WO2022071335A1 - 高純度リチウム塩水溶液の製造方法 - Google Patents
高純度リチウム塩水溶液の製造方法 Download PDFInfo
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- WO2022071335A1 WO2022071335A1 PCT/JP2021/035688 JP2021035688W WO2022071335A1 WO 2022071335 A1 WO2022071335 A1 WO 2022071335A1 JP 2021035688 W JP2021035688 W JP 2021035688W WO 2022071335 A1 WO2022071335 A1 WO 2022071335A1
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- aqueous solution
- lithium
- lithium salt
- phosphate
- salt aqueous
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- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 89
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000012266 salt solution Substances 0.000 title claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 47
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 46
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 44
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 42
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 94
- 239000002244 precipitate Substances 0.000 claims description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 24
- 229910017119 AlPO Inorganic materials 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 13
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229940063656 aluminum chloride Drugs 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum ion Chemical class 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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 method for producing a high-purity lithium salt aqueous solution.
- lithium has been attracting attention as a raw material for lithium-ion batteries such as lithium-ion secondary batteries, and as its supply source, minerals, salt water, seawater, etc. are known as well as those recycled from waste lithium batteries.
- the salt water is obtained from a natural salt lake and usually contains lithium in the form of lithium chloride.
- the concentration of lithium contained in the salt water is about 1 g / L.
- the salt water obtained from a natural salt lake is supplied to an open-air evaporation pond, which is naturally evaporated over a year to concentrate, remove impurities such as Mg, Ca, and B, and then precipitate lithium carbonate. Is being collected.
- the method of concentrating the salt water by natural evaporation requires a long time to concentrate the salt water, is easily affected by natural conditions such as weather, and lithium forms a salt with other impurities in the concentration process. There is a problem of being lost.
- Patent Document 1 a method of adding phosphorus, phosphoric acid or phosphate to the salt water to generate lithium phosphate and concentrating it is known (for example, Patent Document 1). reference).
- an aluminum salt is added to the lithium phosphate to prepare a slurry containing the lithium phosphate and the aluminum salt, and the pH of the slurry is set to 3.8 to 4.6.
- the phosphate ion ( PO 43- ) and aluminum ion (Al 3+ ) contained in the slurry are precipitated as aluminum phosphate (AlPO 4 ), and then the aluminum phosphate (AlPO 4 ) is filtered. By removing it separately, a crude lithium salt aqueous solution is obtained.
- the crude lithium salt aqueous solution can be made into a high-purity lithium salt aqueous solution by further removing impurities and purifying it by pH adjustment, treatment using an ion exchange membrane, or the like. It is said that lithium carbonate can be obtained by adding a carbonate such as sodium carbonate to a high-purity lithium salt aqueous solution.
- Patent Document 1 describes four kinds of compounds as the aluminum salt, aluminum chloride, aluminum sulfate, potassium aluminum sulfate, and aluminum nitrate.
- Patent Document 1 has difficulty in the filterability of aluminum phosphate (AlPO 4 ) that precipitates by adjusting the pH of a slurry containing lithium phosphate and an aluminum salt, and the aluminum phosphate (AlPO 4) is difficult to filter. There is a disadvantage that it takes a long time to filter AlPO 4 ).
- An object of the present invention is to provide a method for producing a high-purity lithium salt aqueous solution capable of eliminating such inconvenience and filtering aluminum phosphate (AlPO 4 ) in a short time.
- the method for producing a high-purity lithium salt aqueous solution of the present invention contains a lithium salt in the range of 0.1 to 70 g / L as lithium from a first lithium salt aqueous solution as a raw material.
- the pH of the slurry containing the obtained mixture of lithium phosphate and aluminum hydroxide is adjusted to the range of 2 to 3, and the step of obtaining a precipitate of aluminum phosphate and the mixture of lithium phosphate and aluminum hydroxide are included.
- It is characterized by comprising a step of filtering and removing the precipitate of aluminum phosphate from the slurry to obtain a second lithium salt aqueous solution, and a step of purifying the second lithium salt aqueous solution to obtain a high-purity lithium salt aqueous solution.
- a slurry containing a mixture of lithium phosphate and aluminum hydroxide is obtained from the first lithium salt aqueous solution as a raw material.
- the first lithium salt aqueous solution is a low-concentration lithium salt aqueous solution containing a lithium salt in the range of 0.1 to 70 g / L as lithium.
- the aluminum hydroxide may be added from the outside of the reaction system to the lithium phosphate-containing slurry obtained from the first lithium salt aqueous solution, and the lithium phosphate-containing slurry may be added from the first lithium salt aqueous solution. When obtained, it may be produced inside the reaction system.
- the pH of the slurry containing the mixture of lithium phosphate and aluminum hydroxide is then adjusted to the range of 2 to 3.
- aluminum phosphate (AlPO 4 ) is generated from the phosphate ions and aluminum ions contained in the slurry and precipitates.
- the precipitate of the aluminum phosphate is removed by filtration from the slurry to obtain a second lithium salt aqueous solution as a filtrate.
- the operation of filtering out the precipitate of aluminum phosphate by forming the aluminum phosphate from the slurry containing lithium phosphate and aluminum hydroxide is short. Can be done in time.
- a high-purity lithium salt aqueous solution can be obtained by removing impurities from the second lithium salt aqueous solution and purifying the aqueous solution.
- an aluminum salt excluding aluminum hydroxide and phosphoric acid are added to the first lithium salt aqueous solution to adjust the pH in the range of 8 to 14. , It is preferable to obtain a mixture of lithium phosphate and aluminum hydroxide.
- the precipitate of aluminum phosphate filtered from a slurry containing a mixture of lithium phosphate and aluminum hydroxide is deposited in the first lithium salt aqueous solution. It is preferable to add it.
- the precipitate of aluminum phosphate acts as an aluminum salt and a phosphoric acid source with respect to the first aqueous solution of lithium salt. Therefore, the product obtained in the reaction system can be conveniently used as a part of the aluminum salt and phosphoric acid to be added to the first aqueous solution of the lithium salt.
- the pH of the slurry containing the mixture of lithium phosphate and aluminum hydroxide obtained from the first lithium salt aqueous solution is adjusted to the range of 2 to 3.
- the mixture of lithium phosphate and aluminum hydroxide was filtered off from the slurry containing the mixture of lithium phosphate and aluminum hydroxide, and the filtered mixture of lithium phosphate and aluminum hydroxide was obtained. It is preferable to disperse it in a smaller amount of water than the first aqueous solution of lithium salt to obtain a slurry containing a concentrated mixture of lithium phosphate and aluminum hydroxide.
- the operation of filtering out the slurry or the precipitate of aluminum phosphate by concentrating the mixture of lithium phosphate and aluminum hydroxide is performed in a shorter time. be able to.
- the purification of the second lithium salt aqueous solution adjusts the pH of the second lithium salt aqueous solution in the range of 7 to 10, and produces lithium phosphate. And, it is preferable to carry out by filtering out the precipitate of aluminum hydroxide. By doing so, it is possible to remove phosphate ions and aluminum ions as impurities contained in the second lithium salt aqueous solution.
- the precipitate of lithium phosphate and aluminum hydroxide filtered out from the second lithium salt aqueous solution is obtained from the first lithium salt aqueous solution. It is preferably added to the mixture of lithium and aluminum hydroxide. Since the precipitates of lithium phosphate and aluminum hydroxide filtered out from the second lithium salt aqueous solution contain lithium phosphate, the precipitates are composed of lithium phosphate and aluminum hydroxide obtained from the first lithium salt aqueous solution. The recovery rate of lithium can be improved by adding it to the mixture of.
- the method for producing a high-purity lithium salt aqueous solution of the present embodiment first, in STEP 1 of FIG. 1, aluminum (Al) is added to a low-concentration lithium (Li) salt aqueous solution as the first lithium salt aqueous solution. ) Add salt and phosphoric acid (H 3 PO 4 ).
- the low-concentration Li salt aqueous solution contains a lithium salt such as lithium chloride in the range of 0.1 to 70 g / L as lithium.
- a low-concentration Li salt aqueous solution for example, salt water obtained from a natural salt lake or the like can be used.
- the Al salt added to the low-concentration Li salt aqueous solution may be any Al salt other than aluminum hydroxide, and for example, aluminum chloride can be used.
- the pH of the low-concentration Li salt aqueous solution to which the Al salt and H 3 PO 4 are added is adjusted to the range of 8 to 14, preferably 10 to 11.
- the pH adjustment in STEP 2 can be performed by adding, for example, sodium hydroxide (NaOH) or an aqueous solution thereof to the low-concentration Li salt aqueous solution to which the Al salt and H 3 PO 4 are added.
- lithium phosphate (Li 3 PO 4 ) and aluminum hydroxide (Al (OH) 3 ) are produced in the low-concentration Li salt aqueous solution to which Al salt and H 3 PO 4 are added.
- a slurry containing a mixture of Li 3 PO 4 and Al (OH) 3 can be obtained.
- the pH of the slurry is adjusted to the range of 2 to 3.
- the pH adjustment in STEP 2 can be performed, for example, by adding hydrochloric acid or sulfuric acid.
- AlPO 4 aluminum phosphate
- Li 3 PO 4 and Al (OH) 3 precipitates.
- the AlPO 4 can be filtered off from the slurry by solid-liquid separation to obtain a filtrate as a second aqueous lithium salt solution.
- the AlPO 4 since the AlPO 4 is produced from the slurry, it contains a small amount of unreacted Al (OH) 3 , and as a result, the filterability of the AlPO 4 is improved, and the filtering operation can be performed in a short time. It is believed that it can be done.
- the slurry containing the mixture of Li 3 PO 4 and Al (OH) 3 obtained in STEP 2 has a pH of 2 to 3 in STEP 3.
- Li 3 PO 4 and Al (OH) 3 may be separated by solid-liquid separation and concentrated by redispersing in a smaller amount of water than the low-concentration Li salt aqueous solution. ..
- the operation of filtering the AlPO 4 from the slurry in STEP 4 can be performed in a shorter time.
- the filtrate obtained in STEP 4 is a lithium chloride aqueous solution when the pH is adjusted by adding hydrochloric acid in STEP 3, and a lithium sulfate aqueous solution when the pH is adjusted by adding sulfuric acid in STEP 3.
- the AlPO 4 a mixture of AlPO 4 and Al (OH) 3 ) containing a trace amount of Al (OH) 3 separated in STEP 4 can be returned to STEP 1.
- the pH of the filtrate obtained in STEP 4 is adjusted to the range of 7 to 10.
- the pH adjustment in STEP 5 can be performed, for example, by adding sodium hydroxide (NaOH) or an aqueous solution thereof. In this way, phosphorus and aluminum as impurities contained in the filtrate are precipitated as Li 3 PO 4 and Al (OH) 3 .
- the high-purity lithium salt aqueous solution obtained in the present embodiment can obtain lithium carbonate by adding a carbonate such as sodium carbonate in STEP7.
- Example 1 In this example, first, 27.5 g of lithium chloride was added to 1.5 L of ion-exchanged water to prepare a low-concentration lithium aqueous solution containing 3 g / L of lithium (Li) as the first lithium salt aqueous solution.
- the first slurry was solid-liquid separated by vacuum filtration using a vacuum pump.
- a Buchner funnel manufactured by Kiriyama Glass Co., Ltd.
- a No. 1 having a reserved particle diameter of 0.5 ⁇ m was used as the filter paper.
- 3 Filter paper manufactured by Kiriyama Glass Co., Ltd.
- the filtered precipitate was washed with 300 mL of ion-exchanged water to obtain 281 g of a hydrous precipitate containing a mixture of lithium phosphate and aluminum hydroxide.
- the time required for the solid-liquid separation was 3 minutes and 50 seconds.
- the third slurry was solid-liquid separated by vacuum filtration using a vacuum pump.
- a Buchner funnel manufactured by Kiriyama Glass Co., Ltd.
- a No. 1 having a reserved particle diameter of 0.5 ⁇ m was used as the filter paper.
- 3 Filter paper manufactured by Kiriyama Glass Co., Ltd. was used.
- the filtered precipitate was washed with 60 mL of ion-exchanged water to obtain 68 g of a hydrous precipitate containing a mixture of aluminum phosphate and aluminum hydroxide and 200 mL of a filtrate as a second aqueous lithium salt solution.
- the time required for the solid-liquid separation for filtering out the hydrous precipitate containing the mixture of aluminum phosphate and aluminum hydroxide from the third slurry was 6 minutes and 5 seconds.
- the filtrate contained 18 g / L of lithium, 0.3 g / L of phosphorus (P), and less than 20 mg / L of aluminum (Al).
- the liquid temperature of the filtrate was maintained at 60 ° C., 0.1 g of a 48% sodium hydroxide aqueous solution was added, and the pH was adjusted to 7.9. Then, the mixture was further stirred for 30 minutes to obtain a precipitate containing a mixture of lithium phosphate and aluminum hydroxide.
- the precipitate was filtered off to obtain a high-purity lithium salt aqueous solution containing 17.6 g / L of lithium and having a concentration of phosphorus and aluminum of less than 1 mg / L. ..
- Example 2 In this example, 17.9 g of 36% hydrochloric acid was added to the concentrated second slurry containing a mixture of lithium phosphate and aluminum hydroxide in STEP 3 shown in FIG. 1 to adjust the pH to 4.3. A high-purity lithium salt aqueous solution was obtained in exactly the same manner as in Example 1.
- the time required for the solid-liquid separation for filtering out the hydrous precipitate containing the mixture of aluminum phosphate and aluminum hydroxide from the third slurry is 5 minutes 28 minutes. It was a second.
- the fifth slurry was made exactly the same as the case of the third slurry in Example 1, solid-liquid separated, and combined with 90.9 g of a hydrous precipitate containing aluminum phosphate. , 200 mL of the filtrate as a second aqueous lithium salt solution was obtained.
- the time required for the solid-liquid separation for filtering out the hydrous precipitate containing aluminum phosphate from the fifth slurry was 1 hour and 24 minutes.
- the filtrate also contained 14.5 g / L of lithium, 30 mg / L of phosphorus and less than 1 mg / L of aluminum.
- the fifth slurry was made exactly the same as the case of the third slurry in Example 1, solid-liquid separated, and 68 g of a hydrous precipitate containing aluminum phosphate and the second slurry. 215 mL of the filtrate as an aqueous solution of the lithium salt of 2 was obtained.
- the time required for the solid-liquid separation for filtering out the hydrous precipitate containing aluminum phosphate from the fifth slurry was 4 hours and 3 minutes.
- the filtrate also contained 16.2 g / L of lithium, 100 mg / L of phosphorus and 200 mg / L of aluminum.
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Abstract
Description
本実施例では、まず、イオン交換水1.5Lに塩化リチウム27.5gを添加し、第1のリチウム塩水溶液として、3g/Lのリチウム(Li)を含む低濃度リチウム水溶液を調製した。
本実施例では、リン酸リチウムと水酸化アルミニウムとの混合物を含む濃縮された第2のスラリーに、図1に示すSTEP3で、36%塩酸17.9gを添加し、pHを4.3に調整した以外は、実施例1と全く同一にして高純度リチウム塩水溶液を得た。
本比較例では、イオン交換水112gに、リン酸三リチウム(Li3PO4)11gと、塩化アルミニウム6水和物24.6gとを添加し、さらに61%硝酸9gを添加して、リン酸リチウムと塩化アルミニウム(AlCl3)との混合物を含む第4のスラリーを得た。本比較例で得られた前記第4のスラリーは、実施例1の第2のスラリーに対応するスラリーである。
本比較例では、イオン交換水95gに、リン酸三リチウム(Li3PO4)11gと、硝酸アルミニウム9水和物38.2gとを添加し、さらに61%硝酸9gを添加して、リン酸リチウムと塩化アルミニウム(AlCl3)との混合物を含む第4のスラリーを得た。
Claims (6)
- リチウム塩をリチウムとして0.1~70g/Lの範囲で含み、原料となる第1のリチウム塩水溶液から得られるリン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーのpHを2~3の範囲に調整し、リン酸アルミニウムの沈殿を得る工程と、
該リン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーから該リン酸アルミニウムの沈殿を濾別して除去し、第2のリチウム塩水溶液を得る工程と、
前記第2のリチウム塩水溶液を精製し、高純度リチウム塩水溶液を得る工程とを備えることを特徴とする高純度リチウム塩水溶液の製造方法。 - 請求項1記載の高純度リチウム塩水溶液の製造方法において、前記第1のリチウム塩水溶液に水酸化アルミニウムを除くアルミニウム塩とリン酸とを添加し、pHを8~14の範囲に調整することにより前記リン酸リチウムと水酸化アルミニウムとの混合物を得ることを特徴とする高純度リチウム塩水溶液の製造方法。
- 請求項2記載の高純度リチウム塩水溶液の製造方法において、前記第1のリチウム塩水溶液に、前記リン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーから濾別された前記リン酸アルミニウムの沈殿を添加することを特徴とする高純度リチウム塩水溶液の製造方法。
- 請求項1~請求項3のいずれか1項記載の高純度リチウム塩水溶液の製造方法において、前記第1のリチウム塩水溶液から得られる前記リン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーのpHを2~3の範囲に調整する前に、該リン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーから該リン酸リチウムと水酸化アルミニウムとの混合物を濾別し、濾別された該リン酸リチウムと水酸化アルミニウムとの混合物を該第1のリチウム塩水溶液よりも少量の水に分散させて、濃縮されたリン酸リチウムと水酸化アルミニウムとの混合物を含むスラリーを得ることを特徴とする高純度リチウム塩水溶液の製造方法。
- 請求項1~請求項4のいずれか1項記載の高純度リチウム塩水溶液の製造方法において、前記第2のリチウム塩水溶液の精製は、該第2のリチウム塩水溶液のpHを7~10の範囲に調整し、生成するリン酸リチウム及び水酸化アルミニウムの沈殿を濾別することにより行うことを特徴とする高純度リチウム塩水溶液の製造方法。
- 請求項5記載の高純度リチウム塩水溶液の製造方法において、前記第2のリチウム塩水溶液から濾別されたリン酸リチウム及び水酸化アルミニウムの沈殿を、前記第1のリチウム塩水溶液から得られるリン酸リチウムと水酸化アルミニウムとの混合物に添加することを特徴とする高純度リチウム塩水溶液の製造方法。
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US17/928,436 US20230145941A1 (en) | 2020-10-02 | 2021-09-28 | Method for producing high-purity aqueous lithium salt solution |
KR1020237013476A KR20230070294A (ko) | 2020-10-02 | 2021-09-28 | 고순도 리튬염 수용액의 제조 방법 |
CN202180040232.8A CN115667145B (zh) | 2020-10-02 | 2021-09-28 | 高纯度锂盐水溶液的制造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023054452A1 (ja) * | 2021-09-30 | 2023-04-06 | 株式会社アサカ理研 | リンの回収方法 |
WO2023140084A1 (ja) * | 2022-01-21 | 2023-07-27 | 株式会社アサカ理研 | リチウム塩を含む水性液からリチウムを回収する方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011020892A (ja) * | 2009-07-15 | 2011-02-03 | Ryoko Lime Industry Co Ltd | ろ過・沈降性に優れたアモルファスリン酸アルミニウムの製造方法 |
WO2018184876A1 (en) * | 2017-04-07 | 2018-10-11 | Umicore | Process for the recovery of lithium |
CN108675323A (zh) | 2018-05-23 | 2018-10-19 | 赣州有色冶金研究所 | 一种低品位磷酸锂酸性转化法制备电池用碳酸锂的方法 |
CN109052436A (zh) * | 2018-09-21 | 2018-12-21 | 深圳市德方纳米科技股份有限公司 | 一种由锂磷铝石制备含锂化合物的方法 |
CN110482511A (zh) * | 2019-07-12 | 2019-11-22 | 湖南大学 | 一种废旧磷酸铁锂电池正极材料的回收方法 |
CN111137869A (zh) * | 2019-12-25 | 2020-05-12 | 佛山市德方纳米科技有限公司 | 磷酸铁锂的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2008302364A1 (en) * | 2007-09-17 | 2009-03-26 | Areva Federal Services Llc | A process for removal of aluminum oxides from aqueous media |
CN105600765A (zh) * | 2016-04-04 | 2016-05-25 | 王嘉兴 | 一种磷酸铝的制备方法 |
CN108862227B (zh) * | 2018-09-21 | 2022-11-11 | 深圳市德方纳米科技股份有限公司 | 一种从锂磷铝石中提取锂并制备含铁的磷酸盐的方法 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011020892A (ja) * | 2009-07-15 | 2011-02-03 | Ryoko Lime Industry Co Ltd | ろ過・沈降性に優れたアモルファスリン酸アルミニウムの製造方法 |
WO2018184876A1 (en) * | 2017-04-07 | 2018-10-11 | Umicore | Process for the recovery of lithium |
CN108675323A (zh) | 2018-05-23 | 2018-10-19 | 赣州有色冶金研究所 | 一种低品位磷酸锂酸性转化法制备电池用碳酸锂的方法 |
CN109052436A (zh) * | 2018-09-21 | 2018-12-21 | 深圳市德方纳米科技股份有限公司 | 一种由锂磷铝石制备含锂化合物的方法 |
CN110482511A (zh) * | 2019-07-12 | 2019-11-22 | 湖南大学 | 一种废旧磷酸铁锂电池正极材料的回收方法 |
CN111137869A (zh) * | 2019-12-25 | 2020-05-12 | 佛山市德方纳米科技有限公司 | 磷酸铁锂的制备方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4144694A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023054452A1 (ja) * | 2021-09-30 | 2023-04-06 | 株式会社アサカ理研 | リンの回収方法 |
WO2023140084A1 (ja) * | 2022-01-21 | 2023-07-27 | 株式会社アサカ理研 | リチウム塩を含む水性液からリチウムを回収する方法 |
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