WO2021166479A1 - 水酸化リチウムの製造方法 - Google Patents

水酸化リチウムの製造方法 Download PDF

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Publication number
WO2021166479A1
WO2021166479A1 PCT/JP2021/000466 JP2021000466W WO2021166479A1 WO 2021166479 A1 WO2021166479 A1 WO 2021166479A1 JP 2021000466 W JP2021000466 W JP 2021000466W WO 2021166479 A1 WO2021166479 A1 WO 2021166479A1
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Prior art keywords
lithium
liquid
ion exchange
containing liquid
lithium hydroxide
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English (en)
French (fr)
Japanese (ja)
Inventor
松本　伸也
雅俊 高野
伸一 平郡
浅野　聡
修 池田
陽平 工藤
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to US17/797,397 priority Critical patent/US20230079295A1/en
Priority to CN202180012969.9A priority patent/CN115052836B/zh
Priority to AU2021222916A priority patent/AU2021222916B2/en
Priority to EP21756744.5A priority patent/EP4108633A4/en
Publication of WO2021166479A1 publication Critical patent/WO2021166479A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • B01D15/362—Cation-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/01—Preparation or separation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/02—Specific process operations before starting the membrane separation process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing lithium hydroxide. More specifically, the present invention relates to a method for producing lithium hydroxide, which obtains a lithium hydroxide-containing liquid from a lithium chloride-containing liquid.
  • Lithium-ion secondary batteries are often used as in-vehicle batteries because of their high energy density and high charge / discharge capacity.
  • Demand for nickel-based positive electrode materials, that is, NCA, as positive electrode materials for lithium-ion secondary batteries is increasing.
  • NCA nickel-based positive electrode materials
  • this NCA is used in a lithium ion secondary battery, it is economically preferable that lithium is supplied as lithium hydroxide.
  • Patent Document 1 discloses a production method for obtaining high-purity lithium hydroxide from lithium chloride by bipolar membrane electrodialysis. Further, in this document, lithium chloride is obtained by reacting lithium carbonate with hydrochloric acid, obtained by extracting lithium-containing ore with hydrochloric acid, or selectively adsorbed and separated from irrigation. Is disclosed.
  • the diaphragm used for electrodialysis is, for example, a combination of a bipolar membrane, an anionic membrane, and a cationic membrane. If there are many divalent or higher ions in these diaphragms, the diaphragm may be burdened and the membrane may be damaged. Therefore, in the liquid before electrodialysis, it is necessary to remove the divalent or higher ions by using an ion exchange resin.
  • an object of the present invention is to provide a method for producing lithium hydroxide, which can reduce the burden of removing divalent or higher ions in an ion exchange resin.
  • the method for producing lithium hydroxide according to the first invention is the following steps (1) to (3): (1) Neutralization step: A step of adding an alkali to the first lithium chloride-containing liquid to obtain a liquid after neutralization. (2) Ion exchange step: A step of contacting the neutralized liquid with an ion exchange resin to obtain a second lithium chloride-containing liquid, (3) Conversion step: The second lithium chloride-containing liquid is subjected to electrodialysis. It is characterized by including a step of obtaining a lithium hydroxide-containing liquid.
  • the method for producing lithium hydroxide according to the second invention is the following steps (1) to (4): (1) Oxidation step: A step of adding an oxidizing agent to the first lithium chloride-containing liquid to obtain a post-oxidation liquid, ( 2) Neutralization step: A step of adding an alkali to the post-oxidation liquid to obtain a post-neutralization liquid, (3) Ion exchange step: The second lithium chloride by contacting the post-neutralization liquid with an ion exchange resin. A step of obtaining a containing liquid, (4) a conversion step: a step of subjecting the second lithium chloride-containing liquid to electrodialysis to obtain a lithium hydroxide-containing liquid.
  • the first lithium chloride-containing liquid is adsorbed by bringing a low lithium-containing liquid into contact with a lithium adsorbent obtained from lithium manganate. It is characterized in that it is obtained through an adsorption step of obtaining lithium post-manganate and an elution step of contacting the post-adsorption lithium manganate with a hydrochloric acid solution to obtain the first lithium chloride-containing liquid.
  • the method for producing lithium hydroxide according to the fourth invention is the method according to any one of the first to third inventions, wherein the ion exchange resin used in the ion exchange step is an iminodiacetic acid type chelate resin or an iminodiacetic acid type chelate. It is characterized by being a resin.
  • the method for producing lithium hydroxide of the fifth invention is characterized in that, in the fourth invention, the functional groups of the iminodiacetic acid type chelate resin and the iminodiacetic acid salt type chelate resin are sodium type.
  • the method for producing lithium hydroxide of the sixth invention is that the ion exchange step is carried out by a method using a column, and after the neutralization passing through the column.
  • the liquid passing speed is SV1 or more and SV7 or less.
  • the method for producing lithium hydroxide of the seventh invention is characterized in that, in the sixth invention, the amount of the neutralized liquid passing through the column is BV10 or more and BV35 or less.
  • the neutralization step of adding an alkali is provided before the ion exchange step using the ion exchange resin, it is possible to roughly remove ions having a valence of 2 or more in the neutralization step. , The load of metal removal by the ion exchange resin can be reduced.
  • the second invention before the ion exchange step using the ion exchange resin, there is an oxidation step of adding an oxidizing agent and a neutralization step of adding an alkali, so that the first lithium chloride-containing liquid contains manganese. Manganese can be removed when the above is contained, and other divalent or higher valent ions can be roughly removed in the neutralization step, and the load of metal removal by the ion exchange resin can be further reduced.
  • the first lithium chloride-containing liquid undergoes an adsorption step in which lithium is adsorbed by a lithium adsorbent obtained from lithium manganate, and an elution step in which lithium is eluted from lithium manganate after adsorption.
  • an adsorption step in which lithium is adsorbed by a lithium adsorbent obtained from lithium manganate
  • elution step in which lithium is eluted from lithium manganate after adsorption.
  • the ion exchange resin used in the ion exchange step is an iminodiacetic acid type chelate resin or an iminodiacetic acid salt type chelate resin
  • the availability of the ion exchange resin is improved.
  • the functional group of the iminodiacetic acid type chelate resin or the like is sodium type
  • the pH of the passing liquid changes when it is hydrogen type, but when it is sodium type, the pH is changed. It does not change and the properties of the liquid during the reaction are stable.
  • the ion exchange step is performed by a method using a column, and the liquid passing speed in the column is SV1 or more and SV7 or less, so that magnesium and calcium, which are divalent metals, can be more reliably obtained. Can be removed.
  • the amount of the neutralized liquid passing through the column is BV10 or more and BV35 or less, magnesium and calcium can be removed more reliably.
  • the method for producing lithium hydroxide according to the present invention includes the following steps (1) to (3): (1) Neutralization step: a step of adding an alkali to the first lithium chloride-containing liquid to obtain a liquid after neutralization. (2) Ion exchange step: A step of contacting the neutralized liquid with an ion exchange resin to obtain a second lithium chloride-containing liquid, (3) Conversion step: The second lithium chloride-containing liquid is subjected to electrodialysis. Includes the step of obtaining a lithium hydroxide-containing liquid. With this configuration, since divalent or higher ions can be roughly removed in the neutralization step, the load of metal removal by the ion exchange resin can be reduced.
  • the method for producing lithium hydroxide according to the present invention is the following steps (1) to (4): (1) Oxidation step: A step of adding an oxidizing agent to the first lithium chloride-containing liquid to obtain a post-oxidation liquid. , (2) Neutralization step: A step of adding alkali to the post-oxidation liquid to obtain a post-neutralization liquid, (3) Ion exchange step: The post-neutralization liquid and an ion exchange resin are brought into contact with each other to obtain a second solution. A step of obtaining a lithium chloride-containing liquid, and (4) a conversion step: a step of subjecting the second lithium chloride-containing liquid to electrodialysis to obtain a lithium hydroxide-containing liquid.
  • manganese can be removed when the first lithium chloride-containing liquid contains manganese, and other divalent or higher ions can be roughly removed in the neutralization step, so that metal can be removed by an ion exchange resin.
  • the load can be transferred by hand.
  • an adsorption step in which the first lithium chloride-containing liquid is brought into contact with a lithium adsorbent obtained from lithium manganate to obtain lithium manganate after adsorption, and the lithium manganate and hydrochloric acid solution after adsorption. It is preferable that the solution is obtained through an elution step of obtaining a first lithium-containing liquid by contacting with. With this configuration, even if a part of manganese is dissolved in the elution step, this manganese is removed by the subsequent neutralization step or the combination of the oxidation step and the neutralization step, so that lithium manganate having excellent adsorption ability is obtained. High-purity lithium hydroxide can be obtained while using.
  • the ion exchange resin used in the ion exchange step is preferably an iminodiacetic acid type chelate resin or an iminodiacetic acid salt type chelate resin. This configuration improves the availability of the ion exchange resin.
  • the functional groups of the iminodiacetic acid type chelate resin and the iminodiacetic acid salt type chelate resin are sodium type.
  • the ion exchange step is performed by a method using a column, and it is preferable that the flow rate of the neutralized liquid passing through the column is SV1 or more and SV7 or less. With this configuration, the divalent metals magnesium and calcium can be removed more reliably.
  • the amount of the neutralized liquid passing through the column is BV10 or more and BV35 or less. With this configuration, magnesium and calcium can be removed more reliably.
  • FIG. 1 shows a flow chart of a method for producing lithium hydroxide according to the first embodiment of the present invention.
  • the method for producing lithium hydroxide according to the present embodiment includes three steps of a neutralization step, an ion exchange step, and a conversion step.
  • the neutralization step shown in FIG. 1 is a step of adding an alkali to the first lithium chloride-containing liquid to obtain a neutralized liquid.
  • a neutralized starch containing impurities other than lithium chloride is obtained.
  • the first lithium chloride-containing liquid refers to a liquid containing lithium chloride when this liquid is crystallized.
  • a liquid obtained by reacting lithium carbonate with hydrochloric acid a liquid obtained by extracting lithium from a lithium-containing ore with hydrochloric acid, or a liquid obtained by selectively adsorbing and separating lithium from irrigation water. ..
  • the first lithium chloride-containing liquid is preferably a liquid obtained by selectively adsorbing and separating lithium from irrigation.
  • alkali is added to remove metals other than lithium.
  • Ion exchange resins are mainly used to remove divalent or higher valent metal ions.
  • the liquid before contact with the ion exchange resin contains a very large amount of divalent or higher metal ions, it becomes necessary to frequently replace the ion exchange resin.
  • the ion exchange resin is expensive, the cost for producing lithium hydroxide increases and the load of the work of exchanging the ion exchange resin increases. In addition, the load of the work of regenerating the ion exchange resin also increases. Therefore, in the neutralization step, an alkali is added to remove a part of the metal other than lithium. Examples of metals other than lithium include divalent magnesium and manganese.
  • the neutralization step magnesium and manganese are precipitated as magnesium hydroxide and manganese hydroxide by adding sodium hydroxide to the first lithium chloride-containing liquid, and the precipitate is recovered to other than lithium. Remove the metal. To remove magnesium and the like by precipitation, it may be alkaline, but if the pH is too high, the cost of the neutralizing agent increases, which is not preferable. Therefore, the pH of the neutralized liquid after the neutralization step is preferably 8.5 or more and 12 or less.
  • the ion exchange step shown in FIG. 1 is a step of bringing the neutralized liquid and the ion exchange resin into contact with each other to obtain a second lithium chloride-containing liquid.
  • the ion exchange step calcium that cannot be removed in the neutralization step, aluminum that remains depending on the pH of the neutralization step, and a very small amount of manganese and magnesium that cannot be removed in the neutralization step are removed.
  • An ion exchange resin is a kind of synthetic resin, and has a structure in which a part of its molecular structure is ionized as an ion exchange group.
  • an ion exchange resin capable of removing divalent or higher metal ions that could not be captured in the neutralization step that is, an iminodiacetic acid type chelate resin or an iminodiacetic acid type chelate resin is preferable.
  • the pH of the neutralized liquid in the ion exchange step is determined by the ion exchange resin to be a preferable value. However, it is preferable to directly perform the ion exchange step on the neutralized liquid obtained in the neutralization step.
  • the functional group is sodium type.
  • the ion exchange resin used in the ion exchange step is an iminodiacetic acid type chelate resin or an iminodiacetic acid salt type chelate resin, the availability of the ion exchange resin is improved.
  • the functional group of the iminodiacetic acid type chelate resin or the like is sodium type
  • the pH of the passing liquid changes when it is hydrogen type, but the pH does not change when it is sodium type, and the reaction occurs.
  • the properties of the liquid at the time are stable.
  • the contact method between the ion exchange resin and the neutralized liquid is preferably a method using a column. However, a batch mixing method may be adopted.
  • the flow rate of the neutralized liquid passing through this column is preferably SV1 or more and SV7 or less.
  • SV is an abbreviation for Space Velocity, and represents the amount of liquid flowing per unit time (1 hour) (the unit is BV described below). If the liquid passing rate is less than SV1, the efficiency of producing lithium hydroxide is deteriorated. Further, if the liquid passing speed is higher than SV7, the liquid flow becomes too fast, and metal may not be captured. With this liquid passing rate, the divalent metals magnesium and calcium can be removed more reliably.
  • the amount of the neutralized liquid passing through the column is preferably BV10 or more and BV35 or less.
  • BV is an abbreviation for Bed Volume, and is a unit representing several times the volume of the ion exchange resin in the column. If the amount of liquid to be passed is less than BV10, the efficiency of producing lithium hydroxide is deteriorated. On the other hand, if the amount of liquid passing through is larger than that of BV35, the ion exchange resin may break through the metal trapping capacity, and the metal may not be trapped. With this amount of liquid passing through, magnesium and calcium can be removed more reliably.
  • the ion exchange resin used in the ion exchange process is recyclable. By immersing the used ion exchange resin in a liquid having a hydrogen concentration of 0.3 mol / L or more and 2.0 mol / L or less, the trapped metal is eluted.
  • ⁇ Conversion process> As shown in FIG. 1, in the conversion step, lithium chloride contained in the second lithium-containing liquid is converted to lithium hydroxide to obtain a lithium hydroxide-containing liquid in which lithium hydroxide is dissolved. Lithium chloride is dissolved in the second lithium-containing liquid.
  • electrodialysis using a bipolar membrane converts these liquids into a lithium hydroxide-containing liquid containing lithium hydroxide and hydrochloric acid. That is, by performing electrodialysis, lithium chloride in the second lithium-containing liquid is decomposed, and lithium ions of lithium chloride pass through the cation film and combine with hydroxide ions to become lithium hydroxide, for example, chloride. The substance ion passes through the anion film and becomes hydrochloric acid. The recovered hydrochloric acid can be recycled in the elution step. As a result, the amount of hydrochloric acid used can be reduced.
  • electrodialysis using an ion exchange membrane corresponds to the conversion step.
  • electrodialysis using an ion exchange membrane corresponds to the conversion step.
  • a cation exchange membrane is used as the ion exchange membrane, lithium hydroxide is generated in the cathode chamber.
  • a neutralization step of adding alkali is provided before the ion exchange step of using the ion exchange resin.
  • ions having a divalent value or higher can be roughly removed in the neutralization step, so that the load of metal removal by the ion exchange resin can be reduced.
  • Lithium hydroxide is obtained by evaporating and drying the lithium hydroxide-containing liquid obtained in the conversion step.
  • alkali metals such as sodium or potassium are present in this lithium hydroxide-containing liquid, and when evaporated to dryness as it is, the solid obtained from the alkali metal contains a large amount of hydroxides other than lithium hydroxide. It becomes. Therefore, after the conversion step, it is preferable to provide a crystallization step for solidifying the lithium hydroxide dissolved in the lithium hydroxide-containing liquid.
  • solid lithium hydroxide is obtained by solidifying lithium hydroxide dissolved in the lithium hydroxide-containing liquid. Together with this solid lithium hydroxide, a crystallization mother liquor is obtained.
  • lithium becomes lithium hydroxide
  • alkali metals such as sodium and potassium also become hydroxides. Therefore, these are also included in the lithium hydroxide-containing liquid obtained in the conversion step.
  • chlorine ions which are anions, are also contained in the lithium hydroxide-containing liquid through the membrane.
  • the difference in solubility of each hydroxide is used to solidify lithium hydroxide and separate impurities contained in it.
  • the lithium hydroxide-containing liquid is heated and concentrated. At this time, the concentration of metal ions contained in the liquid increases, and lithium hydroxide having a relatively low solubility first precipitates and solidifies. The precipitated lithium hydroxide is recovered as solid lithium hydroxide. At this time, sodium hydroxide and potassium hydroxide having relatively high solubility are left in the liquid without being precipitated. This increases the purity of the recovered lithium hydroxide.
  • the solubility of lithium hydroxide at 60 ° C. is 13.2 g / 100 g-water
  • the solubility of lithium hydroxide is higher than that of sodium hydroxide 174 g / 100 g-water and potassium hydroxide 154 g / 100 g-water. It turns out that it is extremely low. Since the chlorine ion is 2 g / L even during the heat concentration operation, it does not precipitate in lithium hydroxide as an alkali metal chloride.
  • the crystallization step can be industrially performed by continuous crystallization using a crystallization can. It can also be performed by batch crystallization.
  • the crystallization mother liquor generated in the crystallization step is a concentrated alkaline aqueous solution. Since this crystallization mother liquor contains lithium hydroxide for the solubility, the lithium recovery rate can be increased by repeating the steps before the neutralization step. In addition, the cost of the neutralizer is reduced.
  • FIG. 2 shows a flow chart of a method for producing lithium hydroxide according to the second embodiment of the present invention.
  • the difference between this embodiment and the first embodiment is that an oxidation step is provided before the neutralization step.
  • Other points are the same as those in the first embodiment.
  • the oxidation process, which is a difference, will be described below.
  • oxidation step an oxidizing agent such as air, oxygen, or sodium hypochlorite is added to the first lithium-containing liquid, and manganese in the first lithium-containing liquid is oxidized to insoluble manganese dioxide in the liquid.
  • This is a step of precipitating and removing manganese dissolved in.
  • Manganese can be removed also in the neutralization step, but by providing the oxidation step, manganese is removed before the neutralization step, so that the load of manganese removal in the neutralization step can be reduced.
  • manganese precipitated and removed in the oxidation step can be reused.
  • the oxidation-reduction potential of the first lithium-containing liquid is set to pH and potential located in the region of manganese dioxide in the potential pH diagram.
  • FIG. 3 shows a flow chart of a method for producing lithium hydroxide according to the third embodiment of the present invention.
  • the difference between the present embodiment and the first embodiment is that an adsorption step and an elution step are provided before the neutralization step, and the first lithium chloride-containing liquid is obtained through these adsorption steps and elution steps. It is a point that is being done. Other points are the same as those in the first embodiment.
  • the difference between the adsorption step and the elution step will be described below.
  • the lithium adsorbent and a low lithium-containing liquid having a relatively low lithium concentration such as salt lake irrigation water are brought into contact with each other, and lithium is selectively adsorbed on the lithium adsorbent from the low lithium-containing liquid. It is a process to make it.
  • the reaction formula in the adsorption step is shown in Equation 1.
  • a reaction formula in which H 1.6 Mn 1.6 O 4 is used as the lithium adsorbent is shown, but the reaction formula is not particularly limited to this.
  • a manganese oxide in which lithium manganate is brought into contact with an acid and lithium in the lithium manganate is desorbed is preferable.
  • the method of contacting these is not particularly limited.
  • the column method and the batch mixing method correspond to the contact method.
  • the liquid passing resistance is high, and continuous liquid passing is often difficult.
  • pellets prepared by kneading a lithium adsorbent (including the case where it is a precursor before becoming a lithium adsorbent) and a binder such as an alumina binder and sintering this are used. preferable.
  • the pH of the low lithium-containing liquid in the adsorption step is preferably 3 or more and 10 or less. Since the reaction in the adsorption step is a reaction that adsorbs lithium to generate an acid, the reaction rate may slow down or the reaction itself may not occur if the pH of the liquid is low. Therefore, it is desirable to raise the pH of the low lithium-containing liquid before bringing the low lithium-containing liquid into contact with the lithium adsorbent. However, when magnesium is contained in the low lithium-containing liquid, magnesium hydroxide precipitates when the pH becomes too high, and this magnesium hydroxide covers the surface of the lithium adsorbent, which physically inhibits the lithium adsorption reaction. Will be done. In particular, when the column method is adopted as the contact method, magnesium hydroxide often causes blockage in the column. From these, the pH of the first lithium-containing liquid is preferably 10 or less.
  • the lower part of the column may not be able to efficiently adsorb lithium.
  • a neutralizing agent to the effluent after passing through the column to adjust the pH to the above range, and then return the solution to the column.
  • the liquid passing rate may be changed according to the required processing amount.
  • the column liquid can be smoothly passed by using a filtration device such as a filter press or a check filter as appropriate. After the adsorption operation, the lithium adsorbent is washed with water after lithium adsorption, if necessary, in order to carry out the elution step of the next step.
  • ⁇ Elution process> As shown in FIG. 3, in the elution step, after adsorption of lithium, lithium manganate and hydrochloric acid are brought into contact with each other to obtain a first lithium-containing liquid.
  • the post-adsorption lithium manganate is in the form of, for example, lithium manganate, and when the post-adsorption lithium manganate and hydrochloric acid come into contact with each other, lithium is eluted.
  • the contact method is generally a column method, but a batch mixing method may also be used, and the contact method does not matter.
  • the reaction formula at the time of lithium elution is shown in Equation 2.
  • Li 1.6 Mn 1.6 O 4 is shown as lithium manganate, but the present invention is not particularly limited to this.
  • a lithium adsorbent obtained from lithium manganate having another spinel structure The concentration of hydrochloric acid should be sufficient to elute lithium, but if the concentration is too high, lithium manganate will dissolve and wear out. Also, if the concentration is too low, lithium will not elute.
  • the concentration of hydrochloric acid is preferably 0.3 mol / L or more and 2.0 mol / L or less. When the column method is used, the liquid passing rate may be changed according to the required processing amount.
  • the eluent obtained in this step contains sodium, potassium, magnesium, and calcium that are slightly associated with the adsorption step.
  • the lithium adsorbent is lithium manganate
  • manganese eluted from the lithium adsorbent is also included.
  • the second lithium-containing liquid contains aluminum.
  • polyvalent metals other than sodium and potassium cause problems such as shortening the life of the film in the subsequent conversion step. Therefore, the above neutralization step or a combination of the oxidation step and the neutralization step is performed. Is removed at.
  • the lithium adsorbent after lithium adsorption returns to the lithium adsorbent and is in a state where lithium can be adsorbed again. Therefore, it can be used again in the adsorption step.
  • the lithium adsorbent is preferably washed with water.
  • FIG. 4 shows a flow chart of a method for producing lithium hydroxide according to the fourth embodiment of the present invention.
  • the difference between the present embodiment and the second embodiment is that an adsorption step and an elution step are provided before the neutralization step. Other points are the same as those of the second embodiment.
  • the details of the adsorption step and the elution step are the same as those in the third embodiment described above.
  • Example 1 ⁇ Neutralization process> Alkali was added to the first lithium chloride-containing liquid to obtain a liquid after neutralization.
  • the first lithium chloride-containing liquid is obtained by eluting lithium adsorbed by a lithium adsorbent with hydrochloric acid.
  • the alkali used in the neutralization step is sodium hydroxide.
  • Table 1 shows the weight per unit volume of the metal ions contained in the obtained neutralized liquid. Analysis of metal concentrations was performed by ICP-AES. In the neutralization step, the weight of aluminum, magnesium and manganese per unit volume is relatively low. However, the weight per unit volume of calcium is very high.
  • ⁇ Ion exchange process> CR11 manufactured by Mitsubishi Chemical Corporation, which is an iminodiacetic acid type chelate resin, was used as the ion exchange resin. 20 ml of this chelate resin was placed in a glass column having a diameter of 20 mm, and an ion exchange step was carried out. The liquid passing speed at this time was set to SV5 (100 ml / h because the capacity is 20 ml). For each BV5 (100 ml because the volume is 20 ml), the weight per unit volume of the above metal ions was measured. The measurement was performed on the same ICP-AES that measured the neutralized liquid. The results are shown in Table 2.
  • the weight per unit volume of the four metal ions is 0.00005 g / L, which is the lower limit of the measured measuring instrument, and it can be seen that these metals are captured by the chelate resin in the ion exchange process. ..
  • the BV exceeds 40 it is considered that the capture capacity of the chelate resin is exceeded, and each metal ion is equal to or close to the weight per unit volume in the neutralized liquid.
  • Example 1 The neutralization step and the ion exchange step were carried out under the same conditions as in Example 1 except that the liquid passing rate in the ion exchange step was SV10 (200 ml / h) and the weight per unit volume was measured for each BV10. The results are shown in Table 3.
  • Example 2 The neutralization step and the ion exchange step were carried out under the same conditions as in Example 1 except that the liquid passing rate in the ion exchange step was SV25 (500 ml / h) and the weight per unit volume was measured for each BV50. The results are shown in Table 4.

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