EP3487596A1 - Procede et systeme pour recuperer des grains magnetiques d'aimants frittes ou de plasto-aimants - Google Patents
Procede et systeme pour recuperer des grains magnetiques d'aimants frittes ou de plasto-aimantsInfo
- Publication number
- EP3487596A1 EP3487596A1 EP17746410.4A EP17746410A EP3487596A1 EP 3487596 A1 EP3487596 A1 EP 3487596A1 EP 17746410 A EP17746410 A EP 17746410A EP 3487596 A1 EP3487596 A1 EP 3487596A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- elements
- matrix
- pressure
- chamber
- 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
Links
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- 239000011159 matrix material Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 18
- 230000009466 transformation Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000011241 protective layer Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
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- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000004296 sodium metabisulphite Substances 0.000 claims description 2
- 239000013256 coordination polymer Substances 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
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- 239000000463 material Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 3
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- 238000007885 magnetic separation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 230000000717 retained effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
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- 238000000137 annealing Methods 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0207—Control systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a method and a system for recovering, for example, magnetic grains in sintered magnets, plastomagnets or magnetic tapes.
- object designates an object composed of a polymer, ceramic or metallic matrix and the “grains” recovered from magnetic, ferroelectric, electrical, optical, mechanical, catalytic, etc. grains of chemical composition interest.
- chemical composition of interest or “elements of interest” designates elements that one wishes to recover and possibly valorize. Examples will be given in the following description.
- a dense fluid corresponds to a fluid whose molar mass is strictly greater than 2.g. mol "1 .
- the term matrix is associated with all the grains and phases allowing the link between the different grains.
- the matrix may be a polymer, ceramic or metallic matrix, for example.
- WEEE waste electrical and electronic equipment
- Hydrogen decrepitation treatment is a known method for "breaking up" rare earth alloys and magnets.
- the hydrogen will first react with the grain boundaries, because these are mostly made of rare earth elements and are therefore highly reactive.
- the hydrogen will be inserted into the magnetic grains and form hydrogenated compounds.
- the embrittlement of the grain boundaries and the expansion of the crystal lattice caused by the insertion of hydrogen (a volume increase of about 5% is observed in the case of the Nd-Fe-B magnets) will induce the spraying of the material. .
- the magnetic grains are then recovered in the form of a powder, and can be used for the manufacture of new magnetic materials.
- US Pat. No. 6,633,837 discloses a method of recovery by dissolving bonded magnets.
- US Patent 8734714 discloses a method of recovering the magnetic phase using hydrogen to recover the rare earths from the magnetic elements.
- the use of gaseous hydrogen imposes very important safety precautions.
- the method according to the invention implements a hydro / solvothermal treatment based on the transformation of the elements and not on the fusion.
- the conditions of temperature and pressure will be chosen in order to remain below the conditions inducing the fusion of an object or elements to be released.
- the invention relates to a method for recovering in an object A elements G present in a matrix M, characterized in that it comprises at least the following steps:
- the method comprises a pretreatment step where the object A is brought into contact with a corrosive solution in order to weaken said protective layer.
- the value of the temperature T 2 and / or the value of the pressure P 2 are chosen to maintain the integrity of the physico-chemical properties of the elements G separated from the matrix M.
- the process will decrease the temperature values below 100 ° C, and / or lower the pressure to a value between 0.1 and 25 MPa to protect the integrity of elements of interest G.
- a dense fluid Fd chosen from the following list: water, distilled water, alcohol, water / alcohol mixture, a mixture of water and sodium chloride, a mixture of water and sodium metabisulphite.
- the step of contacting the object A with the dense fluid Fd allowing the reaction is performed in a first chamber equipped with a temperature sensor Cn and a pressure sensor C PI and the stop step of the reaction is carried out in a second chamber equipped with pressure sensors C P2 and temperature C T2 .
- the process operates under the following temperature and pressure conditions:
- G elements are recovered by sieving or using a cyclone effect.
- the method is implemented for the recovery of magnetic grains in sintered magnets or plastomagnets.
- Object A is, for example, composed of Nd-Fe-B magnet and Nd 2 Fe-i 4 B crystallites and a small amount of neodymium hydroxide Nd (OH) 3 are separated.
- the method includes a pretreatment step contacting the Nd-Fe-B magnet with a solution of distilled water and NaCl at room temperature.
- the invention also relates to a device for recovering from an object A elements G present in a matrix M, characterized in that it comprises at least the following elements:
- the device comprises at least a first chamber containing the object A to be treated, sealing means, a first conduit for introducing a dense fluid Fd, a conduit for evacuating a mixture containing the dense fluid Fd having served for the transformation of the matrix M and the released elements G, the evacuation duct is in connection with a second enclosure comprising a discharge duct provided with a grid or a screen preventing the passage of grains released so as to recover the dense fluid used for the reaction, a dense fluid recycling circuit to the first chamber, the second chamber is equipped with control means adapted to stop the reaction and to preserve the physicochemical properties of the released grains.
- the device comprises at least a first enclosure containing the object A to be treated, sealing means, a first conduit for introducing a dense fluid, a conduit for discharging a mixture containing the dense fluid Fd used for the transformation of the matrix M and the separated elements G, the mixture being introduced into a cyclone-type device equipped with control means the temperature adapted to stop the reaction and preserve the physicochemical properties of the grains released.
- FIG. 1A an apparatus diagram allowing the implementation of the method according to the invention
- FIG. 1B an alternative embodiment
- Nd-Fe-B a magnetic phase (neodymium-iron-boron), Nd-Fe-B, within an object.
- Nd-Fe-B magnetic phase is sintered or bonded by a matrix M.
- the Neodymium-Iron-Boron alloy consists of Nd 2 Fe-i 4 B grains having a size of between 10 and 20 m. It is these grains that give the magnetic properties to the material. Between these grains is an intergranular phase, composed mainly of neodymium and which, for this reason, is called "Nd-rich" in the literature.
- This intergranular phase magnetically disconnects the grains, which provides the material with high coercivity, ie, resistance to demagnetization.
- any magnetic material coated with a matrix can be treated with the process.
- the method can be applied to any element or grain of interest that it is desired to recover and recover and which is dispersed in a matrix, this matrix possibly being an alloy, a ceramic or a polymer.
- FIG. 1A schematizes an autoclave enclosure, for example, in which an object to be treated will be positioned, an Nd-Fe-B magnet directly resulting from the dismantling of the WEEE, for example.
- the chamber 1 comprises an opening 2 for the introduction of the object "A" to be treated, and a lid 3 equipped for example with a seal 4 to ensure a tight seal.
- a first introduction conduit 5 equipped for example a valve 6 makes it possible to inject a dense fluid Fd such as a solvent stored in a reservoir 7.
- the fluid or dense fluid as defined above, has the particularity of causing the transformation of the intergranular phase thus making it possible to release Nd 2 Fe-i 4 B grains, in this example, while preserving the magnetic properties of the grains, under selected operating conditions of temperature and pressure.
- the fact of not using hydrogen during normal operation of the process advantageously makes it possible to overcome safety problems.
- the enclosure may also contain a conduit 15 for continuously introducing the object to be treated stored for example in a container 1 6.
- the object to be treated A is a Neodymium-Fer-Boron sintered permanent magnet consisting of:
- Nd-rich an intergranular phase, mainly composed of neodymium and which, for this reason, is called "Nd-rich” in the literature and Nd 2 Fei 4 B grains having a size of between 10 and 20 m which give the magnetic properties to the material.
- Object A can also be a composite plasto-magnet:
- the matrix will be an inorganic phase.
- the mixture, containing the fluid used for the transformation and the Nd 2 Fe-i 4 B grains, is discharged through a discharge pipe 8 equipped with a valve 9 and which opens, for example, into a second enclosure 10.
- This second enclosure 10 comprises a discharge duct 1 1 provided with a screen or sieve 12 comprising orifices of selected dimensions to prevent the passage of the Nd 2 Fe-i 4 B grains so as to recover mainly the fluid having served to the reaction.
- the fluid is then recycled via the pipe 1 1 and with the aid of a pump 13, for example to the introduction conduit 5 of the main enclosure 1.
- the Nd 2 Fe-i 4 B grains are retained in the second chamber 10.
- the Nd 2 Fe-i 4 B grains can be removed at means of a hatch 14 located at the bottom of the enclosure.
- the storage conditions (temperature and / or pressure) in the second chamber 10 are chosen such that the magnetic grains separated from the matrix do not deteriorate, do not oxidize, and retain their magnetic properties.
- Another solution for recovering the separated grains consists in particular in using a cyclone-type device 24 for the second chamber, as illustrated in FIG. 1B.
- the mixture containing the Nd 2 Fe-i 4 B grains and the fluid is introduced. in the cyclone composed of a body and a conical section by means of a pipe 25.
- the cyclone-type device is equipped with cooling means 21 and temperature and pressure sensors C T2 , C P2 , as indicated in FIG. 1B.
- the Nd 2 Fe-i 4 B grains are separated from the dense fluid and recovered by an evacuation conduit 26.
- the fluid is discharged via a conduit 27 connected for example to a recirculation circuit similar to that of Figure 1 A.
- the chamber 1 or main chamber in which the transformation takes place is also equipped with a heating means 20 to reach the temperature necessary to start the transformation of the matrix or the inter-granular phase to release the grains.
- the heating means 20 is for example a heating resistor or any other suitable heating device.
- the chamber 1 is for example equipped with a temperature sensor Cn and a pressure sensor C PI to monitor the temperature and the pressure prevailing in the main chamber 1 in which the reaction takes place.
- the second enclosure 10 is equipped with temperature sensors
- FIG. 2 shows a computer hard disk 30 comprising a Nd-Fe-B magnet 31, covered with nickel, 33, mounted on a support 32 that can be the object in which the magnet is to be recovered.
- FIG. 3 illustrates the steps implemented for the recovery of the magnetic phase by means of the device illustrated in FIG. 1, for example.
- the first step, 301 is optional and consists of dipping into a corrosive solution, for example a NaCl sodium chloride solution for a nickel layer, the object A to weaken a possible protective layer.
- a corrosive solution for example a NaCl sodium chloride solution for a nickel layer
- This protective layer will be partially attacked, which causes its embrittlement during the reaction in the first chamber 1 and its fragmentation.
- a polymer matrix it will also be depolymerized and solubilized during the treatment in the first chamber 1.
- the object A is immersed or brought into contact with a dense fluid chosen to cause the transformation of the matrix, intergranular phase or organic matrix that encompasses the phase of interest, in order to release the magnetic grains.
- the enclosure 1 is heated and pressurized to a desired temperature ⁇ and pressure P- ⁇ .
- the conditions of temperature and pressure will be chosen so as to be strictly lower than the temperatures inducing the melting of the object A or the magnetic grains to be released, for example at 250 ° C. and 25 MPa in order to trigger the reaction. In fact, there is no melting of the released grains.
- the dense fluid Fd will cause the degradation of the intergranular phases of the materials which leads to the spraying of the bulk magnets following the loosening of the crystallographic grains.
- the method in a third step, 303 decreases the value of the temperature in order to stop the transformation, which corresponds to a transfer of the phase of interest to a region of the installation where the conditions of temperature and pressure allow the preservation of the integrity of the elements obtained.
- the material that has already reacted is set aside, the reaction can continue, in the case of a continuously fed process.
- the temperature T 2 will be lowered by means of the cooling means and maintained at a value below 100 ° C., and the pressure P 2 will be between 0.1 MPa and 25 MPa, in order to stop the transformation reaction. of the intergranular phase.
- the recovered powder is thus composed of metal film residues of a millimeter dimension and a magnetic Nd 2 Fe-i B powder of micrometric size.
- the metal film residues can therefore be removed by simple sieving.
- the magnetic grains will be retained during filtration, to remove the organic species from the medium.
- This protective layer is recovered and can be integrated directly into a conventional metal recycling circuit known to those skilled in the art. From an environmental point of view, this is an additional advantage.
- the grains are extracted from the fluid, by filtration, by magnetic separation, by "cyclone" effect or by any method known to those skilled in the art and adapted to the process.
- the powder thus obtained can serve as a raw material for the manufacture of new magnetic materials.
- the magnetic properties of the final magnet will depend on the processing conditions, but also subsequent manufacturing techniques, sintering, dispersion in a polymer matrix, and so on.
- the two phases can be separated by simple filtration as previously described or by magnetic separation. This makes it possible to enhance these two phases in the most appropriate way.
- the "Nd-rich" matrix is recovered in the form of Nd (OH) 3 hydroxides.
- the Nd 2 Fe-i 4 B fraction can then be recovered as a magnetic raw material and the Nd (OH) 3 fraction can be resold.
- the powder is mainly composed of Nd 2 Fe-i 4 B crystallites with an average size of 10 ⁇ m, as well as a small amount of neodymium hydroxide Nd (OH) 3 .
- the fluid used for the transformation can be extracted for recycling by a suitable circuit in the circuit to the main reactor.
- the fluid or solvent used for the reaction is, for example, water, or distilled water, which has the advantage of being easy to use and inexpensive.
- Other solvents such as alcohols or water / alcohol mixtures can be used.
- the reagents that may be added will be, for example, family of corrosive agents conventionally used in industry. These reagents will facilitate the degradation of the matrix but not adversely affect the integrity of the grains of interest.
- sodium chloride NaCl sodium metabisulfite used in a much smaller amount but having an impact on the reaction time.
- the first pre-treatment step of the objects A consists, for example, in bringing the Nd-Fe-B magnet into contact with a solution composed of a mixture of distilled water, 100 ml, and NaCl, 0.1 g during two hours at room temperature. This step makes it possible in particular to work subsequently in the absence of reagents, to reduce the reaction time and to protect the installations.
- the method will perform the first step 301 before performing the magnetic seed separation steps.
- Neodymium-Iron-Boron permanent magnets which are very sensitive to oxidation, are generally covered with one or more metal films in order to limit their exposure to the open air when they are used in equipment. They may also consist of grains embedded in an elastomer and will then be composed, for example, of an Nd-Fe-B alloy powder in a polymer matrix; they are then said to be related magnets or bonded magnets. The method will perform the first step 301 before performing the magnetic seed separation steps.
- the operating conditions of temperature and pressure for the reaction step are chosen in particular as a function of the fluid used, so that the latter is not degraded.
- the temperature may be between 100 and 400 ° C in the case of water.
- the value of the temperature at the end of the reaction will be chosen in order to stop the physico-chemical process and preserve the magnetic properties of the recovered grains, this value will be less than 100 ° C, but greater than the solidification temperature of the fluid.
- the pressure value can vary between atmospheric pressure Patm and 25MPa. Depending on the technology chosen to perform the separation and storage of the grains in the second chamber, the pressure P 2 may be equal to that of the first chamber in the case of sieving (for example, 25 MPa) or between 0 , 1 and 25 MPa in the case of the use of a cyclone solution, for example.
- the steps described above and carried out in two separate enclosures could be performed within a single enclosure provided with temperature and pressure sensors, and means for regulating the temperature and temperature. pressure adapted to meet all the operating conditions for the process steps.
- the single enclosure in this case will also be equipped with separate grain recovery means and fluid for the reaction, which can be recycled by a recycling circuit.
- the method according to the invention makes it possible, after dismounting the magnets contained in the WEEE, to spray the alloy in the form of a powder, while minimizing the degradation of the material and the impact environmental.
- This powder can be used for the production of new magnetic materials.
- the process is simple in its implementation and easily used on an industrial scale. The procedure has a low impact on the environment, the same reaction bath can theoretically be reused to recycle new magnets. Since the reaction takes place in a closed environment, there is no evaporation in the atmosphere.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1656962A FR3054145B1 (fr) | 2016-07-21 | 2016-07-21 | Procede et systeme pour recuperer des grains magnetiques d'aimants frittes ou de plasto-aimants |
PCT/EP2017/067985 WO2018015331A1 (fr) | 2016-07-21 | 2017-07-17 | Procede et systeme pour recuperer des grains magnetiques d'aimants frittes ou de plasto-aimants |
Publications (1)
Publication Number | Publication Date |
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EP3487596A1 true EP3487596A1 (fr) | 2019-05-29 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP17746410.4A Pending EP3487596A1 (fr) | 2016-07-21 | 2017-07-17 | Procede et systeme pour recuperer des grains magnetiques d'aimants frittes ou de plasto-aimants |
Country Status (6)
Country | Link |
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US (2) | US11685964B2 (fr) |
EP (1) | EP3487596A1 (fr) |
JP (1) | JP7032399B2 (fr) |
CN (1) | CN109641159B (fr) |
FR (1) | FR3054145B1 (fr) |
WO (1) | WO2018015331A1 (fr) |
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EP3660174B1 (fr) * | 2018-11-27 | 2021-10-27 | Institut "Jozef Stefan" | Procédé de récupération de grains nd2fe14b à partir d'aimants nd-fe-b frittés en vrac et/ou de déchets d'aimants par gravure électrochimique |
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FR3042428B1 (fr) * | 2015-10-19 | 2017-12-08 | Centre Nat Rech Scient | Procede et systeme de recuperation de terre rare presente au sein d'un objet |
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-
2016
- 2016-07-21 FR FR1656962A patent/FR3054145B1/fr active Active
-
2017
- 2017-07-17 JP JP2019524513A patent/JP7032399B2/ja active Active
- 2017-07-17 WO PCT/EP2017/067985 patent/WO2018015331A1/fr unknown
- 2017-07-17 CN CN201780044461.0A patent/CN109641159B/zh active Active
- 2017-07-17 US US16/318,490 patent/US11685964B2/en active Active
- 2017-07-17 EP EP17746410.4A patent/EP3487596A1/fr active Pending
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2023
- 2023-05-08 US US18/313,511 patent/US20230272505A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
FR3054145B1 (fr) | 2018-08-31 |
JP7032399B2 (ja) | 2022-03-08 |
US11685964B2 (en) | 2023-06-27 |
WO2018015331A1 (fr) | 2018-01-25 |
CN109641159A (zh) | 2019-04-16 |
US20190226052A1 (en) | 2019-07-25 |
JP2019523134A (ja) | 2019-08-22 |
FR3054145A1 (fr) | 2018-01-26 |
US20230272505A1 (en) | 2023-08-31 |
CN109641159B (zh) | 2022-11-04 |
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