WO2020203937A1 - Procédé de récupération de métaux de valeur - Google Patents

Procédé de récupération de métaux de valeur Download PDF

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Publication number
WO2020203937A1
WO2020203937A1 PCT/JP2020/014401 JP2020014401W WO2020203937A1 WO 2020203937 A1 WO2020203937 A1 WO 2020203937A1 JP 2020014401 W JP2020014401 W JP 2020014401W WO 2020203937 A1 WO2020203937 A1 WO 2020203937A1
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Prior art keywords
mixture
metal
reducing agent
valuable
recovering
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PCT/JP2020/014401
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English (en)
Japanese (ja)
Inventor
昌麟 王
健太郎 浦田
卓 對馬
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株式会社神戸製鋼所
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Priority claimed from JP2019071320A external-priority patent/JP7103293B2/ja
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to CN202080009023.2A priority Critical patent/CN113302005B/zh
Publication of WO2020203937A1 publication Critical patent/WO2020203937A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a technique for recovering a valuable metal such as Co or Ni from an oxide containing Al 2 O 3 or CoO X or NiO X.
  • rare metals such as Co and Ni are used for secondary batteries such as LIB and Ni-MH.
  • LIB lithium-ion rechargeable battery
  • problems such as ubiquitous resources worldwide, and the risk of resource depletion has been pointed out.
  • cobalt and nickel which are indispensable for the production of LIB (lithium-ion rechargeable battery) have problems such as ubiquitous resources worldwide, and the risk of resource depletion has been pointed out.
  • cobalt unfair labor conditions at mines have been reported, and mining alone may not be sufficient to meet the demand.
  • Patent Document 1 describes a method for recovering valuable metals from metal oxides containing alkali metals, which efficiently recovers valuable metals from metal oxides containing alkali metals generated in the process of manufacturing a secondary battery. There is.
  • a reducing agent and a slag-forming agent are added to a metal oxide containing an alkali metal generated in the manufacturing process of a secondary battery, and the valuable metal is reduced and settled. Is to be collected.
  • Patent Document 2 describes a method for easily recovering valuable metals from a used lithium secondary battery in good yield.
  • the method for recovering valuable metals in Patent Document 2 described above includes a step of roasting a used lithium secondary battery to obtain a roasted product, a step of crushing the roasted product to obtain a crushed product, and a step of sieving the crushed product.
  • Patent Document 3 describes a method capable of improving the recovery rate of valuable metals such as cobalt and reducing the recovery cost when a waste battery such as a lithium ion battery is dry-treated.
  • the method for recovering the valuable metal of Patent Document 3 described above is a pre-oxidation step ST20 in which a waste battery containing aluminum and iron is roasted to perform a pre-oxidation treatment, and a melted product obtained by melting the waste battery after the pre-oxidation step ST20.
  • the first slag separation step ST22 for separating and recovering the first slag containing aluminum oxide from the melt, and the first alloy which is the melt after the first slag separation step.
  • Iron is passed through a second slag separation step ST23, which performs an oxidation treatment, and a second slag separation step ST24, which separates and recovers a second slag containing iron from the first alloy after the second oxidation step ST23.
  • the second slag is reused as a flux added to promote the second and subsequent melting steps ST21b. ing.
  • Patent Document 4 describes a recycling method for recovering a metal from a lithium ion battery.
  • the recycling method of Patent Document 4 described above is a method of recovering cobalt from a lithium ion battery containing aluminum and carbon, and includes a step of preparing a bath furnace provided with a means for injecting O 2 and a slag forming agent.
  • the method includes a step of collecting the slag in the phase and a step of separating the slag from the metal phase by boiling water, and the method is expressed in terms of mass% of the metallurgical charge raw material: 153 mass% -3.5 ( Al% + 0.6C%) Self-generated conditions by supplying a fraction of a lithium-ion battery equal to or greater than [Al% and C% represent the mass% of aluminum and carbon in the battery]. It is characterized by being operated with.
  • Patent Document 5 describes a separation step in which a waste secondary battery is physically separated and separated into a separated negative electrode material and a separated positive electrode material, and a valuable metal from the positive electrode material or the separated negative electrode material separated by the separation step.
  • a valuable metal recovery system for recovering valuable metals from a waste secondary battery is described, including a step of recovering the precious metals.
  • the valuable metal recovery system of Patent Document 5 described above includes a separation step of physically separating a waste secondary battery and separating it into a separated negative electrode material and a separated positive electrode material, and a positive electrode material or separation separated by the separation step. It includes a step of recovering valuable metal from the negative electrode material.
  • Patent Document 6 describes a method for reducing the sulfur content generated in the step of recovering the valuable metal contained in the waste battery.
  • the method of Patent Document 6 described above is a method of recovering the valuable metal from a waste battery or process waste containing at least one valuable metal of cobalt or nickel, and (1) pre-roasting treatment, crushing treatment and sieving.
  • a primary concentration step of obtaining a primary concentrate of the valuable metal through a division treatment (2) a secondary concentration step of dissolving the primary concentrate with sulfuric acid and obtaining the solution as a secondary concentrate.
  • Japanese Unexamined Patent Publication No. 2000-226619 Japanese Patent Application Laid-Open No. 10-158751 Japanese Unexamined Patent Publication No. 2012-224877 Special Table 2013-5006048 International Publication No. 2000-025382 Japanese Unexamined Patent Publication No. 2016-037661
  • Patent Document 1 is a technique of recovering a valuable metal as an alloy from a raw material of an oxide containing Li, Mn, Co, Ni, and Fe generated in the manufacturing process of a secondary battery.
  • the raw material does not contain Al in the first place, and cannot be applied when the alloy is recovered from an oxide containing Al. That is, when Al (Al 2 O 3 ) is contained in the raw material, the raw material has a high melting point, so that it cannot be melted and it may be difficult to recover the valuable metal as an alloy. ..
  • Patent Document 3 does not describe the reducing agent ratio required to obtain granular metallic iron.
  • Patent Document 4 As in the case of Patent Document 2, an appropriate reducing agent ratio is not written, and the amount of SiO 2 and CaO added is large, and SiO 2 / Al 2 O 3 and CaO / The value of Al 2 O 3 is high. Therefore, the productivity is low and the cost may be reduced, and the alloy recovery when a large amount of Al 2 O 3 is contained is not included.
  • Patent Document 5 does not contain Al 2 O 3 in the raw material, and cannot be applied when the alloy is recovered from the oxide containing Al.
  • Patent Document 6 is a method of reducing the residue obtained by removing Cu and C from under the sieve after incineration, crushing and sieving with C (coke) or Al, but 100% coke is used as a reducing agent.
  • Patent Documents 1 to 6 are for recovering valuable metals by reducing the recovered material of the secondary battery while melting it, and adding flux to melt the recovered product. It has become.
  • the recovered product is slag containing Al 2 O 3
  • even when flux is added for melting if the amount of flux added is too large, Co and Ni to be recovered in the mixture The amount is reduced and the productivity is directly deteriorated. Therefore, although it is possible to recover the alloys of Co and Ni, there is a concern that the productivity will be deteriorated, the cost will be reduced, and the advantage of relatively low cost, which is a characteristic of pyrometallurgy, will be erased.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for recovering valuable metals such as Co and Ni from a recovered product containing Al 2 O 3 at low cost and efficiently. And.
  • the method for recovering valuable metals of the present invention takes the following technical measures. That is, in the method for recovering valuable metals of the present invention, a recovered product containing valuable metals is obtained by subjecting a used secondary battery to treatments of heating, crushing, sieving, and magnetic separation, and the obtained recovered product is obtained. By mixing the product with a reducing agent and heating it, the valuable metal in the mixture is metallized by reduction and melted to separate the metal and oxide from the mixture, and after cooling, the metal is sorted from the oxide. In the method for recovering the valuable metal to be recovered, the heating temperature of the mixture is set to 1400 ° C.
  • the amount of oxygen compounded with the valuable metal in the mixture is O [mol. / Kg], where the reducing agent content of the reducing agent contained in the mixture is R [mol / kg], 0 ⁇ O / R ⁇ 0.97 is established, and the reducing agent is contained in the mixture.
  • a reducing agent is mixed with the recovered material so that the ratios x and y of the concentrations [wt%] of Al 2 O 3 , SiO 2 , and CaO satisfy the following formulas (1) to (4), and the valuable metal. It is characterized by collecting.
  • Another method for recovering the valuable metal of the present invention was obtained by subjecting a used secondary battery to a treatment of heating, crushing, sieving, and magnetic separation to obtain a recovered product containing the valuable metal.
  • a recovered product containing the valuable metal.
  • the valuable metal in the mixture is metallized by reduction and melted to separate the metal and oxide from the mixture, and after cooling, the metal is separated from the oxide.
  • the amount of oxygen compounded with the valuable metal in the mixed product is O [mol / kg], which is contained in the mixed product.
  • the reducing agent content of the reducing agent is R [mol / kg]
  • 0 ⁇ O / R ⁇ 0.97 is established, and the SiO 2 of SiO 2 with respect to Al 2 O 3 contained in the mixture is satisfied.
  • a reducing agent is mixed with the recovered product so that the ratio x of the concentration [wt%] and the ratio y of the concentration [wt%] of CaO to Al 2 O 3 satisfy the following formulas (1) to (4).
  • the heating temperature for heating the mixture is T [° C.] and the time for heating the mixture is t [min]
  • the following formula It is characterized in that the recovered product is heated so that 5) is established.
  • the reducing agent one having a particle size of 75 ⁇ m or less and having an integrated volume adjusted to 65% or more is used.
  • valuable metals such as Co and Ni can be recovered inexpensively and efficiently from the recovered product containing Al 2 O 3 .
  • the method for recovering valuable metals in the present embodiment is to recover valuable metals from the recovered material of a used secondary battery in the state of a single metal or an alloy by utilizing a reduction reaction. ..
  • the recovery method of the present embodiment targets a recovery product containing a valuable metal obtained by subjecting a used secondary battery to a treatment of heating, crushing, sieving, and magnetic separation. Then, by mixing the recovered product to be recovered with a reducing agent and heating it, the valuable metal in the mixture is metallized by reduction and melted to separate the metal and the oxide from the mixture, and the metal after cooling. Is selected from oxides and recovered.
  • the amount of oxygen compounded with the valuable metal in the mixture is O [mol / kg], and the reducing agent of the reducing agent contained in the mixture is used.
  • the content is R [mol / kg]
  • 0 ⁇ O / R ⁇ 0.97 is established, and the concentrations of Al 2 O 3 , SiO 2 , and Ca O contained in the mixture [wt%].
  • a reducing agent is mixed with the recovered product so that the ratios x and y of the above satisfy the above formulas (1) to (4).
  • the heating temperature of the mixture is 1400 ° C.
  • the heating temperature for heating the mixture is T [° C.] and the time for heating the mixture is t [min], the above formula (5) ) Is established, and the valuable metal is recovered by heating the mixture.
  • the heating temperature T is preferably 1400 ° C. or higher.
  • the recovered product which is the target of the recovery method described above, is obtained by heating, crushing, sieving, or the like a used secondary battery containing a valuable metal such as nickel and cobalt. That is, in the secondary battery, lithium cobalt oxide, lithium nickel oxide, or the like may be used as the positive electrode material, and valuable metals such as Li, Mn, Co, and Ni are contained. Further, since a metal such as copper may be used for the secondary battery, the used secondary battery is appropriately heated, crushed, sieved, etc., and Li, Mn, Co, Ni, etc. To prepare a recovered product in which the valuable metal of the above is easily recovered.
  • the recovered material is first heated to burn a combustible material such as a synthetic resin contained in a secondary battery as a separator or the like.
  • a combustible material such as a synthetic resin contained in a secondary battery as a separator or the like.
  • metals such as Li, Mn, Co, Ni, Fe, and Cu remain in the state of oxides or metals, so that valuable metals can be easily recovered.
  • oxides or metals such as Li, Mn, Co, Ni, Fe, and Cu may be in large lumps, the particle size is appropriately crushed or sorted so as to easily react with the reducing agent described later. It also needs to be adjusted.
  • the non-magnetized metals can be removed as oxides and dust of metals that are not valuable metals by performing appropriate magnetic selection. It is also possible to improve the recovery efficiency of valuable metals.
  • the reducing agent is mixed with the recovered product for the purpose of removing oxygen bound to valuable metals in the oxide by oxidizing itself.
  • the reducing agent is formed in the form of particles (powder) having a small diameter, and is uniformly mixed with the recovered product formed in the form of particles (powder) having a small diameter, and then heated to a desired temperature. As a result, a reduction reaction is caused. When the reduction reaction occurs, the oxide of the valuable metal contained in the recovered product reacts with the reducing agent, and the oxide of the valuable metal is reduced to a single metal or alloy.
  • reducing agents can be used as the reducing agent of the present invention, and for example, coal such as bituminous coal and carbon-based reducing agent (carbon material reducing agent) such as charcoal and bamboo charcoal can be preferably used. .. Since the reaction product of the reduction reaction of the carbon-based reducing agent is carbon dioxide or carbon monoxide, the reaction product can be easily removed from the recovered product, and the valuable metal can be easily recovered as a single metal or alloy. This is to become.
  • the ratio (O / R) When the above-mentioned ratio (O / R) is too high, the amount of the reducing agent is small with respect to the amount of oxygen combined with the valuable metal to be reduced, so that the reduction is insufficient and the oxygen combined with the valuable metal can be sufficiently reduced. It disappears. Therefore, all the valuable metals such as nickel and cobalt cannot be metallized, and the recovery efficiency of the valuable metals is lowered. If the ratio (O / R) is too low, valuable metals such as nickel and cobalt are sufficiently metallized, but the reducing agent is excessive with respect to the amount of oxygen, so that the reducing agent remains even after the reaction. It ends up.
  • the ratio (O / R) described above is preferably 0 ⁇ O / R ⁇ 0.97, preferably 0.46 ⁇ O / R ⁇ 0.97, and more preferably 0.53 ⁇ . It is preferable that O / R ⁇ 0.97.
  • the heating temperature In order to melt the above-mentioned mixture, it is preferable to first maintain the heating temperature at 1400 ° C. or higher. If the heating temperature is maintained at 1400 ° C. or higher, the elemental metal or the valuable metal of the alloy produced by the reduction reaction can be sufficiently melted, and the valuable metal melted after cooling can be agglomerated and separated from the oxide. It will be easy.
  • the composition of the recovered product is also important in order to bring the above-mentioned reduced mixture into a molten state.
  • the above-mentioned recovered product contains oxides such as Al 2 O 3 , SiO 2 , and CaO, and if Al 2 O 3 is present among them, the mixture may be melted. It will be difficult. Therefore, in the method for recovering valuable metals of the present invention, the Al 2 O 3 concentration [wt%], the SiO 2 concentration [wt%], and the Ca O concentration [wt%] in the mixture are the following formulas (1) to (4). ), The composition of the recovered product or mixture is adjusted.
  • valuable metals such as Co and Ni can be recovered inexpensively and efficiently from the recovered product containing Al 2 O 3 .
  • the heating temperature to 1400 ° C. or higher and melting the mixture
  • recovery of valuable metals after cooling becomes cheaper and more efficient than before, but if there is a method for further increasing the recovery rate, that is, the yield.
  • the mixture when the mixture is reduced in a state where the amount of the reducing agent such as graphite is too large (the state where the O / R is very small) with respect to the amount of oxygen in the oxide such as cobalt, the cobalt and the like are reduced and metallized.
  • the amount of the reducing agent since the amount of the reducing agent is originally larger than the amount of oxygen, the reducing agent not used in the reaction remains in the recovered product. If graphite or the like, which is a reducing agent, is present in the recovered product, the aggregation of metals is inhibited, so that the residual reducing agent inhibits the aggregation of metals.
  • the recovered product is recovered in a state of containing extremely fine metal having a particle size of several tens of ⁇ m or less.
  • a particle size of 1 mm or less is difficult to separate at the time of magnetic separation and cannot be recovered with good magnetic selection efficiency, so that the metal can be recovered.
  • the rate drops significantly. Therefore, in the method for recovering valuable metals of the present invention, the agglomeration of the metal is further promoted, and the metal is recovered after growing into particles having a particle size of more than 1 mm.
  • the higher the heating temperature and the longer the heating time the more the metal aggregates. Therefore, in the present invention, when the heating temperature is T [° C.] and the heating time is t [min], the valuable metal is further increased by heating so that the relationship of the above formula (5) is established. It was made possible to collect by yield.
  • Examples and Comparative Examples a waste battery of a lithium ion battery (LIB) is incinerated, crushed, and sieved, and the material separated under the sieve is used as a recovered product to recover valuable metals and a recovery rate. Is calculated. More specifically, Examples and Comparative Examples were carried out according to Experiments 1 to 3 below.
  • LIB lithium ion battery
  • the mixture is heated to any of the predetermined heating temperatures (1300 ° C., 1350 ° C., 1375 ° C., 1400 ° C.), and the temperature is raised at a heating rate of about 100 ° C./min to determine the predetermined heating. After reaching the temperature, the inside of the crucible was kept in a heated state for 6 minutes at a predetermined heating temperature.
  • the yield (recovery rate) of recovery was calculated for valuable metals of 1 mm or more obtained from the mixture after heating. Specifically, this recovery rate is obtained by dividing the "total weight of the recovered valuable metal" by the "total weight of Co, Ni, Mn, Cu, and Fe contained in the mixture from the beginning". It is a ratio, which is the calculated ratio expressed as a percentage.
  • the reaction product obtained from the heated mixture is pulverized and then subjected to magnetic separation.
  • the reaction products selected on the magnetized side in this magnetic selection are sieved with a mesh size of 1 mm, and the weight of the reaction products remaining on the sieve is weighed to obtain the above-mentioned “total recovered valuable metals”. "Weight" can be calculated.
  • recovery was performed by magnetic separation, but the recovery method is not limited to magnetic selection, and other general recovery techniques can be adopted.
  • the total weight of Co, Ni, Mn, Cu, and Fe contained in the mixture from the beginning is obtained, in principle, all the raw materials of the mixture are analyzed for the mixture before heating. That is, when the mixture is composed of a recovered product and a reducing agent, each of the recovered product and the reducing agent is analyzed by ICP (inductively coupled plasma emission spectrometry). In addition, when the mixture contains flux in addition to the recovered product and the reducing agent, or when a plurality of types of recovered products are mixed and used, ICP analysis is also performed on the flux, and ICP analysis is performed on all recovered products. Or do.
  • the calculated weight concentrations of Co, Ni, Mn, Cu, and Fe in the mixture are multiplied by the weight of the mixture charged into the pit, and the Co, Ni, Mn, Cu, contained in the mixture in the pit are multiplied. And Fe were calculated, and the sum of the calculated weights was calculated as the "total weight of recovered valuable metals".
  • the “total weight of Co, Ni, Mn, Cu, and Fe contained in the mixture from the beginning” obtained in this way minus the above-mentioned "total weight of the recovered valuable metal”.
  • the percentage is the recovery rate (yield).
  • Table 1 shows the experimental results related to Experiment 1.
  • the amount of oxygen compounded with the valuable metal in the mixture is O [mol / kg], and the reducing agent content of the reducing agent contained in the mixture is R.
  • the recovery rate is evaluated as “ ⁇ ” or “ ⁇ ”, and the O / R value is larger than 1.03. In that case, it can be seen that the evaluation of the recovery rate is “x”.
  • the "Temperature” column in Table 1 when the heating temperature is 1400 ° C, the evaluation of the recovery rate is " ⁇ " or " ⁇ ”, and when the heating temperature is 1300 ° C, 1350 ° C, or 1375 ° C. It can be seen that the evaluation of the recovery rate is "x”.
  • Table 2 shows the experimental results related to Experiment 2.
  • the concentration of Al 2 O 3 in the mixture is 16.0 wt% to 17.3 wt%
  • the concentration of SiO 2 is 2.0 wt% to 6.3 wt%
  • the concentration of Ca O is 0.5 wt% to 2 It is about the composition of .6 wt%.
  • the concentration of Al 2 O 3 in the mixture is 16.7 wt% to 17.7 wt%
  • the concentration of SiO 2 is 0.6 wt% to 3.4 wt%
  • the concentration of Ca O is 0.5 wt%. It is about a composition of about 3.7 wt%.
  • the evaluation of the recovery rate is ⁇ or ⁇ in the gray shaded portion in the figure.
  • This shaded portion is composed of four boundary lines (I) to (IV).
  • S / A (SiO 2 / Al 2 O 3 ) and C / A (CaO / Al 2 O 3 ) are defined for the following reasons. That is, the used secondary batteries, Co to become a metal is reduced, in addition to Ni, Al 2 O 3 as a component to become slag as oxide, MnO X, Li, are included F, etc., recovered material Has a complex composition.
  • metals such as Co and Ni for recovery from the recovered material, it is necessary to put both the metal and the oxide in a molten state.
  • the heating temperature is T [° C.] and the heating time is t [min]
  • the valuable metal is increased by heating so that the relationship of the formula (5) is established. It is possible to collect by yield.
  • the applicant confirms that the relational expression of the equation (5) is empirically derived and satisfies the actual data.
  • the relationship of the above-mentioned formula (5) (relationship between the heating temperature T [° C.] and the heating time t [min]) is derived from the result of Experiment 3.

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Abstract

Le but de la présente invention est de récupérer de manière peu coûteuse et efficace des métaux de valeur tels que Co ou Ni à partir d'un produit de récupération contenant Al2O3, CoOX ou NiOX.　Dans un procédé de récupération de métaux de valeur selon la présente invention, des batteries secondaires usagées sont soumises à un chauffage, une pulvérisation, un tamisage et une séparation magnétique pour obtenir un produit de récupération contenant des métaux de valeur, et un mélange du produit de récupération obtenu et d'un agent réducteur est chauffé pour réduire les métaux de valeur dans le mélange dans un état de métal fondu, ce qui permet de séparer le mélange en métaux et en oxydes. Lors de la séparation et de la récupération des métaux à partir des oxydes après refroidissement, la température de chauffage du mélange est fixée à 1400 °C ou plus. Lorsque l'agent réducteur est mélangé avec le produit de récupération, l'agent réducteur est mélangé avec le produit de récupération de telle sorte que 0<O/R≤0,97 est satisfait (où, O [mol/kg] est la quantité d'oxygène liée chimiquement à des métaux de valeur dans le mélange, et R [mol/kg] est la quantité de l'agent réducteur contenu dans le mélange), et de telle sorte que x et y, qui sont les rapports des concentrations [% en poids] de Al2O3, SiO2 et CaO contenus dans le mélange, satisfont la relation souhaitée.
PCT/JP2020/014401 2019-04-03 2020-03-27 Procédé de récupération de métaux de valeur WO2020203937A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202080009023.2A CN113302005B (zh) 2019-04-03 2020-03-27 有价金属的回收方法

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Application Number Priority Date Filing Date Title
JP2019071320A JP7103293B2 (ja) 2019-04-03 2019-04-03 有価金属の回収方法
JP2019-071320 2019-04-03
JP2019-225023 2019-12-13
JP2019225023 2019-12-13

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WO2020203937A1 true WO2020203937A1 (fr) 2020-10-08

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