WO2023223399A1 - Procédé d'extraction de métal alcalino-terreux, procédé de fixation de co2, et procédé de fixation de co2 pour récupérer un métal de valeur - Google Patents

Procédé d'extraction de métal alcalino-terreux, procédé de fixation de co2, et procédé de fixation de co2 pour récupérer un métal de valeur Download PDF

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WO2023223399A1
WO2023223399A1 PCT/JP2022/020434 JP2022020434W WO2023223399A1 WO 2023223399 A1 WO2023223399 A1 WO 2023223399A1 JP 2022020434 W JP2022020434 W JP 2022020434W WO 2023223399 A1 WO2023223399 A1 WO 2023223399A1
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alkaline earth
earth metal
liquid phase
mixture
metal
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PCT/JP2022/020434
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English (en)
Japanese (ja)
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翔 藤本
俊介 持田
耕二 小谷野
賢三 左右田
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日揮グローバル株式会社
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Priority to PCT/JP2022/020434 priority Critical patent/WO2023223399A1/fr
Priority to AU2022459285A priority patent/AU2022459285A1/en
Publication of WO2023223399A1 publication Critical patent/WO2023223399A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present disclosure relates to a method for extracting alkaline earth metals, a method for fixing CO2 , and a method for fixing CO2 and recovering valuable metals.
  • the present disclosure also relates to a CO 2 fixation device and a CO 2 fixation and valuable metal recovery device.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2007-222713 states, ⁇ In a method for removing and recovering magnesium and calcium from steel industry by-products such as steel slag, treatment by dissolving with formic acid or citric acid at room temperature is described. "Featured Magnesium and Calcium Removal and Recovery Method” is described.
  • Patent Document 2 International Publication No. 2014/007331 describes “a method for extracting an alkali metal and/or an alkaline earth metal from a solid material containing an alkali metal and/or an alkaline earth metal, ⁇ A method comprising an elution step of adding the solid substance to the amino acid-containing aqueous solution and eluting the alkali metal and/or alkaline earth metal into the amino acid-containing aqueous solution.
  • alkali such as Mg and Ca contained in ore, coal ash, seawater, industrial waste, etc.
  • Mineral carbonation is known, which involves fixing CO2 gas by reacting earth metals with CO2 gas discharged from, for example, factories, power plants, etc.
  • Patent Document 4 Japanese Patent Publication No. 2011-5017266 describes ⁇ ⁇ a method for fixing or binding carbon dioxide (CO 2 ) as carbonate, comprising the following steps: water and coal ash or coal residue. contacting a gas containing CO2 with the aqueous solution; and reacting the CO2 and the aqueous solution to form a carbonate, whereby the CO2 is fixed or bound. ⁇ method including steps'' are described.
  • step d) subjecting at least a portion of the coarse particle size fraction from step c) to a particle size reduction process to provide a particle size reduction fraction; and e) the particle size from step d).
  • step b) by providing an aqueous slurry comprising a reduced fraction, wherein step e) does not include the use of the fine size fraction from step c); and f). an integrated process comprising, in the precipitation stage, precipitating magnesium carbonate from the magnesium ions dissolved in steps b) and e).
  • a method includes providing an aqueous phase to a precipitation device and precipitating an alkaline earth metal carbonate within the precipitation device to produce a precipitation slurry.
  • the present disclosure provides an alkaline earth metal that can efficiently extract alkaline earth metals from alkaline earth metal-containing solids into a liquid phase even at low pressure, and that can reduce costs related to raw materials, equipment, operation, etc.
  • Provided is a method for extracting similar metals.
  • the present disclosure also provides a method of fixing CO 2 using an alkaline earth metal-containing solid, and a method of fixing CO 2 and recovering valuable metals.
  • the present disclosure includes the following aspects.
  • Ions of the alkaline earth metal in the alkaline earth metal-containing particles are removed by stirring the mixture while blowing CO 2 gas into the mixture, which includes a slurry containing the alkaline earth metal-containing particles and an aqueous medium, and an abrasion medium.
  • a method for extracting alkaline earth metals comprising extracting them into a liquid phase.
  • the alkaline earth metal-containing particles are particles of Mg-containing ore, Mg-containing slag, Ca-containing slag, coal ash, clinker kiln dust, waste concrete, concrete sludge, or cement. Method for extraction of alkaline earth metals as described.
  • Ions of the alkaline earth metal in the alkaline earth metal-containing particles are removed by stirring the mixture while blowing CO 2 gas into the mixture, which includes a slurry containing the alkaline earth metal-containing particles and an aqueous medium, and an abrasion medium.
  • a CO 2 fixation method comprising precipitating an alkaline earth metal carbonate from the liquid phase and fixing CO 2 in the alkaline earth metal carbonate.
  • Ions of the alkaline earth metal in the alkaline earth metal-containing particles are removed by stirring the mixture while blowing CO 2 gas into the mixture, which includes a slurry containing the alkaline earth metal-containing particles and an aqueous medium, and an abrasion medium.
  • a stirring extraction tank for extracting into a liquid phase
  • a solid-liquid separator that separates the mixture into a liquid phase containing the alkaline earth metal ions and a solid phase containing the extraction residue
  • a CO 2 fixation device comprising: a precipitation device that precipitates an alkaline earth metal carbonate from the liquid phase and fixes CO 2 in the alkaline earth metal carbonate.
  • a method of fixing CO2 and recovering valuable metals comprising recovering both.
  • a pretreatment device that generates alkaline earth metal-containing particles and valuable metal-containing residue from a starting material containing a valuable metal and an alkaline earth metal;
  • the alkaline earth metal in the alkaline earth metal-containing particles is removed by stirring the mixture while blowing CO 2 gas into the mixture, which includes a slurry containing the alkaline earth metal-containing particles and an aqueous medium, and an abrasion medium.
  • a stirring extraction tank that extracts ions into the liquid phase; a solid-liquid separator that separates the mixture into a liquid phase containing the alkaline earth metal ions and a solid phase containing the extraction residue; a precipitation device that precipitates an alkaline earth metal carbonate from the liquid phase and fixes CO 2 in the alkaline earth metal carbonate;
  • a CO 2 fixation and valuable metal recovery device comprising: a valuable metal recovery device that recovers a valuable metal-containing product, an intermediate, or both from the valuable metal-containing residue.
  • alkaline earth metal extraction method of the present disclosure alkaline earth metal ions can be efficiently extracted from alkaline earth metal-containing particles into the liquid phase even at low pressure, and the raw materials, equipment, and operation It is possible to reduce costs related to such matters.
  • the alkaline earth metal extraction method of the present disclosure can be particularly advantageously applied to a CO 2 fixation method and a method for fixing CO 2 and recovering valuable metals.
  • FIG. 1 is a flow diagram outlining a CO 2 fixation method of one embodiment.
  • FIG. 1 is a flow diagram outlining a method of fixing CO 2 and recovering valuable metals in one embodiment.
  • FIG. 2 is a flow diagram illustrating an overview of the HPAL process.
  • 1 is a particle size distribution of the alkaline earth metal-containing particles of Example 1 before stirring as represented by a Rosin-Rammler diagram.
  • FIG. 2 is a particle size distribution of the alkaline earth metal-containing particles of Example 1 after stirring as represented by a Rosin-Rammler diagram.
  • FIG. This is a graph with the X axis representing the Mg conversion rate (%) and the Y axis representing the power consumption (kW), obtained from calculation of energy consumption per ton of CO 2 immobilized amount.
  • the method for extracting alkaline earth metals includes stirring the mixture while blowing CO2 gas into the mixture, which includes a slurry containing alkaline earth metal-containing particles and an aqueous medium , and an attrition medium. It involves extracting the alkaline earth metal ions in the metal-containing particles into a liquid phase. The CO2 gas blown into the mixture dissolves in the liquid phase of the mixture and makes it acidic. This promotes dissolution and ionization of the alkaline earth metal in the alkaline earth metal-containing particles into the liquid phase.
  • abrasion means reducing the surface of the alkaline earth metal-containing particles to a thinner size without significantly changing the particle size of the alkaline earth metal-containing particles, unlike pulverization.
  • the alkaline earth metal is extracted to a lower alkaline earth metal concentration by contacting an abrasive medium with the alkaline earth metal-containing particles during agitation.
  • the surface layer (alkaline earth metal-depleted layer) of the particles containing the alkaline earth metal is peeled off to expose the fresh particle surface with higher alkaline earth metal content and/or the alkaline earth metal precipitated on the surface of the alkaline earth metal-containing particles.
  • the alkaline earth metal salt such as alkaline earth metal carbonate
  • the alkaline earth metal salt can be scraped off to re-expose the surface of the alkaline earth metal-containing particles. It is thought that these effects allow alkaline earth metal ions to be efficiently extracted into the liquid phase. Fine particles may be generated due to abrasion of the alkaline earth metal-containing particles during stirring, but the average particle size of the alkaline earth metal-containing particles does not change significantly.
  • alkaline earth metal-containing particles are not particularly limited as long as they contain an alkaline earth metal.
  • "alkaline earth metal” means an element of Group 2 of the periodic table.
  • the alkaline earth metal is preferably at least one selected from the group consisting of Mg, Ca, Sr, and Ba, and more preferably at least one selected from the group consisting of Mg and Ca. It is more preferable to include. Since Mg carbonate has a lower solubility in water than Ca carbonate, it can be easily separated from the liquid phase in the CO 2 fixation described below.
  • the alkaline earth metal-containing particles may be formed by pretreating the alkaline earth metal-containing raw material.
  • the alkaline earth metal-containing raw material may be the materials described for the alkaline earth metal-containing particles, such as Mg-containing ore, Mg-containing slag, Ca-containing slag, coal ash, clinker kiln dust, waste concrete, concrete sludge, or cement. It's fine.
  • pretreatment examples include pulverization and heat treatment.
  • the pulverization can be performed using a known pulverizer. Milling can reduce the average particle size of the alkaline earth metal-containing particles and increase their surface area, or expose the active surface of the alkaline earth metal-containing particles. These can improve the extraction efficiency of alkaline earth metals.
  • the pulverization can be carried out under conditions such that the alkaline earth metal-containing particles have a suitable average particle size as described below. If necessary, after pulverization, the alkaline earth metal may be classified using a sieve or the like.
  • the average particle size of the abrasive medium can be, for example, from 0.3 mm to 20 mm, from 0.5 mm to 15 mm, or from 1 mm to 12 mm.
  • the Mohs hardness of the abrasion medium is not particularly limited as long as it can abrade the surface of the alkaline earth metal-containing particles.
  • the abrasive media has a Mohs hardness of 3 or higher.
  • the Mohs hardness of the abrasion medium is preferably 9 or less.
  • the Mohs hardness of the abrasive medium is preferably 3 or more, or 4 or more and 9 or less.
  • a slurry can be prepared by adding alkaline earth metal-containing particles to an aqueous medium and mixing. By adding an attrition medium to the resulting slurry, a mixture for extracting alkaline earth metals can be obtained.
  • a slurry and a mixture for extracting alkaline earth metals may be prepared simultaneously by mixing together the alkaline earth metal-containing particles, aqueous medium, and attrition medium.
  • the slurry contains no externally added acid other than CO 2 gas.
  • stirring is performed under a pressure atmosphere of at least atmospheric pressure and at most 10 MPaG (gauge pressure), preferably at most 1.0 MPaG (gauge pressure), more preferably at most 0.5 MPaG (gauge pressure).
  • pressure atmosphere of at least atmospheric pressure and at most 10 MPaG (gauge pressure), preferably at most 1.0 MPaG (gauge pressure), more preferably at most 0.5 MPaG (gauge pressure).
  • the higher the CO 2 pressure the more CO 2 will be dissolved in the liquid phase of the mixture and therefore the higher the extraction efficiency of alkaline earth metals.
  • alkaline earth metal ions in alkaline earth metal-containing particles can be efficiently liquefied even under a low pressure atmosphere of 10 MPaG (gauge pressure) or less, particularly atmospheric pressure to 1.0 MPaG (gauge pressure). Can be extracted into phases. By using low pressure conditions, power consumption related to extraction of alkaline earth metal ions can be effectively reduced.
  • stirring is performed under an atmospheric pressure atmosphere.
  • the alkaline earth metal ions extracted into the liquid phase may be present in the form of alkaline earth metal hydroxide, alkaline earth metal silicate or alkaline earth metal silicate double salt.
  • alkaline earth metal hydroxides include Mg(OH) 2 and Ca(OH) 2 produced by hydration of MgO or CaO.
  • alkaline earth metal silicates include Mg 2 SiO 4 (magnesium silicate) and Ca 2 SiO 4 .
  • Examples of the alkaline earth metal silicate double salt include silicates of an alkaline earth metal and an alkali metal, Mn, Fe, Co, Ni, Cu, Zn, or Al, or two or more of these.
  • a typical alkaline earth metal silicate double salt is (Mg,Fe)SiO 4 (mafic silicate).
  • the alkaline earth metal ion is present in the form of an alkaline earth metal silicate or alkaline earth metal silicate double salt.
  • alkaline earth metal hydroxides, alkaline earth metal silicates, or alkaline earth metal silicate double salts are converted into alkaline earth metal carbonates during CO 2 fixation.
  • the CO 2 immobilization method includes alkaline earth metal-containing Extracting the alkaline earth metal ions in the particles into the liquid phase; solid-liquid separation of the mixture in which the alkaline earth metal ions are extracted into the liquid phase to form a liquid phase containing the alkaline earth metal ions. and a solid phase comprising an extraction residue; and precipitating an alkaline earth metal carbonate from the liquid phase to immobilize CO 2 in the alkaline earth metal carbonate.
  • FIG. 1 shows a flow diagram outlining an embodiment of a CO 2 fixation method.
  • a boxed area indicates a process or apparatus.
  • alkaline earth metal-containing particles are obtained by pre-treating the alkaline earth metal-containing raw material as an optional step. After further adding an attrition medium to the slurry obtained by adding an aqueous medium to the alkaline earth metal-containing particles, the alkaline earth metal-containing particles are mixed by stirring the mixture while blowing CO 2 gas into the resulting mixture. The alkaline earth metal ions therein are extracted into the liquid phase. Thereafter, solid-liquid separation yields a liquid phase containing alkaline earth metal ions and a solid phase containing the extraction residue. The alkaline earth metal carbonate is precipitated from the liquid phase, and CO 2 is fixed in the alkaline earth metal carbonate.
  • the CO 2 fixation method of one embodiment further includes pretreating the alkaline earth metal-containing feedstock to form alkaline earth metal-containing particles.
  • the alkaline earth metal-containing raw material and pretreatment are as described in the alkaline earth metal extraction method.
  • an alkaline earth metal carbonate is precipitated from the liquid phase to fix CO2 in the alkaline earth metal carbonate.
  • the solubility of alkaline earth metal carbonates decreases as temperature increases. Therefore, precipitation of alkaline earth metal carbonates can be promoted by increasing the temperature of the liquid phase.
  • the precipitation device a tank equipped with a temperature control mechanism can be used.
  • the precipitation device may further include a solid-liquid separation device for separating the precipitated alkaline earth metal salt.
  • alkaline earth metal-containing particles and valuable metal-containing residue are obtained from the starting material.
  • the pretreatment includes a step of changing the chemical composition or chemical properties of the starting material to enable it to be separated into alkaline earth metal-containing particles and valuable metal-containing residue.
  • steps include, for example, oxidative roasting, sulfating roasting, and salt conversion/solid-liquid separation.
  • Oxidative roasting can be performed using a roasting furnace, for example.
  • An exemplary oxidative torrefaction process includes the following steps. Using fuel such as natural gas, oil, coal, sulfur, or pyrite (Pyrite, FeS 2 ), the oxygen partial pressure is increased by supplying oxygen, air, etc., and the starting material is heated to about 500°C to 700°C. Oxidatively decomposed by heating.
  • the alkaline earth metal is converted to alkaline earth metal oxide and recovered as alkaline earth metal-containing particles.
  • high Mg-containing minerals such as olivine and serpentine are pyrolyzed into MgO and SiO2 by oxidative roasting.
  • the pyrolyzate may also include Fe 2 O 3 , Mg 2 SiO 4 , (Mg,Fe)SiO 4 , or combinations thereof. Valuable metals are also recovered in the form of oxides as valuable metal-containing residues.
  • sulfation After sulfation, after forming a metal sulfide using H 2 S gas etc., or after forming a valuable metal hydroxide by adjusting the pH using an alkali such as Ca(OH) 2 or NaOH, By solid-liquid separation, alkaline earth metal-containing particles and valuable metal-containing residues can be separated.
  • Another exemplary sulfating torrefaction involves sulfating the valuable metal by adding concentrated sulfuric acid to the starting material followed by oxidative torrefaction.
  • the dissolved alkaline earth metals and valuable metals can be converted into valuable metal water by forming metal sulfides using H 2 S gas or by adjusting the pH using an alkali such as Ca(OH) 2 or NaOH. After forming the oxide, the alkaline earth metal-containing particles and the valuable metal-containing residue can be separated by solid-liquid separation.
  • the pretreatment includes oxidative roasting.
  • the mixture of alkaline earth metal oxides and valuable metal oxides obtained by oxidizing and roasting the starting materials can be easily separated by a separation process such as specific gravity separation.
  • the pretreatment may include sulfur dioxide exhaust gas treatment.
  • a general sulfuric acid plant can be used as a sulfur dioxide exhaust gas treatment facility. Concentrated sulfuric acid produced by sulfur dioxide exhaust gas treatment can be effectively utilized as a product or in the methods of the present disclosure for valuable metal recovery, particularly valuable metal recovery using high pressure acid leaching (HPAL) methods.
  • HPAL high pressure acid leaching
  • the pretreatment may further include a separation step.
  • the separation method include specific gravity separation, particle size separation, and chemical composition separation.
  • Specific gravity separation is a method of separating particles by utilizing the difference in specific gravity when the particles have different specific gravity depending on their chemical composition.
  • the specific gravity separation can be performed using, for example, a fluidized specific gravity separation device used in coal preparation technology.
  • Particle size separation utilizes differences in particle size when the concentration of valuable metals in the particles differs depending on the size of the particles, or when valuable metals in minerals exist in the form of fine particles. This method separates these particles.
  • Particle size separation can be performed using, for example, a sieve or a centrifuge.
  • Chemical composition separation is a method of separating particles containing special metals such as uranium by analyzing them online using infrared rays and selectively blowing only those particles away with an air gun. It is.
  • the pretreatment preferably includes separating alkaline earth metal-containing particles and valuable metal-containing residues by differential gravity separation.
  • a specific gravity difference separator for example, if a specific gravity of 4 is set, substances with a small specific gravity such as MgO and SiO 2 are used as alkaline earth metal-containing particles, and specific gravity containing valuable metals such as NiO, CoO, and Fe 2 O 3 are Larger materials can be separated as valuable metal-containing residues.
  • the alkaline earth metal-containing particles obtained by the pretreatment may contain, in addition to the alkaline earth metal, other elements such as silicon, aluminum, or two or more of these.
  • the alkaline earth metals and other elements may be present in the alkaline earth metal-containing particles in the form of oxides, sulfates, silicates, or combinations thereof.
  • the alkaline earth metal- containing particles include MgO, SiO2 and Mg2SiO4 .
  • the valuable metal-containing residue may contain, for example, silicon, aluminum, or two or more elements thereof.
  • the valuable metals may be present in the valuable metal-containing residue in the form of oxides, chlorides, sulfides, or combinations thereof.
  • the valuable metal-containing residue contains at least one member selected from the group consisting of NiO, CoO, and Fe 2 O 3 .
  • CO 2 fixation using alkaline earth metal-containing particles is as described in the CO 2 fixation method.
  • the heat generated in the pretreatment for example the roasting step, as a heat source for heating the liquid phase.
  • CO2 emissions associated with heating can be reduced or eliminated.
  • the generated alkaline earth metal carbonate can be used as an alkaline earth metal carbonate product or as a post-process of HPAL treatment when valuable metal recovery in the method of the present disclosure is performed by high pressure acid leaching (HPAL) method. It can be used as a neutralizing agent for primary neutralization, final neutralization, pH adjustment of tailing dams, etc.
  • HPAL high pressure acid leaching
  • MgCO 3 produced by CO 2 fixation is advantageous to use as a neutralizing agent in the primary neutralization, final neutralization, etc. that are subsequent steps of HPAL treatment.
  • Mg contained in MgCO 3 used as a neutralizing agent is converted into the form of MgSO 4 and exists in the liquid phase of the tailing dam. Since regulations regarding Mg ions being released into the ocean are not strict, tailings dams can be disposed of at low cost.
  • the CO 2 gas regenerated by these neutralizations can also be collected and reused for the above-mentioned CO 2 fixation.
  • the liquid phase separated from the alkaline earth metal carbonate may be used as cooling water for other equipment, or as water or an aqueous solution for slurrying alkaline earth metal-containing particles.
  • valuable metal-containing products In valuable metal recovery, valuable metal-containing products, valuable metal-containing intermediates, or both are recovered from valuable metal-containing residues.
  • valuable metal-containing products include nickel sulfate, cobalt sulfate, cobalt chloride, metallic nickel, and metallic cobalt.
  • valuable metal-containing intermediate examples include nickel sulfide sulfide cobalt sulfide mixed sulfide (MSP) and nickel hydroxide cobalt hydroxide mixture (MHP).
  • MSP nickel sulfide sulfide cobalt sulfide mixed sulfide
  • MHP nickel hydroxide cobalt hydroxide mixture
  • Products containing valuable metals, such as nickel sulfate, cobalt sulfate, and cobalt chloride can be produced by refining valuable metal-containing intermediates.
  • Products containing valuable metals such as metallic nickel and metallic cobalt can be produced by electrolytically refining products containing valuable metals such as
  • the chlorine dissolution method for example, hydrochloric acid is added to a residue containing valuable metals to form an aqueous solution containing valuable metal chlorides, and the valuable metals are recovered in the form of valuable metal chlorides, or the valuable metals are recovered by electrolysis or the like. It involves reducing metal chlorides to recover valuable metals.
  • the ammonia dissolution method involves, for example, adding ammonia to a valuable metal-containing residue and thereby extracting it in the form of a metal complex (eg, a nickel complex), and is also known as the Charon method.
  • the electric furnace melting method for example, residues containing valuable metals are melted using an electric furnace, and C, Si, Mn, Cr, P, etc. are oxidized and removed in a mixed gas flow of argon and oxygen, and valuable metals alone or Including recovering those alloys.
  • FIG. 3 shows an overview of the HPAL process in a flow diagram.
  • a leaching slurry is obtained by adding an acid such as concentrated sulfuric acid to a valuable metal-containing residue in the form of a slurry in a reactor such as an autoclave at high temperature and pressure.
  • the valuable metals contained in the valuable metal-containing residue are ionized by reaction with concentrated sulfuric acid and leached into the liquid phase of the leaching slurry.
  • a neutralizing agent is added to the leaching slurry to adjust the pH to about 1.5.
  • the purpose of this pH adjustment is to precipitate metal ions such as Fe and Al contained in the leaching slurry as oxides in the CCD.
  • the leaching slurry is washed in multiple stages by continuous counter current decantation (CCD), and is separated into solid and liquid into a leaching liquid and a leaching residue.
  • Fe is extracted in the form of hematite (Fe 2 O 3 ) in the leaching residue.
  • the leachate from which Fe, Al, etc. have been separated by CCD contains trace amounts of Cu, Zn, etc., so after adjusting the pH and redox potential of the leachate to separate these elements, the pH of the leachate is adjusted to around 5. Ni and Co are selectively separated by precipitation.
  • final neutralization is carried out to remove these alkaline earth metals until the marine discharge standard values are reached.
  • a neutralizing agent is added to the solution to bring the pH of the solution to about 8.5 to about 9.
  • metal ions such as Mn and Mg contained in the solution are precipitated as oxides.
  • concentrated sulfuric acid produced by the exhaust gas treatment of roasting included in the pretreatment can be used as part or all of the acid for HPAL treatment.
  • alkaline earth metal carbonates produced by CO2 fixation can be used as neutralizing agents for primary neutralization, final neutralization, and/or tailing dam pH adjustment.
  • the CO 2 fixation and valuable metal recovery device of one embodiment includes a pretreatment device that generates alkaline earth metal-containing particles and valuable metal-containing residue from a starting material containing a valuable metal and an alkaline earth metal;
  • the alkaline earth metal ions in the alkaline earth metal-containing particles are removed from the alkaline earth metal-containing particles by stirring the mixture while blowing CO 2 gas into the mixture, which includes a slurry containing alkaline earth metal-containing particles and an aqueous medium, and an abrasion medium.
  • the valuable metal recovery device is an HPAL smelter plant.
  • the method and apparatus of the present disclosure can be suitably used for extraction of alkaline earth metals, fixation of CO 2 gas, and recovery of valuable metals.
  • the particle size distribution of the alkaline earth metal-containing particles of Example 1 measured by laser diffraction scattering before and after stirring are shown in FIGS. 4a and 4b, respectively, in the form of a Rosin-Rammler diagram.
  • the volume average particle size (MV) of the alkaline earth metal-containing particles before stirring was 128.7 ⁇ m
  • the volume average particle size (MV) of the alkaline earth metal-containing particles after stirring was 90.03 ⁇ m.
  • the particle size distribution of the alkaline earth metal-containing particles after stirring was bimodal because of the formation of fine particles upon contact with the abrasive media.

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Abstract

L'invention concerne un procédé d'extraction de métal alcalino-terreux grâce auquel il devient possible d'extraire un métal alcalino-terreux d'un matériau solide contenant le métal alcalino-terreux en une phase liquide avec une efficacité élevée même sous une basse pression et il devient également possible de réduire les coûts requis pour les matériaux de départ, les installations, les opérations et analogues. Le procédé d'extraction de métal alcalino-terreux selon un mode de réalisation comprend l'agitation d'un mélange contenant des particules contenant chacune un métal alcalino-terreux, une suspension comprenant un milieu aqueux et un milieu d'abrasion tout en soufflant du CO2 gazeux dans le mélange, ce qui permet d'extraire des ions du métal alcalino-terreux dans les particules contenant le métal alcalino-terreux en une phase liquide.
PCT/JP2022/020434 2022-05-16 2022-05-16 Procédé d'extraction de métal alcalino-terreux, procédé de fixation de co2, et procédé de fixation de co2 pour récupérer un métal de valeur WO2023223399A1 (fr)

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PCT/JP2022/020434 WO2023223399A1 (fr) 2022-05-16 2022-05-16 Procédé d'extraction de métal alcalino-terreux, procédé de fixation de co2, et procédé de fixation de co2 pour récupérer un métal de valeur
AU2022459285A AU2022459285A1 (en) 2022-05-16 2022-05-16 Alkaline earth metal extraction method, co2 fixation method, and method for fixing co2 to recover valuable metal

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JPS5373498A (en) * 1976-12-13 1978-06-29 Shiraishi Kogyo Kaisha Ltd Method of producing belllshaped calicium carbonate having diameters of 0*1 to 1*0 micrometer
US4629130A (en) * 1983-11-02 1986-12-16 A/S Niro Atomizer Process for producing finely divided limestone
CN1539774A (zh) * 2003-10-31 2004-10-27 清华大学 一种从菱镁矿煅烧轻烧粉制备纳米氧化镁的方法
US20050180910A1 (en) * 2003-12-31 2005-08-18 Ah-Hyung Park Carbon dioxide sequestration using alkaline earth metal-bearing minerals
CN101648721A (zh) * 2009-08-31 2010-02-17 吉林大学 制备纳米氧化镁和活性轻质碳酸钙的方法
CN107986312A (zh) * 2017-12-04 2018-05-04 青州宇信钙业股份有限公司 一种高比表面积沉淀碳酸钙的制备方法
JP2018115366A (ja) * 2017-01-18 2018-07-26 日新製鋼株式会社 製鋼スラグからカルシウムを溶出させる方法、および製鋼スラグからカルシウムを回収する方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5373498A (en) * 1976-12-13 1978-06-29 Shiraishi Kogyo Kaisha Ltd Method of producing belllshaped calicium carbonate having diameters of 0*1 to 1*0 micrometer
US4629130A (en) * 1983-11-02 1986-12-16 A/S Niro Atomizer Process for producing finely divided limestone
CN1539774A (zh) * 2003-10-31 2004-10-27 清华大学 一种从菱镁矿煅烧轻烧粉制备纳米氧化镁的方法
US20050180910A1 (en) * 2003-12-31 2005-08-18 Ah-Hyung Park Carbon dioxide sequestration using alkaline earth metal-bearing minerals
CN101648721A (zh) * 2009-08-31 2010-02-17 吉林大学 制备纳米氧化镁和活性轻质碳酸钙的方法
JP2018115366A (ja) * 2017-01-18 2018-07-26 日新製鋼株式会社 製鋼スラグからカルシウムを溶出させる方法、および製鋼スラグからカルシウムを回収する方法
CN107986312A (zh) * 2017-12-04 2018-05-04 青州宇信钙业股份有限公司 一种高比表面积沉淀碳酸钙的制备方法

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