WO2023048196A1 - Treatment method for chlorine gas - Google Patents

Treatment method for chlorine gas 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
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PCT/JP2022/035235
Other languages
French (fr)
Japanese (ja)
Inventor
慶太 山田
幸雄 佐久間
太郎 平岡
順 中澤
Original Assignee
株式会社アサカ理研
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Application filed by 株式会社アサカ理研 filed Critical 株式会社アサカ理研
Priority to JP2023523065A priority Critical patent/JPWO2023048196A1/ja
Publication of WO2023048196A1 publication Critical patent/WO2023048196A1/en
Priority to JP2024029857A priority patent/JP2024055948A/en

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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.

Abstract

Provided is a treatment method for chlorine gas whereby chlorine gas generated when a battery powder is dissolved in hydrochloric acid to leach a valuable metal using the hydrochloric acid can be rendered harmless or used effectively. This treatment method for chlorine gas generated when a battery powder containing a valuable metal obtained from a waste lithium ion battery is dissolved in hydrochloric acid to leach the valuable metal using the hydrochloric acid includes a step for reacting the chlorine gas with at least one substance selected from the group consisting of reducing agents, alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the reducing agent include: a first aqueous ferrous chloride solution containing ferric chloride; and hydrogen gas.

Description

塩素ガスの処理方法Chlorine gas treatment method
　本発明は、塩素ガスの処理方法に関する。 The present invention relates to a chlorine gas treatment method.
　近年、リチウムイオン電池の普及に伴い、廃リチウムイオン電池からリチウム、マンガン、ニッケル、コバルト等の有価金属を回収し、前記リチウムイオン電池の正極活物質として再利用する方法が検討されている。 In recent years, with the spread of lithium-ion batteries, methods of recovering valuable metals such as lithium, manganese, nickel, and cobalt from waste lithium-ion batteries and reusing them as positive electrode active materials for the lithium-ion batteries are being studied.
　従来、前記廃リチウムイオン電池から前記有価金属を回収する際には、該廃リチウムイオン電池を加熱処理（焙焼）して、ないし加熱処理せずに粉砕、分級する等して得られた前記有価金属を含む粉末（以下、電池粉という）を塩酸に溶解し、該有価金属を塩酸により浸出して得られた浸出液を溶媒抽出に供することが行われている（例えば、特許文献１、２参照）。 Conventionally, when recovering the valuable metal from the waste lithium ion battery, 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).
特許第４３８８０９１号公報Japanese Patent No. 4388091 特許第４８６５７４５号公報Japanese Patent No. 4865745
　しかしながら、前記電池粉を塩酸に溶解し、前記有価金属を塩酸により浸出すると、浸出反応により発生する塩素ガスにより、装置が腐食されたり、作業環境が汚染されたりするという不都合がある。 However, when the battery powder is dissolved in hydrochloric acid and the valuable metal is leached with hydrochloric acid, chlorine gas generated by the leaching reaction corrodes the apparatus and contaminates the working environment.
　本発明は、かかる不都合を解消して、前記電池粉を塩酸に溶解し、前記有価金属を塩酸により浸出する際に発生する塩素ガスを無害化又は有効に活用できる塩素ガスの処理方法を提供することを目的とする。 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.
　本発明者らは上記課題に鑑み検討を重ね、廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスを還元剤、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つと反応させ、無害化又は有効に活用できることを見出した。本発明はこれらの知見に基づき完成されるに至ったものである。 In view of the above problems, 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.
　かかる目的を達成するために、本発明の塩素ガスの処理方法は、廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、該塩素ガスを、還元剤、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つと反応させる工程を含むことを特徴とする。
　本発明の塩素ガスの処理方法は、廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスを還元剤、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つと反応させ、無害化又は有効に活用できる。 In order to achieve this object, 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.
In the chlorine gas treatment method of the present invention, 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.
　本発明の塩素ガスの処理方法は、廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスを、第１の塩化第一鉄水溶液に吸収させて、該第１の塩化第一鉄水溶液に対して塩化第二鉄の濃度が増大した、塩化第二鉄を含有する第２の塩化第一鉄水溶液を生成させる工程を含む。
　尚、前記塩化第一鉄水溶液における前記塩化第二鉄の濃度とは、前記塩化第一鉄水溶液が含有する塩化第一鉄と塩化第二鉄との合計モル数に対する塩化第二鉄の割合を意味する。また、前記第２の塩化第一鉄水溶液は、前記第１の塩化第一鉄水溶液に対して塩化第二鉄の濃度が増大しているので、以下、便宜的に塩化第二鉄水溶液と記載することがある。
　前記工程により、前記塩素ガスが塩化第二鉄として固定化されるので、該塩素ガスを無害化できる。 In the chlorine gas treatment method of the present invention, 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. In addition, 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.
　本発明の塩素ガスの処理方法は、好ましくは、前記塩素ガスを、第１の塩化第一鉄水溶液に吸収させることにより生成した、前記塩化第二鉄を含有する第２の塩化第一鉄水溶液を、鉄と接触させて該第２の塩化第一鉄水溶液が含有する塩化第二鉄の少なくとも一部を還元し、該第２の塩化第一鉄水溶液に対して塩化第二鉄の濃度が低減した、塩化第二鉄を含有する第３の塩化第一鉄水溶液を生成させる工程を更に含む。
　前記塩化第二鉄を含有する第２の塩化第一鉄水溶液は、鉄と接触させることにより、含有する塩化第二鉄の少なくとも一部が還元されて塩化第一鉄となり、該第２の塩化第一鉄水溶液に対して塩化第二鉄の濃度が低減した、塩化第二鉄を含む第３の塩化第一鉄水溶液とできる。 In the chlorine gas treatment method of the present invention, 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.
　前記塩化第二鉄を含む第３の塩化第一鉄水溶液の少なくとも一部を前記第１の塩化第一鉄水溶液として、前記塩素ガスの吸収に用いることができるので、前記塩素ガスを有効に活用できる。 Since at least part of the third ferrous chloride aqueous solution containing the ferric chloride can be used as the first ferrous chloride aqueous solution to absorb the chlorine gas, the chlorine gas is effectively used. can.
　本発明の塩素ガスの処理方法は、廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスを、水素ガスと反応させて、塩化水素を生成させる工程と、該塩化水素を水に吸収させて、第２の塩酸を生成させる工程とを含む。この結果、前記塩素ガスを塩酸にすることで、有効に活用できる。 In the chlorine gas treatment method of the present invention, 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 reacted with hydrogen gas. a step of producing hydrogen chloride; and a step of absorbing the hydrogen chloride in water to produce a second hydrochloric acid. As a result, by converting the chlorine gas into hydrochloric acid, it can be effectively utilized.
　本発明の塩素ガスの処理方法は、好ましくは、前記塩素ガスを前記水素ガスと反応させて、前記塩化水素を生成させる工程の前に該塩素ガスを精製し、該塩素ガスに含まれる酸素を除去する工程を更に含む。前記塩化水素を生成させる工程の前に該塩素ガスに含まれる酸素を除去することにより、該塩素ガスを前記水素ガスと反応させる際に、酸素によって水素が消費されることを防ぐことができる。 In the chlorine gas treatment method of the present invention, preferably, 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. 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.
　前記第２の塩酸の少なくとも一部を、好ましくは、前記第１の塩酸として、前記有価金属の浸出に用いる。 At least part of the second hydrochloric acid is preferably used as the first hydrochloric acid for leaching the valuable metal.
　本発明の塩素ガスの処理方法は、塩素ガスを、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つを含むアルカリ性吸収液と接触させ、次亜塩素酸塩を生成させる次亜塩素酸塩生成工程を含む。前記次亜塩素酸塩生成工程を含む本発明の塩素ガスの処理方法は、好ましくは、次亜塩素酸塩と炭素又はアルミニウムを反応させる次亜塩素酸塩の還元工程を更に含む。 In the chlorine gas treatment method of the present invention, 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.
　本発明の塩素ガスの処理方法は、塩素ガスを炭素及び水と反応させ、二酸化炭素を生成させる二酸化炭素生成工程を含む。 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.
　本発明の塩素ガスの処理方法は、塩素ガスをアルミニウムと反応させ、塩化アルミニウムを生成させる塩化アルミニウム生成工程を含む。 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.
本発明の１実施態様の塩素ガスの処理方法を示すフローチャート。1 is a flow chart showing a chlorine gas treatment method according to one embodiment of the present invention. 本発明の１実施態様の塩素ガスの処理方法に用いる装置構成の一例を示すシステム構成図。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; 本発明の１実施態様の塩素ガスの処理方法を示すフローチャート。1 is a flow chart showing a chlorine gas treatment method according to one embodiment of the present invention. 本発明の１実施態様の塩素ガスの処理方法に用いる装置構成の一例を示すシステム構成図。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;
　添付の図面を参照しながら本発明について更に詳細に説明する。
　本発明の塩素ガスの処理方法は、廃リチウムイオン電池から得られた有価金属を含む粉末（電池粉）を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理に用いることができる。 The present invention will be described in more detail with reference to the accompanying drawings.
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.
　本発明の塩素ガスの処理方法において、前記廃リチウムイオン電池とは、電池製品としての寿命が消尽した使用済みのリチウムイオン電池、製造工程で不良品等として廃棄されたリチウムイオン電池、製造工程において製品化に用いられた残余の正極材料等を意味する。 In the chlorine gas treatment method of the present invention, 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.
　前記有価金属を含む粉末は、例えば、次のようにして得ることができる。まず、リチウムイオン電池の製造工程において製品化に用いられた残余の正極材料である正極箔（集電体であるアルミニウム箔に正極活物質を含む正極合剤が塗布されたもの）を、電気炉中、例えば１００～４５０℃の範囲の温度で加熱処理（焙焼）した後、又は加熱処理せずにハンマーミル、ジョークラッシャー等の粉砕機で粉砕し、該廃リチウムイオン電池を構成する筐体、集電体等を篩分けにより除去（分級）して、有価金属を含む粉末として、電池粉を得ることができる。 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.
　あるいは、放電処理後又は加熱処理していない廃リチウムイオン電池を前記粉砕機で粉砕し、筐体、集電体等を篩分けにより除去した後、前記範囲の温度で加熱処理することにより、前記電池粉を得るようにしてもよい。 Alternatively, 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.
　本発明の塩素ガスの処理方法では、前記電池粉を塩酸により浸出する。この結果、前記各種有価金属の浸出液が得られる。 In the chlorine gas treatment method of the present invention, the battery powder is leached with hydrochloric acid. As a result, a leaching solution of the various valuable metals is obtained.
　本発明の塩素ガスの処理方法は、該塩素ガスを、還元剤と反応させる工程を含む。以下、塩素ガスと前記還元剤の反応について更に詳しく説明する。 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.
　本発明の塩素ガスの処理方法の第１の実施態様では、図１に示すように、前記廃リチウムイオン電池に対し、ＳＴＥＰ１で前処理を行い、ＳＴＥＰ２の電池粉を得ることができる。 In the first embodiment of the chlorine gas treatment method of the present invention, as shown in FIG. 1, the waste lithium ion battery is pretreated in STEP 1 to obtain battery powder in STEP 2.
　次に、ＳＴＥＰ３で、前記電池粉を塩酸に溶解し、前記有価金属を塩酸により浸出する。この結果、ＳＴＥＰ４で、前記有価金属の塩酸溶液である浸出液を得ることができる。
　前記浸出液は、ＳＴＥＰ５の溶媒抽出で、中和された後、前記有価金属のうち、マンガン、コバルト、ニッケルが順次溶媒抽出される。そして、ＳＴＥＰ６で、抽出残液としてリチウム塩水溶液を得ることができる。前記リチウム塩水溶液は、炭酸ガス又は炭酸化合物と反応させることにより、炭酸リチウムを得ることができる。 Next, in STEP 3, the battery powder is dissolved in hydrochloric acid, and the valuable metal is leached out with hydrochloric acid. As a result, in STEP 4, a leaching solution, which is a hydrochloric acid solution of the valuable metal, can be obtained.
After the leachate is neutralized in the solvent extraction in STEP 5, manganese, cobalt and nickel among the valuable metals are sequentially solvent-extracted. Then, in STEP 6, 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.
　一方、ＳＴＥＰ３で、前記電池粉を塩酸に溶解すると、前記有価金属が塩酸に浸出される際の浸出反応により、ＳＴＥＰ７で塩素ガスが発生する。第１の実施態様の塩素ガスの処理方法は、ＳＴＥＰ７で発生する塩素ガスの処理方法であり、例えば、図２に示す塩素ガス処理装置１により実施することができる。 On the other hand, when the battery powder is dissolved in hydrochloric acid in STEP 3, chlorine gas is generated in STEP 7 due to the leaching reaction when the valuable metal is leached into hydrochloric acid. 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.
　塩素ガス処理装置１は、廃リチウムイオン電池から得られた電池粉を塩酸に溶解し、該電池粉に含まれる有価金属を塩酸により浸出する塩酸浸出槽２と、塩酸浸出槽２で生成した塩素ガスを第１の塩化第一鉄水溶液（以下、便宜的に、塩化第一鉄水溶液と記載することがある）に吸収させ、塩化第二鉄を含有する第２の塩化第一鉄水溶液を生成させる反応塔３と、反応塔３で生成した塩化第二鉄を含有する第２の塩化第一鉄水溶液を鉄と接触させ、該第２の塩化第一鉄水溶液が含有する塩化第二鉄の少なくとも一部を還元して塩化第一鉄とする還元反応槽４とを備える。 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. and the second ferrous chloride aqueous solution containing ferric chloride produced in the reaction tower 3 is brought into contact with iron, and the ferric chloride contained in the second ferrous chloride aqueous solution is A reduction reactor 4 for reducing at least a portion of the ferrous chloride to ferrous chloride is provided.
　前記第２の塩化第一鉄水溶液は、前記第１の塩化第一鉄水溶液が反応塔３で塩素ガスを吸収して生成された結果、該第１の塩化第一鉄水溶液に対して塩化第二鉄の濃度が増大しているので、以下、便宜的に、塩化第二鉄水溶液と記載することがある。また、前記還元反応槽４では、前記第２の塩化第一鉄水溶液が含有する塩化第二鉄の少なくとも一部が還元されて塩化第一鉄となるので、該第２の塩化第一鉄水溶液に対して塩化第二鉄の濃度が低減した、塩化第二鉄を含む第３の塩化第一鉄水溶液（以下、便宜的に、塩化第一鉄水溶液と記載することがある）が生成される。 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. In addition, in the reduction reaction tank 4, at least part of the ferric chloride contained in the second ferrous chloride aqueous solution is reduced to become ferrous chloride, so that the second 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. .
　塩酸浸出槽２は、塩酸を供給する塩酸供給導管２１と、電池粉を供給する電池粉供給手段２２と、希釈空気を供給する希釈空気供給導管２３とを上部に備える一方、電池粉に含まれる有価金属を塩酸により浸出して得られた浸出液２４を取り出す浸出液取出導管２５を底部に備える。また、塩酸浸出槽２は、前記有価金属を塩酸により浸出する際の浸出反応により生成する塩素ガスを取り出す塩素ガス取出導管２６を上部に備え、塩素ガス取出導管２６は反応塔３に接続されている。 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. In addition, 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. there is
　反応塔３は、底部に塩化第一鉄水溶液３１（第１の塩化第一鉄水溶液）が貯留される一方、塩化第一鉄水溶液３１の上方に充填材が充填された充填材層３２が形成されている。また、反応塔３は、底部に貯留されている塩化第一鉄水溶液３１を取り出し、充填材層３２の上方から供給する循環導管３３を備える。循環導管３３は、途中に第１ポンプ３４を備える一方、第１ポンプ３４の下流側に第１切換弁３５を備える。第１切換弁３５からは、反応塔３で生成した塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）を還元反応槽４に供給する塩化第二鉄水溶液供給導管３６が分岐しており、塩化第二鉄水溶液供給導管３６は還元反応槽４の上部に接続されている。さらに、反応塔３は、空気を大気に解放する空気解放導管３７を充填材層３２の上方の塔頂に備え、空気解放導管３７は、途中に反応塔３内の空気を吸引するブロワー３８を備えている。 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 . From the first switching valve 35, 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 . Furthermore, 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.
　還元反応槽４は、濃度調整水を供給する水供給導管４１と、鉄片等の鉄を供給する鉄供給手段４２とを上部に備える一方、塩化第二鉄水溶液供給導管３６により供給される塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）が含有する塩化第二鉄の少なくとも一部が鉄との反応により還元されて生成する、該第２の塩化第一鉄水溶液に対して塩化第二鉄の濃度が低減した、塩化第二鉄を含む第３の塩化第一鉄水溶液４３を取り出す塩化第一鉄水溶液取出導管４４を底部に備える。塩化第一鉄水溶液取出導管４４は途中に設けられた第２ポンプ４５を介して反応塔３の底部に接続される一方、第２ポンプ４５の下流側に第２切換弁４６を備える。第２切換弁４６からは、塩化第一鉄水溶液４３の増加分を取り出す増加分取出導管４７が分岐している。 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.
　次に、塩素ガス処理装置１による本実施形態の塩素ガスの処理方法について説明する。
　塩素ガス処理装置１では、まず、電池粉供給手段２２からＳＴＥＰ２で得られた電池粉が塩酸浸出槽２に供給される一方、塩酸供給導管２１から塩酸が塩酸浸出槽２に供給される。前記塩酸は、例えば、３～１２モル／Ｌの濃度であり、前記電池粉１ｋｇに対し、例えば３～１５Ｌの量が供給される。この結果、塩酸浸出槽２内で前記電池粉が塩酸に溶解され、前記有価金属が塩酸により浸出されて（ＳＴＥＰ３）、該有価金属の塩酸溶液である浸出液２４を得ることができる（ＳＴＥＰ４）。浸出液２４は、浸出液取出導管２５により取り出され、ＳＴＥＰ５の溶媒抽出に供される。 Next, the chlorine gas treatment method of this embodiment using the chlorine gas treatment apparatus 1 will be described.
In the chlorine gas treatment apparatus 1 , first, 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. As a result, 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.
　また、塩酸浸出槽２では、前記有価金属が塩酸により浸出される際の浸出反応により、塩素ガスが発生する（ＳＴＥＰ７）。前記塩素ガスは、反応塔３の空気解放導管３７に設けられたブロワー３８により、塩素ガス取出導管２６を介して吸引されることにより塩酸浸出槽２から取り出され、反応塔３に導入される。 Also, in the hydrochloric acid leaching tank 2, chlorine gas is generated due to the leaching reaction when the valuable metal is leached with hydrochloric acid (STEP 7). The chlorine gas is taken out from the hydrochloric acid leaching tank 2 and introduced into the reaction tower 3 by being sucked through the chlorine gas extraction conduit 26 by the blower 38 provided in the air release conduit 37 of the reaction tower 3 .
　塩素ガス取出導管２６を介して反応塔３に導入された前記塩素ガスは、ブロワー３８に吸引されることにより、希釈空気供給導管２３から流入する空気と共に、反応塔３内を下方から上方に向かって移動する。一方、反応塔３の底部に貯留される塩化第一鉄水溶液３１は、循環導管３３を介して第１ポンプ３４に吸引されることにより反応塔３から取り出され、充填材層３２の上方から反応塔３内に供給される。 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. On the other hand, 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.
　塩化第一鉄水溶液３１における塩化第二鉄の濃度、すなわち塩化第一鉄水溶液３１が含有する塩化第一鉄と塩化第二鉄との合計モル数に対する塩化第二鉄の割合は、初期状態では、例えば、０．１～３０モル％の範囲である。 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 %.
　そこで、前記塩素ガスは、反応塔３内を下方から上方に向かって移動する間に塩化第一鉄水溶液３１に吸収され（ＳＴＥＰ８）、塩化第一鉄水溶液３１に含まれる塩化第一鉄の一部を塩化第二鉄に酸化し、塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）を生成する（ＳＴＥＰ９）。前記塩素ガスが塩化第一鉄水溶液３１に吸収される反応は気液反応であり、充填材層３２を形成する充填材の表面で両者が接触することにより効率よく進行する。前記充填材としては、ガラス又は合成樹脂からなるメッシュ状リング（例えば、ラシヒ社製ラシヒスーパーリング（登録商標））等を用いることができる。 Therefore, 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 . As the filler, a mesh-like ring made of glass or synthetic resin (for example, Rashihi Super Ring (registered trademark) manufactured by Rashihi Co., Ltd.) or the like can be used.
　また、前記塩素ガスと共に反応塔３に供給される空気は、塩化第一鉄水溶液３１に吸収されることがないので、ブロワー３８に吸引されて、空気解放導管３７から大気中に解放される。 In addition, since the air supplied to the reaction tower 3 together with the chlorine gas is not absorbed by the ferrous chloride aqueous solution 31, it is sucked into the blower 38 and released into the atmosphere through the air release conduit 37.
　前記塩化第一鉄が酸化されて前記塩化第二鉄が生成すると、反応塔３の底部に貯留される塩化第一鉄水溶液３１が含有する塩化第二鉄の濃度が次第に大きくなり、これに伴って前記塩素ガスの吸収効率が次第に低下する。そこで、塩素ガス処理装置１では、前記塩素ガスの吸収効率が低下する程度に塩化第一鉄水溶液３１が含有する塩化第二鉄の濃度が大きくならないように、循環導管３３の途中に設けられた第１切換弁３５を操作し、塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）の一部を、塩化第二鉄水溶液供給導管３６を介して還元反応槽４に供給する。前記塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）の供給は、切換弁３５により塩化第二鉄水溶液供給導管３６の流量を調整することにより常時行ってもよく、切換弁３５を間欠的に操作することにより行ってもよい。 When the ferrous chloride is oxidized to produce the ferric chloride, the concentration of ferric chloride contained in the ferrous chloride aqueous solution 31 stored at the bottom of the reaction tower 3 gradually increases. As a result, 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. supply to 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.
　還元反応槽４では、塩化第二鉄水溶液供給導管３６から供給される前記塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）に対して、鉄供給手段４２から鉄片等の鉄を供給し、該塩化第二鉄水溶液が含有する塩化第二鉄の少なくとも一部を鉄との反応により還元して塩化第一鉄とする（ＳＴＥＰ１０）ことにより、塩化第一鉄水溶液（塩化第二鉄を含む第３の塩化第一鉄水溶液）４３を生成する（ＳＴＥＰ１１）。 In the reduction reaction tank 4, 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).
　このとき、還元反応槽４では、水供給導管４１から供給される濃度調整水により、生成する塩化第一鉄水溶液４３が含有する塩化第二鉄の濃度を反応塔３の底部に貯留される塩化第一鉄水溶液３１の初期状態と同等の０．１～３０モル％の範囲とすることができる。 At this time, in the reduction reaction tank 4 , 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 .
　第３の塩化第一鉄水溶液４３は、塩化第一鉄水溶液取出導管４４を介して第２ポンプ４５に吸引されることにより、少なくともその一部が還元反応槽４から取り出されて反応塔３に還流され、第１の塩化第一鉄水溶液３１として、ＳＴＥＰ８で前記塩素ガスの吸収に用いられる。 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.
　また、還元反応槽４では、水供給導管４１から供給される濃度調整水により、前記塩化第二鉄水溶液（塩化第二鉄を含む第２の塩化第一鉄水溶液）が吸収している前記塩素ガスの量に対応して、生成する塩化第一鉄水溶液４３の量が供給される該塩化第二鉄水溶液の量よりも増加する。そこで、塩化第一鉄水溶液取出導管４４に設けられた切換弁４６を操作することにより、生成する塩化第一鉄水溶液４３の増加分を増加分取出導管４７から取り出してもよい。前記増加分取出導管４７から取り出される増加分の塩化第一鉄水溶液４３は、含有する塩化第一鉄を別途塩素により酸化して塩化第二鉄とすることにより、実質的に塩化第一鉄を含有しない塩化第二鉄水溶液とすることができ、該塩化第二鉄水溶液は、例えば、プリント基板における銅のエッチング液に使用することができる。 In addition, in the reduction reaction tank 4, 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. Corresponding to the amount of gas, 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.
　尚、本実施形態では、切換弁４６を操作することにより、塩化第一鉄水溶液４３の増加分を増加分取出導管４７から取り出すようにしているが、還元反応槽４をオーバーフロー型としておき、前記増加分をオーバーフローさせて図示しない貯留槽に貯留し、該貯留槽から取り出すようにしてもよい。 In this embodiment, by operating the switching valve 46, 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.
　本発明の塩素ガスの処理方法の第２の実施態様では、図３に示すように、前記廃リチウムイオン電池に対し、ＳＴＥＰ１で前処理を行い、ＳＴＥＰ２の電池粉を得ることができる。 In the second embodiment of the chlorine gas treatment method of the present invention, as shown in FIG. 3, the waste lithium ion battery is subjected to pretreatment in STEP 1 to obtain battery powder in STEP 2.
　次に、ＳＴＥＰ３で、前記電池粉を第１の塩酸に溶解し、前記有価金属を第１の塩酸により浸出する。この結果、ＳＴＥＰ４で、前記有価金属の塩酸溶液である浸出液を得ることができる。 Next, in STEP 3, the battery powder is dissolved in the first hydrochloric acid, and the valuable metal is leached out with the first hydrochloric acid. As a result, in STEP 4, a leaching solution, which is a hydrochloric acid solution of the valuable metal, can be obtained.
　前記浸出液は、ＳＴＥＰ５の溶媒抽出で、中和された後、前記有価金属のうち、マンガン、コバルト、ニッケルが順次溶媒抽出される。そして、ＳＴＥＰ６で、抽出残液としてリチウム塩水溶液を得ることができる。前記リチウム塩水溶液は、炭酸ガス又は炭酸化合物と反応させることにより、炭酸リチウムを得ることができる。 After the leachate is neutralized in the solvent extraction in STEP 5, among the valuable metals, manganese, cobalt, and nickel are sequentially solvent-extracted. Then, in STEP 6, 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.
　一方、ＳＴＥＰ３で、前記電池粉を第１の塩酸に溶解すると、前記有価金属が第１の塩酸に浸出される際の浸出反応により、ＳＴＥＰ７で塩素ガスが発生する。本実施形態の塩素ガスの処理方法は、ＳＴＥＰ７で発生する塩素ガスの処理方法であり、例えば、図４に示す塩素ガス処理装置１ａにより実施することができる。 On the other hand, when the battery powder is dissolved in the first hydrochloric acid in STEP 3, chlorine gas is generated in STEP 7 due to the leaching reaction when the valuable metal is leached into the first hydrochloric acid. 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.
　塩素ガス処理装置１ａは、廃リチウムイオン電池から得られた電池粉を第１の塩酸に溶解し、該電池粉に含まれる有価金属を第１の塩酸により浸出する塩酸浸出槽２と、塩酸浸出槽２で生成した塩素ガスから酸素を含む空気や粉塵などを分離・除去し、塩素ガスを精製する塩素精製塔３ａと、水素ガスを精製する水素供給設備４ａと、精製した塩素ガスと水素ガスとを高温下で反応させ、塩化水素を生成させる燃焼塔５と、燃焼塔５で生成した塩化水素を水に吸収させ、第２の塩酸を生成させる塩酸吸収塔６と、塩酸吸収塔６に吸収液を供給する吸収液供給槽７を備える。 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. at a high temperature to produce hydrogen chloride, a hydrochloric acid absorption tower 6 for absorbing the hydrogen chloride produced in the combustion tower 5 into water to produce the second hydrochloric acid, and the hydrochloric acid absorption tower 6 An absorbent supply tank 7 for supplying an absorbent is provided.
　塩酸浸出槽２は、第１の塩酸を供給する塩酸供給導管２１と、電池粉を供給する電池粉供給手段２２とを上部に備える一方、電池粉に含まれる有価金属を第１の塩酸により浸出して得られた浸出液２３ａを取り出す浸出液取出導管２４ａを底部に備える。また、塩酸浸出槽２は、前記有価金属を第１の塩酸により浸出する際の浸出反応により生成する塩素ガスを取り出す塩素ガス取出導管２５ａを上部に備え、塩素ガス取出導管２５ａは塩素精製塔３ａに接続されている。 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. In addition, 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.
　塩素精製塔３ａは、精製した塩素ガスを取り出す精製塩素ガス取出導管３１ａを上部に備え、精製塩素ガス取出導管３１ａは燃焼塔５の塩素バーナ５１に接続されている。 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 .
　水素供給設備４ａは水素ガス取出導管４１ａを上部に備え、水素ガス取出導管４１ａは燃焼塔５の塩素バーナ５１に接続されている。 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 .
　燃焼塔５は、精製塩素ガス取出導管３１ａから供給される塩素ガスと、水素ガス取出導管４１ａから供給される水素ガスとを燃焼させて塩化水素を生成させる塩素バーナ５１を底部に備える一方、生成した塩化水素を冷却する燃焼塔冷却水ジャケット５２を外周部に備える。また、燃焼塔５は、生成した塩化水素を塩酸吸収塔６に供給する塩化水素供給導管５３を上部に備える。燃焼塔冷却水ジャケット５２は、下部に冷却水を供給する燃焼塔冷却水供給導管５４を備え、上部に冷却水を取り出す燃焼塔冷却水取出導管５５を備える。 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.
　塩化水素供給導管５３の上方には、塩化水素を冷却する冷却水を散布する散水槽５６が設けられ、下方には、散水槽５６から散布された冷却水を収容する受水槽５７が設けられている。散水槽５６は冷却水を供給する散水槽冷却水供給導管５８を備え、受水槽５７は冷却水を取り出す受水槽冷却水取出導管５９を備える。 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. there is The sprinkler tank 56 has a sprinkler tank cooling water supply conduit 58 for supplying cooling water, and the water tank 57 has a water tank cooling water extraction conduit 59 for taking out the cooling water.
　塩酸吸収塔６は、生成した第２の塩酸を取り出す塩酸取出導管６１を底部に備える一方、未反応の塩化水素を取り出す塩化水素取出導管６２を下部に備える。また、塩酸吸収塔６は、内部の塔頂の直下に、吸収液供給槽７から吸収液が供給される第１の貯留槽６３を備え、第１の貯留槽６３の下方に内筒６４を備える。内筒６４は上端縁の外周側に第２の貯留槽６５を備える。さらに、塩酸吸収塔６は塩化水素及び生成した第２の塩酸を冷却する塩酸吸収塔冷却水ジャケット６６を外周部に備える。 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.
　塩酸取出導管６１は、途中に設けられた塩酸ポンプ６１ａを介して塩酸浸出槽２に接続されている。塩化水素取出導管６２は途中で設けられたブロワー６２ａを介して吸収液供給槽７の底部に接続されている。塩酸吸収塔冷却水ジャケット６６は、下部に冷却水を供給する塩酸吸収塔冷却水供給導管６７を備え、上部に冷却水を取り出す塩酸吸収塔冷却水取出導管６８を備える。 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.
　吸収液供給槽７は、水を供給する水供給導管７１と、ガスを解放するガス解放導管７２とを上部に備え、塩化水素を吸収して希塩酸となった吸収液を塩酸吸収塔６の上部へ供給する吸収液供給導管７３を下部に備える。ガス解放導管７２は、吸収液供給槽７の内圧が一定以上になると開く逆止弁７４を備える。 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.
　また、塩素ガス処理装置１ａは、塩酸吸収塔冷却水取出導管６８により塩酸吸収塔冷却水ジャケット６６から取り出された冷却水が、散水槽５６、受水槽５７及び燃焼塔冷却水ジャケット５２を介して塩酸吸収塔冷却水取出導管６８に循環されるように構成されていてもよい。この場合、例えば、塩酸吸収塔冷却水取出導管６８は、散水槽５６に冷却水を供給する散水槽冷却水供給導管５８に接続され、受水槽５７から冷却水を取り出す受水槽冷却水取出導管５９は、燃焼塔冷却水ジャケット５２に冷却水を供給する燃焼塔冷却水供給導管５４に接続され、燃焼塔冷却水ジャケット５２から冷却水を取り出す燃焼塔冷却水取出導管５５は、塩酸吸収塔冷却水ジャケット６６に冷却水を供給する塩酸吸収塔冷却水供給導管６７に接続される。また、燃焼塔冷却水取出導管５５と塩酸吸収塔冷却水供給導管６７との途中に熱交換器８１と冷却水ポンプ８２とを設けてもよい。 In addition, in the chlorine gas treatment apparatus 1a, 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 . In this case, for example, 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 . is connected to a combustion tower cooling water supply conduit 54 that supplies cooling water to the combustion tower cooling water jacket 52, and 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 .
　次に、塩素ガス処理装置１ａによる本発明の第２の実施態様の塩素ガスの処理方法について説明する。
　塩素ガス処理装置１ａでは、まず、電池粉供給手段２２からＳＴＥＰ２で得られた電池粉が塩酸浸出槽２に供給される一方、塩酸供給導管２１から第１の塩酸が塩酸浸出槽２に供給される。前記第１の塩酸は、例えば、３～１２モル／Ｌの濃度であり、前記電池粉１ｋｇに対し、例えば３～１５Ｌの量が供給される。この結果、塩酸浸出槽２内で前記電池粉が第１の塩酸に溶解され、前記有価金属が第１の塩酸により浸出されて（ＳＴＥＰ３）、該有価金属の塩酸溶液である浸出液２３ａを得ることができる（ＳＴＥＰ４）。浸出液２３ａは、浸出液取出導管２４ａにより取り出され、ＳＴＥＰ５の溶媒抽出に供される。 Next, the chlorine gas treatment method of the second embodiment of the present invention by the chlorine gas treatment apparatus 1a will be described.
In the chlorine gas treatment apparatus 1a, first, 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. be. 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. As a result, 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.
　また、塩酸浸出槽２では、前記有価金属が第１の塩酸により浸出される際の浸出反応により、塩素ガスが発生する（ＳＴＥＰ７）。前記塩素ガスは、塩素精製塔３ａに設けられた図示しない塩素ガス供給手段により塩素ガス取出導管２５ａを介して塩酸浸出槽２から取り出され、塩素精製塔３ａに供給される。 Also, in the hydrochloric acid leaching tank 2, 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.
　塩素ガス取出導管２５ａを介して塩素精製塔３ａに導入された前記塩素ガスは、水を充填した湿式スクラバ、膜分離法、加圧冷却による塩素の液化等により酸素を含む空気や粉塵などを分離・除去され、精製される（ＳＴＥＰ８）。精製された塩素ガスは前記塩素ガス供給手段により塩素精製塔３ａから取り出され、精製塩素ガス取出導管３１ａを介して燃焼塔５に供給される。 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.
　燃焼塔５に供給された前記塩素ガスは、水素供給設備４ａにより供給された水素ガスと共に塩素バーナ５１により燃焼され（ＳＴＥＰ９）、高温下で反応して塩化水素を生成する（ＳＴＥＰ１０）。生成した塩化水素は、燃焼塔冷却水ジャケット５２により冷却され、塩化水素供給導管５３に導入され、さらに散水槽５６から受水槽５７に散水される冷却水により冷却され、塩酸吸収塔６に導入される。 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.
　塩酸吸収塔６に導入された前記塩化水素は、吸収液供給槽７から供給されて流下する吸収液に吸収されて（ＳＴＥＰ１１）、第２の塩酸を生成する（ＳＴＥＰ１２）。ここで、吸収液供給槽７から供給される吸収液は、一旦第１の貯留槽６３に貯留され、第１の貯留槽６３から溢流した吸収液は第２の貯留槽６５に貯留され、第２の貯留槽６５から溢流した吸収液は内筒６４の外面及び内面に沿って流下する。内筒６４の外面に沿って流下する吸収液は塩化水素を吸収して第２の塩酸を生成し、内筒６４の内面に沿って流下する吸収液は塩酸吸収塔冷却水ジャケット６６と協働して、生成した第２の塩酸を冷却する。生成された第２の塩酸の濃度は、例えば、１～３７質量％の範囲であり、第２の塩酸は、塩酸ポンプ６１ａにより、塩酸取出導管６１を介して塩酸浸出槽２に供給され、第１の塩酸として前記有価金属の浸出に再利用することができる。 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). Here, 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.
　また、塩酸吸収塔６にて未反応の前記塩化水素は、ブロワー６２ａに吸引されることにより、塩化水素取出導管６２を介して吸収液供給槽７に導入される。吸収液供給槽７に導入された前記塩化水素は、水供給導管７１から供給された水に吸収され、希塩酸を生成する。生成した希塩酸は、吸収液供給導管７３を介して、吸収液として塩酸吸収塔６に供給される。吸収液供給槽７において塩化水素が吸収された後の残余に気体は、ガス解放導管７２を通じて塩素ガス処理装置１ａの外部へ排出される。 In addition, 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.
　尚、本発明の第２の実施態様では、塩酸吸収塔６が底部に塩酸取出導管６１を備え、塩酸取出導管６１が塩酸浸出槽２に接続されていることにより、塩酸吸収塔６で生成された第２の塩酸を有価金属の浸出に用いる第１の塩酸として再利用するようにしているが、塩酸取出導管６１を図示しない貯留槽に接続させることで第２の塩酸を該貯留槽に貯留し、取り出すようにしてもよい。 In the second embodiment of the present invention, 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. 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.
　本発明の塩素ガスの処理方法の第３の実施態様は、塩素ガスを、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つを含むアルカリ性吸収液と接触させ、次亜塩素酸塩を生成させる次亜塩素酸塩生成工程を含む。 In a third embodiment of the method for treating chlorine gas of the present invention, 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.
　前記アルカリ金属水酸化物を構成するアルカリ金属は、好ましくはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、及びフランシウムからなる群から選ばれる少なくとも１つを含み、より好ましくはリチウム、ナトリウム、及びカリウムからなる群から選ばれる少なくとも１つを含み、更に好ましくはナトリウム、及びカリウムからなる群から選ばれる少なくとも１つを含む。前記アルカリ土類金属水酸化物を構成するアルカリ土類金属は、好ましくはベリリウム、マグネシウム、カルシウム、ストロンチウム、及びバリウムからなる群から選ばれる少なくとも１つを含み、より好ましくはマグネシウム、カルシウム、及びバリウムからなる群から選ばれる少なくとも１つを含み、更に好ましくはマグネシウム及びカルシウムからなる群から選ばれる少なくとも１つを含む。 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.
　前記アルカリ性吸収液は、好ましくは水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、及び水酸化カルシウムからなる群から選ばれる少なくとも１つを含む水溶液または懸濁液である。 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.
　例えば前記アルカリ性吸収液が水酸化ナトリウムを含む場合、前記次亜塩素酸塩生成工程では、下記式（１）で示される反応が起きる。
　２ＮａＯＨ＋Ｃｌ２→ＮａＣｌＯ＋ＮａＣｌ＋Ｈ２Ｏ　　（１） For example, when the alkaline absorbing liquid contains sodium hydroxide, a reaction represented by the following formula (1) occurs in the hypochlorite generation step.
2NaOH+ Cl2 →NaClO+NaCl+ H2O (1)
　本発明の塩素ガスの処理方法の第３の実施態様は、好ましくは、次亜塩素酸塩と炭素を反応させる第１の次亜塩素酸塩の還元工程を更に含む。次亜塩素酸塩を含有する前記アルカリ性吸収液と還元剤となる炭素を接触させ、塩化物塩と二酸化炭素を生成させる。例えば前記アルカリ性吸収液が水酸化ナトリウムを含む場合、前記第１の次亜塩素酸塩の還元工程では、下記式（２）で示される反応が起きる。
　２ＮａＣｌＯ＋Ｃ→２ＮａＣｌ＋ＣＯ２　　（２） 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. For example, when the alkaline absorbing liquid contains sodium hydroxide, a reaction represented by the following formula (2) occurs in the first hypochlorite reduction step.
2NaClO+C→2NaCl+CO 2 (2)
　本発明の塩素ガスの処理方法の第３の実施態様は、好ましくは、次亜塩素酸塩とアルミニウムを反応させる第２の次亜塩素酸塩の還元工程を更に含む。次亜塩素酸塩を含有する前記アルカリ性吸収液と還元剤となるアルミニウムを接触させ、酸化アルミニウムと塩化物塩を生成させる。例えば前記アルカリ性吸収液が水酸化ナトリウムを含む場合、前記第２の次亜塩素酸塩の還元工程では、下記式（３）で示される反応が起きる。
　３ＮａＣｌＯ＋２Ａｌ→２Ａｌ２Ｏ３＋３ＮａＣｌ　　（３） 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. For example, when the alkaline absorbing liquid contains sodium hydroxide, a reaction represented by the following formula (3) occurs in the second hypochlorite reduction step.
3NaClO+2Al→2Al 2 O 3 +3NaCl (3)
　本発明の塩素ガスの処理方法の第４の実施態様は、塩素ガスを炭素及び水と反応させ、二酸化炭素を生成させる二酸化炭素生成工程を含む。例えば塩素ガスを直接炭素充填塔に通気し、水のシャワーリングまたは水蒸気導入を実施する。前記二酸化炭素生成工程では、下記式（４）で示される反応が起きる。
　２Ｃｌ２＋Ｃ＋２Ｈ２Ｏ→ＣＯ２＋４ＨＣｌ　　（４） 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. For example, chlorine gas is bubbled directly into the carbon-filled column and water showering or steam introduction is performed. In the carbon dioxide generation step, a reaction represented by the following formula (4) occurs.
2Cl2 +C+ 2H2O → CO2 +4HCl (4)
　本発明の塩素ガスの処理方法の第５の実施態様は、塩素ガスをアルミニウムと反応させ、塩化アルミニウムを生成させる塩化アルミニウム生成工程を含む。塩素ガスを直接アルミニウム充填塔に通気して直接還元反応を起こせる。前記塩化アルミニウム生成工程では、下記式（５）で示される反応が起きる。生成した塩化アルミニウムを溶出させるためにアルミニウム充填塔に水のシャワーリングを実施してもよい。
　２Ａｌ＋３Ｃｌ２→２ＡｌＣｌ３　　（５） 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. In the aluminum chloride production step, a reaction represented by the following formula (5) occurs. The aluminum packed column may be showered with water in order to dissolve the produced aluminum chloride.
2Al+3Cl 2 →2AlCl 3 (5)
　１…塩素ガス処理装置、　２…塩酸浸出槽、　３…反応塔、　４…還元反応槽、　２１…塩酸供給導管、　２２…電池粉供給手段、　２３…希釈空気供給導管、　２４…浸出液、　２５…浸出液取出導管、　２６…塩素ガス取出導管、　３１…塩化第一鉄水溶液、　３２…充填材層、　３３…循環導管、　３４…第１ポンプ、　３５…第１切換弁、　３６…塩化第二鉄水溶液供給導管、　３７…空気解放導管、　３８…ブロワー、　４１…水供給導管、　４２…鉄供給手段、　４３…塩化第一鉄水溶液、　４４…塩化第一鉄水溶液取出導管、　４５…第２ポンプ、　４６…第２切換弁、　４７…増加分取出導管、　１ａ…塩素ガス処理装置、　３ａ…塩素精製塔、　４ａ…水素供給装置、　５…燃焼塔、　５１…塩素バーナ、　６…塩酸吸収塔、　７…吸収液供給槽。 1... chlorine gas treatment device, 2... hydrochloric acid leaching tank, 3... reaction tower, 4... reduction reaction tank, 21... hydrochloric acid supply conduit, 22... battery powder supply means, 23... dilution air supply conduit, 24... leachate, 25... 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.

Claims (12)

  1. 　廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスを、還元剤、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つと反応させる工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid and the valuable metals are leached out with hydrochloric acid,
    A method for treating chlorine gas, comprising a step of reacting the chlorine gas with at least one member selected from the group consisting of reducing agents, alkali metal hydroxides, and alkaline earth metal hydroxides.
  2. 　廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスを、第１の塩化第一鉄水溶液に吸収させて、該第１の塩化第一鉄水溶液に対して塩化第二鉄の濃度が増大した、塩化第二鉄を含有する第２の塩化第一鉄水溶液を生成させる工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid and the valuable metals are leached out with hydrochloric acid,
    The chlorine gas is absorbed in the first ferrous chloride aqueous solution to provide a second ferric chloride-containing second ferric chloride solution having an increased concentration of ferric chloride relative to the first ferrous chloride aqueous solution. A method for treating chlorine gas, comprising a step of producing a ferrous chloride aqueous solution.
  3. 　請求項２記載の塩素ガスの処理方法において、前記塩化第二鉄を含有する第２の塩化第一鉄水溶液を、鉄と接触させて該第２の塩化第一鉄水溶液が含有する塩化第二鉄の少なくとも一部を還元し、該第２の塩化第一鉄水溶液に対して塩化第二鉄の濃度が低減した、塩化第二鉄を含有する第３の塩化第一鉄水溶液を生成させる工程を更に含むことを特徴とする塩素ガスの処理方法。 In the method for treating chlorine gas according to claim 2, the second ferrous chloride aqueous solution containing ferric chloride is brought into contact with iron, and the ferrous chloride contained in the second ferrous chloride aqueous solution is reducing at least a portion of the iron to produce a third ferrous chloride-containing aqueous ferrous chloride solution having a reduced concentration of ferric chloride relative to the second aqueous ferrous chloride solution; A method for treating chlorine gas, further comprising:
  4. 　請求項３記載の塩素ガスの処理方法において、前記第３の塩化第一鉄水溶液の少なくとも一部を前記第１の塩化第一鉄水溶液として、前記塩素ガスの吸収に用いることを特徴とする塩素ガスの処理方法。 4. The chlorine gas treatment method according to claim 3, wherein at least part of said third ferrous chloride aqueous solution is used as said first ferrous chloride aqueous solution for absorbing said chlorine gas. Gas treatment method.
  5. 　廃リチウムイオン電池から得られた有価金属を含む粉末を第１の塩酸に溶解し、該有価金属を第１の塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスを、水素ガスと反応させて、塩化水素を生成させる工程と、
    　該塩化水素を水に吸収させて、第２の塩酸を生成させる工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when a powder containing a valuable metal obtained from a waste lithium ion battery is dissolved in a first hydrochloric acid and the valuable metal is leached out with the first hydrochloric acid,
    reacting the chlorine gas with hydrogen gas to produce hydrogen chloride;
    A method for treating chlorine gas, comprising a step of absorbing the hydrogen chloride in water to generate a second hydrochloric acid.
  6. 　請求項５記載の塩素ガスの処理方法において、前記塩素ガスを前記水素ガスと反応させて、前記塩化水素を生成させる工程の前に該塩素ガスを精製し、該塩素ガスに含まれる酸素を除去する工程を更に含むことを特徴とする塩素ガスの処理方法。 6. The method for treating chlorine gas according to claim 5, wherein the chlorine gas is purified to remove oxygen contained in the chlorine gas before the step of reacting the chlorine gas with the hydrogen gas to generate the hydrogen chloride. A chlorine gas treatment method, further comprising the step of:
  7. 　請求項５または６記載の塩素ガスの処理方法において、前記第２の塩酸の少なくとも一部を前記第１の塩酸として、前記有価金属の浸出に用いることを特徴とする塩素ガスの処理方法。 The method for treating chlorine gas according to claim 5 or 6, wherein at least part of said second hydrochloric acid is used as said first hydrochloric acid for leaching said valuable metal.
  8. 　廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスを、アルカリ金属水酸化物、及びアルカリ土類金属水酸化物からなる群から選ばれる少なくとも１つを含むアルカリ性吸収液と接触させ、次亜塩素酸塩を生成させる次亜塩素酸塩生成工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid and the valuable metals are leached out with hydrochloric acid,
    Hypochlorite for producing hypochlorite by contacting the chlorine gas with an alkaline absorbing liquid containing at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. A chlorine gas treatment method, comprising a generation step.
  9. 　請求項８記載の塩素ガスの処理方法において、次亜塩素酸塩と炭素を反応させる第１の次亜塩素酸塩の還元工程を更に含むことを特徴とする塩素ガスの処理方法。 The chlorine gas treatment method according to claim 8, further comprising a first hypochlorite reduction step of reacting hypochlorite with carbon.
  10. 　請求項８記載の塩素ガスの処理方法において、次亜塩素酸塩とアルミニウムを反応させる第２の次亜塩素酸塩の還元工程を更に含むことを特徴とする塩素ガスの処理方法。 The chlorine gas treatment method according to claim 8, further comprising a second hypochlorite reduction step of reacting hypochlorite with aluminum.
  11. 　廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスを炭素及び水と反応させ、二酸化炭素を生成させる二酸化炭素生成工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid and the valuable metals are leached out with hydrochloric acid,
    A method for treating chlorine gas, comprising a step of producing carbon dioxide by reacting the chlorine gas with carbon and water to produce carbon dioxide.
  12. 　廃リチウムイオン電池から得られた有価金属を含む粉末を塩酸に溶解し、該有価金属を塩酸により浸出する際に発生する塩素ガスの処理方法であって、
    　該塩素ガスをアルミニウムと反応させ、塩化アルミニウムを生成させる塩化アルミニウム生成工程を含むことを特徴とする塩素ガスの処理方法。     A method for treating chlorine gas generated when powder containing valuable metals obtained from waste lithium ion batteries is dissolved in hydrochloric acid and the valuable metals are leached out with hydrochloric acid,
    A method for treating chlorine gas, comprising a step of producing aluminum chloride by reacting the chlorine gas with aluminum to produce aluminum chloride.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5193552A (en) * 1975-02-14 1976-08-17 HAIGASUOYOBI HAISUINOSHORIHO
JPH11293356A (en) * 1998-04-14 1999-10-26 Hiroyuki Nakazawa Dissolution of cobaltic acid lithium
JP2000303084A (en) * 1999-04-21 2000-10-31 Shinsei Dental Laboratory:Kk Method for treating chlorine-containing plastic waste
JP2005052724A (en) * 2003-08-04 2005-03-03 Hideki Yamamoto Method and apparatus for detoxifying fluorine-based gas
JP2008110339A (en) * 2006-10-03 2008-05-15 Sumitomo Chemical Co Ltd Method for removal of chlorine gas
JP2010077399A (en) * 2008-08-25 2010-04-08 Kobe Steel Ltd Method of producing carbonized fuel and equipment therefor
JP2012046794A (en) * 2010-08-27 2012-03-08 Hitachi Ltd Metal recovery method and metal recovery device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5193552A (en) * 1975-02-14 1976-08-17 HAIGASUOYOBI HAISUINOSHORIHO
JPH11293356A (en) * 1998-04-14 1999-10-26 Hiroyuki Nakazawa Dissolution of cobaltic acid lithium
JP2000303084A (en) * 1999-04-21 2000-10-31 Shinsei Dental Laboratory:Kk Method for treating chlorine-containing plastic waste
JP2005052724A (en) * 2003-08-04 2005-03-03 Hideki Yamamoto Method and apparatus for detoxifying fluorine-based gas
JP2008110339A (en) * 2006-10-03 2008-05-15 Sumitomo Chemical Co Ltd Method for removal of chlorine gas
JP2010077399A (en) * 2008-08-25 2010-04-08 Kobe Steel Ltd Method of producing carbonized fuel and equipment therefor
JP2012046794A (en) * 2010-08-27 2012-03-08 Hitachi Ltd Metal recovery method and metal recovery device

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