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WO2025115285A1 - Procédé de séparation et de récupération d'un composant de terres rares et d'un composant métallique à partir de déchets non brûlés avant le dégraissage de production ou des déchets non brûlés après dégraissage de production - Google Patents

Procédé de séparation et de récupération d'un composant de terres rares et d'un composant métallique à partir de déchets non brûlés avant le dégraissage de production ou des déchets non brûlés après dégraissage de production Download PDF

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Publication number
WO2025115285A1
WO2025115285A1 PCT/JP2024/026742 JP2024026742W WO2025115285A1 WO 2025115285 A1 WO2025115285 A1 WO 2025115285A1 JP 2024026742 W JP2024026742 W JP 2024026742W WO 2025115285 A1 WO2025115285 A1 WO 2025115285A1
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Prior art keywords
rare earth
powder
degreasing
metal
components
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Pending
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PCT/JP2024/026742
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English (en)
Japanese (ja)
Inventor
健一 山口
大介 濱田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Publication of WO2025115285A1 publication Critical patent/WO2025115285A1/fr
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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C22B7/02—Working-up flue dust
    • 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

  • This invention relates to a method for separating and recovering rare earth and metal components from unfired waste before degreasing or unfired waste after degreasing, which is discharged during the manufacturing process of multilayer ceramic capacitors.
  • a multilayer ceramic capacitor includes a laminate having an internal electrode layer and a ceramic layer, and an external electrode.
  • the internal electrode layer contains a metal component such as Ni, and the ceramic layer is formed of BaTiO 3 , etc.
  • Patent documents 1 to 4 disclose a method for recovering Ni, which is mainly used in the internal electrode layer, and also disclose that BaTiO 3 contained in the ceramic layer is separated in the process of recovering Ni.
  • Patent documents 1 to 4 disclose the recovery of Ni, but do not disclose the recovery of rare earth components. However, it is desirable to be able to recover not only metal components such as Ni, but also rare earth components.
  • the main object of this invention is therefore to provide a method for separating and recovering rare earth and metal components from unfired waste before degreasing or unfired waste after degreasing that is discharged during the manufacturing process of multilayer ceramic capacitors.
  • the method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing comprises the steps of: (A) a step of preparing unsintered waste before firing and degreasing, which is discharged in a manufacturing process of a multilayer ceramic capacitor, the unsintered waste before degreasing, which contains a magnetic metal powder, a ceramic powder, a rare earth powder, and a resin component, and in which the metal powder and the ceramic powder are at least partially adhered to each other; (B) A step of pulverizing the unburned waste before production and degreasing in a slurry generated by mixing the unburned waste before production and degreasing with a solvent; (C) a step of separating and recovering the unfired waste before degreasing after the step (B) into a metal powder-containing material containing a metal powder and a ceramic powder and a rare earth powder-containing material containing a rare earth powder and a ceramic powder using
  • rare earth and metal components can be separated and recovered from unburned waste before production and degreasing.
  • the method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing comprises the steps of: (A) a step of preparing unsintered waste before firing and degreasing, which is discharged in a manufacturing process of a multilayer ceramic capacitor, the unsintered waste before degreasing, which contains a magnetic metal powder, a ceramic powder, a rare earth powder, and a resin component, and in which the metal powder and the ceramic powder are at least partially adhered to each other; (B) A step of finely grinding the unburned waste before degreasing and mixing it with a solvent to generate a slurry; (C) a step of separating and recovering the unfired waste before degreasing after the step (B) into a metal powder-containing material containing a metal powder and a ceramic powder and a rare earth powder-containing material containing a rare earth powder and a ceramic powder using a magnet; (D) dissolving the rare earth powder-containing material
  • rare earth and metal components can be separated and recovered from unburned waste before production and degreasing.
  • the method for separating and recovering rare earth components and metal components from unburned waste after production and degreasing comprises the steps of: (A) a step of preparing unsintered waste after degreasing and before sintering, which is discharged in a manufacturing process of a multilayer ceramic capacitor, the unsintered waste including a magnetic metal powder, a ceramic powder, and a rare earth powder, the metal powder and the ceramic powder being at least partially adhered to each other, and the resin component being degreased in the manufacturing process; (B) pulverizing the unburned waste after manufacturing and degreasing in a slurry produced by mixing the unburned waste after manufacturing and degreasing with a solvent; (C) a step of separating and recovering the unfired waste after the degreasing process in the step (B) into a metal powder-containing material containing a metal powder and a ceramic powder and a rare earth powder-containing material containing a rare earth powder and a ceramic powder using
  • rare earth and metal components can be separated and recovered from unburned waste after manufacturing and degreasing.
  • the method for separating and recovering rare earth components and metal components from unburned waste after production and degreasing comprises the steps of: (A) a step of preparing unsintered waste after degreasing and before sintering, which is discharged in a manufacturing process of a multilayer ceramic capacitor, the unsintered waste including a magnetic metal powder, a ceramic powder, and a rare earth powder, the metal powder and the ceramic powder being at least partially adhered to each other, and the resin component being degreased in the manufacturing process; (B) A step of finely grinding the unburned waste after production and degreasing and mixing it with a solvent to generate a slurry; (C) a step of separating and recovering the unfired waste after the degreasing process in the step (B) into a metal powder-containing material containing a metal powder and a ceramic powder and a rare earth powder-containing material containing a rare earth powder and a ceramic powder using a magnet; (D) dissolving the
  • rare earth and metal components can be separated and recovered from unburned waste after manufacturing and degreasing.
  • This invention provides a method for separating and recovering rare earth and metal components from unfired waste before degreasing or unfired waste after degreasing that is discharged during the manufacturing process of multilayer ceramic capacitors.
  • FIG. 1 is a flow diagram showing a method for separating and recovering rare earth components and metal components from unfired waste before firing (firing of laminated chips) and before degreasing, which is discharged in a manufacturing process of a multilayer ceramic capacitor, according to a first embodiment of the present invention.
  • 1 is an external perspective view showing an example of a multilayer ceramic capacitor according to a first embodiment of the present invention
  • 3 is a cross-sectional view taken along line III-III in FIG. 2.
  • 2 is a cross-sectional view of a laminated chip, the cross-sectional view being parallel to a plane including the length direction and the laminated direction.
  • FIG. 5 is an enlarged view of a portion ⁇ in FIG. 4, and is a schematic diagram showing the state of various powders.
  • FIG. 1 is an external perspective view showing an example of a multilayer ceramic capacitor according to a first embodiment of the present invention
  • 3 is a cross-sectional view taken along line III-III in FIG. 2.
  • 2 is a
  • FIG. 2 is a flow chart showing a separation and recovery method for separating and recovering rare earth components and metal components from unfired waste after manufacturing and degreasing that is discharged in a manufacturing process of a multilayer ceramic capacitor and that is produced and degreased in the manufacturing process and is prior to firing (firing of a laminated chip), according to a second embodiment of the present invention.
  • First Embodiment 1 Separation and Recovery Method A method for separating and recovering rare earth components and metal components from unfired waste before firing (firing of laminated chips) and before degreasing, which is discharged in the manufacturing process of a multilayer ceramic capacitor, according to a first embodiment of the present invention, will be described.
  • FIG. 1 is a flow diagram showing a separation and recovery method according to a first embodiment of the present invention, which separates and recovers rare earth components and metal components from unfired waste before firing (firing of laminated chips) and before degreasing, which is discharged in the manufacturing process of a multilayer ceramic capacitor.
  • unfired waste before firing firing of laminated chips
  • degreasing which is discharged in the manufacturing process of a multilayer ceramic capacitor
  • FIG. 2 is an external perspective view showing an example of a multilayer ceramic capacitor according to a first embodiment of the present invention.
  • Fig. 3 is a cross-sectional view taken along line III-III in Fig. 2.
  • a two-terminal multilayer ceramic capacitor will be described as an example of the multilayer ceramic capacitor 10.
  • the multilayer ceramic capacitor 10 includes, for example, a rectangular parallelepiped laminate 12 and external electrodes 30 arranged on both ends of the laminate 12.
  • the laminate 12 has a plurality of stacked ceramic layers 14 and a plurality of internal electrode layers 16 stacked on the ceramic layers 14. Furthermore, the laminate 12 has a first main surface 12a and a second main surface 12b that face each other in a height direction (stacking direction) x, a first side surface 12c and a second side surface 12d that face each other in a width direction y perpendicular to the height direction x, and a first end surface 12e and a second end surface 12f that face each other in a length direction z perpendicular to the height direction x and the width direction y.
  • the ceramic layers 14 and the internal electrode layers 16 are stacked in the height direction x.
  • the first internal electrode layer 16a and the second internal electrode layer 16b can be made of, for example, a conductive material containing a magnetic metal, and the magnetic metal can be a single metal or an alloy.
  • magnetic metals include Ni and Fe.
  • the ceramic layer 14 can be formed, for example, from a dielectric material as the ceramic material.
  • a dielectric material for example, a dielectric ceramic having a perovskite structure with a perovskite type compound containing components such as BaTiO 3 , CaTiO 3 , SrTiO 3 , or CaZrO 3 as the main component can be used.
  • a rare earth component is added to the dielectric material as an additive according to the desired characteristics of the laminate 12. Examples of the rare earth component to be added include at least one of Dy, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu.
  • the above-mentioned dielectric material may be added with a subcomponent, such as a Mn compound, an Fe compound, a Cr compound, a Co compound, or a Ni compound, which is contained in a smaller amount than the main component.
  • a subcomponent such as a Mn compound, an Fe compound, a Cr compound, a Co compound, or a Ni compound, which is contained in a smaller amount than the main component.
  • at least one of Si, Mg, Ba, and Mn may be added as an additive to the above-mentioned main components.
  • these minor components and additives may cause a deterioration in the quality of the rare earth components during separation and recovery of the rare earth components, these minor components and additives may be omitted.
  • external electrodes 30 are arranged on the first end face 12e side and the second end face 12f side of the laminate 12.
  • the external electrode 30 has a first external electrode 30a and a second external electrode 30b.
  • the first external electrode 30a is connected to the first internal electrode layer 16a and is disposed on at least the surface of the first end face 12e.
  • the second external electrode 30b is connected to the second internal electrode layer 16b and is disposed on at least the surface of the second end face 12f.
  • the external electrode 30 includes a base electrode layer 32 containing a metal component and a plating layer 34 disposed on the base electrode layer 32.
  • the first external electrode 30a includes a first base electrode layer 32a and a first plating layer 34a.
  • the second external electrode 30b includes a second base electrode layer 32b and a second plating layer 34b.
  • the base electrode layer 32 may be formed from a baking layer containing a glass component and a metal component.
  • the metal component of the baking layer may include at least one selected from Cu, Ni, Ag, Pd, Ag-Pd alloy, Au, etc.
  • the glass component of the baking layer may include an oxide containing at least one element selected from B, Si, Ba, Mg, Al, Li, etc.
  • the base electrode layer 32 may also be formed from a thermosetting resin and a conductive resin layer containing a metal component.
  • the metal contained in the conductive resin layer may be, for example, Ag, Cu, Ni, Sn, Bi, or an alloy containing these.
  • the thermosetting resin may be any of various known thermosetting resins such as epoxy resin and phenoxy resin.
  • the plating layer 34 includes, for example, at least one selected from Cu, Ni, Sn, Ag, Pd, Ag-Pd alloy, Au, etc.
  • Step 1 a dielectric sheet for the ceramic layer and a conductive paste for the internal electrode layer are prepared.
  • the dielectric sheet for the ceramic layer is formed from a dielectric slurry containing, but not limited to, BaTiO 3 as a main component and Dy as an additive.
  • the conductive paste for the internal electrode layer is formed from, but not limited to, Ni as a main component.
  • the dielectric sheet and the conductive paste for the internal electrode layer include a binder and a solvent.
  • the binder and the solvent are composed of a resin component, and various known thermosetting resins such as epoxy resin, phenoxy resin, phenol resin, urethane resin, and polyimide resin can be used as the resin component.
  • the resin component does not contain inorganic elements such as Si that are difficult to remove in degreasing (including degreasing such as manufacturing degreasing and recycling degreasing).
  • Step 2 a conductive paste for the internal electrode layers is printed in a predetermined pattern on the dielectric sheet, for example by screen printing or gravure printing. This prepares a dielectric sheet on which the pattern of the first internal electrode layer is formed, and a dielectric sheet on which the pattern of the second internal electrode layer is formed.
  • outer layer dielectric sheets that do not have the internal electrode layer pattern printed on them are also prepared.
  • a predetermined number of dielectric sheets for the outer layers, on which the pattern of the internal electrode layer is not printed, are stacked.
  • a dielectric sheet on which the pattern of the first internal electrode layer is printed, and a dielectric sheet on which the pattern of the second internal electrode layer is printed are stacked in order on top of the dielectric sheets to form an inner layer portion.
  • a predetermined number of dielectric sheets for the outer layers, on which the pattern of the internal electrode layer is not printed, are stacked on top of the inner layer portion.
  • the dielectric sheets are sometimes referred to as the ceramic layers when unfired, that is, the ceramic layers before the laminated chip is fired.
  • the pattern of the internal electrode layers is sometimes referred to as the internal electrode layers when unfired, that is, the internal electrode layers before the laminated chip is fired.
  • Step 3 the laminated sheet is pressed in the stacking direction using a means such as a hydrostatic press to produce a laminated block.
  • FIG. 4 is a cross-sectional view of the laminated chip parallel to a plane including the length direction and the lamination direction.
  • FIG. 5 is an enlarged view of the ⁇ portion of FIG. 4, and is a schematic diagram showing the state of various powders.
  • FIG. 4 shows a cross-sectional view of the laminated chip 12_U on which the external electrode 30 has not yet been formed.
  • the laminated chip 12_U in FIGS. 4 and 5 is in a state prior to the manufacturing degreasing step 5 and the firing of the laminated chip in step 6. However, the resin component contained in the laminated chip 12_U is not shown.
  • the laminated chip 12_U is formed by alternately stacking the unfired internal electrode layers 16_U and the unfired ceramic layers 14_U.
  • Step 5 Next, the resin components in the laminated chip 12_U are removed.
  • the removal of the resin components in step 5 is degreasing in the manufacturing process, and may be referred to as manufacturing degreasing.
  • the degreasing temperature in manufacturing degreasing is, for example, higher than 800° C. and lower than 1000° C.
  • Step 6 the laminated chip 12_U is fired to produce the laminate 12.
  • the firing temperature of the laminated chip 12_U depends on the materials of the ceramic layers and internal electrode layers, which are dielectrics, but is preferably higher than 1000°C and lower than 1400°C, for example.
  • Steps 1 to 6 are the laminate formation process. Note that hereinafter, the firing in step 6 may be referred to as firing the laminated chip. Furthermore, this firing fires the unfired internal electrode layer 16_U and the unfired ceramic layer 14_U, turning them into the internal electrode layer 16 and the ceramic layer 14.
  • Step 7 the paste for the base electrode layer is applied to the first and second end faces 12e, 12f of the laminate 12 and fired to form the base electrode layer 32 of the external electrode 30.
  • the firing temperature is preferably 700°C or higher and 900°C or lower.
  • a plating layer 34 is formed on the base electrode layer 32.
  • the plating layer 34 is formed, for example, by laminating a Ni plating layer and a Sn plating layer in this order on the base electrode layer 32.
  • the multilayer ceramic capacitor 10 is manufactured through the above-mentioned manufacturing process.
  • the unfired waste before manufacturing degreasing is waste that has not yet been degreased in (step 5) of the manufacturing method of the multilayer ceramic capacitor 10 described above, and is waste before the firing of the laminated chip is performed in (step 6).
  • the unfired waste before manufacturing degreasing is waste before (step 5) and (step 6).
  • the unfired waste before manufacturing degreasing is excess laminated blocks such as scraps of laminated blocks that are discharged after the laminated blocks are cut in (step 4).
  • the unfired waste before manufacturing degreasing is defective laminated chips after cutting in (step 4).
  • the unfired waste before manufacturing degreasing is a dielectric sheet on which the pattern of the internal electrode layer prepared in (step 2) is formed. It is preferable that the PET film is removed from the dielectric sheet. Also, the unfired waste before manufacturing degreasing is defective laminated blocks such as those in which the lamination of each dielectric sheet is misaligned in (step 3).
  • the unsintered waste before manufacturing degreasing includes the dielectric slurry prepared in (step 1), unused conductive paste for the internal electrode layer, etc.
  • the unsintered waste before manufacturing degreasing is a dielectric sheet on which the pattern of the internal electrode layer prepared in (step 1) and (step 2) is not printed. It is preferable that the PET film is removed from the dielectric sheet.
  • the unsintered waste before manufacturing degreasing includes the dielectric slurry in (step 1), metal powder, ceramic powder, rare earth powder, resin component, etc. contained in the conductive paste for the internal electrode layer, or unused portions of at least a mixture of these.
  • the separation and recovery method in Fig. 1 includes a common separation and recovery route, a rare earth component separation and recovery route, and a metal component separation and recovery route.
  • the rare earth component separation and recovery route and the metal component separation and recovery route each branch off from the common separation and recovery route.
  • the common separation and recovery route includes, for example, the preparation of unburned waste before manufacturing and degreasing in step (A), recycling and degreasing in step (E), micronization in step (B), and magnetic separation in step (C).
  • the process branches into a separation and recovery route for rare earth components and a separation and recovery route for metal components.
  • the separation and recovery route for rare earth components can include, for example, dissolution of rare earth powder-containing material in step (D), and can further include filtration in step (F) and neutralization in step (G).
  • the separation and recovery route for metal components can include, for example, dissolution of metal powder-containing material in step (H), and can further include various treatments in step (I).
  • unfired waste before firing firing of laminated chips
  • degreasing which is discharged in the manufacturing process of a multilayer ceramic capacitor
  • the unfired waste before degreasing is as described above.
  • the unfired waste before degreasing contains metal powder, ceramic powder, rare earth powder, and a resin component.
  • the metal powder mainly constitutes the internal electrode layer 16_U when unfired.
  • the ceramic powder mainly constitutes the ceramic layer 14_U when unfired.
  • Metal powder is, for example, a collection of metal atoms.
  • the metal powder can be composed of a conductive material containing a magnetic metal, and the magnetic metal can be a single metal or an alloy.
  • magnetic metals include Ni and Fe.
  • metal powder can be manufactured by, for example, using a specified raw material by a CVD (chemical vapor deposition) method, a PVD (physical vapor deposition) method, an atomization method, a chemical reduction method, etc. Then, metal powder having a desired particle size can be obtained by adjusting the manufacturing conditions in various manufacturing methods of metal powder.
  • Patent No. 4280184 discloses a manufacturing method of Ni as metal powder by a CVD method. According to Patent No.
  • metal chlorides such as nickel chloride are heated and evaporated to generate metal chloride gas, and then the metal chloride gas is brought into contact with a reducing gas to cause a gas-phase chemical reaction, producing fine nickel powder with an average particle size of about 5 ⁇ m.
  • Ceramic powder is an aggregate of dielectric materials.
  • examples of the dielectric materials include BaTiO 3 , CaTiO 3 , SrTiO 3 , and CaZrO 3 .
  • ceramic powder can be manufactured by a solid-phase method, a sol-gel method, a hydrothermal method, and the like. Then, ceramic powder having a desired particle size can be obtained by adjusting the manufacturing conditions in various manufacturing methods of ceramic powder.
  • BaTiO 3 which is an example of ceramic powder, can generally be obtained by synthesis by reacting a titanium raw material such as titanium dioxide with a barium raw material such as barium carbonate.
  • Rare earth powder is a collection of rare earth atoms.
  • the rare earth atoms can be at least one of Dy, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu.
  • rare earth powder can be manufactured by spray pyrolysis, CVD, homogeneous precipitation, sol-gel method, reverse micelle method, hydrothermal synthesis, etc.
  • rare earth powder having a desired particle size can be obtained by adjusting the manufacturing conditions in various manufacturing methods of rare earth powder.
  • Rare earth powder can also be manufactured by the manufacturing method of rare earth disclosed in Patent No. 5987778.
  • the ceramic powder includes a first ceramic powder and a second ceramic powder.
  • the second ceramic powder has a smaller particle size than the first ceramic powder.
  • the first ceramic powder mainly constitutes the ceramic layer 14_U when unfired.
  • the first ceramic powder may have a specific surface area of, for example, 1 m 2 /g or more and 10 m 2 /g or less.
  • the second ceramic powder may have a specific surface area of, for example, 10 m 2 /g or more and 100 m 2 /g or less.
  • the metal powder may have a specific surface area of, for example, 1 m 2 /g or more and 10 m 2 /g or less.
  • the second ceramic powder functions as a co-material of the metal powder, so that the particle size is smaller than that of the metal powder. Therefore, the specific surface area is selected so that the second ceramic powder is larger than the metal powder.
  • the metal powder and the ceramic powder are at least partially adhered to each other.
  • the metal powder, the first ceramic powder, the second ceramic powder, and the rare earth powder are at least partially adhered to each other.
  • the metal powder and the second ceramic powder are at least partially adhered to each other, and the rare earth powder and the first ceramic powder are at least partially adhered to each other.
  • the metal powder, ceramic powder, and rare earth powder are attached to each other.
  • the metal powder and ceramic powder are at least partially attached to each other, the ceramic powder and rare earth powder are at least partially attached to each other, the metal powder and rare earth powder are at least partially attached to each other, and the metal powder, ceramic powder, and rare earth powder are at least partially attached to each other.
  • “attached” mainly means that the powders such as the metal powder, ceramic powder, and rare earth powder are not chemically bonded to each other.
  • the meaning of "attached” may also include that the powders such as the metal powder, ceramic powder, and rare earth powder are partially chemically bonded to each other.
  • the chemical bond is a bond in which multiple atoms are attracted to each other by positive and negative charges and are connected to each other, such as an ionic bond, a covalent bond, or a metallic bond.
  • the powder particles in the unfired waste before manufacturing and degreasing are not basically chemically bonded to each other and are instead stuck together.
  • the unfired waste before manufacturing and degreasing is not degreased at the degreasing temperature in step 5 (higher than 800°C and lower than 1000°C), and the laminated chips are not fired in step 6 (higher than 1000°C and lower than 1400°C).
  • the powder particles can be chemically bonded to each other when fired at the firing temperature in step 6 (higher than 1000°C and lower than 1400°C), but the unfired waste before manufacturing and degreasing does not go through step 6, so the powder particles are basically not chemically bonded to each other and are instead stuck together.
  • At least partially adhered to each other can be explained by taking the adhesion between a metal powder and a ceramic powder as an example, as follows.
  • a metal powder and a ceramic powder are at least partially adhered to each other, it is not necessary for all of the metal powder to adhere to the ceramic powder, as long as at least a portion of the metal powder adheres to the ceramic powder.
  • it is not necessary for all of the ceramic powder to adhere to the metal powder as long as at least a portion of the ceramic powder adheres to the metal powder.
  • the same can be said for other adhesions such as between ceramic powder and rare earth powder.
  • the unfired waste before degreasing in the present embodiment includes metal powder, ceramic powder, rare earth powder, and resin component. More specifically, the unfired waste before degreasing in the present embodiment includes metal powder-containing material and rare earth powder-containing material.
  • metal powder-containing material refers to material containing metal powder and ceramic powder.
  • rare earth powder-containing material refers to material containing rare earth powder and ceramic powder.
  • metal powder-containing material refers to material containing metal powder and second ceramic powder, and the metal powder and the second ceramic powder are at least partially adhered to each other.
  • rare earth powder-containing material refers to material containing rare earth powder and first ceramic powder, and the rare earth powder and the first ceramic powder are at least partially adhered to each other.
  • the resin components are binders and solvents for producing conductive pastes for the dielectric sheets and internal electrode layers.
  • the binders and solvents are composed of resin components, and various known thermosetting resins such as epoxy resins, phenoxy resins, phenolic resins, urethane resins, and polyimide resins can be used as the resin components.
  • thermosetting resins such as epoxy resins, phenoxy resins, phenolic resins, urethane resins, and polyimide resins
  • inorganic elements such as Si are difficult to remove even by degreasing (including degreasing in manufacturing degreasing, recycling degreasing, etc.), and these inorganic elements remain as contaminants in the unfired waste before manufacturing degreasing, which adversely affects the separation and recovery of rare earth components and metal components. Therefore, it is preferable that the resin components do not contain inorganic elements such as Si that are difficult to remove in degreasing (including degreasing in manufacturing degreasing
  • the state of the powder in the laminated chip which is the unfired waste before manufacturing and degreasing, will be described with reference to FIG. 5.
  • the unfired waste before manufacturing and degreasing shown in FIG. 5 is waste before undergoing manufacturing and degreasing (step 5) and firing of the laminated chip (step 6).
  • the schematic diagram of FIG. 5 the state of various powders contained in the unfired waste before manufacturing and degreasing is shown. Note that the resin component is omitted in FIG. 5.
  • the ceramic layer 14_U when unfired is mainly composed of the first ceramic powder (BT 1 in FIG. 5). And, in the ceramic layer 14_U when unfired, the first ceramic powder and the rare earth powder (Dy in FIG.
  • the rare earth powder is mainly adhered to the surface of the first ceramic powder, and basically, the rare earth powder does not penetrate into the inside of the first ceramic powder and is not chemically bonded.
  • the unsintered internal electrode layer 16_U is mainly composed of metal powder (Ni in FIG. 5).
  • the metal powder and the second ceramic powder ( BT2 in FIG. 5) are at least partially adhered to each other.
  • the second ceramic powder is mainly adhered to the surface of the metal powder, and the second ceramic powder is not basically infiltrated into the metal powder and chemically bonded thereto.
  • Step (E): Recycling Degreasing resin components are removed from the unburned waste before production degreasing.
  • the removal of resin components here is referred to as recycling degreasing.
  • Recycling degreasing is performed, for example, by degreasing the unburned waste before production degreasing at a predetermined degreasing temperature.
  • the degreasing temperature in recycling degreasing is, for example, a temperature just before chemical bonding begins in at least one of metal powder, ceramic powder, and rare earth powder contained in the unburned waste before production degreasing.
  • the chemical bonding in firing the unburned waste before production degreasing includes, for example, chemical bonding between metal powder and ceramic powder, chemical bonding between ceramic powder and rare earth powder, chemical bonding between metal powder and rare earth powder, and chemical bonding between metal powder, ceramic powder, and rare earth powder.
  • the degreasing temperature in recycling degreasing is preferably, for example, 600°C or higher and 1000°C or lower.
  • the degreasing time in recycling degreasing is preferably performed until the resin components are gone.
  • the degreasing time in the recycling degreasing depends on the amount of unburned waste before the manufacturing degreasing, the degreasing temperature, etc., but is, for example, about 1 hour or more and about 24 hours or less.
  • the recycling degreasing is preferably carried out in a reducing atmosphere such as a nitrogen atmosphere or an atmosphere containing hydrogen and water.
  • Unburned waste before manufacturing and degreasing contains resin components, which may hinder the separation of metal powder-containing materials and rare earth powder-containing materials in, for example, the magnetic separation in step (C). Therefore, in the above-mentioned step (E), recycling degreasing is performed to remove the resin components. Recycling degreasing is performed by degreasing unburned waste before manufacturing and degreasing at, for example, a predetermined degreasing temperature.
  • the powders contained in the unburned waste before manufacturing and degreasing are chemically bonded to each other by this firing, it becomes difficult to separate the metal powder-containing materials and the rare earth powder-containing materials, and thus it becomes difficult to separate and recover the metal components and rare earth components.
  • the degreasing temperature in recycling degreasing is set to a temperature just before chemical bonding begins in at least one of the metal powder, ceramic powder, and rare earth powder contained in the unburned waste before manufacturing and degreasing. This makes it easier to separate the metal powder-containing materials and the rare earth powder-containing materials. This in turn makes it easier to separate and recover the metal components and rare earth components at a high quality.
  • the degreasing temperature in the recycling degreasing is set to 600° C. or higher and 1000° C. or lower.
  • the lower limit of the degreasing temperature in the recycling degreasing can be set in consideration of a temperature higher than the temperature at which the resin components in the unburned waste before the manufacturing degreasing remain in an unburned state, etc.
  • the upper limit of the degreasing temperature in the recycling degreasing can be set in consideration of the amount of electricity required to raise the temperature of the unburned waste before the manufacturing degreasing to the upper limit of the degreasing temperature in the recycling degreasing, the discharge standard into a river for the solution containing the resin components remaining after the recycling degreasing, etc.
  • step (B) the unfired waste before degreasing is pulverized.
  • the unfired waste before degreasing is pulverized by pulverizing.
  • the pulverization is performed, but not limited to, for example, by a method of applying a pulverizing force by vibration to the object using a vibration mill or the like, a method of grinding the object, a method of applying a pulverizing force by impact to the object, and the like.
  • the average particle size of the unfired waste before degreasing after pulverization is not limited.
  • the average particle size can be determined, for example, using a sieve.
  • the unburned waste before degreasing and after being pulverized in the step (B) is magnetically separated using a magnet. That is, the waste is separated into a material containing metal powder and a material containing rare earth powder and then recovered.
  • the metal powder inclusion after magnetic separation mainly contains metal powder such as Ni (Ni of the metal powder inclusion in FIG. 1), which is the main component of the internal electrode layer. Ceramic powder such as BaTiO 3 , specifically the second ceramic powder (BT 2 of the metal powder inclusion in FIG. 1) is attached to the surface of the metal powder in the metal powder inclusion.
  • the metal powder contains a magnetic metal.
  • the second ceramic powder is not magnetic.
  • the second ceramic powder may not necessarily be attached to the surface of the metal powder in the metal powder inclusion, or other powders may be attached to the surface of the metal powder.
  • other powders include the first ceramic powder, rare earth powder, and powders of additives other than ceramic and rare earth components (Mg, Mn, V, etc.).
  • This magnetic separation allows the metal powder-containing material to be separated and recovered as a metal component.
  • a metal powder-containing material containing a metal powder such as Ni with a second ceramic powder BaTiO3 attached to its surface can be separated and recovered as a metal component.
  • the separation and recovery of a metal component includes not only the separation and recovery of the metal component itself, but also the separation and recovery of a metal powder-containing material as a metal component.
  • Metal components include metal atoms themselves, metal component compounds which are reactants of metal atoms chemically reacting with other atoms, solutions of metal atoms, solutions of metal component compounds, etc.
  • the state of the metal component may be any of a liquid state, a solid state, or a mixed state of liquid and solid.
  • the metal component may also be in any of an amorphous state, a crystalline state, or a mixed state of amorphous and crystalline.
  • the rare earth powder-containing material after magnetic separation mainly contains ceramic powder such as BaTiO 3 , which is the main component of the ceramic layer when unfired, specifically the first ceramic powder (BT 1 of the rare earth powder-containing material in FIG. 1).
  • Rare earth powder such as Dy (Dy of the rare earth powder-containing material in FIG. 1) is attached to the surface of the first ceramic powder of this rare earth powder-containing material.
  • the first ceramic powder and the rare earth powder are not magnetic. Therefore, the first ceramic powder and the rare earth powder are separated as non-magnetic materials by magnetic separation.
  • the rare earth powder is not necessarily attached to the surface of the first ceramic powder in the rare earth powder-containing material, and there are cases where other powders are attached to the surface of the first ceramic powder.
  • This magnetic separation allows the rare earth powder-containing material to be separated and recovered as rare earth components.
  • the rare earth powder-containing material mainly containing the first ceramic powder such as BaTiO 3 with the rare earth powder Dy attached to the surface thereof can be separated and recovered as rare earth components.
  • the separation and recovery of the rare earth components includes not only the separation and recovery of the rare earth components themselves, but also the separation and recovery of the rare earth powder-containing material as rare earth components.
  • the rare earth component includes rare earth atoms themselves, rare earth component compounds which are products of chemical reactions of rare earth atoms with other atoms, solutions of rare earth atoms, solutions of rare earth component compounds, etc.
  • the rare earth component may be in a liquid state, a solid state, or a mixed state of liquid and solid.
  • the rare earth component may be in an amorphous state, a crystalline state, or a mixed state of amorphous and crystalline.
  • organic solvents examples include alcohol-based organic solvents and hydrocarbon-based organic solvents.
  • methanol, ethanol, propanol, toluene, xylene, cyclohexane, or mixtures thereof can be used as the organic solvent.
  • the metal powder-containing material and the rare earth powder-containing material contained in the finely divided unburned waste before production and degreasing can be made to be in a dispersed state. Therefore, in step (C), the metal powder-containing material and the rare earth powder-containing material can be easily separated using a magnet.
  • the metal powder-containing material and the rare earth powder-containing material tend to be less dispersed than when in a slurry state. Therefore, for example, when the metal powder-containing material is attracted to a magnet, the rare earth powder-containing material is caught in the metal powder-containing material and attracted to the magnet, making it difficult to separate the metal powder-containing material and the rare earth powder-containing material.
  • the rare earth powder-containing material separated and recovered in step (C) is dissolved in a mineral acid.
  • the mineral acid is, for example, at least one selected from the group including sulfuric acid, nitric acid, and hydrochloric acid.
  • the rare earth component is separated and recovered as a rare earth component-containing solution.
  • the separation and recovery of the rare earth component includes not only the separation and recovery of the rare earth component itself, but also the separation and recovery of the rare earth component-containing solution as a rare earth component.
  • step (D) it is preferable to adjust the pH of the rare earth component-containing solution to 1.5 or more and 2.5 or less by adding a mineral acid.
  • the rare earth component-containing solution is adjusted to a pH of 1.5 or more and 2.5 or less using a mineral acid, so that the rare earth powder can be dissolved in the mineral acid as a rare earth component. Furthermore, if the pH is adjusted to a stronger acid than the above range, the first ceramic powder, etc. may dissolve in the mineral acid, so it is preferable to adjust the pH to within the above range. More preferably, the rare earth component-containing solution is adjusted to a pH of 2 by adding a mineral acid.
  • the separated rare earth powder-containing material is in a slurry state with a pH of about 7.
  • a mineral acid By adding a mineral acid to this slurry, it is also possible to produce a rare earth component-containing solution with an adjusted pH of 1.5 or more and 2.5 or less.
  • the rare earth powder-containing material after magnetic separation does not need to be in a slurry state and may be in a dry state.
  • the first ceramic powder contained in the rare earth powder-containing material is , for example, BaTiO 3
  • sulfuric acid is preferably used.
  • insoluble BaSO 4 is formed on the surface of the first ceramic powder, which is BaTiO 3, so that the first ceramic powder can be precipitated.
  • the rare earth powder can be dissolved in sulfuric acid.
  • a rare earth powder-containing material mainly containing BaTiO 3 with Dy attached to the surface in sulfuric acid BaTiO 3 is precipitated and a dysprosium sulfate (Dy 2 (SO 4 ) 3 ) solution in which Dy is dissolved in sulfuric acid is generated as a rare earth component-containing solution.
  • Dy 2 (SO 4 ) 3 dysprosium sulfate
  • hydrochloric acid or the like can be used as the mineral acid other than sulfuric acid.
  • hydrochloric acid when hydrochloric acid is used as the mineral acid, soluble BaCl 2 is formed on the surface of the first ceramic powder BaTiO 3. Therefore, it is preferable to accurately adjust the pH of hydrochloric acid or the like so as to precipitate the first ceramic powder and dissolve the rare earth powder.
  • the rare earth component-containing solution containing the precipitated first ceramic powder produced in step (D) is filtered to separate the precipitated first ceramic powder and the rare earth component-containing solution into a solid-liquid separation.
  • the rare earth component-containing solution from which the precipitated first ceramic powder has been removed can be separated and recovered as a rare earth component from the rare earth component-containing solution containing the precipitated first ceramic powder.
  • step (D) BaTiO3 is precipitated and a dysprosium sulfate ( Dy2 ( SO4 ) 3 ) solution in which Dy is dissolved in sulfuric acid is generated as a rare earth component-containing solution.
  • Dy2 ( SO4 ) 3 a dysprosium sulfate
  • the dysprosium sulfate solution from which BaTiO3 has been removed can be separated and recovered as rare earth components by filtration in step (F).
  • the filtration can be performed using filter paper (filter cloth). It is preferable that the mesh size of the filter paper (filter cloth) is such that the precipitated first ceramic powder does not pass through the filter paper (filter cloth).
  • the rare earth component-containing solution containing the precipitated first ceramic powder produced in step (D) can be separated into solid and liquid
  • the solid-liquid separation is not limited to filtration, and can be appropriately selected from known methods such as decantation and centrifugation. Filtration is more preferable.
  • the rare earth component-containing solution obtained in step (F) is neutralized to precipitate and recover the rare earth component.
  • the precipitated rare earth component is separated and recovered, for example, by filtering the neutralized rare earth component-containing solution.
  • the rare earth component is separated and recovered as a rare earth component compound (e.g., Dy(OH) 3 , etc.) by neutralization.
  • the separation and recovery of the rare earth component includes not only the separation and recovery of the rare earth component itself, but also the separation and recovery of the rare earth component compound, which is a reaction product of the rare earth component chemically reacted, as the rare earth component.
  • alkali is used for neutralization.
  • alkalis include sodium hydroxide and potassium hydroxide.
  • the rare earth components are recovered by adjusting the pH of the rare earth component-containing solution to between pH 6 and pH 9. This allows the precipitate resulting from the neutralization reaction to be efficiently separated and recovered as rare earth components. More preferably, the rare earth component-containing solution is adjusted to pH 8 by adding an alkali.
  • dysprosium hydroxide (Dy(OH) 3 ) is obtained as a rare earth component compound by neutralization with sodium hydroxide. That is, since the dysprosium sulfate solution is acidic, the rare earth component dysprosium can be precipitated as dysprosium hydroxide (Dy(OH) 3 ) by neutralizing it with an alkali, and separated and recovered.
  • dysprosium hydroxide (Dy(OH) 3 ) can be separated and recovered by filtering the solution obtained by neutralizing the dysprosium sulfate solution with an alkali. In addition to filtration, known methods such as decantation and centrifugation can be used.
  • the rare earth component-containing solution produced in the dissolution in step (D) may contain metal components that are contaminants. These metal components are, for example, Ti, Mn, Ni, etc.
  • an alkali is added to the rare earth component-containing solution to adjust the pH to, for example, from 3 to 5, preferably about pH 4, so that Ti, Mn, etc. can be separated and recovered.
  • Ti precipitates as, for example, Ti(OH) 4
  • Mn precipitates as, for example, Mn(OH) 2. Therefore, the rare earth component-containing solution adjusted to about pH 4 is filtered to recover Ti(OH) 4 , Mn(OH) 2 , etc.
  • the rare earth components are separated and recovered by adding an alkali to the solution containing the rare earth components from which Ti, Mn, etc. have been separated and adjusted to a pH of 6 or more and 9 or less, preferably about pH 8, as described above.
  • Ni and the like can be separated and recovered by adding an alkali to the solution from which Ti, Mn, rare earth components, etc. have been separated, for example, to a pH of more than 9 to a pH of 11 or less, preferably about pH 10.
  • Ni precipitates as, for example, Ni(OH) 2 .
  • the solution adjusted to about pH 10 is filtered to recover Ni(OH) 2 and the like.
  • the rare earth component-containing solution is neutralized to a pH of 3 or more and a pH of 5 or less, preferably about pH 4, before the rare earth components are separated. Therefore, it is possible to first remove contaminants such as Ti and Mn from the rare earth component-containing solution. Since contaminants such as Ti and Mn have been removed from the rare earth component-containing solution in this way, it is possible to further facilitate separation of the rare earth components using the rare earth component-containing solution from which these contaminants have been removed.
  • the metal powder-containing material separated and recovered in step (C) is dissolved in a mineral acid.
  • the mineral acid is, for example, at least one selected from the group including sulfuric acid, nitric acid, and hydrochloric acid.
  • the metal component is separated and recovered as a metal component-containing solution.
  • separation and recovery of the metal component includes not only separation and recovery of the metal component itself, but also separation and recovery of the metal component-containing solution as a metal component.
  • step (H) it is preferable to adjust the metal component-containing solution to a pH of 1.5 or more and 2.5 or less by adding a mineral acid.
  • the metal component-containing solution is adjusted to a pH of 1.5 or more and 2.5 or less using a mineral acid, so that the metal powder can be dissolved in the mineral acid as a metal component. Furthermore, if the pH is adjusted to a stronger acid than the above range, the second ceramic powder, etc. may dissolve in the mineral acid, so it is preferable to adjust the pH to within the above range. More preferably, the metal component-containing solution is adjusted to a pH of 2 by adding a mineral acid.
  • the separated metal powder-containing material is in a slurry state with a pH of about 7.
  • a mineral acid By adding a mineral acid to this slurry, it is also possible to produce a metal component-containing solution with an adjusted pH of 1.5 or more and 2.5 or less.
  • the metal powder-containing material after magnetic separation does not need to be in a slurry state and may be in a dry state.
  • the second ceramic powder contained in the metal powder-containing material is , for example, BaTiO 3
  • sulfuric acid is preferably used.
  • insoluble BaSO 4 is formed on the surface of the second ceramic powder, which is BaTiO 3, so that the second ceramic powder can be precipitated.
  • the metal powder can be dissolved in sulfuric acid.
  • a metal powder-containing material mainly containing Ni with BaTiO 3 attached to the surface in sulfuric acid BaTiO 3 is precipitated and a nickel sulfate (NiSO 4 ) solution in which Ni is dissolved in sulfuric acid is generated as a metal component-containing solution.
  • NiSO 4 nickel sulfate
  • hydrochloric acid or the like can be used as the mineral acid other than sulfuric acid.
  • hydrochloric acid when hydrochloric acid is used as the mineral acid, soluble BaCl 2 is formed on the surface of BaTiO 3 , which is the second ceramic powder. Therefore, it is preferable to accurately adjust the pH of hydrochloric acid or the like so as to precipitate the second ceramic powder and dissolve the metal powder.
  • the metal component-containing solution containing the precipitated second ceramic powder produced in step (H) is subjected to various treatments to recover the metal component.
  • An example of the recovery of the metal component in the various treatments in step (I) is described below.
  • the various treatments in step (I) include filtration.
  • the metal component-containing solution containing the precipitated second ceramic powder is filtered to separate the precipitated second ceramic powder and the metal component-containing solution into solid and liquid. This solid-liquid separation allows the metal component-containing solution from which the precipitated second ceramic powder has been removed to be separated and recovered as metal components from the metal component-containing solution containing the precipitated second ceramic powder.
  • step (H) BaTiO3 is precipitated and a nickel sulfate ( NiSO4 ) solution in which Ni is dissolved in sulfuric acid is generated as a metal component-containing solution.
  • NiSO4 nickel sulfate
  • the nickel sulfate solution from which BaTiO3 has been removed can be obtained by filtration.
  • the filtration can be carried out using filter paper (filter cloth).
  • the mesh size of the filter paper (filter cloth) is preferably such that the precipitated second ceramic powder does not pass through the filter paper (filter cloth).
  • step (I) examples include crystallization and neutralization.
  • the metal components can be separated and recovered, for example, as metal component compounds (e.g., NiSO4 , NiCl2 , etc.).
  • the separation and recovery of metal components includes not only the separation and recovery of the metal components themselves, but also the separation and recovery of metal component compounds, which are the reaction products of the chemical reaction of the metal components, as the metal components.
  • the inventors of the present application have newly focused on the separation and recovery of metal components and rare earth components from unsintered waste before firing (sintering of laminated chips) and before degreasing, which is discharged in the manufacturing process of multilayer ceramic capacitors.
  • the materials constituting the unsintered waste before degreasing such as metal powder, ceramic powder (first and second ceramic powder), and rare earth powder, are not generally chemically bonded to each other by sintering, and at least some of the powders of each material are present in a state of adhering to each other.
  • the unsintered waste before degreasing it is easy to separate each material independently from each other by the process (B) of pulverizing or other fine processing.
  • the metal components and rare earth components in the unsintered waste before degreasing are materials used in the manufacture of multilayer ceramic capacitors, the purity of the metal components and rare earth components is higher than that of naturally occurring ores. Therefore, by carrying out the above separation and recovery method starting from unburned waste before production and degreasing, it is possible to separate and recover high-purity metal components and high-purity rare earth components.
  • the unfired waste before manufacturing and degreasing after being pulverized can be separated into a metal powder-containing material and a rare earth powder-containing material by using a magnet in step (C).
  • the rare earth powder-containing material is dissolved in a mineral acid to produce a rare earth component-containing solution in which the rare earth powder contained in the rare earth powder-containing material is dissolved as a rare earth component.
  • the first ceramic powder contained in the rare earth powder-containing material reacts with the mineral acid to become an undissolved material and precipitate, so that the first ceramic powder and the rare earth powder contained in the rare earth powder-containing material are separated.
  • the rare earth powder-containing material for example, the rare earth powder is attached to the surface of the first ceramic powder, and the first ceramic powder and the rare earth powder are not sintered. Therefore, the first ceramic powder and the rare earth powder are easily separated by the dissolution in step (D).
  • the separation and recovery method including steps (C) and (D)
  • the ratio of rare earth components in the material containing rare earth components increases as each step is passed through. Therefore, rare earth components such as Dy can be recovered at a high quality.
  • a metal component-containing solution can be produced in which the metal powder contained in the metal powder-containing material is dissolved as a metal component.
  • the second ceramic powder contained in the metal powder-containing material reacts with the mineral acid to become an undissolved substance and precipitate, so the second ceramic powder and the metal powder contained in the metal powder-containing material are separated.
  • the unfired waste before production and degreasing is not fired (firing of the laminated chip)
  • the metal powder-containing material for example, the second ceramic powder is attached to the surface of the metal powder, and the metal powder and the second ceramic powder are not sintered. Therefore, the metal powder and the second ceramic powder are easily separated by the dissolution in step (H).
  • unfired waste before degreasing that is discharged during the manufacturing process of multilayer ceramic capacitors is used to separate and recover metal components, rare earth components, etc. Therefore, rather than disposing of the unfired waste before degreasing as waste, it can be used as a resource and the burden on the environment can be reduced.
  • Example 10 g of unsintered waste before manufacturing degreasing was prepared.
  • 10 g of unsintered waste before manufacturing degreasing contained 34 mass% (3.4 g) of Ni, which is a metal powder, 52 mass% (5.2 g) of BaTiO 3 , which is a ceramic powder, 2 mass% (0.2 g) of Dy, which is a rare earth powder, 10 mass% (1.0 g) of a resin component, and 2 mass% (0.2 g) of contaminants such as Mg, Mn, and SiO 2 (step (A)).
  • This unsintered waste before manufacturing degreasing was fired at a degreasing temperature of 800 ° C for 2 hours in order to recycle and degrease (step (E)).
  • the unsintered waste before manufacturing degreasing after recycling degreasing was pulverized and finely divided (step (B)).
  • the unsintered waste before manufacturing degreasing after pulverization and finely divided by pulverization was mixed with 100 ml of water to create a slurry.
  • This slurry was magnetically separated using a magnet. By this magnetic separation, 3.4 g of metal powder containing material mainly containing BaTiO 3 attached to Ni was separated and collected, and 5.0 g of rare earth powder containing material mainly containing Dy attached to BaTiO 3 was separated and collected (step (C)).
  • step (D) 100 ml of water was added to 5.0 g of rare earth powder containing material, and 1 mol% sulfuric acid was added little by little to adjust the pH to 2.
  • the solution in which BaTiO 3 was precipitated and Dy was dissolved in the sulfuric acid solution was filtered to obtain 90 ml of dysprosium sulfate (Dy 2 (SO 4 ) 3 ) solution (step (F)).
  • 1 mol% caustic soda solution was added little by little as an alkali to 90 ml of dysprosium sulfate solution to adjust the pH to 8 (step (G)).
  • This solution was filtered to separate and recover 0.2 g of Dy(OH) 3.
  • approximately 60% of the Dy contained in the unburned waste before degreasing was recovered.
  • step (C) 100 ml of water was added to 3.4 g of metal powder-containing material mainly containing Ni with BaTiO 3 attached thereto, which was recovered in step (C), and 1 mol % of sulfuric acid was added little by little to adjust the pH to 2.
  • BaTiO 3 in the metal powder-containing material mainly containing Ni with BaTiO 3 attached thereto was precipitated, and Ni was dissolved in the sulfuric acid solution (step (H)).
  • the solution in which BaTiO 3 was precipitated and Ni was dissolved in the sulfuric acid solution was filtered to obtain 90 ml of nickel sulfate (Ni(SO 4 )) solution (step (I)).
  • rare earth components and metal components such as high-grade Dy and Ni can be easily separated and refined by using unburned waste before degreasing discharged in the manufacturing process of a multilayer ceramic capacitor as a starting material, and then going through processes such as magnetic separation and leaching by neutralization.
  • unburned waste before degreasing as a starting point, it is possible to separate and refine metals such as high-grade Dy and Ni by a simple process compared to the case of refining Dy and Ni from ore as a starting point.
  • step (B) (1-1) Generation of slurry by organic solvent
  • the unburned waste before manufacturing and degreasing is pulverized and refined in step (B).
  • the unburned waste before manufacturing and degreasing may be pulverized by dispersing it in a slurry state using an organic solvent.
  • wet pulverization the pulverization in which the unburned waste before manufacturing and degreasing is mixed with a solvent (solvent such as an organic solvent or an aqueous solvent) to form a slurry.
  • a solvent solvent such as an organic solvent or an aqueous solvent
  • wet pulverization the pulverization in which the unburned waste before manufacturing and degreasing is pulverized in a slurry formed by mixing the unburned waste before manufacturing and degreasing with a solvent.
  • the separation and recovery method includes, as a common separation and recovery route, the preparation of unburned waste before manufacturing and degreasing in step (A), recycling degreasing in step (E), mixing of unburned waste before manufacturing and degreasing with an organic solvent (performed together with or instead of the micronization (particularly micronization by grinding) in step (B)), and magnetic separation in step (C), in this order.
  • the magnetic separation in step (C) is followed by a distillation step to remove the organic solvent.
  • the separation and recovery method also includes dissolving the rare earth powder-containing material in step (D) as a route for separating and recovering rare earth components, following the common separation and recovery route. Note that in the route for separating and recovering rare earth components, filtration in step (F) and neutralization in step (G) may additionally be performed.
  • the separation and recovery method also includes dissolving the metal powder-containing material in step (H) as a route for separating and recovering metal components, following the common separation and recovery route. Note that in the route for separating and recovering metal components, various treatments in step (I) may additionally be performed.
  • the separation and recovery method preferably includes, as a common separation and recovery route, for example, the preparation of unburned waste before manufacturing and degreasing in step (A), the recycling degreasing in step (E), the generation of a slurry by mixing the unburned waste before manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step of removing the organic solvent after the magnetic separation in step (C).
  • a common separation and recovery route for example, the preparation of unburned waste before manufacturing and degreasing in step (A), the recycling degreasing in step (E), the generation of a slurry by mixing the unburned waste before manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step of removing the organic solvent after the
  • step (A) the preparation of unburned waste before manufacturing and degreasing in step (A), the recycling degreasing in step (E), the fineness in step (B) (particularly, fineness by grinding), the generation of a slurry by mixing the unburned waste before manufacturing and degreasing finely ground by grinding with an organic solvent, and the magnetic separation in step (C) are performed in this order, and further, it is preferable to perform a distillation step of removing the organic solvent after the magnetic separation in step (C).
  • the common separation and recovery route omits the pulverization (particularly pulverization by grinding) in step (B), and preferably includes, for example, the preparation of unburned waste before production and degreasing in step (A), recycling degreasing in step (E), production of a slurry by mixing the unburned waste before production and degreasing with an organic solvent, and magnetic separation in step (C) in this order, and further includes a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • the organic solvent may be an alcohol-based organic solvent or a hydrocarbon-based organic solvent.
  • the organic solvent may be methanol, ethanol, propanol, toluene, xylene, cyclohexane, or a mixture thereof.
  • the resin components in the unburned waste before manufacturing degreasing are removed in the recycling degreasing in step (E).
  • the resin components in the unburned waste before manufacturing degreasing may dissolve in the organic solvent.
  • the resin components in the unburned waste before manufacturing degreasing can be removed, and the recycling degreasing in step (E) can be omitted.
  • step (B) It is also possible to pulverize the unburned waste before degreasing by mixing the unburned waste before degreasing with an organic solvent. In this case, it may be possible to pulverize the unburned waste before degreasing without pulverizing it in step (B).
  • the separation and recovery method includes, as a common separation and recovery route, the preparation of unburned waste before manufacturing and degreasing in step (A), mixing of the unburned waste before manufacturing and degreasing with an organic solvent (performed together with or instead of the fine-graining (particularly fine-graining by grinding) in step (B)), and magnetic separation in step (C). Since the unburned waste before manufacturing and degreasing is mixed with an organic solvent, it is preferable that a distillation step for removing the organic solvent is further included after the magnetic separation in step (C).
  • the separation and recovery method includes dissolution of rare earth powder-containing material in step (D) as a separation and recovery route for rare earth components, following the common separation and recovery route.
  • filtration in step (F) and neutralization in step (G) may be performed in the separation and recovery route for rare earth components.
  • the separation and recovery method includes dissolution of metal powder-containing material in step (H) as a separation and recovery route for metal components, following the common separation and recovery route.
  • various processes in step (I) may be carried out as a route for separating and recovering metal components.
  • the separation and recovery method preferably includes, as a common separation and recovery route, for example, the preparation of unburned waste before manufacturing and degreasing in step (A), the generation of a recycled and degreased slurry by mixing the unburned waste before manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step of removing the organic solvent after the magnetic separation in step (C).
  • a common separation and recovery route for example, the preparation of unburned waste before manufacturing and degreasing in step (A), the generation of a recycled and degreased slurry by mixing the unburned waste before manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step of removing the organic solvent after the magnetic separation in step (C).
  • the separation and recovery method preferably includes the preparation of unburned waste before manufacturing and degreasing in step (A), the fineness in step (B) (particularly, fineness by grinding), the generation of a recycled and degreased slurry by mixing the unburned waste before manufacturing and degreasing finely ground by grinding with an organic solvent, and the magnetic separation in step (C) in this order, and further includes a distillation step of removing the organic solvent after the magnetic separation in step (C).
  • the common separation and recovery route omits the pulverization (particularly pulverization by grinding) in step (B), and preferably includes, in this order, for example, preparation of unburned waste before production and degreasing in step (A), production of a recycled and degreased slurry by mixing the unburned waste before production and degreasing with an organic solvent, and magnetic separation in step (C), and further includes a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • the unburned waste before manufacturing and degreasing which has been pulverized in step (B) is mixed with water or an organic solvent and dispersed to form a slurry state.
  • the unburned waste before manufacturing and degreasing is made into a slurry state using an organic solvent in addition to or instead of the pulverization in step (B)
  • the unburned waste before manufacturing and degreasing in this slurry state may be magnetically separated in step (C). In other words, the effort of generating a slurry state in the magnetic separation in step (C) can be omitted.
  • the separation and recovery method includes, as a common separation and recovery route, the preparation of unburned waste before production and degreasing in step (A), recycling degreasing in step (E), mixing of the unburned waste before production and degreasing with an aqueous solvent (performed together with the fine-graining (particularly fine-graining by grinding) in step (B) or instead of the fine-graining (particularly fine-graining by grinding) in step (B)), and magnetic separation in step (C) in this order.
  • the separation and recovery method includes dissolution of rare earth powder-containing material in step (D) as a separation and recovery route for rare earth components following the common separation and recovery route.
  • filtration in step (F) and neutralization in step (G) may be performed.
  • the separation and recovery method includes dissolution of metal powder-containing material in step (H) as a separation and recovery route for metal components following the common separation and recovery route.
  • various treatments in step (I) may be carried out as a route for separating and recovering metal components.
  • the separation and recovery method includes, as a common separation and recovery route, for example, the preparation of unburned waste before manufacturing and degreasing in step (A), the recycling degreasing in step (E), the generation of a slurry by mixing the unburned waste before manufacturing and degreasing with an aqueous solvent, the pulverization in step (B) (particularly, pulverization by grinding), and the magnetic separation in step (C) in this order.
  • step (A) the preparation of unburned waste before manufacturing and degreasing in step (A), the recycling degreasing in step (E), the pulverization in step (B) (particularly, pulverization by grinding), the generation of a slurry by mixing the unburned waste before manufacturing and degreasing pulverized by grinding with an aqueous solvent, and the magnetic separation in step (C) can also be performed in this order.
  • a common separation and recovery route may omit the pulverization (particularly pulverization by grinding) in step (B), and may include, for example, the following steps in this order: preparation of unburned waste before production and degreasing in step (A), recycling degreasing in step (E), mixing the unburned waste before production and degreasing with an aqueous solvent to produce a slurry, and magnetic separation in step (C).
  • the aqueous solvent for example, water can be used.
  • the unburned waste before manufacturing and degreasing which has been pulverized in step (B) is mixed with water or an organic solvent and dispersed to form a slurry state.
  • the unburned waste before manufacturing and degreasing is made into a slurry state using an aqueous solvent in addition to or instead of the pulverization in step (B)
  • the unburned waste before manufacturing and degreasing in this slurry state may be magnetically separated in step (C). In other words, the effort of generating a slurry state in the magnetic separation in step (C) can be omitted.
  • step (E) Location of recycle degreasing in step (E) in the separation and recovery method
  • the recycle degreasing in step (E) is performed between steps (A) and (B). That is, in Fig. 1, the unburned waste before production degreasing prepared in step (A) is recycled and degreased (step (E)), and then the unburned waste before production degreasing (recycled and degreased unburned waste before production degreasing) is pulverized in step (B).
  • step (E) is not limited to being performed between steps (A) and (B) as long as it is performed before the rare earth powder-containing material and the metal powder-containing material separated by the magnetic separation in step (C) are dissolved in mineral acid in steps (D) and (H).
  • the recycling degreasing in step (E) may be performed between steps (B) and (C).
  • the unburned waste before manufacturing degreasing prepared in step (A) can be pulverized in step (B) and then recycled and degreased.
  • a common separation and recovery route among the separation and recovery methods includes, in this order, the preparation of unburned waste before manufacturing degreasing in step (A), pulverization in step (B), recycling degreasing in step (E), and magnetic separation in step (C).
  • the recycling degreasing in step (E) may be performed between step (C), step (D), and step (H).
  • the rare earth powder-containing material can be recycled and degreased before step (D).
  • the metal powder-containing material can be recycled and degreased before step (H).
  • a common separation and recovery route among the separation and recovery methods includes, in this order, the preparation of unfired waste before manufacturing and degreasing in step (A), the fine particle size reduction in step (B), the magnetic separation in step (C), and the recycling degreasing in step (E).
  • the rare earth powder-containing material recovered in the magnetic separation in step (C) is recycled and degreased, while the metal powder-containing material recovered in the magnetic separation in step (C) is recycled and degreased.
  • the recycling degreasing in step (E) may also be performed in the pulverization in step (B). That is, in the pulverization process in step (B), the resin components can be recycled and degreased from the unburned waste before manufacturing and degreasing.
  • the unburned waste before manufacturing and degreasing can be mixed with an organic solvent to recycle, degrease, and pulverize.
  • a common separation and recovery route among the separation and recovery methods includes, in this order, the preparation of the unburned waste before manufacturing and degreasing in step (A), pulverization by mixing with an organic solvent in step (B), and magnetic separation in step (C).
  • step 5 manufacturing degreasing is performed in step 5, and the laminated chip is fired in step 6.
  • both steps 5 and 6 may be combined into one step.
  • the laminated chip after step 4 is fired at a temperature higher than 1000°C and not higher than 1400°C, thereby manufacturing degreasing the resin components in the laminated chip and firing the laminated chip to sinter it.
  • the unfired waste before manufacturing degreasing is the waste before the step including both steps 5 and 6.
  • the manufacturing method of the multilayer ceramic capacitor 10 includes the formation of a laminated block (step 3), cutting into laminated chips (step 4), manufacturing degreasing (step 5), firing of the laminated chips (step 6), and application and firing of the base electrode layer paste (step 7) in that order.
  • the manufacturing method of the multilayer ceramic capacitor 10 is not limited to this, and for example, there is a case where the manufacturing degreasing and firing are performed after applying the base electrode layer paste to the unfired laminated chip before the manufacturing degreasing in step 5 and before the firing (firing of the laminated chip) in step 6.
  • the base electrode layer paste containing Ni, glass components, resin components, etc. is applied to the laminated chip before the manufacturing degreasing in step 5.
  • the laminated chip to which the base electrode layer paste is applied is manufactured and degreased, and then fired.
  • the temperature during manufacturing degreasing is preferably, for example, higher than 800°C and lower than 1000°C.
  • the firing temperature is preferably, for example, higher than 1000°C and not higher than 1400°C.
  • the unfired waste before manufacturing degreasing includes waste of laminated chips before manufacturing degreasing (before manufacturing degreasing in step 5), which is unfired after the base electrode layer paste is applied (before the firing in step 6 and the firing in step 7 are performed at the same time).
  • the Ni powder in the base electrode layer paste is included in the target for separation and recovery.
  • the base electrode layer paste may further contain a common material made of ceramic powder.
  • Second Embodiment 1 Separation and Recovery Method
  • a separation and recovery method according to a second embodiment of the present invention will be described, which separates and recovers rare earth components and metal components from unfired waste after degreasing, which is discharged in the manufacturing process of a multilayer ceramic capacitor and is degreased in the manufacturing process before firing (firing of a laminated chip).
  • the separation and recovery method according to the second embodiment has a different treatment object from the separation and recovery method according to the first embodiment. That is, the treatment object of the separation and recovery method according to the first embodiment is unfired waste before degreasing, whereas the treatment object of the separation and recovery method according to the second embodiment is unfired waste after degreasing. Descriptions of the same contents as those of the first embodiment will be simplified or omitted.
  • FIG. 6 is a flow diagram showing a separation and recovery method according to a second embodiment of the present invention, which separates and recovers rare earth components and metal components from unfired waste after manufacturing and degreasing before firing (firing of laminated chips) that is discharged in the manufacturing process of a multilayer ceramic capacitor and that has been manufactured and degreased in the manufacturing process.
  • the separation and recovery method according to the second embodiment of the present invention uses unfired waste after manufacturing and degreasing before firing (firing of laminated chips) that is discharged in the manufacturing process of a multilayer ceramic capacitor and that has been manufactured and degreased in the manufacturing process as the starting point for separation and recovery.
  • the unfired waste after manufacturing and degreasing will now be described.
  • the unfired waste after manufacturing and degreasing refers to waste after manufacturing and degreasing in the manufacturing process in (step 5) of the manufacturing method for multilayer ceramic capacitor 10, and waste before firing of the laminated chips in (step 6).
  • the unfired waste after manufacturing and degreasing is defective laminated chips in which the lamination of each dielectric sheet is misaligned after manufacturing and degreasing in (step 5), excess laminated chips that are no longer needed, etc.
  • the separation and recovery method of FIG. 6 includes a common separation and recovery route, a rare earth component separation and recovery route, and a metal component separation and recovery route.
  • the rare earth component separation and recovery route and the metal component separation and recovery route each branch off from the common separation and recovery route.
  • the common separation and recovery route includes, for example, the preparation of unburned waste after manufacturing and degreasing in step (A), the refining in step (B), and the magnetic separation in step (C).
  • the process branches into a rare earth component separation and recovery route and a metal component separation and recovery route.
  • the rare earth component separation and recovery route can include, for example, dissolving rare earth powder-containing material in step (D), and can further include filtration in step (F) and neutralization in step (G).
  • the metal component separation and recovery route can include, for example, dissolving metal powder-containing material in step (H), and can further include various treatments in step (I).
  • unsintered waste after manufacturing degreasing which is discharged in the manufacturing process of a multilayer ceramic capacitor, is prepared.
  • the unsintered waste after manufacturing degreasing includes metal powder, ceramic powder (first ceramic powder, second ceramic powder), and rare earth powder.
  • the metal powder, ceramic powder, and rare earth powder are as described in the first embodiment.
  • the unsintered waste after manufacturing degreasing is waste after the laminated chip is manufactured and degreased in step 5, so the resin component has been almost or completely degreased (removed).
  • the resin component contained in the laminated chip before manufacturing degreasing is the same as in the first embodiment.
  • the metal powder, ceramic powder, and rare earth powder are at least partially adhered to each other, as in the first embodiment.
  • the resin component is not involved in the adhesion between the metal powder, ceramic powder, and rare earth powder.
  • the manner of adhesion between the metal powder, ceramic powder, and rare earth powder in the unfired waste after manufacturing and degreasing is generally the same as the manner of adhesion between the metal powder, ceramic powder, and rare earth powder in the unfired waste before manufacturing and degreasing.
  • the reason why the powder particles in the unfired waste after manufacturing and degreasing are adhered to each other and not basically chemically bonded is that although the unfired waste after manufacturing and degreasing is degreased at the degreasing temperature in step 5 (higher than 800°C and not higher than 1000°C), the firing at the degreasing temperature in step 5 is not performed to a degree that would allow the powder particles to chemically bond to each other.
  • the firing at the firing temperature in step 6 (higher than 1000°C and not higher than 1400°C) can cause the powder particles to chemically bond to each other, but the unfired waste after manufacturing and degreasing does not go through step 6, so the powder particles are basically not chemically bonded to each other and are just adhered to each other.
  • the unfired waste after manufacturing degreasing in this embodiment contains metal powder, ceramic powder, and rare earth powder. More specifically, the unfired waste after manufacturing degreasing in this embodiment contains metal powder-containing material and rare earth powder-containing material.
  • the configurations of the metal powder-containing material and the rare earth powder-containing material are the same as those in the first embodiment.
  • the metal powder-containing material refers to a material containing metal powder and ceramic powder.
  • the rare earth powder-containing material refers to a material containing rare earth powder and ceramic powder.
  • the metal powder-containing material refers to a material containing metal powder and second ceramic powder, and the metal powder and the second ceramic powder are at least partially adhered to each other.
  • the rare earth powder-containing material refers to a material containing rare earth powder and first ceramic powder, and the rare earth powder and the first ceramic powder are at least partially adhered to each other.
  • the state of the powder of such unfired waste after manufacturing degreasing is generally similar to the state of the powder of unfired waste before manufacturing degreasing described in FIG. 5 of the first embodiment, except that it does not contain a resin component.
  • the separation and recovery method according to the first embodiment and the separation and recovery method according to the second embodiment differ in that the object to be treated is unburned waste before manufacturing and degreasing, or unburned waste after manufacturing and degreasing.
  • the separation and recovery method according to the second embodiment does not include the recycle degreasing of step (E) in the common separation and recovery route.
  • the separation and recovery route for rare earth components and the separation and recovery route for metal components are the same in the separation and recovery methods according to the first and second embodiments, since they are steps that occur after the resin components have been degreased.
  • the inventors of the present application have newly focused on the separation and recovery of metal components and rare earth components from unfired waste discharged before firing (firing of laminated chips) and after manufacturing and degreasing in the manufacturing process of multilayer ceramic capacitors.
  • the materials constituting the unfired waste after manufacturing and degreasing such as metal powder, ceramic powder (first and second ceramic powder), and rare earth powder, are not generally chemically bonded to each other by sintering, and at least some of the powders of each material are present in a state of adhering to each other.
  • each material can be easily separated independently by a process (B) of pulverizing or other fine processing.
  • the metal components and rare earth components in the unfired waste after manufacturing and degreasing are materials used in the manufacture of multilayer ceramic capacitors, the purity of the metal components and rare earth components is higher than that of naturally occurring ores. Therefore, by carrying out the above separation and recovery method starting from unburned waste after manufacturing and degreasing, it is possible to separate and recover high-purity metal components and high-purity rare earth components.
  • the unfired waste after the manufacturing and degreasing process after the fine particle size can be separated into a metal powder-containing material and a rare earth powder-containing material by using a magnet in step (C).
  • the rare earth powder-containing material is dissolved in a mineral acid to produce a rare earth component-containing solution in which the rare earth powder contained in the rare earth powder-containing material is dissolved as a rare earth component.
  • the first ceramic powder contained in the rare earth powder-containing material reacts with the mineral acid to become an undissolved material and precipitate, so that the first ceramic powder and the rare earth powder contained in the rare earth powder-containing material are separated.
  • the rare earth powder-containing material for example, the rare earth powder is attached to the surface of the first ceramic powder, and the first ceramic powder and the rare earth powder are not sintered. Therefore, the first ceramic powder and the rare earth powder are easily separated by the dissolution in step (D).
  • the separation and recovery method including steps (C) and (D)
  • the proportion of rare earth components in the material containing rare earth components increases as each step is passed through. Therefore, it is possible to recover rare earth components such as Dy at a high quality.
  • a metal component-containing solution can be produced in which the metal powder contained in the metal powder-containing material is dissolved as a metal component.
  • the second ceramic powder contained in the metal powder-containing material reacts with the mineral acid to become an undissolved substance and precipitate, so the second ceramic powder and the metal powder contained in the metal powder-containing material are separated.
  • the unfired waste after production and degreasing is not fired (firing of the laminated chip)
  • the metal powder-containing material for example, the second ceramic powder is attached to the surface of the metal powder, and the metal powder and the second ceramic powder are not sintered. Therefore, the metal powder and the second ceramic powder are easily separated by the dissolution in step (H).
  • the separation and recovery method including steps (C) and (H)
  • the proportion of the metal components in the material containing the metal components increases as each step is passed through. Therefore, it is possible to recover metal components such as Ni at a high quality.
  • the unfired waste after degreasing that is discharged during the manufacturing process of multilayer ceramic capacitors is used to separate and recover metal components, rare earth components, etc., so the unfired waste after degreasing can be used as a resource rather than being discarded as waste, reducing the burden on the environment.
  • step (B) (1-1) Generation of slurry by organic solvent
  • the unburned waste after manufacturing and degreasing is pulverized and refined in step (B).
  • the unburned waste after manufacturing and degreasing may be pulverized by dispersing it in a slurry state using an organic solvent.
  • wet pulverization the pulverization in which the unburned waste after manufacturing and degreasing is mixed with a solvent (solvent such as an organic solvent and an aqueous solvent) to form a slurry.
  • a solvent solvent such as an organic solvent and an aqueous solvent
  • wet pulverization the pulverization in which the unburned waste after manufacturing and degreasing is pulverized in a slurry formed by mixing the unburned waste after manufacturing and degreasing with a solvent.
  • the separation and recovery method includes, as a common separation and recovery route, in this order: preparation of unburned waste after manufacturing and degreasing in step (A), mixing of the unburned waste after manufacturing and degreasing with an organic solvent (performed together with or instead of the micronization (particularly micronization by grinding) in step (B)), and magnetic separation in step (C).
  • preparation of unburned waste after manufacturing and degreasing in step (A) preparation of unburned waste after manufacturing and degreasing in step (A), mixing of the unburned waste after manufacturing and degreasing with an organic solvent (performed together with or instead of the micronization (particularly micronization by grinding) in step (B)), and magnetic separation in step (C).
  • the magnetic separation in step (C) is followed by a further distillation step of removing the organic solvent.
  • the separation and recovery method also includes dissolving the rare earth powder-containing material in step (D) as a route for separating and recovering rare earth components, following the common separation and recovery route. Note that in the route for separating and recovering rare earth components, filtration in step (F) and neutralization in step (G) may additionally be performed.
  • the separation and recovery method also includes dissolving the metal powder-containing material in step (H) as a route for separating and recovering metal components, following the common separation and recovery route. Note that in the route for separating and recovering metal components, various treatments in step (I) may additionally be performed.
  • the separation and recovery method preferably includes, as a common separation and recovery route, for example, the preparation of unburned waste after manufacturing and degreasing in step (A), the generation of a slurry by mixing the unburned waste after manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • a common separation and recovery route for example, the preparation of unburned waste after manufacturing and degreasing in step (A), the generation of a slurry by mixing the unburned waste after manufacturing and degreasing with an organic solvent, the fineness in step (B) (particularly, fineness by grinding), and the magnetic separation in step (C) in this order, and further includes a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • step (A) the preparation of unburned waste after manufacturing and degreasing in step (A), the fineness in step (B) (particularly, fineness by grinding), the generation of a slurry by mixing the unburned waste after manufacturing and degreasing finely ground by grinding with an organic solvent, and the magnetic separation in step (C) are performed in this order, and further, it is preferable to perform a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • the common separation and recovery route omits the pulverization (particularly pulverization by grinding) of step (B), and preferably includes, in this order, for example, preparation of unburned waste after production and degreasing in step (A), generation of a slurry by mixing the unburned waste after production and degreasing with an organic solvent, and magnetic separation in step (C), and further includes a distillation step for removing the organic solvent after the magnetic separation in step (C).
  • the organic solvent may be an alcohol-based organic solvent or a hydrocarbon-based organic solvent.
  • the organic solvent may be methanol, ethanol, propanol, toluene, xylene, cyclohexane, or a mixture thereof.
  • the unburned waste after manufacturing and degreasing that has been pulverized in step (B) is mixed with water or an organic solvent and dispersed to form a slurry state.
  • the unburned waste after manufacturing and degreasing is made into a slurry state using an organic solvent in addition to or instead of the pulverization in step (B)
  • the unburned waste after manufacturing and degreasing that has become a slurry state may be magnetically separated in step (C). In other words, the effort of generating a slurry state in the magnetic separation in step (C) can be omitted.
  • the separation and recovery method includes, as a common separation and recovery route, the preparation of unburned waste after manufacturing and degreasing in step (A), mixing of the unburned waste after manufacturing and degreasing with an aqueous solvent (performed together with the fine-graining (particularly fine-graining by grinding) in step (B) or instead of the fine-graining (particularly fine-graining by grinding) in step (B), and magnetic separation in step (C) in this order.
  • the separation and recovery method includes dissolution of rare earth powder-containing material in step (D) as a separation and recovery route for rare earth components following the common separation and recovery route.
  • filtration in step (F) and neutralization in step (G) may be performed.
  • the separation and recovery method includes dissolution of metal powder-containing material in step (H) as a separation and recovery route for metal components following the common separation and recovery route.
  • various treatments in step (I) may be carried out as a route for separating and recovering metal components.
  • the separation and recovery method includes, as a common separation and recovery route, for example, the steps of preparing unburned waste after manufacturing and degreasing in step (A), mixing the unburned waste after manufacturing and degreasing with an aqueous solvent to generate a slurry, pulverizing (particularly, pulverizing by grinding) in step (B), and magnetic separation in step (C) in this order.
  • step (A) the steps of preparing unburned waste after manufacturing and degreasing in step (A), pulverizing (particularly, pulverizing by grinding) in step (B), mixing the unburned waste after manufacturing and degreasing finely pulverized by grinding with an aqueous solvent to generate a slurry, and magnetic separation in step (C) can also be performed in this order.
  • a common separation and recovery route omits the pulverization (particularly pulverization by grinding) in step (B), and includes, for example, the steps of preparing unburned waste after production and degreasing in step (A), mixing the unburned waste after production and degreasing with an aqueous solvent to produce a slurry, and magnetic separation in step (C), in this order.
  • aqueous solvent for example, water can be used.
  • the unburned waste after manufacturing and degreasing that has been pulverized in step (B) is mixed with water or an organic solvent and dispersed to form a slurry state.
  • the unburned waste after manufacturing and degreasing is made into a slurry state using an aqueous solvent in step (B)
  • the unburned waste after manufacturing and degreasing that has become a slurry state may be magnetically separated in step (C).
  • the effort of generating a slurry state in the magnetic separation in step (C) can be omitted.
  • the manufacturing method of the multilayer ceramic capacitor 10 includes the formation of a laminated block in (step 3), cutting into laminated chips in (step 4), manufacturing and degreasing in (step 5), firing of the laminated chips in (step 6), and application and firing of the base electrode layer paste in (step 7) in that order.
  • the manufacturing method of the multilayer ceramic capacitor 10 is not limited to this, and for example, before the manufacturing and degreasing in step 5 and before the firing (firing of the laminated chips) in step 6, the manufacturing and degreasing and firing may be performed after applying the base electrode layer paste to the unfired laminated chips.
  • the base electrode layer paste containing Ni, glass components, resin components, etc. is applied to the laminated chips before the manufacturing and degreasing in step 5.
  • the laminated chips to which the base electrode layer paste is applied are manufactured and degreased, and then fired.
  • the temperature during the manufacturing and degreasing is preferably, for example, higher than 800°C and lower than 1000°C.
  • the firing temperature is preferably, for example, higher than 1000°C and not higher than 1400°C.
  • the unfired waste after manufacturing and degreasing includes, in addition to those listed in the above embodiment, waste of laminated chips after manufacturing and degreasing that are unfired after the base electrode layer paste is applied (before the firing in step 6 and the firing in step 7 are performed at the same time).
  • the Ni powder in the base electrode layer paste is included in the target for separation and recovery.
  • the base electrode layer paste may further contain a common material made of ceramic powder.
  • the subject of application of the present invention is unfired waste before degreasing or unfired waste after degreasing discharged in the manufacturing process of a multilayer ceramic capacitor having an internal electrode layer containing metal powder such as Ni , and a ceramic layer containing a dielectric material such as BaTiO 3 and rare earth powder as an additive such as Dy. Therefore, the present invention may be applied to unfired waste before degreasing or unfired waste after degreasing discharged in the manufacturing process of a three-terminal multilayer ceramic capacitor, for example.
  • a three-terminal multilayer ceramic capacitor has a laminate 12 similar to those of the first and second embodiments described above, and first to fourth external electrodes.
  • the internal electrode layer 16 has a first internal electrode layer extended to the first end face 12e and the second end face 12f, and a second internal electrode layer extended to the first side face 12c and the second side face 12d.
  • a first external electrode is disposed on the first end face 12e of the laminate 12. The first external electrode is electrically connected to the first internal electrode layer exposed at the first end face 12e of the laminate 12.
  • a second external electrode is disposed on the second end face 12f of the laminate 12. The second external electrode is electrically connected to the first internal electrode layer exposed at the second end face 12f of the laminate 12.
  • a third external electrode is disposed on the first side face 12c of the laminate 12.
  • the third external electrode is electrically connected to the second internal electrode layer exposed at the first side surface 12c of the laminate 12.
  • a fourth external electrode is disposed on the second side surface 12d of the laminate 12. The fourth external electrode is electrically connected to the second internal electrode layer exposed at the second side surface 12d of the laminate 12.
  • step (F) When the rare earth powder-containing material is dissolved in mineral acid in step (D), the first ceramic powder contained in the rare earth powder-containing material reacts with the mineral acid to become undissolved and precipitate. Meanwhile, the rare earth powder dissolves to produce a rare earth component-containing solution.
  • the rare earth component-containing solution containing the undissolved matter can also be recovered as the rare earth component.
  • the solid-liquid separation step (F) such as filtration, can be omitted.
  • step (G) Omission of neutralization in step (G)
  • the rare earth components in the dissolution of the rare earth powder-containing material in step (D), the rare earth components can be separated and recovered as a rare earth component-containing solution. Therefore, the neutralization in step (G) can be omitted.
  • Step (I) Omission of Various Treatments in Step (I)
  • the metal component-containing solution in the dissolution of the metal powder-containing material in step (H), the metal component-containing solution can be separated and recovered as metal components. Therefore, the various treatments in step (I) can be omitted.
  • rare earth component compounds such as Dy(OH) 3 are separated and recovered as rare earth components in the neutralization step (G).
  • the method for separating and recovering rare earth components is not limited to this.
  • the rare earth components can be recovered as follows.
  • step (a) The rare earth component compound obtained by neutralization in step (G) is heat-treated to produce an oxide, and the oxide can be recovered as the rare earth component.
  • the rare earth component compound obtained after the neutralization in step (G) is Dy(OH) 3
  • dysprosium oxide (Dy 2 O 3 ) can be recovered as the rare earth component by heat treating Dy(OH) 3 .
  • the rare earth component compound obtained by neutralization in step (G) is dissolved in hydrochloric acid to produce a chloride, and the chloride can be recovered as the rare earth component.
  • the rare earth component compound obtained after the neutralization in step (G) is Dy(OH) 3
  • Dy(OH) 3 is dissolved in hydrochloric acid to produce a dysprosium chloride ( DyCl3 ) solution.
  • the dysprosium chloride solution is distilled to evaporate the solvent, and dysprosium chloride hexahydrate ( DyCl3.6H2O ) can be recovered as the rare earth component.
  • the rare earth component compound Dy(OH) 3 obtained after neutralization in step (G) is dissolved in hydrochloric acid to produce a dysprosium chloride solution, which is then further purified to recover a high-purity rare earth component.
  • the dysprosium chloride solution produced as described above can be purified by solvent extraction, and a high-purity dysprosium chloride solution can be recovered as a rare earth component.
  • Solvent extraction is a separation and purification method that utilizes the partitioning of solutes, in which a solute dissolved in one of the oil phase and the water phase, which are immiscible liquids, is transferred to the other phase.
  • an ion exchange resin method can be used as a method other than solvent extraction.
  • high-purity dysprosium oxide can be recovered from the high-purity dysprosium chloride solution obtained by the solvent extraction in (c) above.
  • oxalic acid is added to the high-purity dysprosium chloride solution to precipitate dysprosium oxalate.
  • high-purity dysprosium oxalate hexahydrate Dy2 ( C2O4 ) 3.6H2O ) is recovered .
  • high-purity dysprosium oxide ( Dy2O3 ) can be recovered as a rare earth component.
  • high-purity dysprosium chloride hexahydrate can be recovered from the high-purity dysprosium chloride solution obtained by the solvent extraction in (c) above.
  • high-purity dysprosium chloride hexahydrate is recovered by distilling off the high-purity dysprosium chloride solution and evaporating the solvent.
  • the rare earth component-containing solution separated and recovered in the filtration of step (F) is input to the neutralization of step (G).
  • the rare earth component-containing solution separated and recovered in the filtration of step (F) may be treated in a rare earth component concentration step and then input to the neutralization of step (G).
  • the rare earth component concentration step is performed after the filtration of step (F) and before the neutralization of step (G).
  • the rare earth component concentration process is not limited as long as it is a method that can improve the recovery amount of rare earth components in the rare earth component-containing solution.
  • Examples of rare earth component concentration processes include, but are not limited to, (f1) ion exchange method, (f2) solvent extraction method, and (f3) distillation of the solvent from the solution. Below, (f1) to (f3) are each explained as a representative example.
  • the ion exchange method is a method in which dissolved ions dissolved in a solvent are adsorbed to an ion exchanger such as an ion exchange resin and a chelating resin.
  • an ion exchanger such as an ion exchange resin and a chelating resin.
  • a rare earth component-containing solution is passed through an ion exchanger, so that the rare earth components in the rare earth component-containing solution are adsorbed to the ion exchanger.
  • the ion exchange method is not limited, but is carried out, for example, by passing a rare earth component-containing solution through a column filled with an ion exchanger.
  • the column is formed of a cylindrical body with an open upper and lower ends, and the rare earth component-containing solution is introduced into the column from the upper end side of the column, and the rare earth component is adsorbed to the ion exchanger in the process of passing through the ion exchanger. The remaining liquid of the rare earth component-containing solution that has passed through the ion exchanger is discharged from the lower end side of the column.
  • the rare earth components adsorbed on the ion exchanger are eluted from the ion exchanger using an eluent.
  • the eluent is passed through the bottom end of a column packed with the ion exchanger to which the rare earth components are adsorbed.
  • the rare earth components are eluted from the ion exchanger into the eluent by the eluent.
  • the eluent from which the rare earth components have been eluted is collected from the top end of the column.
  • the rare earth components can be collected by filtering the eluent in which the rare earth components are dissolved, for example, using a filter.
  • the concentration of the rare earth components contained in the eluent can be made higher than the concentration of the rare earth components contained in the rare earth component-containing solution.
  • the rare earth component-containing solution is passed from the top to the bottom of the column, and then the eluent is passed from the bottom to the top of the column.
  • the rare earth components can be dissolved in the eluent after being adsorbed by the ion exchanger, there is no limitation on the direction in which the rare earth component-containing solution and eluent are passed through the column.
  • the series of steps (1) including steps (A) to (F) and the rare earth component concentration step by ion exchange may be carried out only once.
  • the series of steps (1) is carried out only once by passing the rare earth component-containing solution after steps (A) to (F) through an ion exchanger once.
  • a series of steps (1) including steps (A) to (F) and a rare earth component concentration step by ion exchange may be performed multiple times.
  • a series of steps (1) in which the rare earth component-containing solution after steps (A) to (F) is passed through an ion exchanger is performed multiple times.
  • the same ion exchanger can be used in each series of steps (1).
  • a series of steps (2) including steps (A) to (F) is performed multiple times, and the rare earth component-containing solution obtained in each series of steps (2) is temporarily stored.
  • the accumulated rare earth component-containing solution may then be treated all at once in a rare earth component concentration step using an ion exchange method.
  • the amount of rare earth component-containing solution accumulated after multiple series of steps (2) is greater than the amount of rare earth component-containing solution obtained by one series of steps (2). Therefore, by passing the accumulated rare earth component-containing solution through an ion exchanger, more rare earth components can be adsorbed onto the ion exchanger, thereby increasing the amount of rare earth components recovered.
  • the concentration of rare earth components in the rare earth component-containing solution after one pass of the series of steps (2) from step (A) to step (F) is low, even if the rare earth component-containing solution is filtered using a filter, the amount of rare earth components that accumulate on the filter is small. Therefore, the recovery amount of rare earth components may not be high. However, the recovery amount of rare earth components can be increased by performing the rare earth component concentration step as described above.
  • Ion exchange resins which are ion exchangers, include, but are not limited to, cation exchange resins and chelating resins.
  • Cation exchange resins include, but are not limited to, gel-type cation exchange resins, strong acid cation exchange resins, and weak acid cation exchange resins.
  • Specific examples of cation exchange resins include, but are not limited to, Amberlite IR-120B (manufactured by Organo Corporation), Duolite C20J (manufactured by Sumika Chemtex Corporation), DIAION SK-110 (manufactured by Mitsubishi Chemical Corporation), and Purolite C100 (manufactured by Purolite Corporation).
  • the chelating resin which is an ion exchanger, is not limited to, but may be, for example, a resin having a chelating group or chelating ability, such as a thiourea group, a thiouronium group, a phosphonic acid, an amino phosphoric acid, an amino carboxylic acid, an alkylamino group, a pyridine ring, a cyclic cyanine, or a cyclic ether.
  • Specific examples of the chelating resin include, but are not limited to, Sumichelate MC700 (manufactured by Sumika Chemtex Corporation) and Purolite MTS9300 (manufactured by Purolite Corporation).
  • the solvent extraction method includes, for example, a solvent extraction step and a stripping step.
  • the solvent extraction process is a process in which a water-insoluble organic phase containing a metal extractant is contacted and mixed with a rare earth-containing solution in order to separate rare earth components from the rare earth-containing solution.
  • a phase separation step is carried out to separate the rare earth-containing water-insoluble organic phase from the aqueous phase.
  • the phases are separated by utilizing the specific gravity difference between the rare earth-containing water-insoluble organic phase and the aqueous phase that have been subjected to the solvent extraction step.
  • the rare earth-containing water-insoluble organic phase obtained through the phase separation process is contacted and mixed with an acidic aqueous solution, thereby back-extracting the rare earth components in the water-insoluble organic phase into the acidic aqueous solution.
  • steps (1) including steps (A) to (F) and the rare earth component concentration step using a solvent extraction method may be carried out only once.
  • a series of steps (1) including steps (A) to (F) and a rare earth component concentration step by a solvent extraction method may be performed multiple times.
  • a series of steps (1) in which the rare earth component-containing solution after steps (A) to (F) is mixed with an organic solvent is performed multiple times. For example, by repeatedly mixing the rare earth component-containing solution recovered from steps (A) to (F) multiple times with the same organic solvent, more rare earth components are transferred to the organic solvent than when the rare earth component-containing solution recovered from steps (A) to (F) is mixed with the organic solvent once. This makes it possible to increase the amount of rare earth components recovered.
  • the rare earth component-containing solution obtained in each series of steps (2) is temporarily stored. After that, the stored rare earth component-containing solution may be treated all at once in a rare earth component concentration step using a solvent extraction method.
  • Removal of solvent from solution involves removing the solvent from a solution in which dissolved ions are dissolved.
  • the removal of the solvent can be carried out, for example, using an evaporator, but is not limited thereto.
  • the evaporator is a device that evaporates the solvent by, for example, heating and reducing the pressure inside an evaporator in which a solution is placed. Examples of the evaporator include a rotary evaporator and a flash evaporator.
  • the operating conditions of the evaporator are appropriately adjusted depending on the amount of unburned waste to be processed before or after the production and degreasing, various additive components to the unburned waste, and the like.
  • steps (1) including steps (A) to (F) and the step of concentrating the rare earth components by distilling off the solvent from the solution may be carried out once or multiple times.
  • the rare earth component-containing solution obtained in each series of steps (2) is temporarily stored. After that, the accumulated rare earth component-containing solution may be treated all at once to distill off the solvent.
  • the state of the recovered rare earth component may be any of a liquid state, a solid state, and a mixed state of liquid and solid.
  • the crystal lattice of the rare earth component may be any of an amorphous state, a crystalline state, and a mixed state of amorphous and crystalline.
  • the metal powder-containing material is dissolved in a mineral acid in the dissolution of the metal powder-containing material in step (H).
  • the metal component-containing solution is then separated and recovered as a metal component.
  • the metal component-containing solution containing the precipitated second ceramic powder is filtered, and the metal component-containing solution from which the second ceramic powder has been removed is separated and recovered as a metal component.
  • the separation and recovery of the metal component is not limited to this.
  • the metal component can be recovered as follows.
  • the metal component compound By crystallizing the metal component-containing solution, the metal component compound can be recovered as the metal component.
  • the metal component-containing solution obtained after dissolving the metal powder-containing material in step (H) is a nickel sulfate ( NiSO4 ) solution
  • nickel sulfate hexahydrate ( NiSO4.6H2O ) can be recovered as the metal component by crystallizing and filtering the nickel sulfate solution.
  • step (b) By purifying the metal component-containing solution obtained after dissolving the material containing metal powder in step (H), it is possible to recover high-purity metal components.
  • a nickel sulfate (NiSO 4 ) solution containing metal components can be purified by an ion exchange resin method, a solvent extraction method, or the like, and a high-purity nickel sulfate solution can be recovered as the metal components.
  • the metal component-containing solution obtained after dissolving the metal powder-containing material in step (H) can be purified by a method other than the above-mentioned (b) to recover high-purity metal components.
  • a nickel sulfate solution which is a metal component-containing solution
  • high-purity solid Ni can be precipitated and recovered as a metal component by a method of precipitating a solid dissolved in the solution, such as electrolytic deposition.
  • nickel chloride hexahydrate NiCl2.6H2O
  • NiCl2 nickel chloride hexahydrate
  • the metal component-containing solution obtained after dissolving the metal powder-containing material in step (H) is neutralized to generate chlorides, and the chlorides can be recovered as the metal components.
  • a nickel sulfate solution which is a metal component-containing solution, is neutralized by adjusting the pH to, for example, about 10 (pH 9 or more and pH 11 or less) with an alkali such as sodium hydroxide or potassium hydroxide, and nickel hydroxide (Ni(OH) 2 ) is precipitated.
  • the precipitated nickel hydroxide (Ni(OH) 2 ) is separated and recovered, for example, by filtration.
  • nickel hydroxide is dissolved in hydrochloric acid to produce a nickel chloride ( NiCl2 ) solution.
  • nickel chloride hexahydrate NiCl2.6H2O
  • the state of the recovered metal component may be any of liquid, solid, and mixed liquid and solid.
  • the crystal lattice of the metal component may be any of amorphous, crystalline, and mixed amorphous and crystalline.
  • the ceramic powder includes a first ceramic powder and a second ceramic powder having a smaller particle size than the first ceramic powder; In the metal powder inclusion, the metal powder and the second ceramic powder are at least partially adhered to each other, The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to ⁇ 1> or ⁇ 2>, wherein in the rare earth powder-containing material, the rare earth powder and the first ceramic powder are at least partially adhered to each other.
  • ⁇ 4> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to ⁇ 1> or ⁇ 2>, wherein the pulverization in the step (B) is carried out by at least one of pulverization and introduction of an organic solvent.
  • step (B) the resin component is recycled and degreased from the unburned waste before production and degreasing, and then the unburned waste before production and degreasing after the recycled degreasing is mixed with an aqueous solvent as the solvent to produce a slurry, and the slurry is pulverized in the slurry.
  • ⁇ 6> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to any one of ⁇ 1>, ⁇ 3> and ⁇ 4>, wherein in the step (B), the unburned waste before production and degreasing is mixed with an organic solvent as the solvent to produce a slurry, and the rare earth components and metal components are pulverized in the slurry.
  • ⁇ 8> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to ⁇ 7>, wherein the degreasing temperature in the recycle degreasing in the step (E) is 600° C. or higher and 1000° C. or lower.
  • ⁇ 10> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to ⁇ 9>, further comprising a rare earth component concentration step of concentrating the rare earth components in the rare earth component-containing solution after the step (F) and before the neutralization step (G).
  • the rare earth component-containing solution is adjusted to a pH of 6 or more and a pH of 9 or less to recover the rare earth component.
  • ⁇ 13> Any one of ⁇ 1> to ⁇ 12>, wherein in the step (D), the rare earth component-containing solution is adjusted to a pH of 1.5 or more and 2.5 or less by adding the mineral acid.
  • ⁇ 14> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to any one of ⁇ 1> to ⁇ 13>, wherein the metal component is Ni and the ceramic powder is BaTiO 3 .
  • ⁇ 15> The method for separating and recovering rare earth components and metal components from unburned waste before production and degreasing according to any one of ⁇ 1> to ⁇ 14>, wherein the rare earth components are at least one of Dy, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu.
  • Multilayer ceramic capacitor 12 Laminate 12a: First main surface 12b: Second main surface 12c: First side surface 12d: Second side surface 12e: First end surface 12f: Second end surface 14: Ceramic layer 14_U: Unsintered ceramic layer 16: Internal electrode layer 16_U: Unsintered internal electrode layer 16a: First internal electrode layer 16b: Second internal electrode layer 30: External electrode 30a: First external electrode 30b: Second external electrode 32: Base electrode layer 32a: First base electrode layer 32b: Second base electrode layer 34: Plating layer 34a: First plating layer 34b: Second plating layer x: Height direction y: Width direction z: Length direction

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Abstract

L'invention concerne un procédé de séparation et de récupération d'un composant de terres rares et d'un composant métallique à partir de déchets non torréfiés. Ce procédé de séparation et de récupération comprend: (A) une étape de préparation d'un déchet non torréfié avant dégraissage de production, le déchet comprenant une poudre métallique ayant un magnétisme, une poudre céramique, une poudre de terre rare et un composant de résine, et dans lequel la poudre métallique et la poudre céramique sont au moins partiellement collées l'une à l'autre; (B) une étape de raffinage des déchets non torréfiés avant le dégraissage de production, dans une suspension générée par mélange des déchets non torréfiés et d'un solvant; (C) une étape de séparation et de récupération d'un matériau contenant de la poudre métallique et d'un matériau contenant de la poudre de terres rares au moyen d'un aimant après l'étape (B); (D) une étape de dissolution du matériau contenant de la poudre de terres rares dans un acide minéral pour précipiter une poudre céramique et la génération d'une solution contenant un composant de terres rares dans laquelle la poudre de terres rares est dissoute; et (H) une étape de dissolution du matériau contenant de la poudre métallique dans un acide minéral pour précipiter une poudre céramique et de la génération d'une solution contenant un composant métallique dans laquelle la poudre métallique est dissoute.
PCT/JP2024/026742 2023-11-29 2024-07-26 Procédé de séparation et de récupération d'un composant de terres rares et d'un composant métallique à partir de déchets non brûlés avant le dégraissage de production ou des déchets non brûlés après dégraissage de production Pending WO2025115285A1 (fr)

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PCT/JP2024/026742 Pending WO2025115285A1 (fr) 2023-11-29 2024-07-26 Procédé de séparation et de récupération d'un composant de terres rares et d'un composant métallique à partir de déchets non brûlés avant le dégraissage de production ou des déchets non brûlés après dégraissage de production

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US5129945A (en) * 1990-10-24 1992-07-14 The United States Of America As Represented By The Secretary Of The Interior Scrap treatment method for rare earth transition metal alloys
JP2007231382A (ja) * 2006-03-01 2007-09-13 Mitsui Mining & Smelting Co Ltd 希土類元素の回収方法
WO2017037625A1 (fr) * 2015-09-02 2017-03-09 Attero Recycling Pvt. Ltd. Procédé et processus de récupération de métaux précieux contenus dans des condensateurs céramiques monolithiques usagés
JP2018530673A (ja) * 2015-09-18 2018-10-18 ザ トラスティーズ オブ コロンビア ユニバーシティ イン ザ シティ オブ ニューヨークＴｈｅ Ｔｒｕｓｔｅｅｓ Ｏｆ Ｃｏｌｕｍｂｉａ Ｕｎｉｖｅｒｓｉｔｙ Ｉｎ Ｔｈｅ Ｃｉｔｙ Ｏｆ Ｎｅｗ Ｙｏｒｋ 鉄鋼スラグから製品を再生する方法およびシステム
WO2023156345A1 (fr) * 2022-02-18 2023-08-24 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de recyclage de néodyme à partir de cartes de circuits imprimés usagées

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CN111039495B (zh) * 2020-01-06 2024-05-17 湖南景翌湘台环保高新技术开发有限公司 一种废稀土抛光粉和钢铁酸洗废液的综合回收方法
CN115772599A (zh) * 2022-11-30 2023-03-10 江西闪凝科技有限公司 一种钕铁硼焙砂中有价金属元素的分离方法

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Publication number Priority date Publication date Assignee Title
US5129945A (en) * 1990-10-24 1992-07-14 The United States Of America As Represented By The Secretary Of The Interior Scrap treatment method for rare earth transition metal alloys
JP2007231382A (ja) * 2006-03-01 2007-09-13 Mitsui Mining & Smelting Co Ltd 希土類元素の回収方法
WO2017037625A1 (fr) * 2015-09-02 2017-03-09 Attero Recycling Pvt. Ltd. Procédé et processus de récupération de métaux précieux contenus dans des condensateurs céramiques monolithiques usagés
JP2018530673A (ja) * 2015-09-18 2018-10-18 ザ トラスティーズ オブ コロンビア ユニバーシティ イン ザ シティ オブ ニューヨークＴｈｅ Ｔｒｕｓｔｅｅｓ Ｏｆ Ｃｏｌｕｍｂｉａ Ｕｎｉｖｅｒｓｉｔｙ Ｉｎ Ｔｈｅ Ｃｉｔｙ Ｏｆ Ｎｅｗ Ｙｏｒｋ 鉄鋼スラグから製品を再生する方法およびシステム
WO2023156345A1 (fr) * 2022-02-18 2023-08-24 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de recyclage de néodyme à partir de cartes de circuits imprimés usagées

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