WO2023149017A1 - リチウムイオン電池廃棄物の熱処理方法 - Google Patents

リチウムイオン電池廃棄物の熱処理方法 Download PDF

Info

Publication number
WO2023149017A1
WO2023149017A1 PCT/JP2022/037172 JP2022037172W WO2023149017A1 WO 2023149017 A1 WO2023149017 A1 WO 2023149017A1 JP 2022037172 W JP2022037172 W JP 2022037172W WO 2023149017 A1 WO2023149017 A1 WO 2023149017A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat treatment
gas
furnace
ion battery
lithium ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/037172
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
洋 宮永
康文 芳賀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Advanced Metals Corp
Original Assignee
JX Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Metals Corp filed Critical JX Metals Corp
Priority to US18/832,470 priority Critical patent/US20250105386A1/en
Priority to CA3251193A priority patent/CA3251193A1/en
Priority to EP22924922.2A priority patent/EP4475273A1/en
Priority to JP2023578370A priority patent/JP7711229B2/ja
Publication of WO2023149017A1 publication Critical patent/WO2023149017A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/20—Arrangements for treatment or cleaning of waste gases
    • F27D17/28—Arrangements for treatment or cleaning of waste gases for cooling waste gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining or circulating atmospheres in heating chambers
    • F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • This specification discloses a heat treatment method for lithium-ion battery waste.
  • Patent Document 1 "When recovering lithium from battery waste, battery powder obtained by heating and heat-treating battery waste in a heat treatment furnace and then crushing and sieving, etc. leaching the lithium in water into water,” and ”using heat treatment to convert lithium in lithium compounds such as lithium composite oxides that may be contained in battery waste into lithium carbonate, which is easily leached into water.” is described.
  • Patent Document 1 discloses, for the purpose of “stable production of lithium carbonate", "a method for heat-treating battery waste containing lithium, comprising: An atmospheric gas containing oxygen and at least one selected from the group consisting of nitrogen, carbon dioxide and water vapor is flowed to adjust the oxygen partial pressure in the furnace while heating the battery waste.
  • the lithium-ion battery waste since the lithium-ion battery waste is heat treated in an inert atmosphere, it may be heated in a heat treatment furnace while supplying an inert gas. At this time, a relatively large amount of combustible gas derived from the electrolyte and other components may be generated from the lithium ion battery waste. In order to burn such generated gas, it is conceivable to install a gas combustion furnace side by side with the heat treatment furnace.
  • the oxygen concentration in the heat treatment furnace may not reach a certain level, and the generated gas may leak out of the heat treatment furnace.
  • the heat treatment of lithium ion battery waste can be maintained at a relatively low oxygen concentration in the heat treatment furnace while suppressing the leakage of gas generated from the lithium ion battery waste in the heat treatment furnace to the outside. provide a way.
  • the heat treatment method for lithium ion battery waste disclosed in this specification includes a battery heating step of heating the lithium ion battery waste in a heat treatment furnace while supplying an inert gas, and a gas combustion step of sending a gas into a gas combustion furnace and burning the generated gas in the gas combustion furnace, and in the battery heating step, while supplying an inert gas into the heat treatment furnace, the lithium ions
  • the gauge pressure in the heat treatment furnace is maintained within the range of -0.20 kPa to -0.01 kPa.
  • the inside of the heat treatment furnace is maintained at a relatively low oxygen concentration while suppressing the leakage of gas generated from the lithium ion battery waste in the heat treatment furnace to the outside. can be done.
  • FIG. 1 is a schematic diagram showing an example of equipment including a heat treatment furnace and a gas combustion furnace capable of carrying out a heat treatment method for lithium ion battery waste according to one embodiment.
  • 5 is a graph showing an example of temporal changes in the temperature of the lithium ion battery waste when heating the lithium ion battery waste and the LPG combustion flow rate of the gas combustion furnace.
  • the heat treatment method of one embodiment includes, for example, a battery heating step of heating lithium ion battery waste while supplying an inert gas in a heat treatment furnace 1 in a facility as shown in FIG. and a gas combustion step of sending gas generated in the heat treatment furnace 1 (generated gas) into the gas combustion furnace 2 and burning the generated gas in the gas combustion furnace 2 .
  • inert gas is supplied to adjust the atmosphere inside the furnace while heating the lithium-ion battery waste.
  • the oxygen concentration in the heat treatment furnace 1 is lowered to some extent, the metal contained in the lithium ion battery waste can be effectively changed into a form that can be easily processed later.
  • the pressure in the heat treatment furnace 1 is lower than the atmospheric pressure, the air outside the furnace tends to flow into the heat treatment furnace 1, so if the purpose is only to lower the oxygen concentration in the heat treatment furnace 1, the heat treatment It may also be desirable to maintain the furnace 1 at an internal pressure above atmospheric pressure (ie, positive pressure).
  • the lithium-ion battery waste is heated in the heat treatment furnace 1, combustible gases derived from the electrolyte and other components contained in the lithium-ion battery waste are generated from the lithium-ion battery waste.
  • Such generated gas is fed into a gas combustion furnace 2 connected to the heat treatment furnace 1 and burned.
  • the inside of the heat treatment furnace 1 is maintained at a positive pressure, the generated gas leaks out of the heat treatment furnace 1 .
  • the internal pressure of the heat treatment furnace 1 is too low, air or outside air flows into the heat treatment furnace 1, making it impossible to maintain a predetermined low oxygen concentration.
  • the gauge pressure in the heat treatment furnace 1 is kept at -0. Maintain within the range of 20 kPa to -0.01 kPa. As a result, the inside of the heat treatment furnace 1 can be maintained at a desired low oxygen concentration while suppressing leakage of generated gas.
  • the target lithium-ion battery waste is lithium-ion secondary batteries for vehicle or consumer use, which are discarded due to the life of the battery product, manufacturing defects, or other reasons.
  • Vehicle-mounted lithium-ion secondary batteries include those included in vehicle-mounted battery packs mounted in vehicles such as hybrid vehicles and electric vehicles.
  • Lithium ion secondary batteries for consumer use include those used in mobile phones and various other electronic devices. Recovery of cobalt, nickel and other valuable metals from such lithium ion battery waste is required from the viewpoint of effective utilization of resources.
  • Lithium-ion battery waste refers to lithium-ion batteries subject to recycling, regardless of whether the lithium-ion batteries are traded for value, free of charge, or treated as industrial waste. .
  • a vehicle battery pack including a lithium ion secondary battery for vehicle use generally consists of a metal case that constitutes a surrounding housing, and a lithium ion secondary battery or the like that is housed inside the case and has a plurality of battery cells. battery and other components. A plurality of battery cells are sometimes included in an on-vehicle battery pack as a battery module in which they are bundled. Vehicle-mounted battery packs come in a variety of shapes depending on the space constraints of the vehicle in which they are mounted. Some have external shapes.
  • Lithium-ion battery waste is usually treated as a positive electrode active material consisting of a single metal oxide of one or more of lithium, nickel, cobalt and manganese, or a composite metal oxide of two or more of them, which is aluminum foil (positive electrode base material). ), for example, polyvinylidene fluoride (PVDF) or other organic binder applied and fixed to the positive electrode material, the negative electrode material made of a carbon-based material, etc., an organic electrolyte such as ethylene carbonate or diethyl carbonate, etc. and electrolytes.
  • PVDF polyvinylidene fluoride
  • organic binder applied and fixed to the positive electrode material
  • the negative electrode material made of a carbon-based material, etc.
  • an organic electrolyte such as ethylene carbonate or diethyl carbonate, etc. and electrolytes.
  • lithium ion battery waste may contain copper, iron, and the like.
  • Lithium-ion battery waste includes in-vehicle battery packs as well as battery cells removed from in-vehicle battery packs.
  • Battery modules in which battery cells are bundled may be treated as lithium-ion battery waste.
  • a battery cell may contain an electrolytic solution or a resin, and generate gas when heated. Therefore, it may be necessary to prevent leakage of the generated gas and maintain the oxygen concentration in the heat treatment furnace 1 as described above.
  • the positive electrode material with aluminum foil and the battery powder which have been taken out from the battery cell or the like and optionally subjected to any treatment, may be treated as lithium ion battery waste. That is, the heat treatment method of this embodiment can be applied to vehicle battery packs, battery cells, battery modules, positive electrode materials with aluminum foil, battery powder, and the like.
  • the lithium ion battery waste is heated in the heat treatment furnace 1 under an inert atmosphere while supplying an inert gas.
  • the explosive combustion of the organic electrolyte and the like that may be contained in the lithium ion battery waste is suppressed, making it easier to control the temperature in the heat treatment furnace 1.
  • nickel oxide and oxide The recovery rate of valuable metals is increased by suppressing the production of cobalt and promoting the production of cobalt and nickel, which are metals that are easily dissolved in acid.
  • the aluminum foil that has not reacted to lithium aluminate can be easily separated in the sieving process.
  • the aluminum foil becomes brittle and easily mixed with the battery powder in the sieving process.
  • an inert gas is supplied into the heat treatment furnace 1 .
  • the inert gas can be gas containing at least one selected from the group consisting of nitrogen, carbon dioxide and water vapor. Among them, a gas mainly containing nitrogen is preferable. Oxygen may be contained as long as it is trace amount to some extent.
  • the oxygen partial pressure during heat treatment is maintained, for example, within the range of 0 atm to 4 ⁇ 10 ⁇ 2 atm, preferably 1 ⁇ 10 ⁇ 2 atm or less, more preferably 1 ⁇ 10 ⁇ 3 atm or less. This makes it possible to suppress the embrittlement of aluminum in the lithium ion battery waste.
  • the oxygen concentration in the heat treatment furnace 1 is, for example, 0.05% by volume to 4.00% by volume, preferably less than 1% by volume, and more preferably less than 0.1% by volume. It is desirable to keep the oxygen partial pressure and oxygen concentration in the heat treatment furnace 1 low as described above from when the temperature of the lithium ion battery waste is raised by starting heating to when the temperature is maintained at a predetermined temperature. . In this case, the gas generated during the temperature rise (electrolytic solution, gas derived from resin decomposition, etc.) is not ignited in the heat treatment furnace 1, but can be burned in the gas combustion furnace 2 as intended.
  • Oxygen partial pressure and oxygen concentration can be measured with a zirconia oxygen concentration meter.
  • the above oxygen partial pressure and oxygen concentration mean that at least the values measured when the measurement is possible should be within the range. For example, when the organic electrolyte evaporates, it may not be possible to measure, but the oxygen partial pressure and oxygen concentration during such unmeasurable period are irrelevant.
  • the flow rate of the inert gas supplied into the heat treatment furnace 1 is preferably 1 Nm 3 /h to 60 Nm 3 /h, more preferably 6 Nm 3 /h to 60 Nm 3 /h, particularly 7 Nm 3 /h to 12 Nm 3 /h. It is even more preferable to If the flow rate of the inert gas is too high, there is a concern that the temperature distribution during heat treatment will become large and heat treatment will not be possible at the optimum temperature. On the other hand, if the flow rate of the inert gas is too low, the oxygen partial pressure distribution during the heat treatment becomes large, and there is a possibility that the heat treatment cannot be performed at the optimum oxygen partial pressure.
  • the lithium ion battery waste can be heated to reach and maintain a temperature of 300°C to 800°C.
  • gas is generated from the housing of the lithium-ion battery waste due to the electrolyte and the like. Since such generated gas is combustible and needs to be burned, it is sent from the heat treatment furnace 1 to the gas combustion furnace 2 and burned in the gas combustion furnace 2 in the gas combustion process.
  • the gauge pressure in the heat treatment furnace 1 (that is, the pressure obtained by subtracting the atmospheric pressure from the absolute pressure) is reduced to -0 .20 kPa to -0.01 kPa.
  • the generated gas is prevented from leaking out of the heat treatment furnace 1, and oxygen into the heat treatment furnace 1 is prevented. is suppressed, and it becomes easier to maintain the inside of the heat treatment furnace 1 at a predetermined oxygen concentration.
  • the gauge pressure inside the heat treatment furnace 1 is higher than ⁇ 0.01 kPa, the generated gas may leak out of the heat treatment furnace 1 .
  • the gauge pressure in the heat treatment furnace 1 is lower than -0.20 kPa, outside air may flow into the heat treatment furnace 1 and the desired oxygen concentration may not be achieved.
  • the gauge pressure in the heat treatment furnace 1 by setting the gauge pressure in the heat treatment furnace 1 to ⁇ 0.20 kPa to ⁇ 0.01 kPa, the load on the gas combustion furnace 2 that burns the generated gas sent from the heat treatment furnace 1 is reduced. be able to. This allows a relatively small gas-fired furnace 2 to be used.
  • the gauge pressure in the heat treatment furnace 1 is made higher than ⁇ 0.01 kPa to make the inside of the heat treatment furnace 1 positive pressure, the generated gas in the heat treatment furnace 1 becomes difficult to flow into the gas combustion furnace 2, and the heat treatment furnace 1 After it accumulates inside, it is sent to the gas combustion furnace 2 all at once at a certain timing.
  • the generated gas is combustible, it is necessary to limit the amount of heat supplied from the heat source of the gas combustion furnace 2 to maintain the temperature inside the gas combustion furnace 2 at a constant temperature. Once sent to the combustion furnace 2, it becomes difficult to maintain the temperature inside the gas combustion furnace 2. Further, if the gauge pressure in the heat treatment furnace 1 is made lower than -0.20 kPa, the generated gas will immediately flow into the gas combustion furnace 2, so the load on the gas combustion furnace 2 will increase in this case as well.
  • the heat treatment furnace 1 and the gas combustion furnace 2 can be connected by a connecting pipe 3 as shown in FIG.
  • Generated gas in the heat treatment furnace 1 is led to the gas combustion furnace 2 through the connection pipe 3 .
  • the pressure in the heat treatment furnace 1 is high, the flow velocity of the generated gas from the heat treatment furnace 1 to the gas combustion furnace 2 becomes slow, and the tar flowing into the gas combustion furnace 2 together with the generated gas aggregates in the connecting pipe 3, Clogging in the connection pipe 3 is likely to occur.
  • the internal pressure of the heat treatment furnace 1 is lowered as described above, it is possible to effectively suppress the occurrence of tar agglomeration and clogging within the connecting pipe 3 .
  • the gauge pressure in the heat treatment furnace is more preferably -0.16 kPa to -0.13 kPa.
  • the gauge pressure inside the heat treatment furnace 1 can be measured with a pressure gauge. Specifically, for example, a pipe for measurement is inserted into the heat treatment furnace 1, the pipe is connected to a pressure gauge installed outside the heat treatment furnace 1, and the gauge pressure inside the heat treatment furnace 1 is measured with the pressure gauge. I have something to do.
  • the gas treatment equipment 4 is not particularly limited as long as it can appropriately treat the exhaust gas derived from the electrolyte or the like. and washing device 6 .
  • a furnace pressure adjustment mechanism for adjusting the internal pressure of the heat treatment furnace 1 as described above is preferably provided downstream of the heat treatment furnace 1 and the gas combustion furnace 2 in the gas flow direction.
  • a valve 7 and an exhaust fan 8 are provided on the downstream side of the heat treatment furnace 1 and the gas combustion furnace 2 in the gas flow direction, and on the downstream side of the gas processing equipment 4. .
  • the opening of the valve 7 is automatically or manually adjusted downstream of the gas processing equipment 4. and/or by adjusting the rotation speed of the exhaust fan 8, the internal pressure of the heat treatment furnace 1 can be controlled.
  • either the valve 7 or the exhaust fan 8 can adjust the internal pressure of the heat treatment furnace 1, so either the valve 7 or the exhaust fan 8 may be omitted.
  • the furnace pressure adjusting mechanism is not limited to the valve 7 and the exhaust fan 8 shown in FIG. 1, and various structures can be used.
  • a special furnace such as a vacuum furnace may be used, but it is also possible to use a general furnace which is not as airtight as a vacuum furnace.
  • a small amount of air (oxygen) may flow in from the outside, but by adjusting the internal pressure and other conditions as described above, the oxygen concentration in the furnace can be kept sufficiently low.
  • the sealing structure of the furnace door, the chamber for creating a vacuum environment, the installation of vacuum pumps and vacuum valves to create a vacuum, and the strengthening of the sealing of the installation ports of instrumentation equipment for measuring the temperature and pressure inside the furnace. etc. can be done.
  • some vacuum furnaces are not suitable for relatively gas-producing processes, such as heat treatment of lithium-ion battery waste.
  • the heat treatment furnace 1 can be a continuous type as well as a batch type. This embodiment can also be applied when a continuous heat treatment furnace 1 is used.
  • the heat treatment furnace 1 can be a furnace in which the heat source is exposed to the target of heat treatment (lithium ion battery waste, etc.), but it may be a muffle furnace in which the target of heat treatment is isolated from the heat source. .
  • the muffle furnace has a highly airtight structure, which can suppress the inflow of outside air and eliminate the influence of oxygen released from the refractories.
  • the heat treatment furnace 1 when the heat treatment furnace 1 is a muffle furnace, the supply flow rate of the inert gas into the heat treatment furnace 1 may be reduced. If it is desired to reduce the supply flow rate of the inert gas to, for example, 6 Nm 3 /h or less, it is desirable to employ a muffle furnace as the heat treatment furnace 1 .
  • the lithium-ion battery waste may be subjected to heat treatment in an air atmosphere before or after the heat treatment in an inert atmosphere as described above, preferably after the heat treatment in an inert atmosphere, if necessary.
  • Heat treatment in an air atmosphere is preferable in that adjustment of the atmosphere is unnecessary and can be easily performed.
  • Thermal treatment under atmospheric conditions can heat the lithium ion battery waste to reach and maintain a temperature of 300°C to 800°C.
  • Gas combustion process In the gas combustion process, the generated gas sent from the heat treatment furnace 1 to the gas combustion furnace 2 is burned at a predetermined high temperature in the gas combustion furnace 2 to render it harmless.
  • the gas after combustion is discharged from the gas combustion furnace 2 as an exhaust gas and may be sent to the gas treatment facility 4 as previously described.
  • the inside of the gas combustion furnace 2 can be maintained at preferably 800°C to 1000°C, more preferably 850°C to 900°C. If the temperature in the gas combustion furnace 2 is too low, there is a concern that the generated gas will not burn effectively, and if the temperature is too high, the time required for the generated gas to burn effectively in the gas combustion furnace 2 is concerned. cannot be secured, or the capacity of the gas processing equipment 4 in the latter stage may be exceeded.
  • the temperature tends to rise due to combustion of the generated gas. In that case, it is preferable to adjust the temperature in the gas combustion furnace 2 by changing the amount of heat supplied from the heat source of the gas combustion furnace 2 according to the combustion of the generated gas in the gas combustion furnace 2 .
  • the amount of LPG gas supplied is such that the temperature in the gas combustion furnace 2 does not exceed a predetermined temperature as the generated gas is burned.
  • the temperature of the lithium ion battery waste rises as time elapses after the start of heating the lithium ion battery waste in the heat treatment furnace 1.
  • the generated gas in the heat treatment furnace 1 flows into the gas combustion furnace 2 and burns in the gas combustion furnace 2, so that the temperature inside the gas combustion furnace 2 does not exceed a predetermined temperature according to the combustion.
  • LPG combustion flow rate which is the heat source of the gas combustion furnace 2
  • LPG combustion flow rate which is the heat source of the gas combustion furnace 2
  • LPG burners often mix and burn LPG gas and air, and the above-mentioned LPG combustion flow rate and ⁇ LPG described later are not the flow rate of mixed gas with air, but the flow rate of LPG gas.
  • the throttle amount of the LPG combustion flow rate is referred to as ⁇ LPG here. If ⁇ LPG becomes too large, the LPG combustion flow rate reaches the minimum flow (minimum amount of LPG combustion flow rate), and as a result, the LPG combustion flow rate cannot be reduced any further, and as a result, the temperature inside the gas combustion furnace 2 reaches a predetermined level. There is concern that the temperature will be exceeded.
  • the LPG combustion flow rate is rapidly reduced twice. The first time is considered to be when a large amount of gas derived from the electrolyte is generated, and the second time is when CH-based gas is generated due to resin decomposition. .
  • ⁇ LPG per battery module is 1.0 Nm 3 /hr or less when gas derived from the electrolyte is generated, and furthermore, 0 .40 Nm 3 /hr or less, particularly 0.37 Nm 3 /hr or less, typically 0.15 to 0.25 Nm 3 /hr, and 1.0 Nm 3 /hr when CH-based gas is generated by resin decomposition.
  • ⁇ LPG per unit mass (1 kg) of the electrolyte contained in the lithium ion battery waste is 1.5 Nm 3 /hr or less, further 0.60 Nm 3 /hr or less when the gas derived from the electrolyte is generated.
  • it may be suppressed to 0.56 Nm 3 /hr or less, typically 0.20 to 0.40 Nm 3 /hr.
  • ⁇ LPG per unit mass (1 kg) of resin contained in lithium ion battery waste is 4.5 Nm 3 /hr or less, further 1.8 Nm 3 /hr or less when CH-based gas is generated by resin decomposition, especially In some cases, it can be suppressed to 1.3 Nm 3 /hr or less, typically 1.1 to 1.6 Nm 3 /hr.
  • the generation of gas derived from the electrolyte means the time when the temperature of the lithium ion battery waste reaches 150.degree. C. to 190.degree. Typically around 170°C.
  • the constituents of the internal electrolyte which have a low boiling point, evaporate one by one, and when the temperature reaches the above temperature range, the internal pressure reaches a predetermined level.
  • the safety valve opens and gas derived from the electrolyte is generated.
  • the CH-based gas when the CH-based gas is generated, it means when the temperature of the lithium ion battery waste reaches 380.degree. C. to 420.degree.
  • This temperature range corresponds to the decomposition (vaporization) temperature of the resin attached to the battery module of the lithium ion battery waste, and is typically around 400.degree.
  • the resin decomposition gas is a mixture of multiple hydrocarbon compounds.
  • One piece of lithium ion battery waste may contain 662 g of electrolyte and 230 g of resin.
  • ⁇ LPG may change depending on whether or not the lithium ion battery waste explodes during heat treatment, the residual voltage of the lithium ion battery waste, which will be described later, and the like. However, if the conditions are substantially the same, if the gauge pressure in the heat treatment furnace is maintained within the range of -0.20 kPa to -0.01 kPa, the ⁇ LPG will be smaller than when it is outside that range. can do.
  • lithium-ion battery waste with a residual voltage of less than 2.4V.
  • ⁇ LPG tends to increase when gas derived from the electrolyte is generated.
  • the lithium ion battery waste with a relatively high residual voltage is subjected to heat treatment, the lithium ion battery waste with a residual voltage higher than a predetermined voltage is subjected to a discharge process, and the residual voltage is lower than the predetermined voltage.
  • the discharge step may be omitted for some lithium ion battery waste, such as not subjecting the lithium ion battery waste to the discharge step. Even in this case, the throughput of the discharge process can be reduced, and the cost required for the discharge process can be kept low.
  • LPG gas liquefied petroleum gas whose main component is propane or butane
  • LNG gas liquefied natural gas whose main component is methane and is used as city gas, etc.
  • heavy oil or recycled oil.
  • the lithium-ion battery waste that has passed through the battery heating process described above can be subjected to a crushing process, a crushing/pulverizing process, and a sieving process, if necessary.
  • crushing the battery is taken out from the case of lithium-ion battery waste such as an automotive battery pack, the housing of the battery is destroyed, and the positive electrode active material is selectively separated from the aluminum foil coated with the positive electrode active material.
  • various known apparatuses or devices can be used, but a specific example thereof is an impact-type crusher capable of crushing lithium-ion battery waste by applying an impact while cutting, such as a sample crusher. Mills, hammer mills, pin mills, wing mills, tornado mills, hammer crushers and the like can be mentioned.
  • a screen can be installed at the outlet of the crusher, so that the battery is discharged from the crusher through the screen when it is crushed to a size that allows it to pass through the screen.
  • the crushed battery may be lightly crushed into powder, and then sieved using an appropriate sieve.
  • the pulverization and pulverization improve the separability from the aluminum foil of the positive electrode active material adhering to the aluminum foil.
  • pulverization and pulverization may be omitted.
  • the above battery powder is brought into contact with either a weakly acidic solution, water, or an alkaline solution in the lithium dissolution process to dissolve the lithium contained in the battery powder into the solution.
  • Lithium in the lithium solution can be recovered as lithium carbonate by subjecting the lithium solution to treatments such as solvent extraction, neutralization, and carbonation.
  • the residue that remains without being dissolved in water or solution in the lithium dissolution process can be extracted by solid-liquid separation using a filter press, thickener, etc., and then leached with acid in the acid leaching process.
  • the acid leaching step can be performed by a known method or conditions.
  • the pH may be 0.0-3.0.
  • Various metals such as cobalt and nickel can be recovered by subjecting the post-leaching solution obtained by acid leaching and solid-liquid separation in the acid leaching process to neutralization, solvent extraction and other processes.
  • the lithium ion battery waste was heated to 600 ° C. while supplying nitrogen gas in the heat treatment furnace, and the generated gas was burned in the gas combustion furnace. .
  • the lithium-ion battery waste to be heat-treated was three battery modules bundled with battery cells contained in a vehicle battery pack.
  • the flow rate of nitrogen gas supplied into the heat treatment furnace was set at 7.8 Nm 3 /h, and the LPG combustion flow rate and the like were adjusted so that the temperature inside the gas combustion furnace was maintained at 850°C.
  • Example 1 The internal pressure (gauge pressure, furnace pressure) of the heat treatment furnace was controlled within the range of -0.16 kPa to -0.13 kPa. As a result, the oxygen concentration in the heat treatment furnace could be reduced to less than 0.1% by volume. The oxygen partial pressure in the heat treatment furnace was 0.998 ⁇ 10 ⁇ 3 atm. In addition, no leakage of generated gas to the outside of the heat treatment furnace was confirmed. The flow rate of gas (generated gas and nitrogen gas) in the connecting pipe connecting the heat treatment furnace and the gas combustion furnace was 28.2 m 3 /h. As shown in Table 1, ⁇ LPG was able to be kept relatively small both when gas originating from the electrolytic solution and when CH-based gas was generated.
  • the residual voltage (cell voltage) of the battery cells in the lithium ion battery waste before the heat treatment was approximately 0V. Since three battery modules were treated here, the overall ⁇ LPG (total ⁇ LPG) was almost three times the ⁇ LPG per module in Table 1, and was about 0.67 Nm when electrolyte was generated. 3 /h, and 0.86 Nm 3 /h when CH-based gas was generated.
  • Example 2 Same as Example 1, except that the residual voltage of the lithium ion battery waste before heat treatment was 2.4V. As a result, ⁇ LPG when the gas originating from the electrolytic solution was generated was slightly larger than in Example 1. The oxygen concentration and oxygen partial pressure in the heat treatment furnace were the same as in Example 1. The total ⁇ LPG was about 1.11 Nm 3 /h when the electrolytic solution was generated, and about 0.86 Nm 3 /h when the CH-based gas was generated.
  • Example 1 The same as Example 1 except that the internal pressure of the heat treatment furnace was in the range of -0.50 kPa to -0.30 kPa. In this case, the oxygen concentration in the heat treatment furnace could not be lowered to 0.1% by volume. It is considered that this is because air flowed into the inside from the outside of the heat treatment furnace. In Comparative Example 1, since the oxygen concentration did not fall below 0.1% by volume, the heating test of the lithium ion battery waste could not be performed.
  • Comparative example 2 The same as Example 1 except that the internal pressure of the heat treatment furnace was 0 kPa. In this case, it was confirmed that the generated gas leaked out of the heat treatment furnace. Therefore, even in Comparative Example 2, the heating test of the lithium ion battery waste could not be performed.
  • the inside of the heat treatment furnace can be maintained at a relatively low oxygen concentration while suppressing the leakage of gas generated from the lithium ion battery waste in the heat treatment furnace to the outside. rice field.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Electrochemistry (AREA)
  • Secondary Cells (AREA)
  • Processing Of Solid Wastes (AREA)
PCT/JP2022/037172 2022-02-01 2022-10-04 リチウムイオン電池廃棄物の熱処理方法 Ceased WO2023149017A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/832,470 US20250105386A1 (en) 2022-02-01 2022-10-04 Heat treatment method for lithium ion battery waste
CA3251193A CA3251193A1 (en) 2022-02-01 2022-10-04 THERMAL TREATMENT PROCESS FOR LITHIUM-ION BATTERY WASTE
EP22924922.2A EP4475273A1 (en) 2022-02-01 2022-10-04 Heat treatment method for lithium ion battery waste
JP2023578370A JP7711229B2 (ja) 2022-02-01 2022-10-04 リチウムイオン電池廃棄物の熱処理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022014414 2022-02-01
JP2022-014414 2022-02-01

Publications (1)

Publication Number Publication Date
WO2023149017A1 true WO2023149017A1 (ja) 2023-08-10

Family

ID=87552045

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/037172 Ceased WO2023149017A1 (ja) 2022-02-01 2022-10-04 リチウムイオン電池廃棄物の熱処理方法

Country Status (5)

Country Link
US (1) US20250105386A1 (https=)
EP (1) EP4475273A1 (https=)
JP (1) JP7711229B2 (https=)
CA (1) CA3251193A1 (https=)
WO (1) WO2023149017A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7768518B1 (ja) 2024-06-12 2025-11-12 エーケー ツリー カンパニー，リミテッド 廃リチウムイオン二次電池のリサイクル方法及びそれから得られるリチウムイオン電池正極材用原料物質

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105509062A (zh) * 2016-01-20 2016-04-20 南京工业大学 全尺度电子电器废弃物连续热解焚烧装置
JP2018159477A (ja) * 2017-03-22 2018-10-11 太平洋セメント株式会社 廃リチウムイオン電池の処理方法
JP2019034254A (ja) * 2017-08-10 2019-03-07 太平洋セメント株式会社 廃リチウムイオン電池の処理装置及び処理方法
CN208849035U (zh) * 2018-09-25 2019-05-10 荆门市格林美新材料有限公司 一种废旧锂电池处理设备
CN113161640A (zh) * 2021-02-03 2021-07-23 顺尔茨环保(北京)有限公司 一种废旧锂电池多级热解回收黑粉的系统及方法
JP2021163645A (ja) * 2020-03-31 2021-10-11 Ｊｘ金属株式会社 電池廃棄物の熱処理方法及び、リチウム回収方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109326843B (zh) 2018-11-26 2021-01-15 荆门市格林美新材料有限公司 一种废旧电池正极材料回收再利用工艺

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105509062A (zh) * 2016-01-20 2016-04-20 南京工业大学 全尺度电子电器废弃物连续热解焚烧装置
JP2018159477A (ja) * 2017-03-22 2018-10-11 太平洋セメント株式会社 廃リチウムイオン電池の処理方法
JP2019034254A (ja) * 2017-08-10 2019-03-07 太平洋セメント株式会社 廃リチウムイオン電池の処理装置及び処理方法
CN208849035U (zh) * 2018-09-25 2019-05-10 荆门市格林美新材料有限公司 一种废旧锂电池处理设备
JP2021163645A (ja) * 2020-03-31 2021-10-11 Ｊｘ金属株式会社 電池廃棄物の熱処理方法及び、リチウム回収方法
CN113161640A (zh) * 2021-02-03 2021-07-23 顺尔茨环保(北京)有限公司 一种废旧锂电池多级热解回收黑粉的系统及方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Abfallforschungstage 2004", 31 December 2004, CUVILLIER VERLAG, Göttingen, article HANS-JOACHIM GEHRMANN: "Pyrolyse -Chancen und Grenzen in der thermischen Abfallbehandlung", XP093163188 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7768518B1 (ja) 2024-06-12 2025-11-12 エーケー ツリー カンパニー，リミテッド 廃リチウムイオン二次電池のリサイクル方法及びそれから得られるリチウムイオン電池正極材用原料物質
JP2025186985A (ja) * 2024-06-12 2025-12-24 エーケー ツリー カンパニー，リミテッド 廃リチウムイオン二次電池のリサイクル方法及びそれから得られるリチウムイオン電池正極材用原料物質

Also Published As

Publication number Publication date
JPWO2023149017A1 (https=) 2023-08-10
US20250105386A1 (en) 2025-03-27
CA3251193A1 (en) 2025-02-25
EP4475273A1 (en) 2024-12-11
JP7711229B2 (ja) 2025-07-22

Similar Documents

Publication Publication Date Title
TWI757135B (zh) 電池廢棄物之熱處理方法及鋰回收方法
US12334522B2 (en) Method, apparatus, and system for lithium ion battery recycling
US6228143B1 (en) Rotary thermal oxidizer for battery recycling and process
EP4119245A1 (en) Method for recovering lithium and method for processing lithium ion secondary battery
US11316214B2 (en) Waste lithium battery recovery system
US20240186604A1 (en) Treatment method for battery waste
CN118510921A (zh) 有价金属回收合金、有价金属回收组合物以及有价金属回收方法
WO2022209421A1 (ja) 電池廃棄物の処理方法
JP2019034254A (ja) 廃リチウムイオン電池の処理装置及び処理方法
WO2022230861A1 (ja) 廃リチウムイオン電池の処理方法
WO2023149017A1 (ja) リチウムイオン電池廃棄物の熱処理方法
JP7707443B2 (ja) リチウムイオン電池廃棄物の熱処理方法
JP2024513015A (ja) 廃電池のリサイクルのための処理方法
CN216698489U (zh) 废旧三元动力电池处理系统
CN112520741A (zh) 一种锂电池负极材料用碳包硅粉生产方法
KR20250105644A (ko) Lfp 배터리 재활용 플랜트 및 방법
TW202436635A (zh) 電池再循環設備及方法
CN113921926B (zh) 废旧三元动力电池处理系统和方法
CN112952229A (zh) 水离子裂解锂电池系统
CN121358881A (zh) 有价金属回收组合物及有价金属回收方法
RU111134U1 (ru) Устройство для переработки твердых отходов с органическими составляющими
KR20250040810A (ko) 폐 리튬 이온 배터리 분쇄 공정을 위한 불활성가스 순환 시스템
Lillie Mild Thermal Treatment of Lithium-Ion Batteries to Optimize Black Mass Production

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22924922

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023578370

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 18832470

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2022924922

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022924922

Country of ref document: EP

Effective date: 20240902

WWP Wipo information: published in national office

Ref document number: 18832470

Country of ref document: US