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WO2023048196A1 - Procédé de traitement de chlore gazeux - Google Patents

Procédé de traitement de chlore gazeux Download PDF

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Publication number
WO2023048196A1
WO2023048196A1 PCT/JP2022/035235 JP2022035235W WO2023048196A1 WO 2023048196 A1 WO2023048196 A1 WO 2023048196A1 JP 2022035235 W JP2022035235 W JP 2022035235W WO 2023048196 A1 WO2023048196 A1 WO 2023048196A1
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WIPO (PCT)
Prior art keywords
chlorine gas
hydrochloric acid
aqueous solution
ferrous chloride
chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/035235
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English (en)
Japanese (ja)
Inventor
慶太 山田
幸雄 佐久間
太郎 平岡
順 中澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asaka Riken Co Ltd
Original Assignee
Asaka Riken Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asaka Riken Co Ltd filed Critical Asaka Riken Co Ltd
Priority to JP2023523065A priority Critical patent/JP7498991B2/ja
Publication of WO2023048196A1 publication Critical patent/WO2023048196A1/fr
Priority to JP2024029857A priority patent/JP2024055948A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01D53/68—Halogens or halogen compounds
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • 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
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a chlorine gas treatment method.
  • the waste lithium ion battery is heat-treated (roasted) or pulverized and classified without heat treatment.
  • Powder containing a valuable metal (hereinafter referred to as battery powder) is dissolved in hydrochloric acid, and the resulting leached solution is subjected to solvent extraction (for example, Patent Documents 1 and 2). reference).
  • the present invention provides a chlorine gas treatment method that eliminates such inconveniences and that can detoxify or effectively utilize the chlorine gas generated when the battery powder is dissolved in hydrochloric acid and the valuable metal is leached with hydrochloric acid. for the purpose.
  • the present inventors have conducted repeated studies, dissolving a powder containing a valuable metal obtained from a waste lithium ion battery in hydrochloric acid, and using chlorine gas generated when the valuable metal is leached with hydrochloric acid as a reducing agent. It has been found that by reacting with at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, it can be detoxified or effectively utilized.
  • the present invention has been completed based on these findings.
  • the chlorine gas treatment method of the present invention dissolves powder containing valuable metals obtained from waste lithium ion batteries in hydrochloric acid, and removes chlorine generated when the valuable metals are leached out with hydrochloric acid.
  • a gas treatment method characterized by comprising a step of reacting the chlorine gas with at least one selected from the group consisting of reducing agents, alkali metal hydroxides, and alkaline earth metal hydroxides.
  • powder containing a valuable metal obtained from a waste lithium-ion battery is dissolved in hydrochloric acid, and the chlorine gas generated when the valuable metal is leached out with hydrochloric acid is treated as a reducing agent and alkali metal water. It can be rendered harmless or effectively utilized by reacting with at least one selected from the group consisting of oxides and alkaline earth metal hydroxides.
  • powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid, and the chlorine gas generated when the valuable metals are leached out with hydrochloric acid is treated with the first chloride.
  • Absorbing in an aqueous solution of ferrous chloride to produce a second aqueous solution of ferrous chloride containing ferric chloride having an increased concentration of ferric chloride relative to the first aqueous solution of ferrous chloride include.
  • the concentration of ferric chloride in the ferrous chloride aqueous solution is the ratio of ferric chloride to the total number of moles of ferrous chloride and ferric chloride contained in the ferrous chloride aqueous solution. means.
  • ferric chloride aqueous solution since the second ferrous chloride aqueous solution has a higher concentration of ferric chloride than the first ferrous chloride aqueous solution, it is hereinafter referred to as ferric chloride aqueous solution for convenience. I have something to do. Since the chlorine gas is fixed as ferric chloride by the above step, the chlorine gas can be rendered harmless.
  • the second aqueous ferrous chloride solution containing the ferric chloride is preferably produced by allowing the chlorine gas to be absorbed in the first aqueous ferrous chloride solution. is brought into contact with iron to reduce at least a portion of the ferric chloride contained in the second aqueous ferrous chloride solution, and the concentration of ferric chloride with respect to the second aqueous ferrous chloride solution is Further comprising producing a third ferrous chloride aqueous solution containing reduced ferric chloride.
  • the second ferrous chloride aqueous solution containing the ferric chloride is brought into contact with iron, so that at least part of the ferric chloride contained is reduced to become ferrous chloride, and the second chloride
  • a third aqueous solution of ferrous chloride containing ferric chloride having a reduced concentration of ferric chloride relative to the aqueous solution of ferrous chloride can be obtained.
  • the chlorine gas is effectively used. can.
  • the chlorine gas is purified before the step of reacting the chlorine gas with the hydrogen gas to generate the hydrogen chloride, and the oxygen contained in the chlorine gas is removed. Further comprising the step of removing.
  • oxygen contained in the chlorine gas By removing oxygen contained in the chlorine gas before the step of generating hydrogen chloride, hydrogen can be prevented from being consumed by oxygen when reacting the chlorine gas with the hydrogen gas.
  • At least part of the second hydrochloric acid is preferably used as the first hydrochloric acid for leaching the valuable metal.
  • chlorine gas is brought into contact with an alkaline absorbing liquid containing at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and hypochlorous acid It includes a hypochlorite generation step for generating salt.
  • the chlorine gas treatment method of the present invention including the hypochlorite generation step preferably further includes a hypochlorite reduction step of reacting hypochlorite with carbon or aluminum.
  • the chlorine gas treatment method of the present invention includes a carbon dioxide generation step of reacting chlorine gas with carbon and water to generate carbon dioxide.
  • the chlorine gas treatment method of the present invention includes an aluminum chloride production step of reacting chlorine gas with aluminum to produce aluminum chloride.
  • FIG. 1 is a flow chart showing a chlorine gas treatment method according to one embodiment of the present invention.
  • FIG. 1 is a system configuration diagram showing an example of an apparatus configuration used in a method for treating chlorine gas according to one embodiment of the present invention
  • 1 is a flow chart showing a chlorine gas treatment method according to one embodiment of the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a system configuration diagram showing an example of an apparatus configuration used in a method for treating chlorine gas according to one embodiment of the present invention;
  • the chlorine gas treatment method of the present invention dissolves powder containing valuable metals (battery powder) obtained from waste lithium ion batteries in hydrochloric acid, and is used to treat chlorine gas generated when the valuable metals are leached out with hydrochloric acid. can be used.
  • the waste lithium ion battery includes a used lithium ion battery whose life as a battery product has been exhausted, a lithium ion battery discarded as a defective product in the manufacturing process, and a It means the residual positive electrode material and the like used for commercialization.
  • the powder containing the valuable metal can be obtained, for example, as follows. First, the positive electrode foil (a current collector coated with a positive electrode mixture containing a positive electrode active material), which is the remaining positive electrode material used for commercialization in the manufacturing process of a lithium-ion battery, is placed in an electric furnace. Medium, for example, after heat treatment (roasting) at a temperature in the range of 100 to 450 ° C., or without heat treatment and pulverized with a crusher such as a hammer mill or jaw crusher, the casing constituting the waste lithium ion battery
  • the battery powder can be obtained as a powder containing a valuable metal by removing (classifying) the current collector and the like by sieving.
  • the waste lithium ion battery after discharge treatment or without heat treatment is pulverized with the pulverizer, the housing, current collector, etc. are removed by sieving, and then heat treatment is performed at a temperature in the above range to obtain the above Battery powder may be obtained.
  • the battery powder is leached with hydrochloric acid.
  • a leaching solution of the various valuable metals is obtained.
  • the chlorine gas treatment method of the present invention includes a step of reacting the chlorine gas with a reducing agent.
  • the reaction between chlorine gas and the reducing agent will be described in more detail below.
  • the waste lithium ion battery is pretreated in STEP 1 to obtain battery powder in STEP 2.
  • the battery powder is dissolved in hydrochloric acid, and the valuable metal is leached out with hydrochloric acid.
  • a leaching solution which is a hydrochloric acid solution of the valuable metal, can be obtained.
  • manganese, cobalt and nickel among the valuable metals are sequentially solvent-extracted.
  • an aqueous lithium salt solution can be obtained as an extraction residue.
  • Lithium carbonate can be obtained by reacting the lithium salt aqueous solution with carbon dioxide gas or a carbonate compound.
  • the method for treating chlorine gas of the first embodiment is a method for treating chlorine gas generated in STEP 7, and can be carried out, for example, by the chlorine gas treatment apparatus 1 shown in FIG.
  • the chlorine gas treatment device 1 includes a hydrochloric acid leaching tank 2 for dissolving battery powder obtained from waste lithium-ion batteries in hydrochloric acid, leaching valuable metals contained in the battery powder with hydrochloric acid, and chlorine generated in the hydrochloric acid leaching tank 2.
  • the gas is absorbed into the first ferrous chloride aqueous solution (hereinafter sometimes referred to as ferrous chloride aqueous solution for convenience) to produce a second ferrous chloride aqueous solution containing ferric chloride.
  • a reduction reactor 4 for reducing at least a portion of the ferrous chloride to ferrous chloride is provided.
  • the second ferrous chloride aqueous solution is produced by the first ferrous chloride aqueous solution absorbing chlorine gas in the reaction tower 3, and as a result, the first ferrous chloride aqueous solution has a ferrous chloride Since the concentration of ferric acid is increased, hereinafter, it may be referred to as an aqueous solution of ferric chloride for convenience.
  • ferrous chloride aqueous solution A third ferrous chloride aqueous solution containing ferric chloride (hereinafter, for convenience, may be referred to as a ferrous chloride aqueous solution) with a reduced concentration of ferric chloride is produced. .
  • the hydrochloric acid leaching tank 2 is provided with a hydrochloric acid supply conduit 21 for supplying hydrochloric acid, a battery powder supply means 22 for supplying battery powder, and a dilution air supply conduit 23 for supplying dilution air at the top.
  • a leachate extraction conduit 25 for extracting a leachate 24 obtained by leaching valuable metals with hydrochloric acid is provided at the bottom.
  • the hydrochloric acid leaching tank 2 is provided with a chlorine gas extraction conduit 26 in the upper part for extracting chlorine gas generated by the leaching reaction when the valuable metal is leached with hydrochloric acid, and the chlorine gas extraction conduit 26 is connected to the reaction tower 3.
  • a ferrous chloride aqueous solution 31 (first ferrous chloride aqueous solution) is stored in the bottom of the reaction tower 3, while a filler layer 32 filled with a filler is formed above the ferrous chloride aqueous solution 31. It is The reaction tower 3 is also provided with a circulation conduit 33 for taking out the ferrous chloride aqueous solution 31 stored at the bottom and supplying it from above the packing layer 32 .
  • the circulation conduit 33 has a first pump 34 in the middle and a first switching valve 35 downstream of the first pump 34 .
  • a ferric chloride aqueous solution supply conduit for supplying the ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) produced in the reaction tower 3 to the reduction reaction tank 4 36 is branched, and the ferric chloride aqueous solution supply conduit 36 is connected to the upper portion of the reduction reactor 4 .
  • the reaction tower 3 is equipped with an air release conduit 37 at the top of the tower above the packing material layer 32 for releasing air to the atmosphere, and the air release conduit 37 has a blower 38 along the way for sucking the air in the reaction tower 3. I have.
  • the reduction reaction tank 4 is equipped with a water supply conduit 41 for supplying concentration-adjusted water and an iron supply means 42 for supplying iron such as iron pieces in the upper part, while the ferric chloride aqueous solution supply conduit 36 supplies the ferric chloride solution.
  • the second ferrous chloride produced by reducing at least part of the ferric chloride contained in the ferrous aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) by reaction with iron
  • a ferrous chloride aqueous solution take-out conduit 44 is provided at the bottom for taking out a third ferrous chloride-containing aqueous ferrous chloride solution 43 in which the concentration of ferric chloride is reduced with respect to the aqueous solution.
  • the ferrous chloride aqueous solution extraction conduit 44 is connected to the bottom of the reaction tower 3 via a second pump 45 provided midway, and a second switching valve 46 is provided downstream of the second pump 45 . From the second switching valve 46, an increment take-out conduit 47 for taking out the increment of the ferrous chloride aqueous solution 43 branches off.
  • the chlorine gas treatment method of this embodiment using the chlorine gas treatment apparatus 1 will be described.
  • the battery powder obtained in STEP 2 is supplied from the battery powder supply means 22 to the hydrochloric acid leaching tank 2 , while hydrochloric acid is supplied to the hydrochloric acid leaching tank 2 from the hydrochloric acid supply conduit 21 .
  • the hydrochloric acid has a concentration of, for example, 3 to 12 mol/L, and is supplied in an amount of, for example, 3 to 15 L with respect to 1 kg of the battery powder.
  • the battery powder is dissolved in hydrochloric acid in the hydrochloric acid leaching tank 2, and the valuable metal is leached with hydrochloric acid (STEP 3), thereby obtaining a leaching solution 24, which is a hydrochloric acid solution of the valuable metal (STEP 4).
  • the exudate 24 is taken out through the exudate take-out conduit 25 and subjected to solvent extraction in STEP5.
  • the chlorine gas introduced into the reaction tower 3 through the chlorine gas take-out conduit 26 is sucked into the blower 38, and then flows upward in the reaction tower 3 together with the air flowing in from the dilution air supply conduit 23. to move.
  • the ferrous chloride aqueous solution 31 stored at the bottom of the reaction tower 3 is taken out from the reaction tower 3 by being sucked by the first pump 34 through the circulation conduit 33, and reacted from above the packing material layer 32. It is fed into column 3.
  • the concentration of ferric chloride in the ferrous chloride aqueous solution 31, that is, the ratio of ferric chloride to the total number of moles of ferrous chloride and ferric chloride contained in the ferrous chloride aqueous solution 31 is, in the initial state, , for example, in the range of 0.1 to 30 mol %.
  • the chlorine gas is absorbed by the ferrous chloride aqueous solution 31 while moving upward in the reaction tower 3 (STEP 8), and the amount of ferrous chloride contained in the ferrous chloride aqueous solution 31 is Part is oxidized to ferric chloride to produce a ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) (STEP 9).
  • the reaction in which the chlorine gas is absorbed by the ferrous chloride aqueous solution 31 is a gas-liquid reaction, which proceeds efficiently when the two come into contact with each other on the surface of the filler forming the filler layer 32 .
  • a mesh-like ring made of glass or synthetic resin for example, Rashihi Super Ring (registered trademark) manufactured by Rashihi Co., Ltd.
  • the concentration of ferric chloride contained in the ferrous chloride aqueous solution 31 stored at the bottom of the reaction tower 3 gradually increases.
  • the absorption efficiency of the chlorine gas gradually decreases. Therefore, in the chlorine gas treatment apparatus 1, a By operating the first switching valve 35, a portion of the ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) is supplied to the reduction reaction tank 4 through the ferric chloride aqueous solution supply conduit 36.
  • the ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) may be constantly supplied by adjusting the flow rate of the ferric chloride aqueous solution supply conduit 36 with the switching valve 35. , the switching valve 35 may be operated intermittently.
  • the ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) supplied from the ferric chloride aqueous solution supply conduit 36 is supplied with iron pieces from the iron supply means 42. and the like, and at least part of the ferric chloride contained in the ferric chloride aqueous solution is reduced to ferrous chloride by reaction with iron (STEP 10), thereby obtaining a ferrous chloride aqueous solution (Third ferrous chloride aqueous solution containing ferric chloride) 43 is produced (STEP 11).
  • the concentration-adjusted water supplied from the water supply conduit 41 reduces the concentration of ferric chloride contained in the generated ferrous chloride aqueous solution 43 to the chloride stored at the bottom of the reaction tower 3 . It can be in the range of 0.1 to 30 mol %, which is equivalent to the initial state of the ferrous iron aqueous solution 31 .
  • the third ferrous chloride aqueous solution 43 is sucked into the second pump 45 via the ferrous chloride aqueous solution extraction conduit 44, so that at least part of it is extracted from the reduction reactor 4 and sent to the reaction tower 3. It is refluxed and used as the first ferrous chloride aqueous solution 31 for absorbing the chlorine gas in STEP8.
  • the chlorine absorbed by the ferric chloride aqueous solution (second ferrous chloride aqueous solution containing ferric chloride) is removed from the concentration-adjusted water supplied from the water supply conduit 41.
  • the amount of the aqueous ferrous chloride solution 43 produced is greater than the amount of the aqueous ferric chloride solution supplied. Therefore, by operating the switching valve 46 provided in the ferrous chloride aqueous solution extraction conduit 44 , the increased amount of the generated ferrous chloride aqueous solution 43 may be extracted from the increased amount extraction conduit 47 .
  • the ferrous chloride aqueous solution 43 for the increment taken out from the increment take-out conduit 47 is obtained by oxidizing the contained ferrous chloride separately with chlorine into ferric chloride, thereby substantially removing the ferrous chloride. It can be an aqueous ferric chloride solution that does not contain ferric chloride, and the aqueous ferric chloride solution can be used, for example, as an etching solution for copper in printed circuit boards.
  • the increased amount of the ferrous chloride aqueous solution 43 is taken out from the increased amount take-out conduit 47.
  • the increased amount may be overflowed, stored in a storage tank (not shown), and taken out from the storage tank.
  • the waste lithium ion battery is subjected to pretreatment in STEP 1 to obtain battery powder in STEP 2.
  • aqueous lithium salt solution can be obtained as an extraction residue.
  • Lithium carbonate can be obtained by reacting the lithium salt aqueous solution with carbon dioxide gas or a carbonate compound.
  • the method for treating chlorine gas of this embodiment is a method for treating chlorine gas generated in STEP 7, and can be carried out, for example, by the chlorine gas treatment apparatus 1a shown in FIG.
  • the chlorine gas treatment apparatus 1a includes a hydrochloric acid leaching tank 2 for dissolving battery powder obtained from waste lithium ion batteries in a first hydrochloric acid and leaching valuable metals contained in the battery powder with the first hydrochloric acid, and hydrochloric acid leaching.
  • a chlorine purification tower 3a for separating and removing oxygen-containing air and dust from the chlorine gas produced in the tank 2 to purify the chlorine gas
  • a hydrogen supply facility 4a for purifying hydrogen gas, and purified chlorine gas and hydrogen gas.
  • An absorbent supply tank 7 for supplying an absorbent is provided.
  • the hydrochloric acid leaching tank 2 has a hydrochloric acid supply conduit 21 for supplying first hydrochloric acid and a battery powder supply means 22 for supplying battery powder at the upper part thereof, while the valuable metal contained in the battery powder is leached by the first hydrochloric acid.
  • the bottom is provided with an exudate extraction conduit 24a for extracting the exudate 23a thus obtained.
  • the hydrochloric acid leaching tank 2 is provided with a chlorine gas extraction conduit 25a in its upper part for extracting chlorine gas produced by the leaching reaction when the valuable metal is leached with the first hydrochloric acid. It is connected to the.
  • the chlorine refining tower 3 a has a refined chlorine gas take-out conduit 31 a for taking out refined chlorine gas at its top, and the refined chlorine gas take-out conduit 31 a is connected to the chlorine burner 51 of the combustion tower 5 .
  • the hydrogen supply facility 4 a has a hydrogen gas extraction conduit 41 a at its top, and the hydrogen gas extraction conduit 41 a is connected to the chlorine burner 51 of the combustion tower 5 .
  • the combustion tower 5 is equipped with a chlorine burner 51 at the bottom for generating hydrogen chloride by combusting the chlorine gas supplied from the refined chlorine gas extraction conduit 31a and the hydrogen gas supplied from the hydrogen gas extraction conduit 41a.
  • a combustion tower cooling water jacket 52 for cooling the hydrogen chloride is provided on the outer periphery.
  • the combustion tower 5 also has a hydrogen chloride supply conduit 53 in its upper part for supplying the produced hydrogen chloride to the hydrochloric acid absorption tower 6 .
  • the combustion tower cooling water jacket 52 has a combustion tower cooling water supply conduit 54 for supplying cooling water at its lower part, and a combustion tower cooling water extraction conduit 55 for taking out cooling water at its upper part.
  • a sprinkling tank 56 for spraying cooling water for cooling hydrogen chloride is provided above the hydrogen chloride supply conduit 53, and a receiving tank 57 for containing the cooling water sprayed from the sprinkling tank 56 is provided below.
  • the sprinkler tank 56 has a sprinkler tank cooling water supply conduit 58 for supplying cooling water
  • the water tank 57 has a water tank cooling water extraction conduit 59 for taking out the cooling water.
  • the hydrochloric acid absorption tower 6 has a hydrochloric acid take-out conduit 61 at the bottom for taking out the second hydrochloric acid produced, and a hydrogen chloride take-out conduit 62 at the bottom for taking out unreacted hydrogen chloride. Further, the hydrochloric acid absorption tower 6 is provided with a first storage tank 63 directly below the top of the inside of the tower to which the absorbent is supplied from the absorbent supply tank 7, and an inner cylinder 64 is provided below the first storage tank 63. Prepare. The inner cylinder 64 has a second storage tank 65 on the outer peripheral side of the upper edge. Further, the hydrochloric acid absorption tower 6 is provided with a hydrochloric acid absorption tower cooling water jacket 66 for cooling the hydrogen chloride and the produced second hydrochloric acid at the outer peripheral portion.
  • the hydrochloric acid extraction conduit 61 is connected to the hydrochloric acid leaching tank 2 via a hydrochloric acid pump 61a provided midway.
  • the hydrogen chloride extraction conduit 62 is connected to the bottom of the absorbent supply tank 7 via a blower 62a provided midway.
  • the hydrochloric acid absorber cooling water jacket 66 has a hydrochloric acid absorber cooling water supply conduit 67 for supplying cooling water at its lower part, and a hydrochloric acid absorber cooling water take-out conduit 68 for taking out cooling water at its upper part.
  • the absorbent supply tank 7 is equipped with a water supply conduit 71 for supplying water and a gas release conduit 72 for releasing gas at its upper part.
  • An absorbent supply conduit 73 is provided at the bottom.
  • the gas release conduit 72 has a check valve 74 that opens when the internal pressure of the absorbent supply tank 7 exceeds a certain level.
  • the cooling water taken out from the hydrochloric acid absorption tower cooling water jacket 66 by the hydrochloric acid absorption tower cooling water extraction conduit 68 is passed through the sprinkling tank 56, the receiving tank 57 and the combustion tower cooling water jacket 52. It may be configured to be circulated to the hydrochloric acid absorption tower cooling water extraction conduit 68 .
  • the hydrochloric acid absorption tower cooling water take-out conduit 68 is connected to a sprinkler tank cooling water supply conduit 58 that supplies cooling water to the sprinkler tank 56 , and a water tank cooling water take-out conduit 59 takes out cooling water from the water tank 57 .
  • combustion tower cooling water supply conduit 54 that supplies cooling water to the combustion tower cooling water jacket 52
  • a combustion tower cooling water extraction conduit 55 that takes out cooling water from the combustion tower cooling water jacket 52 is connected to the hydrochloric acid absorption tower cooling water. It is connected to a hydrochloric acid absorption tower cooling water supply conduit 67 that supplies cooling water to the jacket 66 .
  • a heat exchanger 81 and a cooling water pump 82 may be provided between the combustion tower cooling water extraction conduit 55 and the hydrochloric acid absorption tower cooling water supply conduit 67 .
  • the chlorine gas treatment method of the second embodiment of the present invention by the chlorine gas treatment apparatus 1a will be described.
  • the battery powder obtained in STEP 2 is supplied from the battery powder supply means 22 to the hydrochloric acid leaching tank 2, and the first hydrochloric acid is supplied to the hydrochloric acid leaching tank 2 from the hydrochloric acid supply conduit 21.
  • the first hydrochloric acid has a concentration of, for example, 3 to 12 mol/L, and is supplied in an amount of, for example, 3 to 15 L with respect to 1 kg of the battery powder.
  • the battery powder is dissolved in the first hydrochloric acid in the hydrochloric acid leaching tank 2, and the valuable metal is leached by the first hydrochloric acid (STEP 3) to obtain a leaching solution 23a which is a hydrochloric acid solution of the valuable metal. (STEP 4).
  • the exudate 23a is taken out by the exudate take-out conduit 24a and subjected to solvent extraction in STEP5.
  • chlorine gas is generated due to the leaching reaction when the valuable metal is leached with the first hydrochloric acid (STEP 7).
  • the chlorine gas is taken out from the hydrochloric acid leaching tank 2 through a chlorine gas take-out conduit 25a by chlorine gas supply means (not shown) provided in the chlorine purification tower 3a and supplied to the chlorine purification tower 3a.
  • the chlorine gas introduced into the chlorine purification tower 3a through the chlorine gas extraction conduit 25a is separated into oxygen-containing air, dust, etc. by means of a wet scrubber filled with water, a membrane separation method, liquefaction of chlorine by pressurized cooling, or the like. - Removed and purified (STEP8).
  • the purified chlorine gas is taken out from the chlorine purification tower 3a by the chlorine gas supply means and supplied to the combustion tower 5 through the purified chlorine gas extraction conduit 31a.
  • the chlorine gas supplied to the combustion tower 5 is combusted by the chlorine burner 51 together with the hydrogen gas supplied by the hydrogen supply equipment 4a (STEP 9), and reacts at a high temperature to produce hydrogen chloride (STEP 10).
  • the produced hydrogen chloride is cooled by the combustion tower cooling water jacket 52, introduced into the hydrogen chloride supply conduit 53, further cooled by the cooling water sprinkled from the sprinkling tank 56 to the receiving tank 57, and introduced into the hydrochloric acid absorption tower 6. be.
  • the hydrogen chloride introduced into the hydrochloric acid absorption tower 6 is absorbed by the absorbent supplied from the absorbent supply tank 7 and flowing down (STEP 11) to produce the second hydrochloric acid (STEP 12).
  • the absorbent supplied from the absorbent supply tank 7 is temporarily stored in the first storage tank 63, and the absorbent overflowing from the first storage tank 63 is stored in the second storage tank 65, The absorbent overflowing from the second storage tank 65 flows down along the outer and inner surfaces of the inner cylinder 64 .
  • the absorbent flowing down along the outer surface of the inner cylinder 64 absorbs hydrogen chloride to produce the second hydrochloric acid, and the absorbing liquid flowing down along the inner surface of the inner cylinder 64 cooperates with the hydrochloric acid absorption tower cooling water jacket 66. to cool the second hydrochloric acid produced.
  • the concentration of the generated second hydrochloric acid is, for example, in the range of 1 to 37% by mass, and the second hydrochloric acid is supplied to the hydrochloric acid leaching tank 2 through the hydrochloric acid extraction conduit 61 by the hydrochloric acid pump 61a, and 1 hydrochloric acid can be reused for leaching the valuable metals.
  • the unreacted hydrogen chloride in the hydrochloric acid absorption tower 6 is introduced into the absorbent supply tank 7 via the hydrogen chloride extraction conduit 62 by being sucked into the blower 62a.
  • the hydrogen chloride introduced into the absorbent supply tank 7 is absorbed by the water supplied from the water supply conduit 71 to produce dilute hydrochloric acid.
  • the generated dilute hydrochloric acid is supplied to the hydrochloric acid absorption tower 6 as an absorbent via an absorbent supply conduit 73 .
  • the remaining gas after hydrogen chloride is absorbed in the absorbent supply tank 7 is discharged to the outside of the chlorine gas treatment apparatus 1a through a gas release conduit 72. As shown in FIG.
  • the hydrochloric acid absorption tower 6 is provided with a hydrochloric acid extraction conduit 61 at the bottom, and the hydrochloric acid extraction conduit 61 is connected to the hydrochloric acid leaching tank 2, so that the hydrochloric acid produced in the hydrochloric acid absorption tower 6 is
  • the second hydrochloric acid is reused as the first hydrochloric acid for leaching the valuable metals.
  • the hydrochloric acid extraction conduit 61 By connecting the hydrochloric acid extraction conduit 61 to a storage tank (not shown), the second hydrochloric acid is stored in the storage tank. and may be taken out.
  • chlorine gas is brought into contact with an alkaline absorbing liquid containing at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. and a hypochlorite generation step for generating hypochlorite.
  • the alkali metal constituting the alkali metal hydroxide preferably contains at least one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and francium, more preferably lithium, sodium, and potassium. It contains at least one selected from the group, and more preferably contains at least one selected from the group consisting of sodium and potassium.
  • the alkaline earth metal constituting the alkaline earth metal hydroxide preferably contains at least one selected from the group consisting of beryllium, magnesium, calcium, strontium and barium, more preferably magnesium, calcium and barium. At least one selected from the group consisting of, more preferably at least one selected from the group consisting of magnesium and calcium.
  • the alkaline absorption liquid is preferably an aqueous solution or suspension containing at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.
  • the third embodiment of the method for treating chlorine gas of the present invention preferably further includes a first hypochlorite reduction step of reacting hypochlorite with carbon.
  • the alkaline absorbing liquid containing hypochlorite is brought into contact with carbon as a reducing agent to generate a chloride salt and carbon dioxide.
  • a reaction represented by the following formula (2) occurs in the first hypochlorite reduction step. 2NaClO+C ⁇ 2NaCl+CO 2 (2)
  • the third embodiment of the method for treating chlorine gas of the present invention preferably further includes a second hypochlorite reduction step of reacting hypochlorite with aluminum.
  • the alkaline absorbing liquid containing hypochlorite is brought into contact with aluminum as a reducing agent to produce aluminum oxide and a chloride salt.
  • a reaction represented by the following formula (3) occurs in the second hypochlorite reduction step. 3NaClO+2Al ⁇ 2Al 2 O 3 +3NaCl (3)
  • a fourth embodiment of the method for treating chlorine gas of the present invention includes a carbon dioxide generation step of reacting chlorine gas with carbon and water to generate carbon dioxide.
  • chlorine gas is bubbled directly into the carbon-filled column and water showering or steam introduction is performed.
  • a reaction represented by the following formula (4) occurs. 2Cl2 +C+ 2H2O ⁇ CO2 +4HCl (4)
  • a fifth embodiment of the method for treating chlorine gas of the present invention includes an aluminum chloride producing step of reacting chlorine gas with aluminum to produce aluminum chloride.
  • Chlorine gas can be passed directly through an aluminum packed column to cause a direct reduction reaction.
  • a reaction represented by the following formula (5) occurs in the aluminum chloride production step.
  • the aluminum packed column may be showered with water in order to dissolve the produced aluminum chloride. 2Al+3Cl 2 ⁇ 2AlCl 3 (5)
  • Leachate extraction conduit 26 Chlorine gas extraction conduit 31 Ferrous chloride aqueous solution 32 Filling material layer 33 Circulation conduit 34 First pump 35 First switching valve 36 Ferric chloride aqueous solution Supply conduit 37 Air release conduit 38 Blower 41 Water supply conduit 42 Iron supply means 43 Ferrous chloride aqueous solution 44 Ferrous chloride aqueous solution extraction conduit 45 Second pump 46 ...second switching valve 47...increase take-out conduit 1a...chlorine gas treatment device 3a...chlorine purification tower 4a...hydrogen supply apparatus 5...combustion tower 51...chlorine burner 6...hydrochloric acid absorption tower 7... Absorbent supply tank.

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Abstract

L'invention concerne un procédé de traitement de chlore gazeux selon lequel le chlore gazeux généré lorsqu'une poudre de batterie est dissoute dans de l'acide chlorhydrique pour lixivier un métal précieux à l'aide de l'acide chlorhydrique peut être rendu inoffensif ou utilisé efficacement. Ce procédé de traitement de chlore gazeux généré lorsqu'une poudre de batterie contenant un métal précieux obtenu à partir d'une batterie au lithium-ion usagée est dissoute dans de l'acide chlorhydrique pour lixivier le métal précieux à l'aide de l'acide chlorhydrique comprend une étape consistant à faire réagir le chlore gazeux avec au moins une substance choisie dans le groupe constitué par les agents réducteurs, les hydroxydes de métaux alcalins et les hydroxydes de métaux alcalino-terreux. Des exemples de l'agent réducteur comprennent : une première solution aqueuse de chlorure ferreux contenant du chlorure ferrique ; et de l'hydrogène gazeux.
PCT/JP2022/035235 2021-09-22 2022-09-21 Procédé de traitement de chlore gazeux Ceased WO2023048196A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2025005714A (ja) * 2023-06-28 2025-01-17 株式会社アサカ理研 リチウム膜電解後の淡塩水の処理方法
WO2025192009A1 (fr) * 2024-03-14 2025-09-18 Ｊｆｅスチール株式会社 Procédé de récupération de solution aqueuse

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5193552A (ja) * 1975-02-14 1976-08-17 Haigasuoyobihaisuinoshoriho
JPH11293356A (ja) * 1998-04-14 1999-10-26 Hiroyuki Nakazawa コバルト酸リチウムの溶解方法
JP2000303084A (ja) * 1999-04-21 2000-10-31 Shinsei Dental Laboratory:Kk 塩素含有プラスチック廃棄物の処理方法
JP2005052724A (ja) * 2003-08-04 2005-03-03 Hideki Yamamoto フッ素系ガスの無害化処理方法および無害化処理装置
JP2008110339A (ja) * 2006-10-03 2008-05-15 Sumitomo Chemical Co Ltd 塩素ガスの除害方法
JP2010077399A (ja) * 2008-08-25 2010-04-08 Kobe Steel Ltd 炭化燃料の製造方法およびその装置
JP2012046794A (ja) * 2010-08-27 2012-03-08 Hitachi Ltd 金属回収方法及び金属回収装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000264641A (ja) 1999-03-19 2000-09-26 Hiroyuki Nakazawa リチウムイオン二次電池の正極材料からの酸化コバルトの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5193552A (ja) * 1975-02-14 1976-08-17 Haigasuoyobihaisuinoshoriho
JPH11293356A (ja) * 1998-04-14 1999-10-26 Hiroyuki Nakazawa コバルト酸リチウムの溶解方法
JP2000303084A (ja) * 1999-04-21 2000-10-31 Shinsei Dental Laboratory:Kk 塩素含有プラスチック廃棄物の処理方法
JP2005052724A (ja) * 2003-08-04 2005-03-03 Hideki Yamamoto フッ素系ガスの無害化処理方法および無害化処理装置
JP2008110339A (ja) * 2006-10-03 2008-05-15 Sumitomo Chemical Co Ltd 塩素ガスの除害方法
JP2010077399A (ja) * 2008-08-25 2010-04-08 Kobe Steel Ltd 炭化燃料の製造方法およびその装置
JP2012046794A (ja) * 2010-08-27 2012-03-08 Hitachi Ltd 金属回収方法及び金属回収装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2025005714A (ja) * 2023-06-28 2025-01-17 株式会社アサカ理研 リチウム膜電解後の淡塩水の処理方法
JP7713736B2 (ja) 2023-06-28 2025-07-28 株式会社アサカ理研 リチウム膜電解後の淡塩水の処理方法
WO2025192009A1 (fr) * 2024-03-14 2025-09-18 Ｊｆｅスチール株式会社 Procédé de récupération de solution aqueuse

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