneously with the crushed material after the crushing step.

The method for recovering valuable metals from waste batteries according to claim 2 is characterized in that, in claim 1, the crushing step is performed by applying a shock load to the roasted material at the bottom of the vertically installed rotating shaft. It has a plurality of metal chains with one end fixed and the other end free at a height that can discharge crushed materials like sweeping with a broom when the rotation speed of the metal chain is slowed down. A chain-type crushing means is provided, and based on the impact force of the chain-type crushing means, it is set for each type of the waste battery so that the waste battery can be separated into solid matter and powder matter according to the constituent members of the waste battery. It is characterized in that the chain-type crushing means is actuated and crushed at a predetermined amount to be charged and for a predetermined crushing time.

The method for recovering valuable metals from waste batteries according to claim 3 is characterized in that, in claim 1 or 2, the magnetic separation/sieving step has a size capable of sieving crushed powders of a predetermined size. A sieve vibrating device having a screen having mesh openings, the downstream side of which is slanted downward; The crushed material after the crushing step is separated into crushed magnetic material, crushed non-magnetic material having a size equal to or larger than a predetermined size, and crushed non-magnetic material having a size smaller than a predetermined size.

In the method for recovering valuable metals from waste batteries according to claim 1, a metal that melts at the roasting temperature applied in the roasting process, such as aluminum, which is the material of the case of the waste battery, is mixed with unmelted members of the waste battery. There is an effect that it is possible to recover the product in a state of high purity. In addition, since the materials that do not melt at the roasting temperature of the waste battery do not mix with the molten aluminum, there is an effect that the recovery rate of the materials that do not melt at the roasting temperature increases.

The method for recovering valuable metals from waste batteries according to claim 2 is characterized in that, based on the size and strength of the material of the metal chain itself of the chain-type crushing means and the impact force generated by the number of revolutions of the metal chain, the waste All the constituent members of the battery can be crushed, and the constituent members can be separated into solids and powders, and the waste batteries are crushed in a predetermined amount and for a predetermined crushing time for each type of waste battery, so the crushing rate of the roasted product can be set to 100%, the roasted product to be recovered as a solid can be recovered as a solid without crushing it to powder by making the crushing time too long, and the roasted product to be recovered as a powder can be recovered as a solid by shortening the crushing time too much. Therefore, it is possible to collect the powder as a crushed powder rather than as a solid substance.

In the method for recovering valuable metals from waste batteries according to claim 3, since the crushing rate is 100%, there is no crushed material in which the magnetic material and the non-magnetic material are stuck together. , the copper foil of the negative electrode plate, which is the internal material, can be recovered as a solid matter, and the nickel, cobalt, and lithium of the positive electrode plate, which are the internal materials, can be recovered as powders, so the recovery rate of valuable metals is increased. It has the effect of increasing.

1 is a flowchart of a method for recovering valuable metals from waste batteries according to the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the iron-made container, (a) is explanatory drawing of the iron-made container which provided the some air hole of this invention, (b) is explanatory drawing of the conventional drum of a comparative example. FIG. 2 is an explanatory longitudinal cross-sectional view of an iron container and an iron saucer containing waste batteries in the roasting process of the present invention; Fig. 2 is a schematic explanatory view showing only the parts to be explained, showing the state before carrying the loading/unloading stand on which the iron container and the iron saucer are placed into the roasting furnace. FIG. 2 is a schematic longitudinal sectional view showing only the parts to be explained, in a state where an iron container or the like is set in the roasting furnace of the roasting step of the present invention. It is a vertical cross-sectional explanatory view of the saucer taken out after roasting in the roasting process of the present invention, (a) is a vertical cross-sectional explanatory view of the state immediately after being taken out from the roasting furnace, and (b) is an iron container taken out. It is a vertical cross-sectional explanatory view of the state, and (c) is a vertical cross-sectional explanatory view of a state in which the molten metal that has melted and adhered to the tray is peeled off. FIG. 10 is a schematic explanatory view showing only a portion to be explained of a loading/unloading table on which drums of a comparative example are placed before being loaded into a roasting furnace; FIG. 10 is a schematic vertical cross-sectional explanatory view showing only a portion to be explained of a comparative example in which a comparative drum containing waste batteries is set in a roasting furnace. FIG. 3 is a vertical cross-sectional explanatory view of a drum of a comparative example taken out from a roasting furnace; FIG. 10 is an explanatory diagram of the state of the residue of the drum of the comparative example after the roasted product is taken out; It is an outline explanatory drawing of the left side view of the apparatus of a magnetic separation and sieving process. FIG. 12 is a schematic explanatory view of the upstream side in the AA cross section in FIG. 11;

Method 1 for recovering valuable metals from waste batteries of the present invention uses cobalt and nickel from used waste batteries 20 of small secondary batteries such as lithium ion batteries, for which recovery and recycling are required. , a method for recovering valuable metals such as lithium. Lithium-ion batteries, in particular, are used in mobile phones, personal computer batteries, vehicle batteries, etc., and the market is expected to expand rapidly due to the worldwide shift to electric vehicles.

The lithium ion battery includes an electrolytic solution, a case made of iron or aluminum, a positive electrode plate containing nickel, cobalt, lithium or the like, and a negative electrode plate containing copper coated with graphite or lithium titanate.

The method 1 for recovering valuable metals from waste batteries includes, as shown in FIG. A roasting step 2 of roasting the waste battery 20 in a state where a substantially tray-shaped iron receiving tray 7 having a plurality of containers 5 placed thereon is placed in a roasting furnace 10, and the iron container after the roasting step 2. A crushing step 3 for removing the roasted product 21 from 5 and crushing the roasted product 21 with an impact load, and a magnetic separation/sieving step 4 for performing magnetic separation and sieving on the crushed product after the crushing step 3, Prepare.

In the roasting step 2, as shown in FIG. 2(a), the waste battery 20 is stored in an iron container 5 having a plurality of air holes 6 in the peripheral wall including the vicinity of the bottom wall. The waste battery 20 is roasted in a roasting furnace 10 in a state in which a substantially tray-shaped iron tray 7 on which a plurality of the waste batteries 20 are placed is placed. The diameter of the air hole 6 is, for example, 1.5 cm, which is large enough to allow the molten metal 22 to flow out of the iron container 5 and prevent the unmelted members of the waste battery 20 from flowing out of the iron container 5 during roasting. The diameter may be of any size.

As shown in FIG. 2(a), the air hole 6 is formed near the bottom wall of the peripheral wall of the iron container 5, i. It is necessary to provide an air hole 6a at a plurality of locations in the circumferential direction. Furthermore, since it becomes difficult for air to flow into the air hole 6a provided near the bottom wall of the peripheral wall, i.e., at the lower end, due to the outflow of the molten metal 22, a plurality of air holes 6b and 6c are provided upward from the lower end of the peripheral wall. , 6d are also provided, and a plurality of air holes 6b, 6c, 6d are also provided in the circumferential direction.

The roasting temperature is 800°C to 1200°C. Since the temperature is 1455° C., cobalt is 1495° C., and lithium titanate is 1533° C., aluminum melts in roasting step 2, but iron, copper, nickel, cobalt, and lithium titanate do not melt.

As a comparative example, the molten aluminum was placed in a drum 31 having an internal volume of 200 liters without an air hole 6 as shown in FIG. is stored and roasted, as shown in FIG. coagulate.

As a result, as shown in FIG. 10, aluminum melted and solidified at the roasting temperature is melted at the roasting temperature of the waste battery in the lower part of the drum 31 after removing the roasted material 21 that is not melted in the upper part. It is difficult to remove and recover lumps of the waste battery material mixed molten material 23, which is solidified by the mixed waste battery material mixed with non-removable materials. In addition, there is a problem that it is impossible to recover high-purity aluminum and that waste battery members that should be recovered cannot be recovered.

The iron container 5, as shown in FIG. 2(a), is a lidless container having a cylindrical portion with a circular or square horizontal cross section and an air hole 6 provided in at least the lower end of the peripheral wall. , The air hole 6, depending on the part, introduces air during roasting to promote strong heating below the melting point of the material to be recovered as a solid or powder without melting, or material to be melted and recovered has a function of flowing out, for example, the aluminum of the molten metal 22 that has been melted. The aluminum of the molten metal 22 melted and flowed out of the iron container 5 is deposited in the substantially tray-shaped iron receiving pan 7 .

The iron tray 7 has a tray-like shape having a short peripheral wall on the peripheral edge of a rectangular or circular flat plate. The iron containers 5 can be arranged in a single stack, for example, can be placed on the fixed floor 12 in the roasting furnace 10 of the fixed floor furnace type, and the aluminum of the molten metal 22 is melted and flowed out. It can be used as a saucer.

The roasting furnace 10 is of a batch type, and the hearth has a fixed floor 12 that slides inside and outside the roasting furnace, as shown in FIGS. Any form may be used as long as the iron container 5 can be taken in and out. The roasting furnace 10 has a structure capable of supplying air during roasting. The furnace lid 13 is opened, the iron tray 7 is slid, and the iron tray 7 is thrown into the furnace, and the furnace lid 13 is closed to seal the inside of the furnace. A structure that can be used is good.

Next, the method of roasting step 2 will be described. First, as shown in FIG. 4, outside the roasting furnace 10, waste batteries 20 of the same type and having the same shape and case material, for example, lithium-ion batteries whose terminals are insulated, are collected. Then, waste batteries 20 of the same type are stored so as to be filled in an iron container 5 having an air hole 6 near the bottom wall of the peripheral wall. A plurality of such iron containers 5, for example four, are prepared.

Then, as shown in FIG. 3, a plurality of, for example, four iron containers 5 containing waste batteries 20 are placed on the iron tray 7 . As shown in FIGS. 4 and 5, the placed iron tray 7 is set on the fixed floor 12 which is slid out of the roasting furnace 10 by opening the furnace lid 13, and after the setting, the above-described The fixed bed 12 is slid into the roasting furnace 10, and the furnace cover 13 is closed to make the inside of the roasting furnace 10 airtight.

Next, the ignition burner 11 is ignited, and the waste battery 20 is roasted while introducing new air into the furnace. When the waste battery 20 is ignited, the ignition burner 11 is extinguished. Then, the roasting treatment is performed while maintaining the temperature in the furnace within the range of 800°C to 1200°C.

After the roasting treatment for about 4 hours, the furnace cover 13 of the roasting furnace 10 is opened, and the iron tray 7 on which the iron container 5 is placed is taken out from the roasting furnace 10 and cooled to room temperature. put. As shown in FIG. 6( a ), the aluminum of the molten metal 22 melted at the roasting temperature flows out and accumulates on the iron receiving pan 7 taken out from the roasting furnace 10 . contains no molten metal 22 melted at the roasting temperature and contains the roasted material 21 that does not melt at the roasting temperature.

After cooling, the iron container 5 is taken out from the iron tray 7, and then, as shown in FIG. remove it. As a result, the molten metal 22 containing very few impurities, such as aluminum, can be easily recovered. After that, as shown in FIG. 6(c), since there is no deposit generated after roasting in the metal tray 7, the metal tray 7 can be used repeatedly.

Next, the crushing step 3 will be described. In the crushing step 3, a metal chain with one end fixed and the other end free at a predetermined height at which an impact load can be applied to the roasted product 21 below the vertically installed rotating shaft. A chain-type crushing means (not shown) having a plurality of In this step, the chain-type crushing means is operated to crush waste batteries 20 at a predetermined amount and for a predetermined crushing time set for each type of waste battery 20 .

After the roasting step 2, the roasted product 21 is taken out from the iron container 5, and the roasted product 21 is crushed by an impact load. As a device for crushing by the impact load, one end is fixed at a predetermined height at which the impact load can be applied to the roasted product 21 at the bottom of the vertically installed rotating shaft, and the other end is a free end. A chain crushing means (not shown) having multiple metal chains is used.

There are various types of waste batteries 20 having different sizes, shapes, and materials, such as batteries for mobile phones, batteries for personal computers, and batteries for vehicles. Since it is different, it is considered that the state to be collected is divided into magnetic substances, solid substances that are non-magnetic substances, and powder substances that are non-magnetic substances for each part constituting each waste battery 20. Make the crushing method feasible.

The impact force of the chain-type crushing means when the chain rotates is determined by the material, thickness, and rotation speed of the metal chain. The material and thickness of the metal chain are constant for each device, and the number of rotations of the chain can be adjusted depending on the device, but the number of rotations can also be set constant. When the number of rotations is constant, that is, when the impact force is constant, for example, the solid material, which is the roasted material 21, is crushed and reduced in size depending on the rotation time, that is, the crushing time, and the amount of the roasted material 21 input. The input amount and the crushing time are adjusted based on the hardness and size of the materials of the waste battery 20 so that the solids that are the roasted product 21 are crushed into powder. , it is possible to adjust whether it is a solid with a reduced size or a powder.

Therefore, in order to be able to classify the collected state into either a magnetic substance, a non-magnetic solid substance, or a non-magnetic powder substance for each part constituting each waste battery 20, Based on the impact force of the chain-type crushing means, the waste battery 20 is divided into solids and powders according to the components of the waste battery 20. A predetermined crushing time is set, and the chain-type crushing means is operated to crush.

As the chain-type crushing means, for example, there is a vertical chain-type crusher, which is a batch type. The rotation of the two iron chains with free ends crushes the roasted food 21 by the impact of the chain and the roasted food 21 thrown in and falling is bounced off by the chain, so that the roasted food 21 collides with each other. Fragmentation due to impact caused by Further, the crushed material 24 after crushing can be discharged from a discharge port provided in the lower part of the peripheral wall of the crushing chamber of the vertical chain crusher as if sweeping with a broom by slowing down the rotation speed of the chain.

In the crushing step 3, the roasted product 21 is taken out from the iron container 5 that has been cooled while being placed on the iron receiving plate 7, and the roasted product 21 is put into a feeding belt conveyor (not shown) in fixed amounts. do. Then, by the belt conveyor for feeding, the roasted product 21 is batch-type, and one end is attached and fixed at equal intervals in the horizontal direction to the lower part of the rotating shaft vertically installed in the center, and the other end is a free end. It is put into a crushing chamber (not shown) of the vertical chain crusher equipped with two iron chains.

Then, the metal chain is rotated to crush the toasted material 21 for a predetermined crushing time and a predetermined amount of charge set according to the type of the waste battery 20 put in. When the crushing time is over, the rotation speed of the chain is slowed down to sweep out the crushed material in the crushing chamber.

Next, the magnetic separation/sieving step 4 will be described. The magnetic separation/sieving step 4 is a step of performing magnetic separation and sieving of the crushed material after the crushing step 3. As shown in FIGS. A sieve vibrating device 41 having a screen having openings large enough to sift objects, and a sieve vibrating device 41 inclined downward on the downstream side; A magnetic separation means 42 having an attractable magnet 42a is provided, and the crushed material 24 after the crushing step 3 is divided into the crushed material 24 of the magnetic body 51, the crushed material of the non-magnetic solid body 53 having a predetermined size or more, and , to separate crushed non-magnetic powders 52 having a size smaller than a predetermined size.

The magnetic separation means 42 is installed above the sieve vibration device 41. For example, as shown in FIGS. 11 and 12, there is a structure in which a large magnet 42a is installed inside a rotating belt conveyor 42b. The magnetic separation means 42 can attract the magnetic material 51 from the crushed material 24 on the sieve vibrating device 41 . The belt conveyor 42b rotates in the direction K, and since there is no magnet 42a near the roller at the end of the belt conveyor 42b, the magnetic material 51 attracted here falls and is collected in the magnetic material collection box 51a. .

The sieving is performed by a sieve vibrating device 41 equipped with a screen having openings large enough to sift crushed powdery materials of a predetermined size, and a coil connected to a swinging means is attached to the screen. Vibration is given by the spring 41a or the like. When the vibration is applied, the crushed materials 24 on the sieve vibrating device 41 obliquely installed with the downstream side facing downward are gradually moved downstream while being sieved. Moreover, the size of the predetermined mesh opening is preferably a size that enables sieving of the solid and powder of the material to be recovered, and is, for example, 3 mm, and the screen has a porous structure with a diameter of 3 mm. The size of the opening is such that the powdery crushed material 24 and the solid crushed material 24 are mixed in the crushed material 24 after the crushing step 3, so that the powdery form and the solid form can be separated. set to size.

When the crushed material 24 after the crushing step 3 is placed on the sieve vibrating device 41, the crushed material 24 of magnetic material is attracted to the belt conveyor 42b of the magnetic means 42, and the non-magnetic material having a size of less than 3 mm is generated. The crushed material falls under the sieve, and non-magnetic crushed material with a size of 3 mm or more remains on the sieve. As a result, the crushed magnetic material 24, the crushed solid non-magnetic material 24 of a predetermined size or more, and the crushed powder 24 of non-magnetic material less than a predetermined size are separated and recovered. can be done.

For example, the iron in the case can be recovered as the crushed material 24 of the magnetic material 51, the copper in the negative electrode plate can be recovered as the non-magnetic solid body 53 having a predetermined size or more, and the non-magnetic powder having a size less than a predetermined size can be recovered. As 52, for example, nickel, cobalt, and lithium of the positive plate can be recovered. The non-magnetic powder 52 that has fallen under the sieve is transported by a belt conveyor 43 installed substantially parallel in the vertical direction below the sieve vibrating device 41, collected in a non-magnetic powder collection box 52a, and subjected to the sieve vibration. The non-magnetic solids 52 remaining on the device 41 are gradually lowered by the vibration of the sieve vibrating device 41 and collected in the non-magnetic solids collection box 53a.

A lithium-ion battery with a box-shaped casing made of iron and a size of 3 cm long, 15 cm wide, and 10 cm high is abbreviated as a 200-liter drum containing a plurality of air holes 6 on the peripheral wall including the vicinity of the bottom wall. The iron containers 5 are stored in cylindrical iron containers 5 of the same size, and the four iron containers 5 stored are placed on the iron receiving pan 7 in one stage, set in the roasting furnace 10, and roasted at a temperature of 800 ° C. Roasted at ~1200°C for about 4 hours. Thereafter, 4.5 kg of the roasted product 21 was crushed by the vertical chain type crusher having a predetermined impact force for two crushing times of 10 seconds and 13 seconds. After that, vibration was applied by a sieve vibrating device 41 having a porous screen with a diameter of 3 mm and having the magnetic separation means 42 provided above.

As a result, the waste battery 20 after roasting can be easily taken out from the iron container 5, there is no roasted material 21 that is not crushed, and the crushing rate is 100%, and the particle size of the crushed material 24 is 10 seconds. 0.5 cm to 13 cm, and 0.5 cm to 4 cm for 13 seconds. Since the case of this waste battery 20 is made of iron instead of aluminum, there is no metal that melts at the roasting temperature. Then, the iron of the magnetic substance 51, the copper foil of the non-magnetic solid substance 53, and the nickel, cobalt and lithium of the non-magnetic powder substance 52 were recovered.

From the above results, in the crushing process 3 of lithium ion batteries having a box shape, a casing made of iron, and a size of 3 cm long × 15 cm wide × 10 cm high, the amount of input to the crushing chamber of the vertical chain crusher is The weight was set to 4 to 6 kg, and the crushing time was set to 12 to 14 seconds.

A 200-liter drum containing a lithium-ion battery with a box-shaped casing made of aluminum and a size of 1 cm long x 12 cm wide x 10 cm high is provided with a plurality of air holes 6 on the peripheral wall including the vicinity of the bottom wall. Stored in iron containers 5 of approximately the same size, four of the stored iron containers 5 are placed on the iron tray 7 in one stage, set in the roasting furnace 10, and roasted at a temperature of 800 ° C. to 1200. ℃ for about 4 hours. Thereafter, 3 kg of the roasted product 21 was crushed by the vertical chain type crusher having a predetermined impact force for two crushing times of 10 seconds and 13 seconds. After that, vibration was applied by a sieve vibrating device 41 having a porous screen with a diameter of 3 mm and having the magnetic separation means 42 provided above.

As a result, the aluminum that has flowed out and solidified from the iron receiving pan 7 and is not mixed with members that have not melted at the roasting temperature can be recovered, and the waste battery 20 after roasting can be easily taken out from the iron container 5. A crushing rate of 100% was achieved without any uncrushed roasted product 21, and the particle size of the crushed product 24 was 0.5 cm to 7 cm for 10 seconds and 0.5 cm to 4 cm for 13 seconds. . The iron of the magnetic material 51, the copper foil of the non-magnetic solid material 53, and the nickel, cobalt, and lithium of the non-magnetic powder material 52 could be recovered at a high recovery rate without being caught in the aluminum of the molten metal 22, respectively.

From the above results, in the crushing step 3 of the lithium-ion battery with a box-shaped casing made of aluminum and a size of 1 cm long × 12 cm wide × 10 cm high, the amount of input to the crushing chamber of the vertical chain crusher was set to 3 kg, and the crushing time was set to 8 to 10 seconds.

A cylindrical lithium-ion battery with a casing made of iron and a size of 1.5 cm in diameter and 3 cm in height is provided with a plurality of air holes 6 on the peripheral wall including the vicinity of the bottom wall, and is approximately the same size as a 200-liter drum. It is stored in a cylindrical iron container 5 with a thickness, and the four iron containers 5 stored are placed in one stage on an iron saucer 7 and set in a roasting furnace 10 at a roasting temperature of 800 ° C. to 1200. ℃ for about 4 hours. Thereafter, 4 kg of the roasted product 21 was crushed by the vertical chain type crusher having a predetermined impact force for two crushing times of 10 seconds and 13 seconds. After that, vibration was applied by a sieve vibrating device 41 having a porous screen with a diameter of 3 mm and having the magnetic separation means 42 provided above.

As a result, the waste battery 20 after roasting can be easily removed from the iron container 5, and the crushing rate is 95% when the crushing time is 10 seconds, and the crushing rate is 95% when the crushing time is 13 seconds. was 100%. The grain size of the crushed material obtained at that time was 0.5 cm to 5 cm. Then, the iron of the magnetic substance 51, the copper foil of the non-magnetic solid substance 53, and the nickel, cobalt and lithium of the non-magnetic powder substance 52 were recovered.

From the above results, in the crushing step 3 of the lithium ion battery having a cylindrical shape, a casing made of iron, and a size of 1.5 cm in diameter and 3 cm in height, the amount of input to the crushing chamber of the vertical chain crusher was set to 4 kg. , and the crushing time was set to 13 seconds.

As described above, in the method 1 for recovering valuable metals from waste batteries of the present invention, in the roasting step 2, waste batteries 20 of the same type are stored in an iron container 5 provided with an air hole 6, and the iron container 5 is made of iron. When placed on the tray 7 and roasted, the aluminum that is the molten metal 22 can be recovered in a high-purity state, and the waste battery 20 is placed in the aluminum solidified mass of the molten metal 22 melted at the roasting temperature. Therefore, the recovery rate of the members not melted at the roasting temperature of the waste battery 20 is improved.

Further, in the crushing step 3, a vertical chain type crushing device is used, based on the impact force of the chain type crushing means, so that the waste battery can be separated into solid matter and powdery matter according to the constituent members of the waste battery. By setting a predetermined input amount and a predetermined crushing time for each type of the waste battery 20 and operating the chain-type crushing means to crush, a crushing rate of 100% can be achieved. The detachment progressed, and the magnetic material with the non-magnetic material stuck to it decreased sharply in the magnetic material 51 attracted by the magnetic separation means 42, the amount of the non-magnetic material increased, and the recovery rate of the material improved.

1 Valuable metal recovery method 2 Roasting process 3 Crushing process 4 Magnetic separation/sieving process 5 Iron vessel 6 Air hole 7 Iron saucer 10 Roasting furnace 11 Ignition burner 12 Fixed bed 13 Furnace lid 20 Waste battery 21 Roasted material 22 Molten metal 23 Mixed melted waste battery materials 24 Crushed material 31 Drum can 40 Magnetic separation/sieving means 41 Sieve vibration device 41a Coil spring 42 Magnetic separation means 42a Magnet 42b Belt conveyor 43 Belt conveyor 51 Magnetic material 51a Magnetic material collection box 52 Non-magnetic powder 52a Non-magnetic powder collection box 53 Non-magnetic solid body 53a Non-magnetic solid body collection box

Claims (3)

A waste battery is stored in an iron container having a plurality of air holes in the peripheral wall including the vicinity of the bottom wall, and a tray-like iron saucer on which a plurality of the iron containers are placed is placed in the roasting furnace. a roasting step of roasting the waste battery in the state of
A crushing step of removing the roasted product from the iron container after the roasting step and crushing the roasted product with an impact load;
A method for recovering valuable metals from waste batteries, characterized by comprising a magnetic separation/sieving step in which, after the crushing step, magnetic separation and sieving of the crushed materials are carried out at the same time. In the crushing step, when the rotation speed of the metal chain is lowered to a predetermined height where the impact load can be applied to the roasted product at the bottom of the vertically installed rotating shaft, crushing is performed by sweeping with a broom. Equipped with chain-type crushing means having a plurality of metal chains with one end fixed and the other end free at a height that allows objects to be discharged , based on the impact force of the chain-type crushing means, The chain-type crushing means is operated and crushed at a predetermined amount and crushing time set for each type of the waste battery so that the waste battery can be separated into solid matter and powder matter according to the constituent members of the waste battery. The method for recovering valuable metals from waste batteries according to claim 1, characterized in that: In the magnetic separation/sieving step, a sieve vibrating device having a screen having openings of a size capable of sieving crushed powdery materials of a predetermined size and having a downstream side inclined downward; A magnetic separation means having a magnet capable of attracting the crushed magnetic material above the vibrating device for sieve is provided, and the crushed material after the crushing step is separated from the crushed magnetic material, the non-magnetic material having a predetermined size or more. 3. The method for recovering valuable metals from waste batteries according to claim 1 or 2, wherein the crushed substances are separated into crushed substances of a size less than a predetermined size and non-magnetic crushed substances smaller than a predetermined size.

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