JP2017131795A - Treatment equipment and treatment method for discarded lithium ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably treat a discarded large-sized lithium ion secondary battery in large quantity by simple work.SOLUTION: Treatment equipment 1 for a discarded lithium ion battery is provided that comprises: a heat-resistant container 2 for storing a lithium ion battery and having an obliquely upward projecting exhaust pipe 2g; a heat treatment furnace 3 having a cylindrical furnace wall 7 and comprising a burner 8 jetting fuel in the horizontal direction along an inner surface of the furnace wall, an exhaust pipe 28 in a central part of a top-view circular ceiling part and a thermometer 13 in the vicinity of a top-view circular hearth 17; and a container conveyance device 4 capable of charging and discharging the heat-resistant container to and from the heat treatment furnace. The treatment equipment 1 can comprises a damper 33 for adjusting internal pressure of the heat treatment furnace, inside the exhaust pipe in the vicinity of the ceiling part of the heat treatment furnace.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a processing apparatus and a processing method for a waste lithium ion battery used as a power source for a hybrid vehicle or an electric vehicle.

  A lithium ion battery used as a power source for an electric vehicle such as a hybrid vehicle or an electric vehicle is arranged in a plurality of battery modules as lithium ion battery cells, and a battery in which a plurality of battery modules are housed in a resin or metal box-shaped housing. Mounted on the vehicle as a pack. In this battery pack, a plurality of battery modules are electrically connected by a wire harness or the like, and the battery pack is further mounted with a circuit, a switch, and the like for cutting off the battery control system and the high-power circuit.

  A lithium ion battery is composed of a positive electrode material in which lithium, cobalt, nickel or the like is applied to an aluminum foil, a negative electrode material in which graphite or the like is applied to a copper foil, an electrolytic solution, a separator, and the like, so that lithium, cobalt, nickel, copper Including valuable materials such as aluminum. Therefore, recovering these valuable materials from discarded lithium batteries is extremely beneficial for Japan, which is scarce of resources.

  In order to recover the valuable materials from the waste lithium ion battery, separation and recovery are performed by roasting, crushing or crushing, sieving, sorting, and the like. The purpose of the roasting treatment is to thermally decompose and remove an organic solvent such as propylene carbonate and ethylene carbonate, a supporting salt of lithium hexafluorophosphate, and a separator such as polyethylene and polypropylene contained in the electrolytic solution. The roasting treatment of the lithium ion secondary battery is described in Patent Documents 1 to 5 and the like.

JP-A-6-346160 JP 7-245126 A JP 2012-79630 A JP 55-152138 A JP 2012-112027 A

  In the techniques described in Patent Document 1 and Patent Document 2, roasting is performed in an air atmosphere, and in Patent Document 3, an air atmosphere, an oxidizing atmosphere, an inert atmosphere, a reducing atmosphere, and the like are exemplified. An air atmosphere (air atmosphere) that allows easy control of the atmosphere is preferred. When the roasting process is performed in an air atmosphere, the organic matter in the electrolyte and separator is decomposed, ignited, and burned, so the temperature in the furnace rises rapidly.

Therefore, in order to suppress the rapid temperature rise, in the invention described in Patent Document 4, a gas such as nitrogen gas, argon gas, CO, CO ₂ or the like is passed through the furnace, and the inside of the furnace is non-oxidizing atmosphere, that is, reducing atmosphere. This prevents the temperature from rising due to sudden combustion.

  Patent Document 5 describes that the inside of the furnace is made a reducing atmosphere using a carbon source such as wood, charcoal, coal, coke, and activated carbon. However, since the carbon source is also flammable, a large amount of carbon source is required in order to suppress ignition and combustion of the lithium battery in a reducing atmosphere inside the furnace.

  With a small amount of treatment of a small lithium ion secondary battery, temperature changes due to rapid combustion are unlikely to occur, and by increasing the processing furnace or controlling the ventilation speed to suppress temperature rise due to rapid combustion It is possible to reduce the fluctuation. However, it is not easy to adjust the roasting atmosphere in the case of mass treatment or mass treatment of a large lithium ion secondary battery. For example, in the case of a large unit, it contains a large amount of organic compounds, so Burning causes a rapid temperature rise. In particular, when an undischarged lithium ion secondary battery is burned, oxygen is simultaneously generated from the electrode, so that burning becomes more intense. As a result, a processed product with stable quality cannot be obtained, and the recovery rate of valuable materials is lowered.

  Accordingly, the present invention has been made in view of the above-described problems in the prior art, and provides an apparatus and method for stably processing a large amount of discarded lithium ion secondary batteries with a simple operation. With the goal.

  In order to achieve the above object, the present invention is a treatment apparatus for waste lithium ion batteries, comprising a heat-resistant container that houses a lithium ion battery and has an exhaust pipe that projects obliquely upward, and a cylindrical furnace wall. A burner that jets fuel in a horizontal direction along the inner surface of the furnace wall, an exhaust pipe at the center of the circular ceiling when viewed from above, and a heat treatment furnace having a thermometer near the circular hearth when viewed from above. The heat treatment furnace includes a container transfer device capable of charging and discharging the heat-resistant container. Here, a plurality of waste lithium ion batteries may be introduced into the heat-resistant container, or a battery module in which a plurality of lithium ion battery cells are arranged after being used in a hybrid vehicle or the like is placed in a box-type housing. A plurality of battery packs or battery modules stored in the battery pack may be inserted.

  According to the present invention, the battery pack or battery module is subjected to heat treatment without individually removing the battery cells, so that the battery pack or battery module is dry-distilled to separate the carbonized mixture. The resin casing, the resin frame sandwiching each battery cell of the battery module, the carbon used for the negative electrode material of the lithium ion battery, and the like are separated from the metal containing the useful metal as a carbonized mixture.

  In addition, after storing the battery pack or battery module in a heat-resistant container provided with an exhaust pipe, it is put into a heat treatment furnace and heated from the outside of the heat-resistant container. The module can be carbonized to separate the carbonized mixture. At this time, the low-boiling electrolyte in the battery volatilizes and is discharged from the exhaust pipe of the heat-resistant container into the heat treatment furnace and the air in the heat-resistant container is discharged, and the battery pack or the battery module is placed in a heat-resistant container in a reducing atmosphere. Since it is protected, the risk of explosion of the waste lithium ion battery in the furnace can be suppressed.

  Furthermore, from the exhaust pipe of the heat-resistant container, two types of organic gases, gas generated by volatilization of the electrolyte and gas generated by pyrolysis of combustible materials such as plastic, are exhausted into the heat treatment furnace. Since these are used as fuel for heat treatment, the fuel cost can be reduced. In adjusting the temperature by burning these organic gases in the furnace, the temperature can be easily controlled by controlling the amount of oxygen.

  When the heat treatment is performed in a reducing atmosphere, combustible materials such as plastic are not burned, so that dioxins are not easily generated, and slag formation due to metal oxidation is also suppressed. The lithium ion battery can be rendered harmless. Further, temperature runaway due to burning of plastic or the like can be prevented, and the recycling process can be carried out with extremely simple work.

  In addition, since the heat-resistant container has an exhaust pipe projecting obliquely upward, even if the organic compound burns violently during dry distillation of the lithium ion secondary battery and the combustion gas is ejected from the exhaust pipe, the combustion gas is ejected obliquely upward Therefore, stable vortex combustion inside the heat treatment furnace is not hindered by the combustion gas, and a typical temperature of the entire furnace can be measured with a thermometer installed in the vicinity of the hearth. An ion battery can be processed stably, and a processed product of stable quality can be obtained.

  The said processing apparatus can be equipped with the damper for adjusting the pressure inside this heat processing furnace inside the exhaust pipe of the vicinity of the ceiling part of the said heat processing furnace. As a result, even if the organic compound in the lithium ion secondary battery burns violently and the pressure inside the heat treatment furnace suddenly rises, the pressure can be quickly released by the damper, and the negative pressure inside the heat treatment furnace becomes possible. Can be maintained stably.

  The processing apparatus includes a hearth rotating device for horizontally rotating a hearth of the heat treatment furnace, and the heat-resistant container is continuously charged through the container conveying device so that a plurality of heat-resistant containers are annularly arranged on the hearth. It is possible to continuously discharge the heat-resistant container that has been turned around from the hearth. By making the heat treatment furnace into a continuous rotary furnace, the hot gas circulates in the furnace while swirling, thereby making the furnace temperature uniform, so the processing temperature is set lower for safety due to temperature unevenness There is no need, and the treatment temperature can be set higher and heated efficiently. Moreover, since the kind and quantity of the unburned gas exhausted from the heat treatment furnace are stabilized by the continuous treatment, control for treating the unburned gas can be easily performed thereafter.

  The present invention also relates to a method for treating a waste lithium ion battery, comprising a heat-resistant container that houses a lithium ion battery and has an exhaust pipe projecting obliquely upward, and a cylindrical furnace wall. A burner that jets fuel in a horizontal direction along the inner surface, an exhaust pipe at the center of a circular ceiling when viewed from above, a heat treatment furnace having a thermometer near the circular hearth when viewed from above, and the heat treatment furnace The heat-resistant container is heated by the burner at a temperature lower than the melting point of aluminum from the outside using a processing apparatus including a container transfer device capable of loading and discharging the heat-resistant container. The inside of the negative electrode material of the lithium ion battery is dry-distilled to separate the carbonized mixture, and the electrolyte in the battery is volatilized and discharged from the exhaust pipe of the heat-resistant container into the heat treatment furnace, using the thermometer The And adjusting the temperature inside of the processing furnace.

  Furthermore, the present invention is a method for treating a waste lithium ion battery, wherein a battery pack in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged is housed in a box-shaped housing or the battery module is stored. A heat-resistant container having an exhaust pipe projecting obliquely upward, a burner having a cylindrical furnace wall, and jetting fuel in a horizontal direction along the inner surface of the furnace wall, and a central part of a circular ceiling part when viewed from above A heat treatment furnace having a thermometer in the vicinity of a circular hearth when viewed from above, and a container transport device capable of loading and unloading the heat-resistant container into the heat treatment furnace. The charged heat-resistant container is heated from the outside at a temperature lower than the melting point of aluminum by the burner, and the battery pack or the battery module inside the heat-resistant container is dry-distilled to separate the carbonized mixture. With, an electrolytic solution of the electrolyte Ikeuchi is evaporated is discharged to the heat treatment furnace through the exhaust pipe of the heat-resistant container, and adjusting the temperature inside the heat treatment furnace using the thermometer.

  According to both the above inventions, a large amount of waste lithium ion batteries can be stably recycled with extremely simple operations, and the heating temperature is not changed. Thus, it is possible to easily separate the useful metal from the treated product, and the recovery rate is increased.

  In the above processing method, using a damper disposed inside the exhaust pipe near the ceiling of the heat treatment furnace, the pressure inside the heat treatment furnace can be adjusted, and the organic compound of the lithium ion secondary battery is intense Even when the pressure inside the heat treatment furnace suddenly increases due to combustion, the pressure can be quickly released by the damper, and the negative pressure in the heat treatment furnace can be stably maintained.

  In the said processing method, the temperature inside the said heat processing furnace can be adjusted to 400 degreeC or more and 650 degrees C or less. Thereby, the resin material is easily decomposed and separated from the metal at a plastic decomposition temperature (300 ° C.) or higher, and the aluminum is not melted by setting the temperature to 650 ° C. or lower. In addition, it is possible to obtain a processed product that is easy to collect valuables with stable quality.

  In the above processing method, the gas discharged through the exhaust pipe of the heat treatment furnace can be introduced into a region of 350 ° C. or higher of the preheater of the cement adjusting device. As a result, there is no need to provide a new facility as a secondary combustion chamber, and the fluoride in the combustion gas generated by the thermal decomposition of the fluorine compound contained in the electrolyte of the waste lithium ion battery can be captured by the cement preparation raw material. VOCs (volatile organic compounds) generated by thermal decomposition of combustible materials such as plastics of waste lithium ion batteries can be burned, and unburned gas can be made harmless.

  As described above, according to the present invention, a discarded lithium ion secondary battery can be stably processed in a large amount by a simple operation.

1 is an overall cross-sectional view showing an embodiment of a treatment apparatus for a waste lithium ion battery according to the present invention. 1 is an overall longitudinal sectional view showing an embodiment of a processing apparatus for a waste lithium ion battery according to the present invention. It is a figure which shows the container main body of the heat-resistant container used for the processing apparatus of FIG.1 and FIG.2, (a) is a front view, (b) is a top view, (c) is a bottom view. It is a figure which shows the lid | cover of the heat-resistant container used for the processing apparatus of FIG.1 and FIG.2, Comprising: (a) is a front view, (b) is a top view. It is a longitudinal cross-sectional view which shows the state which comprised the container main body of FIG. 3, and the lid | cover of FIG. 4 and comprised the heat-resistant container. It is a cross-sectional view which shows the heat-resistant container just before thrown into the heat treatment furnace in the processing apparatus of FIG.1 and FIG.2. It is a longitudinal cross-sectional view which shows the heat-resistant container just before thrown into the heat treatment furnace in the processing apparatus of FIG.1 and FIG.2. It is a graph which shows the experimental result of a comparative example, Comprising: A vertical axis | shaft represents the furnace temperature (degreeC), and the horizontal axis represents the operation time. It is a graph which shows the experimental result of an Example, Comprising: A vertical axis | shaft represents the furnace temperature (degreeC), and the horizontal axis represents the operation time.

  Next, an embodiment of the present invention will be described in detail with reference to the drawings.

  As shown in FIGS. 1 and 2, a waste lithium ion battery processing apparatus 1 according to the present invention includes a battery pack 50 in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged are housed in a box-shaped housing. The heat treatment is performed to recover useful metals, mainly a plurality of heat-resistant containers 2 for storing the battery pack 50, a heat treatment furnace 3, and a container transport for charging and discharging the heat-resistant containers 2 to and from the heat treatment furnace 3. A device 4 is provided. This processing apparatus 1 is particularly useful when the input amount per container (one batch) in which the calorific value generated from the battery is high is 50 kg or more, and is particularly useful for a secondary battery in which intense combustion occurs.

  As shown in FIGS. 3 to 5, the heat resistant container 2 includes a container body 2 </ b> A and a lid 2 </ b> B. The material of the container body 2A and the lid 2B is stainless steel (SUS304) or the like, and has a heat resistant temperature of at least 650 ° C.

  As shown in FIG. 3, the container main body 2A includes an inner cylinder 2a that is open upward and is formed in a cylindrical shape, and an outer cylinder 2b that is larger in diameter than the inner cylinder 2a and is disposed so as to surround the inner cylinder 2a. A plurality of wheels 2c disposed on the bottom surfaces of the inner cylinder 2a and the outer cylinder 2b, two handles 2e fixed to the peripheral surface 2d of the outer cylinder 2b, and a hanger protruding from the peripheral surface 2d of the outer cylinder 2b 2f.

  On the other hand, as shown in FIG. 4, the lid 2B includes a main body 2n formed in a cylindrical shape that opens downward, an exhaust pipe 2g that opens in the peripheral surface of the main body 2n and protrudes obliquely upward, and a ceiling of the main body 2n. And a handle 2m provided on the surface 2h. The angle formed by the exhaust pipe 2g and the horizontal plane is set to about 45 °, but is not limited to this. The direction of the exhaust pipe 2g is set so that the horizontal component of the velocity vector of the combustion gas ejected from the exhaust pipe 2g is in the same direction as the vortex combustion direction of the heat treatment furnace 3. Moreover, the installation position of the exhaust pipe 2g should just be a position lower than the four gas burners 8 (8A-8D) and higher than the front-end | tip 28a of the exhaust pipe 28, as shown in FIG.

  In order to configure the heat-resistant container 2 with the container body 2A and the lid 2B, as shown in FIG. 5, the lower end 2k of the body 2n of the lid 2B is formed in the groove 2j between the inner cylinder 2a and the outer cylinder 2b of the container body 2A. Is inserted, and the groove 2j is filled with sand to form a sand seal, and the lid 2B is attached to the container body 2A in a state where it can be lifted by a certain distance L. Since the lid 2B can be lifted with respect to the container main body 2A by the sand seal structure, even if the pressure inside the heat-resistant container 2 is increased due to a reaction during the heat treatment, the pressure increased by lifting the lid 2B is released. Further, damage to the heat-resistant container 2 can be prevented.

  In addition, the structure of the heat-resistant container 2 is not limited to the above-described one. For example, a structure provided with a buffer mechanism may be used as long as the cover 2B has a structure that releases the increased pressure with respect to the container body 2A. Can be used.

  In addition, the battery pack 50 need not be divided as long as it can store a plurality of battery packs 50, has excellent heat resistance, and is provided with the exhaust pipe 2g on the top.

  Furthermore, a recess (not shown) is formed in the container main body 2A of the heat-resistant container 2 to receive and accumulate a melted material such as plastic during heat treatment, thereby preventing the melted material such as plastic from spilling out of the heat-resistant container 2. May be.

  As shown in FIGS. 1 and 2, the heat treatment furnace 3 is a cylindrical vertical furnace in which a furnace wall 7 is formed of a steel plate covered with a refractory material, and four gas burners 8 (8A to 8D). Heated by. In the vicinity of the gas burner 8, nozzles 11 (11A to 11D) are provided, and combustion and cooling air A sent through a fan (not shown) is supplied into the furnace. A thermometer 13 and a pressure gauge 14 are provided for measuring the temperature and pressure in the furnace. The thermometer 13 is installed near the hearth 17 of the heat treatment furnace 3 to be described later so as not to be affected by the gas burner 8 and the exhaust pipe 2g. The number of gas burners 8 and nozzles 11 installed is not limited to four, and may be three or less or five or more.

  The hearth 17 of the heat treatment furnace 3 is made of a steel plate covered with a refractory material in the same manner as the furnace wall 7, and is rotated around a vertical axis by a hearth rotating device 19 equipped with an electric motor (not shown). (Not shown).

  An opening 7a is formed in a part of the furnace wall 7 of the heat treatment furnace 3 so as to be separated from the outside by an openable / closable furnace body door 7b. A container transfer device 4 that puts the heat-resistant container 2 into the heat treatment furnace 3 from the opening 7 a at a position facing the opening 7 a and discharges the heat-resistant container 2 after making a round in the heat treatment furnace 3 from the heat treatment furnace 3. Provided.

  As shown in FIGS. 1, 2, 6, and 7, the container transfer device 4 extends in the direction (the left-right direction in FIG. 1) on the line connecting the opening 7 a of the heat treatment furnace 3 and the center of the heat treatment furnace 3. The pusher portion 4a that abuts the heat-resistant container 2 by pushing the motor 18 in the forward direction and pushes the heat-resistant container 2 into the heat treatment furnace 3, and a nail that holds the hanger 2f provided on the outer periphery of the container body 2A of the heat-resistant container 2 4c is provided at the tip, and includes a pull-out portion 4b that pulls the heat-resistant container 2 out of the heat treatment furnace 3 by negative rotation of the motor 18. The pusher portion 4a is disposed immediately above the pull-out portion 4b.

  Further, immediately before the heat-resistant container 2 is put into the heat treatment furnace 3, that is, when it is located outside the openable furnace body door 7b, the tangential direction of the heat treatment furnace 3 (vertical direction in FIG. 1). The slide base 21 is placed on a slide base 21 that is freely movable and connected to an end of the slide base 21. The slide base 21 is provided in a furnace front chamber 23 (see FIG. 1) and a stand 25 positioned outside the open / close type furnace front chamber door 24. The furnace front chamber 23 is separated from the outside by a furnace front chamber door 24, and is separated from the heat treatment furnace 3 by a furnace body door 7 b so as to suppress a temperature change when the furnace body door 7 b is opened. I have to. Moreover, by providing the furnace front chamber 23, the atmosphere in the heat treatment furnace 3 can be maintained, and dangerous gas leakage and hot air blowing can be prevented.

  When the slide base 21 moves onto the stand 25, the heat-resistant container 2 before being heated by a crane (not shown) is placed on the slide base 21 and then carried to the furnace front chamber 23 by the base moving device 22. The heat-resistant container 2 after being heated is similarly transported from the furnace front chamber 23 to the stand 25 by the base moving device 22 and then automatically moved to the cooling chamber (not shown). The base moving device 22 moves the slide base 21 connected to the tip of the shaft 22b by expanding and contracting the shaft 22b by driving the motor 22a.

  As shown in FIGS. 1 and 2, a secondary combustion chamber 27 is provided at a position away from the heat treatment furnace 3, and the secondary combustion chamber 27 and the heat treatment furnace 3 are connected by an exhaust pipe 28. The exhaust pipe 28 is provided with a fan 29 that sends unburned gas in the heat treatment furnace 3 to the secondary combustion chamber 27 through the exhaust pipe 28.

  The secondary combustion chamber 27 is also heated by the gas burner 34, and uncombusted gas combustion air is supplied into the secondary combustion chamber 27 through the fan 30 in the secondary combustion chamber 27. The temperature in the secondary combustion chamber 27 is measured by a thermometer 32. The secondary combustion chamber 27 is provided with an exhaust chimney 31.

  As shown in FIG. 2, the heat treatment furnace 3 side of the exhaust pipe 28 is led into the heat treatment furnace 3 from the center of the ceiling portion of the heat treatment furnace 3, and the position of the tip 28 a of the battery pack 50 in the heat resistant container 2. It is set to be lower than the upper surface position. Here, the position of the front end (lower end) 28a of the exhaust pipe 28 is set to the same position as the height between the third and fourth stages from the top of the battery pack 50 stacked in four stages in the heat-resistant container 2. In this way, by setting the heat treatment furnace side tip 28a of the exhaust pipe 28 to be lower than the upper surface position of the battery pack 50 in the heat-resistant container 2, the hot air is greatly increased from above to below and from below to above in the heat treatment furnace 3. Due to the convection, the internal battery pack 50 is efficiently dry-distilled. Accordingly, even if a plurality of battery packs 50 are stacked in the heat-resistant container 2 (four stages in the present embodiment), the battery pack 50 can be sufficiently recycled, so even if the number of battery packs 50 to be processed is large, a short time is required. Can be processed. Moreover, it can process regardless of whether the lithium ion battery in the battery pack 50 is discharged.

  A damper 33 for adjusting the pressure inside the heat treatment furnace 3 is provided immediately above the heat treatment furnace 3 in the exhaust pipe 28. For example, when the pressure in the heat treatment furnace 3 increases, the damper 33 is opened and the heat treatment furnace 3 is opened. The negative pressure inside is maintained. As the damper 33, the illustrated butterfly valve or the like can be used.

  A waste lithium ion battery processing method using the waste lithium ion battery processing apparatus 1 having the above-described configuration will be described. In the following description, a case where the processing device 1 processes the battery pack 50 that has been removed from the hybrid vehicle, the electric vehicle, or the like will be exemplified.

  (1) After performing a pre-purge for discharging the residual gas inside the heat treatment furnace 3 to the outside of the furnace, the gas burner 8 is ignited and the furnace temperature is raised to about 620 ° C. so that the upper limit of the control range does not exceed 650 ° C. Warm to keep temperature constant.

  (2) The furnace front chamber door 24 is opened, and the slide base 21 is advanced to the position of the stand 25 provided outside the furnace front chamber 23 via the base moving device 22. Then, using a crane (not shown), eight used battery packs 50 are stored as shown in FIGS. 6 and 7 (stored in a state in which two sets of four-tiered ones are butted together) ) Place the heat-resistant container 2 on the slide base 21 moved to the position of the stand 25.

  (3) The slide base 21 is retracted from the position of the stand 25 into the furnace front chamber 23 via the base moving device 22 and the furnace front chamber door 24 is closed.

  (4) After opening the furnace body door 7 b, the pusher portion 4 a of the container transport device 4 is advanced to put the heat-resistant container 2 into the heat treatment furnace 3. As a result, the heat-resistant container 2 is placed on the hearth 17 of the heat treatment furnace 3, at the 9 o'clock position in FIG.

  (5) After retracting the pusher portion 4a of the container transfer device 4, the furnace body door 7b is closed, and the hearth 17 is rotated 45 ° counterclockwise via the hearth rotating device 19. The 45 ° rotation is not particularly limited. For example, the hearth 17 is set to rotate once every 57.5 by rotating the hearth 17 by 45 ° every 37.5 minutes. ing.

  (6) By repeating the processes (1) to (5) seven times, adjacent heat-resistant containers 2 are spaced apart on the hearth 17 of the heat treatment furnace 3 as shown in FIG. In this state, eight heat-resistant containers 2 are placed in a ring shape.

  During the above operation, the heat-resistant container 2 is heated from the outside during one round in the heat treatment furnace 3, so that the inside of the heat-resistant container 2 becomes a reducing atmosphere, and the battery pack 50 stored in the heat-resistant container 2 is made of resin. Plastics such as housings are separated from materials containing useful metals such as lithium, cobalt, nickel, and manganese as carbonized mixtures by dry distillation. The heat-resistant container 2 is heated at a temperature (620 ° C.) lower than the melting point of aluminum (660 ° C.), so that the aluminum component used in the battery pack 50 does not melt out. Further, the electrolyte in the battery volatilizes and is discharged into the heat treatment furnace 3 from the exhaust pipe 2g of the heat-resistant container 2 together with a gas generated by thermal decomposition of a combustible substance such as plastic. The two types of gases discharged from the exhaust pipe 2g of the heat-resistant container 2 are combustible gases, burn in the heat treatment furnace 3, and are reused as heat sources.

  During the heat treatment, the temperature in the heat treatment furnace 3 is such that the flammability released into the heat treatment furnace 3 from the exhaust pipe 2g of the heat-resistant container 2 by adjusting the oxygen amount of the air supplied through the nozzle 11. The amount of gas combustion is controlled so that the measured value by the thermometer 13 becomes a desired value or range. At this time, the lid 2B of the heat-resistant container 2 includes an exhaust pipe 2g that opens on the peripheral surface of the main body 2n and protrudes obliquely upward, so that the organic compound burns violently during the dry distillation of the battery pack 50 and the combustion gas is exhausted. Even if it is ejected from 2 g, the combustion gas is ejected obliquely upward, so that stable vortex combustion inside the heat treatment furnace 3 is not hindered by the combustion gas, and the thermometer 13 installed in the vicinity of the hearth 17 The overall representative temperature can be measured, and the stable operation of the heat treatment furnace 3 can be maintained.

  On the other hand, when the inside of the heat treatment furnace 3 becomes a positive pressure, hot gas is ejected from the opening 7a of the heat treatment furnace 3 to the outside of the furnace, and it becomes difficult to charge and discharge the heat-resistant container 2 to the heat treatment furnace 3. It is necessary to maintain the inside of 3 at a negative pressure. Therefore, the damper 33 is opened and closed according to the measured value of the pressure gauge 14 to maintain the inside of the heat treatment furnace 3 at a desired value or range. For example, even when the organic compound of the lithium ion secondary battery burns violently during the dry distillation of the battery pack 50 and the pressure inside the heat treatment furnace suddenly rises, the damper 33 is opened to quickly release the pressure, and the heat treatment furnace 3 maintains the negative pressure inside. Since the damper 33 is disposed inside the exhaust pipe 28 in the vicinity of the ceiling portion of the heat treatment furnace 3, it is possible to quickly cope with a pressure change inside the heat treatment furnace 3.

  The unburned gas in the heat treatment furnace 3 is guided to the secondary combustion chamber 27 and burns at a temperature (800 ° C.) higher than the temperature of the heat treatment furnace 3.

  (7) When the heat-resistant container 2 makes one round in the heat treatment furnace 3, the furnace body door 7b is opened and the pull-out portion 4b of the container transport device 4 is advanced to the position of the heat-resistant container 2, and as shown in FIG. The claw 4c provided at the tip of the part 4b is engaged with the hanger 2f provided in the heat-resistant container 2. Then, the pull-out portion 4b is retracted, the heat-resistant container 2 is pulled out from the heat treatment furnace 3 and placed on the slide base 21, and the furnace body door 7b is closed.

  (8) Next, after opening the furnace chamber door 24, the slide base 21 on which the heat-treated heat-resistant container 2 is placed is advanced to the position of the stand 25 via the base moving device 22. In this state, when the furnace front chamber door 24 is half closed and the slide base 21 is returned to the original position, the heat-resistant container 2 comes into contact with the furnace front chamber door 24 in the half closed state and is placed on the stand 25. The furnace chamber door 24 is fully closed.

  (9) Thereafter, the heat-treated heat-resistant container 2 on the slide base 21 that has been moved to the position of the stand 25 is placed on a transfer conveyor (not shown) and carried to a cooling chamber (not shown). In (8), the heat-resistant container 2 can be placed on the transfer conveyor and automatically conveyed by contacting the half-closed furnace front chamber door 24. Then, instead of the heat-treated heat-resistant container 2, on the slide base 21, a crane (not shown) is used similarly to the one shown in (2), and eight used battery packs 50 are provided. The stored new heat-resistant container 2 is installed, and (3) the following processes are repeated.

  Since the hearth rotating device 19 of the heat treatment furnace 3 can freely rotate forward and backward, the eight heat-resistant containers 2 on the hearth 17 can be discharged to the outside without being limited to the order of loading. That is, by installing a plurality of site holes on the wall surface of the heat treatment furnace 3 and operating while checking the state of the inside of the furnace, a flame can be seen from the exhaust pipe 2g of the heat-resistant container 2 even after a predetermined treatment time has elapsed. In this case, the next heat-resistant container 2 can be discharged without any delay by discharging it first. It is expected that various types of lithium batteries newly developed in the future will behave differently during heat treatment. However, the behavior of the heat treatment furnace 3 that can be taken in and out freely also supports lithium batteries whose behavior is unknown. An operation method in which the processing time is finely adjusted is also possible.

  The heat-resistant container 2 that has been heated to the cooling chamber is subjected to a process of further separating useful metals such as lithium, cobalt, nickel, and manganese after crushing and classifying the internal battery pack 50 to remove the carbonized mixture. Done. Moreover, the crushed material of the battery pack 50 is subjected to a magnetic separator, and separated into magnetic deposits such as iron housings and screws, and Mick metal composed of copper and aluminum, and the Mick metal is subjected to specific gravity selection to obtain aluminum lump, copper lump, and copper. After dividing into a foil and a laminate of aluminum foil, it can be further divided into copper foil and aluminum foil by a sorter.

  According to the processing apparatus and the processing method of the waste lithium ion battery configured as described above, the battery pack 50 in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged is housed in a box-shaped housing, After storing in the heat-resistant container 2 provided with the exhaust pipe 2g, the battery pack 50 inside the heat-resistant container 2 is dry-distilled by putting it in the heat treatment furnace 3 and heating from the outside of the heat-resistant container 2, so that the carbonized mixture is separated. The resin casing of the battery pack 50 and the carbon used for the negative electrode material of the lithium ion battery are separated from the metal containing the useful metal as the carbonized mixture. Moreover, the heating temperature at that time is set to be about 620 ° C. so that the upper limit of the furnace temperature control range does not exceed 650 ° C., and the aluminum is not melted at a temperature lower than the melting point of aluminum (660 ° C.). Therefore, compared with the case where aluminum melts, the process which isolate | separates a useful metal from the metal in which a useful metal is contained as a subsequent process can be performed easily.

  At this time, the electrolytic solution in the battery is volatilized, and the volatile gas is discharged from the exhaust pipe 2g of the heat-resistant container 2 into the heat treatment furnace 3, so that the inside of the heat-resistant container 2 naturally becomes a reducing atmosphere. It is not necessary to introduce a reducing gas or a carbon source into the battery pack 50 and the battery pack 50 is protected by the heat-resistant container 2 in a reducing atmosphere, so that it is possible to suppress the risk of the waste lithium ion battery exploding in the heat treatment furnace 3. it can. Further, since combustible materials such as plastic are not burned, temperature runaway can be prevented, and slag formation due to metal oxidation is also suppressed, so that the waste lithium ion battery can be rendered harmless.

  Further, since the unburned gas is introduced from the heat treatment furnace 3 to the secondary combustion chamber 27 and burned at a temperature (800 ° C.) higher than the temperature of the heat treatment furnace 3, the generation of odor can be suppressed.

  In the present embodiment, the uniform heat treatment is performed by using the heat treatment furnace 3 in which the hearth 17 rotates. However, by heating the heat-resistant container 2 from the outside at a temperature lower than the melting point of aluminum. If the heat treatment furnace is capable of separating the carbonized mixture by dry distillation of the internal battery pack 50, the hearth 17 may not necessarily rotate. Further, a plurality of heat-resistant containers 2 are continuously charged and discharged into the heat treatment furnace 3, but a batch type can also be applied.

  In addition, the furnace temperature in the heat treatment furnace 3 can be set to 650 ° C., which is as high as possible within a range in which aluminum does not melt in consideration of the controllable range, so that the treatment time can be shortened. Since it will decompose | disassemble and isolate | separate from a metal if it is more than decomposition temperature (300 degreeC), it will not specifically limit. However, 400 ° C. or higher, more preferably 500 ° C. or higher is suitable for the processing because of the processing time.

  Furthermore, although the heat-resistant container 2 storing the battery pack 50 is put into the heat treatment furnace 3 in an oxidizing atmosphere and heat-treated, it can be applied in a reducing atmosphere or an inert atmosphere.

  Moreover, although the heat processing furnace 3 which uses gas as a heat source for heat processing was used, the various furnaces which use electricity and heavy oil as a heat source can also be used. Moreover, effective use of thermal energy can be achieved by using exhaust gas from an existing production facility, for example, a cement baking apparatus, as a heat source.

  Furthermore, the gas exhausted through the exhaust pipe 28 of the heat treatment furnace 3 can be introduced into the secondary heater chamber 27 in the region of 350 ° C. or higher of the preheater of the cement adjusting device. As a result, the secondary combustion chamber 27 becomes unnecessary, and the fluoride in the combustion gas can be captured by the cement preparation raw material, or VOC (volatile organic compound) can be burned, thereby making the unburned gas harmless. You can also. According to experiments in an electric furnace, the concentration of fluoride in the combustion gas can be reduced to about 0.4% and the concentration of hydrogen fluoride can be reduced to about 0.45% by the cement preparation raw material, and the calcium carbide can be dry-treated. When used as an agent, there is a reduction effect of about 20 times.

  Moreover, although the battery pack 50 was heat-processed as it was without removing the battery cells individually, a battery module disassembled from the battery pack 50 (in this case, the battery cells were not individually removed) The stored heat-resistant container 2 may be put into the heat treatment furnace 3 and subjected to heat treatment, whereby the battery module is dry-distilled to separate the carbonized mixture and the electrolyte in the battery can be volatilized. Furthermore, the battery cell removed individually can also be heat-processed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this Example.

  As a comparative example, the temperature in the heat treatment furnace 3 is set to 500 ° C. in a conventional processing apparatus not provided with the exhaust pipe 2g projecting obliquely upward (see FIG. 4 and the like) and the damper 33 (see FIG. 2). Then, an experiment was conducted in which 100 kg of discharged lithium ion secondary batteries were charged per one heat-resistant container 2 and four heat-resistant containers 2 were charged into the processing apparatus 1 every 37 minutes and 30 seconds. As a result, as shown in FIG. 8, a flame was generated violently from the heat-resistant container about 1 hour after the addition, and the furnace temperature rose by 50 ° C. or more from the set temperature.

  On the other hand, as an example, in the processing apparatus 1 having the above-described configuration, the temperature in the heat treatment furnace 3 is set to 450 ° C., and 100 kg of an undischarged lithium ion secondary battery is charged per one heat-resistant container 2, An experiment was conducted in which the heat-resistant container 2 was continuously charged every 37 minutes and 30 seconds. As a result, as shown in FIG. 9, a flame was generated more intensely than the heat-resistant container 2 in about 1 hour after charging, but the furnace temperature was stable within a range of about ± 25 ° C. with respect to the set temperature even after 12 hours. It changed.

  According to the above experiment, the furnace temperature in the example is more stable, so continuous operation (24-hour operation) is possible, and even in the treatment of an undischarged lithium ion secondary battery, the treatment amount per day is 3 t. It was able to increase to. On the other hand, in the comparative example, in the case of an undischarged lithium ion secondary battery, it is necessary to reduce the amount charged into the heat-resistant container, and the stable treatment amount is 20% (600 kg) to 50% 1.5t).

DESCRIPTION OF SYMBOLS 1 Processing apparatus of waste lithium ion battery 2 Heat-resistant container 2A Container main body 2B Lid 2a Inner cylinder 2b Outer cylinder 2c Wheel 2d Circumferential surface 2e Handle 2f Hanger 2g Exhaust pipe 2h Ceiling surface 2j Groove 2k Lower end 2m Handle 2n Main body 3 Heat treatment furnace 4 Container Conveying device 4a Pusher portion 4b Pull-out portion 4c Claw 7 Furnace wall 7a Opening 7b Furnace door 8 (8A to 8D) Gas burner 11 (11A to 11D) Nozzle 13 Thermometer 14 Pressure gauge 17 Hearth 18 Motor 19 Hearth rotation Device 21 Slide base 22 Base moving device 22a Motor 22b Shaft 23 Furnace chamber 24 Furnace chamber door 25 Stand 27 Secondary combustion chamber 28 Exhaust pipe 28a Tip 29 Fan 30 Fan 31 Chimney 32 Thermometer 33 Damper 34 Gas burner 50 Battery pack

Claims (8)

A heat-resistant container containing a lithium ion battery and having an exhaust pipe projecting obliquely upward;
A burner that has a cylindrical furnace wall, jets fuel in a horizontal direction along the inner surface of the furnace wall, an exhaust pipe at the center of the circular ceiling when viewed from above, and a circular hearth when viewed from above. A heat treatment furnace having a thermometer;
A treatment apparatus for a waste lithium ion battery, comprising: a container transfer device capable of loading and unloading the heat-resistant container in the heat treatment furnace.   The processing apparatus for a waste lithium ion battery according to claim 1, further comprising a damper for adjusting a pressure inside the heat treatment furnace in an exhaust pipe near a ceiling portion of the heat treatment furnace. A hearth rotating device for horizontally rotating the hearth of the heat treatment furnace,
Via the container transfer device, the heat-resistant containers are continuously charged to place a plurality of heat-resistant containers on the hearth in a ring shape, and the one-time heat-resistant containers are continuously discharged from the hearth. The processing apparatus of the waste lithium ion battery of Claim 1 or 2 characterized by the above-mentioned. A heat-resistant container containing a lithium ion battery and having an exhaust pipe projecting obliquely upward;
A burner that has a cylindrical furnace wall, jets fuel in a horizontal direction along the inner surface of the furnace wall, an exhaust pipe at the center of the circular ceiling when viewed from above, and a circular hearth when viewed from above. A heat treatment furnace having a thermometer;
Using a processing apparatus comprising a container transfer device capable of charging and discharging the heat-resistant container to the heat treatment furnace,
The heat-resistant container put in the heat treatment furnace is heated from the outside at a temperature lower than the melting point of aluminum with the burner to dry-distill the negative electrode material of the lithium ion battery inside the heat-resistant container and separate the carbonized mixture Waste lithium ions characterized in that the electrolyte in the battery is volatilized and discharged from the exhaust pipe of the heat-resistant container into the heat treatment furnace, and the temperature inside the heat treatment furnace is adjusted using the thermometer. Battery processing method. A battery pack in which a plurality of battery modules in which a plurality of lithium ion battery cells are arranged are housed in a box-shaped housing or a heat-resistant container having an exhaust pipe projecting obliquely upward;
A burner that has a cylindrical furnace wall, jets fuel in a horizontal direction along the inner surface of the furnace wall, an exhaust pipe at the center of the circular ceiling when viewed from above, and a circular hearth when viewed from above. A heat treatment furnace having a thermometer;
Using a processing apparatus comprising a container transfer device capable of charging and discharging the heat-resistant container to the heat treatment furnace,
The heat-resistant container charged in the heat treatment furnace is heated from the outside at a temperature lower than the melting point of aluminum by the burner to dry-distill the battery pack or the battery module inside the heat-resistant container and separate the carbonized mixture. Waste lithium ions characterized in that the electrolyte in the battery is volatilized and discharged from the exhaust pipe of the heat-resistant container into the heat treatment furnace, and the temperature inside the heat treatment furnace is adjusted using the thermometer. Battery processing method.   6. The treatment of a waste lithium ion battery according to claim 4 or 5, wherein a damper disposed inside an exhaust pipe in the vicinity of the ceiling portion of the heat treatment furnace is used to adjust a pressure inside the heat treatment furnace. Method.   The method for treating a waste lithium ion battery according to claim 4, wherein the temperature inside the heat treatment furnace is adjusted to 400 ° C. or more and 650 ° C. or less.   The treatment of a waste lithium ion battery according to any one of claims 4 to 7, wherein the gas discharged through the exhaust pipe of the heat treatment furnace is introduced into a region of 350 ° C or higher of the preheater of the cement adjusting device. Method.

Images