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EP4499569A1 - Procédé et système d'obtention de graphite - Google Patents

Procédé et système d'obtention de graphite

Info

Publication number
EP4499569A1
EP4499569A1 EP23715824.1A EP23715824A EP4499569A1 EP 4499569 A1 EP4499569 A1 EP 4499569A1 EP 23715824 A EP23715824 A EP 23715824A EP 4499569 A1 EP4499569 A1 EP 4499569A1
Authority
EP
European Patent Office
Prior art keywords
fraction
graphite
size
separated
batteries
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.)
Pending
Application number
EP23715824.1A
Other languages
German (de)
English (en)
Inventor
Michael Breuer
Joachim Gier-Zucketto
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.)
Primobius GmbH
Original Assignee
Primobius GmbH
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
Priority claimed from DE102023201760.1A external-priority patent/DE102023201760A1/de
Application filed by Primobius GmbH filed Critical Primobius GmbH
Publication of EP4499569A1 publication Critical patent/EP4499569A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
    • 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
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
    • 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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • 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
    • C22B7/006—Wet processes
    • 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

  • the present invention relates to a method for obtaining graphite and possibly valuable metals, which are preferably selected from at least one of the metals of the first and/or the third main group and/or at least one of the metals of the 7th to 11th subgroups, from lithium-ion batteries; and a system for extracting graphite and possibly valuable metals from lithium-ion batteries, which is preferably designed to carry out the method according to the invention.
  • lithium-ion batteries Due to the increasing use of lithium-ion batteries as an energy source in electrically powered vehicles, large quantities of lithium-ion batteries will soon be generated as waste during production and at the end of their service life. These batteries are made of various valuable materials that are present in combination. Essentially these are:
  • Plastics ferrous metals, copper, aluminum, graphite as anode material, metal oxides as cathode material, lithium, cobalt, nickel, manganese and other rare valuable materials as well as electrolyte.
  • the battery modules consist of the so-called “black mass”, in which the particularly valuable raw materials are bound and which essentially consists of fine graphite and lithium metal oxides with a size in the range of 0.5 to 10 pm.
  • nickel, manganese, copper and cobalt are also particularly valuable components.
  • connection of the battery blocks is such that controlled dismantling, for example by loosening a screw connection, is practically impossible.
  • very different formats are commercially available. Therefore, the manufacturer's instructions must always be observed before and during the discharging and disassembly process.
  • the components After the battery has been opened and discharged, the components must be separated.
  • the metals and the Plastics in the housing can be sorted separately and fed into the circular economy, with suitable recycling processes already being used.
  • the remaining battery blocks consist of individual battery cells and/or modules. Depending on the design of the battery, it is possible to simply separate the cells, but there are also batteries in which the separation of the battery blocks is very complex, so that there is currently no satisfactory method for recycling the blocks in the state of the art which gives cells.
  • the unpleasant characteristic of these batteries is that a complete discharge takes a very long time and after a discharge cycle the batteries regain voltage, i.e. a state of charge, after a short time.
  • a battery that is not completely discharged usually suffers a short circuit when opened, which can ignite the electrolyte due to the heat. The result is unpredictable deflagrations and even fires.
  • a method for comminuting batteries containing LiPF6 in which the battery is subjected to a comminution process, which is realized by means of at least one tool that acts mechanically on the battery, the comminution process being carried out in an ambient fluid surrounding the battery takes place, which at least one Has alkaline earth metal.
  • the ambient fluid is an aqueous solution that contains calcium or magnesium, which are present as basic hydroxides Ca(OH)2 or Mg(OH)2 and in aqueous solution with the hydrogen fluoride (HF for short) formed when LiPF6 decomposes to form poorly soluble CaF2 or .MgF2 react and are thus bound.
  • the object of the present invention is to provide an effective method in which valuable raw materials are obtained from batteries that either come from production rejects or have reached the end of their service life for the circular economy, in particular graphite and, if necessary, valuable metals can be obtained.
  • the process according to the invention for obtaining graphite, and possibly valuable metals which are preferably selected from at least one of the metals of the first and/or the third main group and/or at least one of the metals of the 7th to 11th subgroup, from lithium ion batteries; comprises at least one step in which the batteries having a maximum remaining charge of 30% are shredded in a shredding device with the addition of water, so that a mixture of shredded batteries and water is obtained; wherein the mixture comprising the crushed batteries and the water is separated into a first aqueous graphite-enriched fraction, which may also contain metal oxides, and a second non-aqueous graphite-depleted fraction; and wherein the first aqueous graphite-enriched fraction is then freed of water, so that a dried graphite-containing fraction, which optionally also contains metal oxides, is obtained.
  • the proposed process is characterized by a high level of effectiveness, which makes it possible to return more than around 95% of the valuable raw materials back into the circular industry (recycling) in a very energy-efficient manner.
  • the dried graphite-containing fraction obtained according to the invention contains one a large part of the valuable so-called black mass, whereby this term in the sense of the present invention means the most valuable raw materials, which on the one hand are graphite and on the other hand the valuable metals, which are preferably selected from at least one of the metals of the first and / or the third main group and / or at least one of the metals from 7th to 11th. Subgroup, include.
  • no setting agents are preferably used to set the Li PF 6 , as is described, for example, in DE 10 2011 082 187 A1.
  • Further advantageous embodiments of the invention are specified in the dependent claims.
  • the features listed individually in the dependent claims can be combined with one another in a technologically sensible manner and can define further embodiments of the invention.
  • the features specified in the claims are specified and explained in more detail in the description, with further preferred embodiments of the invention being presented.
  • the dried graphite-containing fraction is mixed with concentrated acid, in particular sulfuric acid, so that a graphite-containing digestion is obtained, the resulting graphite-containing digestion being then filtered directly, so that graphite and a possibly .sulfuric acid solution can be obtained.
  • the filtered graphite can then preferably be cleaned, in particular rinsed with water.
  • the optionally sulfuric acid solution which contains at least one metal of the first and/or the third main group and/or at least one metal of the 7th to 11th.
  • Subgroup includes, wet-chemically separated and / or wet-chemically extracted.
  • the so-called black mass obtained in the separation process described according to the invention is then preferably further processed in a wet chemical process, in particular dissolved using sulfuric acid until the metals have dissolved in the acid.
  • the graphite can be separated, collected and recycled using a screen press.
  • the individual metals in particular selected from the series including lithium, aluminum, manganese, iron, cobalt, nickel, copper, can be precipitated from the acid solution, collected and also fed into the circular economy, for example by specifically adjusting the acid concentration and/or the temperature. Acids or special intermediate products that are of particular interest to the raw materials industry can also be taken directly from the process. It is particularly preferred here that the acid is conducted in a circulatory system.
  • acids important for the raw materials industry can be removed from the wet chemical process.
  • sulfuric acid and/or ammonia are used in particular for the dissolution process.
  • the setting of the temperature and the acid concentration preferably follows the precipitation rules for the respective metals one after the other in a cascade, whereby separate containers can be used depending on the setting.
  • the black mass and the intermediate products can be brought into solution using sulfuric acid and/or ammonia and/or water peroxide and/or water and/or organic solvents, whereby these can be used individually or as a solvent mixture;
  • the graphite can be separated from the liquid using a filter press
  • the liquid can be further processed in a step-by-step process
  • the liquid can be passed from one process stage to the following process stage;
  • the liquid is preferably circulated
  • Ammonium sulfate and metal sulfates are formed as end products, which can be removed from the system for further utilization; - the metals in the liquid can be separated from the liquid as sulfates, in particular gradually, by adjusting the pH value and/or phase separation and/or crystallization;
  • copper can be separated individually;
  • Nickel can, for example, be separated individually and/or
  • the separation into the first and second fractions takes place via two separate process stages, such that the mixture is initially converted into a first aqueous graphite-enriched fraction comprising particulate components in a first process stage, for example in a friction washer i).
  • a size of ⁇ 5000 pm preferably with a size of ⁇ 4000 pm, more preferably with a size of ⁇ 3000 pm, even more preferably with a size of ⁇ 2000 pm
  • a second non-aqueous graphite-depleted fraction comprising particulate components a size of > 5000 pm, preferably with a size of > 4000 pm, more preferably with a size of > 3000 pm, even more preferably with a size of > 2000 pm.
  • a shredder can be used for the shredding, with the first fraction then being collected in a buffer tank below this shredder and then preferably being separated further. It is preferably provided that ii) the first aqueous graphite-enriched fraction comprising the particulate components with a size of ⁇ 5000 pm, preferably with a size of ⁇ 4000 pm, more preferably with a size of ⁇ 3000 pm, even more preferably with a size of ⁇ 2000 pm then in a second process stage, in particular by means of a sieving stage, into a first aqueous graphite-enriched fraction freed from the particulate components, in particular a fraction of particles with a size of less than 500 pm, and a non- aqueous graphite fraction depleted and loaded with the particulate components, in particular a fraction of particles with a size of more than 500 pm is separated.
  • the second non-aqueous graphite-depleted fraction comprises particulate components with a size of > 5000 pm, preferably with a size of > 4000 pm, more preferably with a size of > 3000 pm, even more preferably with a size of > 2000 pm, via a separating device, in particular a zigzag classifier or a zigzag separator, and into a heavy fraction containing particulate components with a bulk density of at least 0, 02 kg/m 3 and separated into a light fraction containing particulate components with a maximum bulk density of 0.4 kg/m 3 .
  • the desired bulk density can be adjusted as required.
  • the second non-aqueous graphite-depleted fraction may comprise particulate components with a size of >5000 pm, preferably with a size of >4000 pm, more preferably with a size of >3000 pm, even more preferably with a size of > 2000 pm, are passed over a separating device which separates the two fractions in a vortex (cyclone) air flow using centrifugal forces.
  • the heavy fraction containing a first graphite-containing secondary fraction can first be comminuted and then separated into pure fractions.
  • An impact mill can preferably be used as the comminution device. It is particularly preferred that the first graphite-containing secondary fraction then obtained is also fed to the wet chemical process.
  • the aerosol which arises during the separation process and/or the comminution process and contains part of the first graphite-containing secondary fraction can preferably be sucked off and the part of the first graphite-containing secondary fraction contained therein can be separated off, in particular filtered off and then mixed with the remaining first graphite-containing secondary fraction be united.
  • the previously described preferred further separation process can be described as follows.
  • the metals and plastics are preferably separated in a separation process that exploits the differences in density, with transverse air flows in free fall ensuring that the heavier metals are separated from the lighter plastic residues and film residues.
  • Another shredding device, in particular an impact mill knocks off the black mass on the metals.
  • a suction system collects the dust, which essentially consists of black mass.
  • a sieve cascade preferably separates the components sorted according to their size. Magnetic separators can be used, for example, to separate the ferromagnetic components. The remaining metals can be separated from each other, for example, by exploiting the density differences with an air separation table or the like. The metals are preferably collected and collected separately and can be fed into the circular economy. The lighter plastics are preferably also collected and can be fed into the circular economy. The black mass is also preferably collected in order to then be sent for further wet-chemical processing.
  • the non-aqueous graphite-depleted fraction loaded with the particulate components is dried, if necessary using a drying device, in particular a vacuum dryer.
  • a drying device in particular a vacuum dryer.
  • the moist small parts with adhering black mass pass through a vacuum dryer in particular, whereby the same process steps for further separation can preferably be carried out as previously described in the separation process.
  • the vaporous condensate water created during the drying process can, for example, first be condensed into hot water and, if necessary, then cooled via a heat exchanger.
  • the water then obtained can also be fed back to the comminution device and/or to the mixture comprising the comminuted batteries and the water.
  • the non-aqueous graphite-depleted fraction containing a second graphite-containing secondary fraction and loaded with the particulate components can first be dried, then comminuted and then separated into further pure fractions.
  • An impact mill can preferably be used as the comminution device. It is particularly preferred that the second graphite-containing secondary fraction then obtained is also fed to the wet chemical process.
  • the further aerosol which arises during the comminution process and contains part of the second graphite-containing secondary fraction is preferably sucked off, the part of the second graphite-containing secondary fraction contained therein being separated off, in particular filtered off, and then combined with the remaining second graphite-containing secondary fraction becomes.
  • the water is preferably supplied in an amount of 20 to 200 m 3 /h based on a quantity of 1000 kg of batteries per hour. Due to the large and continuous volume flow, the heat generated during the mechanical shredding of the batteries and in the hydrolysis process is immediately dissipated. According to the present invention, the comminution therefore preferably does not take place in a standing water reservoir, but rather the comminution device in which the comminution takes place, water is constantly supplied and removed again, so that the heat generated in the process is also permanently dissipated.
  • the batteries when shredding the batteries, for example, ordinary tap water with a temperature below room temperature can be supplied. However, it is preferably provided that the water is supplied at a temperature in the range from 5 °C to 20 °C.
  • Water management for example, can be designed as a circular system.
  • the water can be fed to the comminution and/or separation process from a storage container and collected again downstream, for example where separated particles are dried, for example in a screen press, and then fed into the comminution and/or separation process to be led back.
  • filter systems can also be used to treat the circulating water, so that the exhaust air from a vacuum pump used in the system, for example, condenses and the condensate can be fed back to the storage container. If additional water is needed, this can be supplied from the pipe network (so-called make-up water).
  • the circulating water can be monitored for various parameters, such as pH, conductivity, biocity, color or the like.
  • the amount of circulating water required for the separation process according to the invention is approximately 20 to 200 m 3 /h/t batteries.
  • the use of at least 20 m 3 /h/t is recommended, preferably at least 50 m 3 /h/t.
  • at least 50 m 3 /h/t of circulating water is preferably used, particularly preferably about 100 m 3 /h per ton of batteries.
  • the batteries are comminuted in at least two stages, such that they are first coarsely pre-comminuted in a first stage before they are comminuted more finely in a subsequent second stage.
  • the selection of the number of comminution stages depends on the size of the material introduced. For complete battery modules with a size of more than 0.5 m, for example, a three-stage shredding system is advantageous. For individual battery cells or smaller units measuring less than, for example, 0.5 m, a two-stage system is usually sufficient.
  • the clear knife width in the shredding device which is used in the last shredding stage, is preferably less than approximately 12 mm, preferably less than approximately 9 mm.
  • the clear knife width in the penultimate stage can then be, for example, less than 25 mm, preferably around 19 mm. If there are more than two comminution stages, the clear knife width of the third to last stage is, for example, less than approximately 60 mm, preferably less than approximately 45 mm.
  • the specific drive power, i.e. the drive power per throughput in kg/h of battery cells and/or modules for the knife shafts is approximately 50 W/kg of battery cells and/or modules per hour, preferably approximately 80 to 120 W/kg/h.
  • the water obtained in the drying process can be collected, then cooled via a heat exchanger and then fed back to the shredding device and/or the mixture comprising the shredded batteries and the water.
  • the water can have particulate components with a size of, for example, up to 500 pm.
  • the water can also be supplied to the process via a friction washer, which is arranged downstream of the comminution device.
  • car batteries which are usually designed as relatively large components
  • the construction and electrical connections are fundamentally different, as each automobile manufacturer has its own specific structure.
  • additional measures or modifications to the processing process may make sense.
  • the car batteries can be identified by manufacturer and specifically discharged and dismantled until the individual battery cells and/or modules are separated.
  • the battery housing is also dismantled and sorted specifically for the recycling industry, as are existing conductors, insulators and other components.
  • the discharge can take place either on the entire car battery or on the individual battery cells and/or modules after assembly.
  • the discharge energy from the batteries is preferably recycled, for example through direct power supply, buffer storage or the like.
  • the mixer shaft of the separator or shredder used in the first separation process can in particular be operated at a speed of at least 500 rpm, preferably more than 1000 rpm, more preferably at more than 1500 rpm in order to achieve effective flow conditions and movements of the particles in the shredding device.
  • the vacuum dryer can, for example, be operated at a pressure of less than 900 mbar.
  • the temperature inside the dryer should preferably be more than 100 °C.
  • control system with process monitoring that is suitable for recording and/or monitoring the water supply and/or the quantity of batteries, in particular the battery cells and/or battery modules, and/or the concentration of the black mass.
  • the connected suction systems preferably used in the method according to the invention can collect the dusts and pass them through a filter system comprising, for example, a wet scrubber and/or ultra-fine filter with activated carbon and/or cyclone separator in order to reduce environmental pollution to a minimum.
  • a filter system comprising, for example, a wet scrubber and/or ultra-fine filter with activated carbon and/or cyclone separator in order to reduce environmental pollution to a minimum.
  • the process according to the invention can be carried out either continuously or discontinuously, while the processes previously known from the prior art are always only batch processes.
  • the comminution device according to the invention preferably works continuously.
  • the subsequent process steps are burdened with significantly less material and can therefore be operated more effectively and cost-effectively.
  • the majority of the black mass can, for example, be fed directly to the wet chemical part of the process via the filter cake of a filter press, although vacuum drying is not necessarily necessary, so that the process can be carried out very energy-efficiently. Virtually no valuable raw material is lost during the process.
  • the black mass adhering to the plastics cannot be removed economically due to the high van der Wals forces and therefore significantly determines the proportion of material that cannot be recycled into processing.
  • the subject of the present invention is also a plant for the extraction of graphite, and possibly valuable metals, which are preferably selected from at least one of the metals of the first and / or the third main group and / or at least one of the metals 7th to 11th subgroup, consisting of lithium-ion batteries, which are preferably designed to carry out the method according to the invention, comprising at least one comminution device which has a comminution unit which can be flushed with an aqueous medium, at least one first separating device connected downstream of the comminution device in the transport path, which preferably comprises at least one sieve, suitable for separating material obtained in the shredding device into at least two fractions of different particle sizes; and at least one drying device downstream of the first separating device in the transport path, preferably a filter press, for drying the fraction separated in the first separating device.
  • at least one comminution device which has a comminution unit which can be flushed with an aqueous medium
  • the comminution unit comprises at least two comminution stages arranged one below the other in accordance with gravity.
  • the system in the transport path downstream of the at least one comminution device comprises at least one system area in which the particles of at least one previously separated fraction are brought into solution in a liquid medium and then subjected to a further separation process, this system area being in particular a device for sieving and/or pressing and/or adjusting the pH and/or extracting and/or crystallizing.
  • the at least one first separating device has a further separating device connected downstream in the transport path, which comprises at least one sieve, suitable for separating at least one fraction previously separated in the first separating device into at least two further fractions of different particle sizes.
  • the system comprises at least one further separating device, by means of which lighter and heavier particles are separated from one another by an air flow, this further separating device being connected downstream in the transport path of at least one separating device which comprises a sieve.
  • this further separating device being connected downstream in the transport path of at least one separating device which comprises a sieve.
  • the lighter and heavier particles are separated from one another via a cross air flow in free fall or using centrifugal forces in a rbel (cyclone) air flow.
  • Figure 1 shows an exemplary schematic description of the preliminary process in the method according to the invention
  • Figure 2 shows an exemplary schematic description of the
  • Figure 3 shows an exemplary schematic description of another
  • Figure 4 shows an exemplary schematic description of a further sub-process of the method according to the invention.
  • Figure 5 shows an exemplary schematic description of the chemical sub-process of the method according to the invention
  • Figure 6 shows a schematically simplified flow diagram of a first phase of an exemplary process according to the invention
  • Figure 7 shows a schematically simplified flow diagram of a subsequent separation process, which is part of the method according to the invention.
  • Figure 8 shows a schematically simplified flow diagram of a further, subsequent separation process, which is also part of the method according to the invention.
  • Figure 9 shows a schematically simplified flow diagram of a further, subsequent separation process, which is also part of the method according to the invention.
  • the actual process for shredding the batteries and separating the components is initially preceded by a preliminary process 1, which is described in the schematic representation according to FIG.
  • batteries 2 originating from vehicles which have, for example, reached the end of their service life, and possibly battery cells and/or battery modules which were sorted out during production and require dismantling, are first dismantled.
  • These batteries, battery cells and/or battery modules 2, which will be understood below under the general term batteries 2 are discharged once, if necessary after the type has been identified (step 3), (step 4), but according to the invention, this is deliberately not a complete discharge Discharge is provided because this - as already explained - is very complex. In addition, it was surprisingly found that complete discharge is not necessary for the subsequent processing process.
  • the electrical energy 5 obtained when the batteries 2 are partially discharged can be used for other purposes.
  • the other components 7 of the batteries 2 that arise during dismantling 6, such as in particular the housing, the cabling, fittings and the like, are sorted and fed into the circular economy.
  • the different materials are separated from each other and sorted (step 8), whereby the residual materials 9, which are then separated according to type, can then be recycled.
  • the batteries, battery cells and/or battery modules 10 separated from the batteries 2 in this pre-process are then fed to the first sub-process 11, which is described in Figure 2 and will be explained below based on this illustration.
  • the isolated batteries, battery cells and/or battery modules which will be understood below under the general term isolated batteries 10, are first mixed with water 12 and preferably comminuted in a multi-stage comminution process 13, for example by means of a shredder.
  • the water 12 is constantly supplied and serves, among other things, to dissipate the heat generated in the process so that hydrogen fluoride (HF for short) is not released.
  • the mixture comprising the comminuted batteries and the water can be separated into a first aqueous graphite-enriched fraction 15 and a second non-aqueous graphite-depleted fraction 16 (separation step 14), for example in which the mixture centrifuged and spun.
  • the first aqueous graphite-enriched fraction 15 obtained according to the separation step 14, which contains the majority of the black mass, preferably comprises particulate components with a size of ⁇ 3 mm
  • the second non-aqueous graphite-depleted fraction 16 preferably includes particulate components with a size of > 3 mm.
  • the first aqueous graphite Enriched fraction 15 can be freed directly from the water according to a drying step 17, so that a dried graphite-containing fraction 18, which contains the majority of the black mass, is obtained.
  • black mass refers to the mostly valuable raw materials that can then be separated in a wet chemical process, as shown in Figure 5.
  • the first aqueous graphite-enriched fraction 15 can also first be separated into a first aqueous graphite-enriched fraction 19 freed from the particulate components and into a non-aqueous graphite-depleted fraction 20 loaded with the particulate components. For example, this can be screened in several steps, first coarsely (step 21) and then finely (step 22) in order to obtain the non-aqueous graphite-depleted fraction 20 loaded with the particulate components. The then obtained first aqueous graphite-enriched fraction 19 freed from the particulate components can then be freed of the water, for example by pressing (step 23). The contaminated water 24 can be returned to the water cycle and used again in the process after it has optionally been cleaned and treated using suitable measures (step 25).
  • the second non-aqueous graphite-depleted fraction 16 which can contain, for example, still-moist small parts with a particle size in the range of about 3 mm to about 10 mm as well as foils and metals, is fed to a second sub-process 26 for processing, which is shown in Figure 3 and will be explained in more detail below based on this illustration.
  • the second non-aqueous graphite-depleted fraction 16 is separated into a light and a heavier fraction 28, 29 by means of a further separation step 27, for which purpose, for example, a cross air flow can be used when the particles are in free fall .
  • the aerosol 31 that arises during the separation step or process 27 and contains part of a first graphite-containing secondary fraction 33 can be removed from the separation step 27 by a suction step 30 and passed through a Separation step 32 are filtered, so that the part of the first graphite-containing secondary fraction 33 contained therein is separated, in particular filtered off.
  • the heavier metallic particles (heavy fraction 29), which contain the majority of the first graphite-containing secondary fraction 33, can, after the separation described above in accordance with separation step 27, be fed to a comminution device, in particular an impact mill 34, in which further comminution takes place.
  • the different fractions obtained here can then be separated from one another by a sieving process 35, namely into a first middle fraction with particles with a size in the range of about 250 pm to about 100 pm, a coarser fraction with particles in a size of more than 250 pm and a third finer fraction with particles on a scale of less than 100 pm.
  • the third, finer fraction then comprises the main part of the first graphite-containing secondary fraction 33, which is combined with the black mass fraction obtained after passing through the separation step or filter system 32 and can also be fed to the wet-chemical processing (see Figure 5).
  • the coarser fraction shown in Figure 3 (>250 pm) generally contains predominantly plastics 37. This can be collected 38 and returned to a circular economy 39, as is also shown in Figure 3.
  • the middle fraction can be further separated, for example using an air separation table and/or a magnetic separator 40, in order to collect the metals copper, aluminum and iron according to type 41.
  • a third sub-process 42 is shown in FIG. 4, which describes the further processing of the non-aqueous graphite-depleted fraction 20 loaded with the particulate components (see FIG. 2). Reference will be made to this below.
  • This fraction 20 can first be dried in a drying device, in particular in a vacuum dryer 43, whereby the resulting condensate water 44 can be fed to the water circuit 25.
  • the material can be fed to a comminution device, in particular an impact mill 45, in which further comminution takes place takes place.
  • the comminution step is then followed by a sieving process 46 to separate the fractions obtained.
  • the several fractions (for example three) can be of the same order of magnitude as in the sieving process 35 previously described with reference to FIG 100 pm, a coarser fraction comprising particles on a scale of more than 250 pm and a third finer fraction comprising particles on a scale of less than 100 pm.
  • This third, finer fraction includes a further fraction 47 containing black mass, which in this case may contain water.
  • the water can be removed by means of a separation step, for example by sieving and pressing 48.
  • the coarser fraction usually contains predominantly plastics 50. This can be collected by type (step 51) and also fed into the circular economy 39.
  • the middle fraction can be further separated, for example by means of an air separation table and/or a magnetic separator 52, in order to collect the metals copper, aluminum and iron according to type and also feed them to the circular economy 39.
  • the aerosol 55 that arises during the comminution step 45 and contains part of the second graphite-containing secondary fraction 49 can be removed from it by a suction step 53 and filtered via a separation step 56, so that the part of the second graphite-containing secondary fraction 49 contained therein is separated, in particular filtered becomes.
  • the black mass fraction 54 obtained after passing through the separation step or filter system 56 can also be combined directly or, if necessary, with the remaining fractions 18, 33, 49 and then fed to the wet chemical processing (see Figure 5).
  • the process of wet-chemical processing (fourth sub-process 57) of the various black mass-containing fractions 18, 33, 49, 54 is explained in more detail below using the illustration in FIG.
  • the individual or possibly combined black mass-containing fractions 18, 33, 49, 54 can be brought into solution, for example, using aqueous sulfuric acid, ammonia, hydrogen peroxide and/or using organic solvents 58 (step 59) and then a sieving and/or filtering process 60 will be subjected.
  • Graphite 61 can be separated, collected 62 and returned to the circular economy 39.
  • the metals 63 obtained after this separation are in a solution, the pH of which may be adjusted accordingly depending on the metal (step 64).
  • An extraction 65 can then take place, in which the metals can be obtained, for example, as metal sulfates and crystallized or extracted again. Adjusting the pH value (step 64) depending on the metal and extraction can be done in several stages.
  • the metal sulfates 66 of the individual metals of each stage can then be collected separately and sorted (step 67) and thus obtained as raw materials 68 for the basic industry. Excess ammonium sulfate 69 can be removed as shown in FIG. 5 and recycled 70.
  • the batteries 2 are first sorted out, dismantled and discharged in the preliminary process 1.
  • the isolated batteries, battery cells and/or battery modules 10 then obtained are fed via a conveyor device, in particular a conveyor belt 72 ascending in the conveying direction, to a shredding device 73, for example a shredder, and are shredded in two stages as a whole with the addition of water 12.
  • a shredding device 73 for example a shredder
  • a friction washer 76 which includes a screw conveyor equipped with paddles.
  • the friction washer 76 includes an inclined below the arranged sieve arranged on the screw conveyor. If the shredded material, in particular the mixture comprising the shredded batteries and the water, is conveyed by means of the screw conveyor from the input end 75 to the axially opposite output end 77 of the screw conveyor (from left to right in the drawing), then the finer material falls with a particle size of for example less than 1 to less than 3 mm (for example the first aqueous graphite-enriched fraction 15) through the sieve and reaches a buffer tank 79 via a line 78 below the inlet end 75.
  • the coarser material with a particle size of, for example, more than 1 to more than 3 mm (for example the second non-aqueous graphite-depleted fraction 16) is, however, transported via the screw conveyor arranged in the friction washer 76 to its output end 77, falls down via the opening there and first reaches a silo via line 80 81 from which it is fed to the second sub-process 26. This will be explained in more detail later with reference to Figure 8.
  • the fraction of finer particles with a size of, for example, less than 1 to less than 3 mm is conveyed by means of a pump 82 to a sieve 83, by means of which a further separation into the two fractions 19, 20 takes place, namely a fraction 19 with a particle size of less than, for example, 500 pm, which contains the largest part, for example about 95% of the black mass and about 5% metals, and a fraction 20 with a particle size of more than, for example, 500 pm, which contains metals such as copper and aluminum as well as plastics contains adhering black mass.
  • This fraction 20 is fed via line 84 and screw conveyor 85 to the third sub-process 42, which will be explained in more detail later with reference to FIG.
  • the separation process 11 shown as an example in Appendix 71 can therefore be described in summary as follows.
  • the shredder 73 to which water 12 and isolated batteries, battery cells and/or modules 10 are fed, also serves as a separator in which the materials are initially separated. Water is supplied to the shredder 73 in order to essentially remove the black mass from the other components of the isolated batteries 10 and then transport them away.
  • the shredder 73 is a largely closed container, which has the housing of the friction washer arranged under the container 76, in which the screw conveyor is located, is combined.
  • the combined device has two offset outlets.
  • the first outlet which is arranged in the entrance area 75 of the friction washer 76, is connected to the line 78.
  • the second outlet which is arranged in the exit area 77 of the friction washer 76, is, however, connected to the line 80.
  • the size of the smaller particles that the sieve allows to pass through to the first outlet can be determined via the mesh size of the sieve of the friction washer 76, which is located around the screw conveyor.
  • the screw conveyor in the friction washer 76 below the shredder 73 comprises at least one mixer shaft with radially arranged levers, which, due to their shape, in addition to the turbulence, force a direction of movement from the input end 75 to the output end 77 with the second outlet.
  • the metal and plastic parts leave the device via the second outlet in the exit area 77 of the screw conveyor, while the black mass falls through the sieve with the water and the device via the first outlet in the entrance area 75 screw conveyor leaves.
  • the further separation of this material then takes place via the additional sieve 83, through which larger particles, especially plastic particles with a size of, for example, more than 500 ⁇ m, are separated from the black mass transported in the water.
  • the mesh size of the further sieve 83 can vary, so that, for example, smaller particles in the range from approximately 100 pm to approximately 1 mm, preferably in the range from approximately 100 pm to approximately 500 pm, are separated.
  • the finer fraction of particles with a size of less than 500 pm reaches the tank 86 and is then fed via line 88 by means of a further pump 87 to a further separation process of the first sub-process 11, which is explained in more detail below with reference to FIG becomes. 7, this finer fraction 19 is conveyed through line 88 into a circulation tank 89, which is equipped with a stirrer, with a partial flow leaving this circulation tank 89 via line 90 and being conveyed to a filter press 91, where by separation Drying takes place with water.
  • Organic exhaust gases can be used for heating, which are fed to the filter press 91 via line 92.
  • compressed air is supplied to the filter press 91 via line 93.
  • a partial stream of this particle fraction diluted with water can be conveyed via line 94 by means of pump 95 through a heat exchanger 96 and from there returned via return line 97 into the process according to FIG.
  • the heat exchanger 96 is flowed through in countercurrent by hot tap water, which reaches the heat exchanger 96 via the line 98, so that the returned material flow can be preheated in this way.
  • the product of the process shown in Figure 7 is the dried fraction 18 containing black mass, which leaves the filter press 91 via line 99 and can be temporarily stored in a barrel 100.
  • the black mass is already quite high in purity, for example around 95%, with a residual moisture in the range of around 20% to 30%.
  • This fraction 18 containing black mass can be used as feed material for a further wet chemical processing process, which is shown in FIG. 5 and has already been described above.
  • the further separation process 26 relating to the fraction of the coarse material 16 resulting after the first shredding process according to FIG. 6 is explained in more detail below with reference to FIG. 8.
  • This separation process 26 primarily serves to separate the separator film of the isolated batteries 10 from the plastic and metal particles.
  • the coarse fraction first travels from the silo 81 via line 101 to a cyclone 102, in which centrifugal separation takes place.
  • the fraction is then fed to a zigzag separator 103, in which the metals and plastics are separated using a process that exploits the density differences. In free fall, transverse air currents separate the heavier metals from the lighter plastic and film residues.
  • the black mass on the metals can then be chipped off in an impact mill, as already explained with reference to FIG. 3 has been.
  • the lighter plastic particles can be fed to another cyclone 107 via a blower 106 and the particles separated there can be collected in a container 108.
  • the exhaust gas from the two cyclones 102, 107 can be discharged via line 109 and, for example, fed to cleaning, such as a scrubber or the like.
  • the medium-coarse fraction 20 separated in the separation process according to FIG Figure 9 is further discussed, which is explained in more detail below.
  • This material reaches a vacuum dryer 111 via the feed line 110, in which it is dried.
  • the dry black mass fraction 49 obtained can be fed from the vacuum dryer 111 via line 112 to a barrel 113, in which it is collected. From there, this black mass fraction 49 can be fed via the output line 114 to the black mass fractions obtained in the other separation processes and processed wet-chemically, as has already been described with reference to FIG. 5.
  • the water vapor separated in the vacuum dryer 111 can be fed via line 115 to a condenser 116 and condensed there, in order to then be collected in the condensate tank 117.
  • Industrial cooling water can be used to cool the water vapor, which is fed to the condenser 116 via line 118.

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Abstract

L'invention se rapporte à un procédé permettant d'obtenir du graphite, et éventuellement des métaux de valeur, qui sont de préférence choisis parmi au moins l'un des métaux du premier et/ou du troisième groupe principal et/ou au moins l'un des métaux du 7ème au 11ème groupe secondaire, à partir de batteries au lithium-ion. Les batteries (2, 10) ayant une charge résiduelle de max 30 % sont broyées dans une unité de broyage (73) avec l'ajout d'eau (12), de telle sorte qu'un mélange de batteries broyées et d'eau est obtenu, le mélange comprenant les batteries broyées et l'eau étant divisé en une première fraction aqueuse enrichie en graphite (15), contenant éventuellement également des oxydes métalliques, et une seconde fraction non aqueuse appauvrie en graphite (16), et l'eau étant ensuite éliminée de la première fraction aqueuse enrichie en graphite (15) de telle sorte qu'une fraction contenant du graphite séchée (18), contenant éventuellement également des oxydes métalliques, est obtenue. L'invention se rapporte également à un système (71) correspondant.
EP23715824.1A 2022-03-29 2023-03-28 Procédé et système d'obtention de graphite Pending EP4499569A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102022203084 2022-03-29
DE102023200645 2023-01-26
DE102023201760.1A DE102023201760A1 (de) 2022-03-29 2023-02-27 Verfahren und Anlage zur Gewinnung von Grafit
PCT/EP2023/057997 WO2023186891A1 (fr) 2022-03-29 2023-03-28 Procédé et système d'obtention de graphite

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EP4499569A1 true EP4499569A1 (fr) 2025-02-05

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EP (1) EP4499569A1 (fr)
AU (1) AU2023244463A1 (fr)
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WO (1) WO2023186891A1 (fr)

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DE102011082187B4 (de) 2011-09-06 2021-07-08 Robert Bosch Gmbh Verfahren und Vorrichtung zur Zerkleinerung von Lithiumhexafluorophosphat (LiPF6) enthaltenden Batterien
EP4050701A1 (fr) * 2017-05-30 2022-08-31 Li-Cycle Corp. Procédé, appareil et système de récupération de matériaux à partir de batteries
EP3670686A1 (fr) 2018-12-21 2020-06-24 A.C.N. 630 589 507 Pty Ltd Procédé de recyclage de batterie

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US20250214845A1 (en) 2025-07-03
AU2023244463A1 (en) 2024-10-10
WO2023186891A1 (fr) 2023-10-05

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