WO2023286683A1 - 高純度硫酸ニッケルの製造方法 - Google Patents
高純度硫酸ニッケルの製造方法 Download PDFInfo
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- WO2023286683A1 WO2023286683A1 PCT/JP2022/026911 JP2022026911W WO2023286683A1 WO 2023286683 A1 WO2023286683 A1 WO 2023286683A1 JP 2022026911 W JP2022026911 W JP 2022026911W WO 2023286683 A1 WO2023286683 A1 WO 2023286683A1
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- WIPO (PCT)
- Prior art keywords
- nickel sulfate
- crystallization
- nickel
- solid
- lithium
- Prior art date
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 117
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 89
- 239000011777 magnesium Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 65
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 64
- 239000007787 solid Substances 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 53
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 24
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims abstract description 16
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims description 127
- 230000008025 crystallization Effects 0.000 claims description 123
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 41
- 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 claims description 39
- 238000001816 cooling Methods 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 37
- 239000012452 mother liquor Substances 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 238000010979 pH adjustment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 17
- 230000021523 carboxylation Effects 0.000 abstract 2
- 238000006473 carboxylation reaction Methods 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 118
- 229910052759 nickel Inorganic materials 0.000 description 57
- 239000002994 raw material Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 18
- 239000000654 additive Substances 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000000638 solvent extraction Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical class [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 that is Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- 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
- C22B3/08—Sulfuric acid, other sulfurated 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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 method for producing high-purity nickel sulfate. More particularly, the present invention relates to a method for removing magnesium, especially contained as an impurity, from nickel sulfate. INDUSTRIAL APPLICABILITY
- the present invention can be applied to aqueous solutions of nickel sulfate generated in the extraction of nickel from ores, the recycling process of lithium-ion secondary batteries, the acid treatment process of lithium-nickel composites, and the like.
- Nickel sulfate is obtained as a product or by-product through the extraction of nickel from ores, the recycling process of lithium-ion secondary batteries, or the acid treatment process of lithium-nickel composites.
- Nickel sulfate thus obtained is used as a synthetic raw material for lithium ion secondary battery positive electrode materials, primary battery positive electrode materials, various catalysts, and the like.
- nickel sulfate When using nickel sulfate as a raw material for the above applications, one of the important physical properties of nickel sulfate is its high purity. In order to meet this demand, crystallization methods, solvent extraction methods, and precipitation methods using alkali hydroxide have been developed as methods for purifying nickel sulfate.
- Non-Patent Document 1 reports that sodium, chlorine, and magnesium tend to be mixed into nickel sulfate crystals by cooling crystallization, and magnesium is contained in nickel sulfate more than other elements. It has been shown to be easy to remain. As shown in this example, using crystallization to remove magnesium is not an efficient technique.
- Patent Document 1 describes a technique in which an organic phase retaining nickel and a crude nickel sulfate solution containing impurities are brought into contact in countercurrent flow to separate the impurities from nickel through a substitution reaction. ing. Although magnesium in the nickel solution is reduced by this method, its removal rate is low because magnesium's reaction behavior is similar to that of nickel. As seen in this example, solvent extraction is not a technique that can effectively remove magnesium from nickel sulfate.
- Patent Document 2 discloses that an alkali hydroxide such as calcium hydroxide is added to an aqueous solution of nickel sulfate containing magnesium as an impurity, and nickel is removed by solid-liquid separation to form a nickel hydroxide precipitate. and separates the magnesium into a filtrate, and separates and recovers the dissolved magnesium as a precipitate by neutralization.
- an alkali hydroxide such as calcium hydroxide
- This method utilizes the property that nickel and magnesium precipitate in an aqueous solution with different pH values. It is difficult to say that it is an advantageous method because it requires a very high level of skill in order to maximize the operation.
- the nickel hydroxide precipitate obtained by the addition of alkali hydroxide has a strong tendency to precipitate as fine particles.
- problems that hinder practical operation such as the need to prepare a relatively large solid-liquid separation device in order to obtain it, or the economic efficiency decreases due to the introduction of a special filtration device. Not an efficient technique.
- Patent Document 3 discloses a technique that combines a carbonation process, a solid-liquid separation process, and a neutralization process in order to selectively separate and remove magnesium contained in an aqueous nickel sulfate solution.
- the pH adjustment will be easier than when using an alkali hydroxide, and the filterability of the precipitate will be improved.
- the problem is that the high magnesium removal rate obtained by the method cannot be obtained.
- the yield of nickel which is the main component, is greatly reduced if the operation is performed under conditions that increase the removal rate of magnesium. Therefore, although it is possible to reduce magnesium, it is not an efficient technique for magnesium removal that achieves both a nickel yield and a magnesium removal rate.
- Patent Document 4 describes a technique that combines a hydroxylation process, a carbonation process, a solid-liquid separation process, and a neutralization process. Using this technique, it is possible to precipitate hydroxides with alkali hydroxide under conditions that allow easy pH adjustment. be recovered. This technique avoids the problem of pH adjustment, which requires a high degree of control, and improves nickel yields and magnesium removal rates.
- the amount of carbonation additive used in the carbonation process is increased, the amount of alkali metal derived from the carbonation additive mixed in the process of repeating nickel reuse increases and is incorporated into nickel. As the amount of alkali metals added increases, nickel sulfate, which is the final product, is contaminated with alkali metals.
- Patent Document 5 describes a method of producing basic nickel carbonate with excellent filterability by using an alkali carbonate and adding an alkali hydroxide as necessary.
- sodium carbonate is used as the alkali metal carbonate.
- Patent Literature 1 discloses a method of reducing impurities in a nickel solution using an exchange reaction. This technique allows the sodium contained in the aqueous nickel sulfate solution to be separated. Although the amount of by-products generated is reduced by applying solvent extraction using pH adjustment to a portion of the nickel sulfate that requires treatment, a certain percentage of raw nickel is extracted and processed.
- Non-Patent Document 1 a method of removing sodium by crystallization to obtain high-purity nickel sulfate crystals is also conceivable.
- sodium is concentrated in the crystallization mother liquor by continuing this operation, and the amount of sodium mixed in the nickel sulfate crystals gradually increases. continue.
- a certain nickel/sodium concentration ratio is reached, a double salt of nickel sulfate and sodium sulfate begins to precipitate, making it impossible to obtain high-purity nickel sulfate crystals by crystallization.
- the technique of recovering high-purity nickel by adding alkali hydroxide or alkali carbonate which is considered to be superior to the crystallization method and solvent extraction method, is also effective in removing magnesium while yielding high nickel yields.
- the technology to achieve this was not established.
- the carbonated nickel is used repeatedly, the amount of impurities mixed in the regenerated nickel sulfate is kept at a low level, and the quality of high-purity nickel sulfate is maintained. The technology to do so was not established.
- the present invention has been devised in view of the above-mentioned circumstances, and solves these problems related to the removal of magnesium and the improvement of its purity at the same time.
- the purpose is to significantly improve performance.
- the method disclosed by the present invention is to select the appropriate chemical species as a carbonation additive to separate nickel and magnesium, and apply it to a two-stage crystallization process as a nickel sulfate manufacturing process. It is a manufacturing method characterized by
- lithium carbonate as a carbonation additive, which has never been used before.
- the precipitate obtained in this step not only has a high precipitation rate but is also excellent in filterability, so solid-liquid separation is easy.
- a certain amount of lithium is contained as an impurity in the solid content recovered by solid-liquid separation.
- This precipitate is regenerated into an aqueous nickel sulfate solution using sulfuric acid or an aqueous nickel sulfate solution containing excess sulfuric acid.
- this aqueous solution is supplied to a step in which a concentrated crystallization operation and a cooling crystallization operation are alternately repeated, whereby high-purity lithium sulfate crystals are obtained by the concentrated crystallization operation, and high-purity nickel sulfate crystals are obtained by the cooling crystallization. can get.
- the liquid generated by solid-liquid separation becomes an aqueous solution in which magnesium, a small amount of nickel, and lithium are dissolved.
- Lithium hydroxide is added to this aqueous solution, and magnesium and a small amount of nickel are recovered as solids. Dissolved lithium sulfate can be introduced into the concentrated crystallization step after appropriate pH adjustment.
- the first gist of the present invention is a production method characterized by comprising the following steps (1) to (3) as steps for producing a nickel sulfate aqueous solution in which magnesium is removed from nickel sulfate. resides in (1) A carbonation step of mixing an aqueous solution of nickel sulfate and lithium carbonate to obtain a slurry containing nickel carbonate as a solid content (2) A solid-liquid separation step of separating the slurry obtained in the carbonation step into solid and liquid ( 3) A dissolution step of dissolving the solid content obtained in the above step with a solution containing sulfuric acid
- the second gist of the present invention is that the lithium-containing nickel sulfate aqueous solution obtained in the dissolving step (3) of dissolving in a solution containing sulfuric acid is subjected to concentrated crystallization to obtain a slurry containing lithium sulfate as a solid content.
- the nickel sulfate aqueous solution according to the first aspect which includes a solid-liquid separation step of separating the slurry obtained in the precipitation step and the concentration crystallization step into solid and liquid to obtain the solid content of lithium sulfate crystals and the crystallization mother liquor. It depends on the manufacturing method.
- the third gist of the present invention is a cooling crystallization step of obtaining a slurry containing nickel sulfate as a solid content by cooling the crystallization mother liquor separated in the concentration crystallization step, and the slurry obtained by the cooling crystallization. is separated into a solid and a liquid to obtain a solid content of nickel sulfate crystals and a crystallization mother liquor, and the nickel sulfate is taken out as crystals.
- the fourth gist of the present invention resides in the method for producing an aqueous nickel sulfate solution according to the second or third gist, including the operation of returning the crystallization mother liquor separated in the cooling crystallization step to the concentrated crystallization step.
- the fifth gist of the present invention is a solution obtained by subjecting the liquid obtained in the solid-liquid separation step (2) after the carbonation step to pH adjustment and solid-liquid separation to remove dissolved carbonic acid and polyvalent metals. and introducing the obtained solution into the concentrated crystallization step.
- the sixth gist of the present invention resides in the method for producing an aqueous nickel sulfate solution according to any one of the second to fifth gists, wherein the operating temperature in the concentrated crystallization step is 40°C or higher.
- the seventh gist of the present invention is the production of the nickel sulfate aqueous solution according to any one of the third to sixth gists, wherein the operating temperature in the cooling crystallization step is 20°C or more lower than the operating temperature in the concentrated crystallization step. It depends on the method.
- a solid content containing nickel carbonate is obtained as a precipitate.
- One of the effects of the present invention is that even if the amount of lithium carbonate added is less than the theoretical equivalent, it is possible to recover nickel with high yield and high purity.
- the nickel carbonate-containing solid content obtained in this way has a large aggregate particle diameter, so that it has a high sedimentation velocity and is excellent in filterability, so solid-liquid separation can be easily carried out. Therefore, even if it is a general-purpose filtration apparatus, solid content can be efficiently collect
- This nickel carbonate-containing solid content is further dissolved in an aqueous solution containing sulfuric acid.
- This solution contains nickel sulfate and trace amounts of lithium sulfate.
- lithium sulfate crystals are obtained as a solid content, and nickel sulfate is concentrated in the crystallization mother liquor.
- High-purity lithium sulfate crystals can be obtained by appropriately washing the solid content.
- the lithium sulfate obtained in this step has a quality suitable for reuse as a raw material for producing lithium carbonate and lithium hydroxide.
- the concentrated crystallization mother liquor is further transferred to the cooling crystallization step to obtain nickel sulfate as crystals.
- nickel sulfate as crystals.
- high-purity nickel sulfate crystals can be obtained.
- the liquid generated in the carbonation process also becomes a lithium sulfate solution after removing the magnesium component, and this solution can be introduced into the concentrated crystallization process. Therefore, the waste liquid treatment of the carbonation step and the step of recovering lithium sulfate, which is a valuable material, can be carried out in one step, so that the steps can be simplified and the economic efficiency can be further improved.
- Carbon dioxide gas is generated in the process of dissolving nickel carbonate-containing solids with sulfuric acid. If it is desired to reduce the amount of carbon dioxide gas emitted, it is possible to synthesize lithium carbonate by absorbing carbon dioxide gas through a reaction with lithium hydroxide. The lithium carbonate thus obtained can be reused as a carbonating additive for nickel sulfate. Therefore, the carbon dioxide gas is repeatedly used in the process, and the amount continuously discharged out of the process can be greatly reduced.
- FIG. 1 is a production flow diagram of high-purity nickel sulfate and high-purity lithium sulfate of the present invention.
- FIG. FIG. 4 is a diagram showing the relationship between the magnesium removal rate with respect to the solid content obtained in the carbonation step and the carbonation temperature in Examples using the present invention.
- FIG. 4 is a diagram showing the relationship between the yield of solids obtained in the carbonation step and the carbonation temperature in Examples using the present invention.
- FIG. 5 is a diagram showing the relationship between the yield of solids obtained in the carbonation step and the magnesium removal rate, for examples using the present invention and comparative examples using a known technique.
- an example manufacturing flow consists of carbonation, decarboxylation, neutralization, dissolution, concentration crystallization, cooling crystallization, and solid-liquid separation steps.
- the combination of unit operations that constitute the actual process is not limited to this example, and a person skilled in the art who has experience with such technology can make modifications without departing from the spirit of the present invention. can be done.
- nickel sulfate containing magnesium as an impurity is mixed with an aqueous solution of lithium carbonate to precipitate nickel carbonate-containing solids.
- the equivalent ratio of lithium carbonate to nickel is preferably 1 or less, more preferably 0.9 or less.
- the precipitation temperature is preferably 50°C or higher.
- the difference in temperature does not significantly affect the removal rate of magnesium, but does change the yield of nickel. Therefore, from the viewpoint of nickel yield, the temperature is preferably 70° C. or higher. Although it is possible to operate at a temperature higher than 70°C, it is more advantageous to operate in a temperature range of around 70°C because there are many restrictions on the materials of usable equipment and equipment design. From the above point of view, the upper limit of the precipitation temperature is preferably 110°C.
- the concentration of the raw material solution can be determined arbitrarily, but the higher the nickel sulfate concentration, the higher the efficiency. At room temperature, a solution with a concentration of 26% by weight of nickel sulfate can be easily prepared. A higher temperature may be used to prepare a raw material solution in which a larger amount of nickel sulfate is dissolved. For the reaction at 70° C., the raw material solution may also be heated to 70° C. to dissolve, for example, 35% by weight of nickel sulfate.
- the upper limit of the concentration of the raw material solution is preferably not more than the saturated concentration that can be stably handled at the temperature at which the solution is prepared.
- the nickel carbonate-containing solid content tends to precipitate, so it is necessary to properly stir the reaction tank.
- the stirring method a known method can be used and can be selected as appropriate.
- the carbonation process may be carried out by any operation of batch type, continuous type, or semi-batch type. However, it is preferable to secure a residence time or reaction time of the slurry in the reaction vessel for 1 hour or longer. If this time is too short, the reaction between lithium carbonate and nickel sulfate may not be completed. If the residence time of the slurry or the reaction time is too long, the reaction will complete, but the efficiency will be poor in terms of time.
- the nickel carbonate-containing solid content obtained in the carbonation step is separated into solid content and liquid content in the solid-liquid separation step.
- the solid-liquid separation device an appropriate device such as a vacuum filtration type or a pressure filtration type may be selected.
- a vacuum filtration type or a pressure filtration type may be selected.
- a large amount of nickel is dissolved under conditions that increase the magnesium removal rate. It is very different from the effect brought about by the invention.
- the solid content obtained in this process is regenerated into a nickel sulfate aqueous solution by adding sulfuric acid.
- concentration of nickel sulfate can be set arbitrarily, it is preferable to set the concentration as high as possible in order to proceed advantageously with the subsequent concentration crystallization step.
- the nickel-containing precipitate is contaminated with sodium derived from the carbonating agent, and even if an attempt is made to obtain high-purity nickel sulfate by crystallization, sodium sulfate is concentrated in the crystallization mother liquor. It formed a double salt with nickel sulfate, making separation and purification difficult.
- lithium carbonate as a carbonating additive, it is possible to solve the problem of double salt formation in the crystallization process and obtain high-purity nickel sulfate.
- the lithium-containing nickel sulfate aqueous solution obtained in the dissolution step is subjected to a concentrated crystallization operation by a known method using either heating or reduced pressure, or a combination of both. Since the solubility of lithium sulfate tends to decrease as the temperature rises, it is advantageous to carry out the concentration crystallization operation in a high temperature range. C. to 110.degree. C., preferably 60.degree. C. to 90.degree.
- the solid content of the lithium sulfate crystals obtained by the concentration crystallization operation is separated by a solid-liquid separator.
- a centrifugal separator is generally used as this device, but other types may also be used.
- the crystals are washed using an aqueous medium such as water, hot water, or an aqueous solution of lithium sulfate with high purity. Since a cleaning liquid such as ethanol in which lithium sulfate is difficult to dissolve can be used, the cleaning liquid should be selected in consideration of the increase in waste liquid treatment cost. If washing is performed with water, hot water, or an aqueous solution of lithium sulfate, the washing waste liquid can be directly returned to the concentration and crystallization step.
- a part of the concentrated crystallization mother liquor is extracted and transferred to the cooling crystallizer.
- nickel sulfate precipitates as crystals due to the change in solubility.
- This crystal is also washed by a suitable solid-liquid separation and washing device.
- a centrifugal separator is generally used, and an aqueous medium such as a small amount of water, cold water, or a highly pure nickel sulfate aqueous solution is used as a washing liquid.
- This washing waste liquid can be returned to the cooling crystallization step, but since the efficiency of the cooling crystallization is lowered, it is more operationally advantageous to return it to the concentrated crystallization step.
- a part of the cooling crystallization mother liquor is extracted and returned to the concentrated crystallizer. Lithium sulfate remaining in the mother liquor forms crystals by a concentration crystallization operation, and nickel sulfate is concentrated again.
- the solubility of nickel sulfate decreases as the temperature decreases, it is preferable to carry out the cooling crystallization operation at a lower temperature. °C to 60 °C. If the difference from the operating temperature of the concentration crystallization step is small, the efficiency of crystal precipitation in each step is lowered, so it is preferable to set the temperature difference to 30° C. or more. For example, if the concentrated crystallization is operated at 70° C. and the cooling crystallization is operated at 35° C., the load of heating and cooling can be reduced.
- Eutectic Freeze Crystallization can also be applied to cooling crystallization.
- water crystals (ice) are generated as floating matter in the process of obtaining nickel sulfate crystals as a precipitate, and by solid-liquid separation of these, the concentration of the crystallization mother liquor can be achieved at the same time.
- the vaporization energy required for concentration of the solution can be reduced as a whole system without departing from the concept of the present invention.
- the liquid generated in the carbonation process and the subsequent solid-liquid separation process contains lithium sulfate and trace amounts of nickel and magnesium.
- sulfuric acid is first added to lower the pH to liberate and remove the carbon dioxide gas.
- the pH is controlled to be 4 or less.
- a depressurization operation may be carried out together.
- the neutralization step is to remove the minute amounts of nickel and magnesium that are dissolved by neutralization as solids.
- Any alkaline hydroxide can be selected as the neutralizing agent, but lithium hydroxide is preferably used if the solution is to be treated in the crystallization step. If the liquid component is supplied to the crystallization step using any other alkali hydroxide, the concentration of impurities in the lithium sulfate obtained in the crystallization step increases.
- the pH is adjusted so that nickel and magnesium are sufficiently precipitated.
- the pH is preferably 8 or higher, more preferably 10 or higher.
- the liquid obtained from the neutralization process and the solid-liquid separation process becomes a lithium sulfate aqueous solution.
- sulfuric acid is added in advance such that lithium ions and sulfate ions are stoichiometrically equivalent.
- the pH of the lithium sulfate solution is preferably adjusted to about 3.5 to 6.0.
- the content of magnesium in the high-purity nickel sulfate obtained in the present invention is usually 300 (mg (Mg) / kg (Ni)) or less, preferably 100 ( mg (Mg)/kg (Ni)) or less.
- the nickel concentration in the raw material solution and the high-concentration nickel content in the solid content recovered after the carbonation process were measured by a known chelate titration method using a copper ion selective electrode.
- the contents of nickel, lithium, and magnesium contained at low concentrations were measured using an ICP emission spectrometer iCAP6500 Duo (manufactured by Thermo Fisher Scientific Co., Ltd.).
- the pH of the slurry obtained by carbonation was measured using a pH meter HM-30P (manufactured by Toa DKK Co., Ltd.).
- Examples 1-4 ⁇ Separation of nickel and magnesium in carbonation step and yield of nickel>
- a simulated raw material aqueous solution was prepared so as to have a nickel sulfate concentration of 316 g/L and a magnesium sulfate concentration of 371 mg/L. About 40 mL of this solution was measured and transferred to a 1 L stainless steel container.
- An aqueous solution of lithium carbonate (concentration shown in Table 1) was prepared as a carbonation additive and heated at 50°C (Example 1), 60°C (Example 2), 70°C (Example 3), and 80°C (Example 4). ) was added to the above simulated solution over about 90 minutes while maintaining each temperature so that the equivalence ratio shown in Table 1 was obtained.
- the magnesium content shown in Table 1 is the magnesium element content (mg (Mg)/kg (Ni)) normalized by the nickel element content.
- Fig. 2 shows the proportion of magnesium dissolved in the liquid that was contained in the simulated mother liquor but did not migrate into the nickel precipitate, that is, the magnesium removal rate relative to the solid content. It can be seen that the removal rate is as high as about 90% under any treatment conditions.
- Figure 3 shows the percentage of nickel recovered as a solid content, that is, the yield of nickel. It can be seen that the yield of nickel is higher when the treatment temperature is 70 and 80°C than when the treatment temperature is 50 and 60°C.
- Comparative Example 1 ⁇ Separation of Nickel and Magnesium and Nickel Yield in Carbonation Process Based on Conventional Technology> Experiments were conducted according to the prior art for magnesium removal using sodium carbonate as the carbonating additive.
- the holding temperature of the reaction vessel was 40° C.
- the concentration of the additive solution was adjusted to 3.10% by weight by using an aqueous solution of sodium carbonate instead of the aqueous solution of lithium carbonate, and the equivalent ratio of sodium carbonate to nickel sulfate was 0.
- Processing was carried out as in Example 1, except that 0.68 was used.
- Comparative Example 2 In an experiment similar to Comparative Example 1, the equivalent ratio of sodium carbonate to nickel sulfate was 1.18.
- FIG. 4 shows the relationship between the percentage of nickel recovered as a solid content and the magnesium removal rate of the solid content for the samples obtained in Comparative Examples 1 and 2, together with the results of Examples 1 and 4.
- a high nickel recovery rate about 80% or more
- a high magnesium removal rate about 80% or more
- Example 5 ⁇ Filtration rate of solid content cake obtained in the carbonation step> A carbonation reaction was carried out in the same manner as in Example 4 except that about 75 mL of the raw material solution was used, a 2 L stainless steel container was used as the reaction vessel, and the retention time after addition of lithium carbonate was set to 3 hours.
- Comparative Example 3 ⁇ Filtration rate of solid content cake obtained by alkali hydroxide method based on conventional technology> 65 mL of the raw material solution was used, a 2 L stainless steel vessel was used as the reaction vessel, an aqueous solution of lithium hydroxide was used as the precipitation additive, the equivalent ratio of the additive was 0.9, and the amount of washing water was 200 mL. Except for this, the precipitation reaction and filtration rate were measured in the same manner as in Example 5. At this time, the lithium concentration in the lithium hydroxide aqueous solution was adjusted to be the same as the lithium concentration in the lithium carbonate aqueous solution in Example 5. The results are shown in Table 2.
- Comparative Example 4 ⁇ Filtration rate of solid content cake obtained in carbonation process based on conventional technology> The carbonation reaction was carried out in the same manner as in Example 5, except that sodium carbonate was used as the precipitating additive.
- Example 5 From Table 2, it can be seen that the yield of nickel in Example 5 and Comparative Examples 3 and 4 is almost the same. At this time, it is clear that the solid content cake obtained in Example 5 is significantly superior to that obtained in Comparative Example 3 in filterability. Furthermore, it is clear that the filterability of Example 5 is significantly superior to Comparative Example 4 using sodium carbonate as an additive.
- Example 6 ⁇ Separation of nickel sulfate and lithium sulfate by crystallization> Even when lithium is concentrated in the crystallization mother liquor, lithium sulfate can be separated by concentrated crystallization according to the present invention, and high-purity nickel sulfate crystals are obtained by subsequent cooling crystallization. Simulated mother liquors were prepared from nickel sulfate and lithium sulfate reagents to confirm that the The simulated mother liquor was made to contain nickel sulfate and lithium sulfate in an amount of 5.08% by weight in terms of metallic nickel and 1.23% by weight in terms of metallic lithium, respectively.
- a 1.52-fold concentration of the simulated mother liquor used in concentration crystallization was used as the starting mother liquor for cooling crystallization, and 3.1 L of this concentrate was placed in the crystallization vessel.
- the temperature of the cooling water flowing through the heat insulating jacket was controlled so that the inside of the vessel was maintained at 25° C. during cooling crystallization.
- Table 3 shows the analysis results of the crystals obtained by a series of operations, the simulated mother liquor, and the crystallization mother liquor after cooling crystallization.
- the cooling crystallization mother liquor has a nickel/lithium ratio equal to that of the raw material solution, the cooling crystallization mother liquor can be returned to the concentrated crystallization step as it is, and can be repeatedly used for crystallization of lithium sulfate crystals. I understand.
- nickel and magnesium can be effectively separated, and a precipitate with excellent filterability can be obtained. Further, after the precipitate is regenerated into an aqueous solution of nickel sulfate, nickel sulfate and lithium sulfate contained in the aqueous solution are separated by concentrated crystallization and cooling crystallization according to the present invention, and high-purity nickel sulfate is obtained. Obtainable.
- Magnesium contained in the raw material can be removed out of the system through the neutralization process, and lithium derived from the carbonation additive is recovered as lithium sulfate in the crystallization process, so it is possible to use it in the process of refining nickel sulfate. Accumulation of impurities in the product does not affect the nickel sulfate crystals. Therefore, nickel sulfate from which magnesium has been removed can be continuously obtained in the form of an aqueous solution or crystals at a high yield throughout the purification process.
- the method for producing high-purity nickel sulfate of the present invention can be easily applied to existing equipment, can produce nickel sulfate efficiently with high yield, and can reuse chemical products other than the target product generated in each process. Because it can be done, it is extremely economical.
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Abstract
Description
このように、従来から利用されている溶媒抽出法や晶析法でマグネシウムを効率的に除去することは難しく、沈殿法であっても沈殿物の濾過性、高いマグネシウム除去効率、高いニッケル収率を同時に満たすような経済的な手法が確立されているとは言い難い。
ニッケル中にナトリウムが混入した場合、これを除去して高純度の硫酸ニッケルを得る手法としても溶媒抽出法が挙げられる。例えば、特許文献1には、交換反応を利用してニッケル溶液中の不純物を低減する手法が公開されている。この技術によって、硫酸ニッケル水溶液に含有されるナトリウムを分離することができる。処理を必要とする硫酸ニッケルの一部についてpH調整を利用した溶媒抽出を適用することで、副生成物の発生量を低減しているとはいえども、原料ニッケルに対して一定割合で抽出・逆抽出操作を繰り返す必要があるため、使用される酸とアルカリから副生成物として中和塩が大量に発生することは避けられない。pH調整剤として硫酸と水酸化ナトリウムが用いられる場合では、硫酸ナトリウムが大量に発生することになる。したがって、溶媒抽出法による硫酸ニッケル水溶液からナトリウムを除去する手法では、膨大な副生成物を処理する必要が追加で生じるために、経済的な技術とは言い難いものになる。
(1)硫酸ニッケル水溶液と炭酸リチウムとを混合して炭酸ニッケルを含む固形分とするスラリーを得る炭酸化工程
(2)前記炭酸化工程で得られるスラリーを固液に分離する固液分離工程
(3)前記工程で得られる固形分について、硫酸を含む溶液で溶解する溶解工程
不純物としてマグネシウムを含有する硫酸ニッケルと炭酸リチウム水溶液とを混合して、炭酸ニッケル含有固形分を析出させるのが炭酸化工程である。このとき、ニッケルに対する炭酸リチウムの当量比は1以下であることが好ましく、0.9以下であることがより好ましい。このように制御を行うと、混合スラリーのpHは8以下となり、当量比を0.86とすればpHは7.3以下となる。
<炭酸化工程におけるニッケルとマグネシウムの分離とニッケルの収率>
硫酸ニッケル濃度として316g/L、硫酸マグネシウム濃度として371mg/Lとなるように模擬原料水溶液を準備した。この溶液を約40mL計り取り、1Lのステンレス容器へと移した。炭酸化添加剤として炭酸リチウムの水溶液(表1に示す濃度)を準備し、50℃(実施例1)、60℃(実施例2)、70℃(実施例3)、80℃(実施例4)の各温度を維持しながら約90分かけて上記の模擬溶液へ、表1に示す当量比になるように添加した。これらの操作を準備・実施している間は、容器内が十分に撹拌されているように維持した。添加が完了した後、所定の保持時間において液分だけをサンプリングし、液中に含まれるマグネシウムの量を分析した。5時間の保持時間を経たスラリーについて、pHを測定した。ブフナー漏斗を用いた減圧濾過によって固液分離を行い、得られた固形分のケーキは水で洗浄した。これらの処理条件を表1に示す。表1中に示すマグネシウム含有量は、ニッケル元素の含有量で規格化したマグネシウム元素の含有量(mg(Mg)/kg(Ni))としている。
<従来の技術に基づく炭酸化工程におけるニッケルとマグネシウムの分離とニッケルの収率>
炭酸化添加剤として炭酸ナトリウムを用いたマグネシウム除去について、従来の技術に基づいて実験を行った。反応容器の保持温度を40℃としたこと、炭酸リチウムの水溶液にかえて炭酸ナトリウムの水溶液を用いて3.10重量%の添加液濃度に調製したこと、硫酸ニッケルに対する炭酸ナトリウムの当量比を0.68としたことを除いては、実施例1と同様に処理を行った。
比較例1と同様の実験において、硫酸ニッケルに対する炭酸ナトリウムの当量比を1.18とした。
図4に、比較例1~2で得られたサンプルについて、固形分として回収されたニッケルの割合と固形分のマグネシウム除去率との関係を、実施例1~4の結果と合わせて示す。
本発明を適用した実施例においては固形分としての高いニッケル回収率(約80%以上)と高いマグネシウム除去率(約80%以上)を両立しているのに対し、従来技術を利用した比較例では両立できていないことがわかる。
<炭酸化工程で得られる固形分ケーキの濾過速度>
原料溶液を約75mL使用し、反応容器として2Lのステンレス容器を使用し、炭酸リチウム添加後の保持時間を3時間としたこと以外は、実施例4と同様にして炭酸化の反応を実施した。
<従来の技術に基づく水酸化アルカリ法で得られる固形分ケーキの濾過速度>
原料溶液を65mL使用し、反応容器として2Lのステンレス容器を使用し、沈殿添加剤として水酸化リチウム水溶液を用いて、添加剤の当量比を0.9とし、洗浄水の量を200mLとしたこと以外は、実施例5と同様にして沈殿反応および濾過速度の測定を実施した。このとき、水酸化リチウム水溶液中のリチウム濃度が実施例5における炭酸リチウム水溶液中のリチウム濃度と同じになるように濃度を調整した。この結果を表2に示す。
<従来の技術に基づく炭酸化工程で得られる固形分ケーキの濾過速度>
沈殿添加剤として炭酸ナトリウムを用いたこと以外は、実施例5と同様にして炭酸化の反応を実施した。
<晶析操作による硫酸ニッケルと硫酸リチウムの分離>
晶析母液中にリチウムが濃縮された場合であっても、本発明による濃縮晶析によって硫酸リチウムを分離することができ、これに続く冷却晶析で高純度の硫酸ニッケル結晶が晶析によって得られることを確認するために、硫酸ニッケルと硫酸リチウム試薬から模擬母液を準備した。この模擬母液に金属ニッケル換算で5.08重量%、金属リチウム換算で1.23重量%の硫酸ニッケルおよび硫酸リチウムがそれぞれ含まれるようにした。
Claims (7)
- 硫酸ニッケルからマグネシウムが除去された硫酸ニッケル水溶液を製造する工程として、下記(1)から(3)に示す工程から構成されることを特徴とする製造方法。
(1)硫酸ニッケル水溶液と炭酸リチウムとを混合して炭酸ニッケルを含む固形分とするスラリーを得る炭酸化工程
(2)前記炭酸化工程で得られるスラリーを固液に分離する固液分離工程
(3)前記工程で得られる固形分について、硫酸を含む溶液で溶解する溶解工程 - 更に、前記(3)硫酸を含む溶液で溶解する溶解工程で得られたリチウム含有硫酸ニッケル水溶液を濃縮晶析によって硫酸リチウムを固形分とするスラリーを得る濃縮晶析工程、および、濃縮晶析工程で得られるスラリーを固液に分離し、硫酸リチウム結晶の固形分と晶析母液とを得る固液分離工程を含む請求項1に記載の硫酸ニッケル水溶液の製造方法。
- 更に、前記濃縮晶析工程で分離された晶析母液を冷却晶析によって硫酸ニッケルを固形分とするスラリーを得る冷却晶析工程、冷却晶析で得られるスラリーを固液に分離し、硫酸ニッケル結晶の固形分と晶析母液とを得る固液分離工程を含む請求項2に記載の硫酸ニッケル水溶液の製造方法。
-
前記冷却晶析工程で分離された晶析母液を前記濃縮晶析工程へ戻す操作を含む請求項2又は3に記載の硫酸ニッケル水溶液の製造方法。 - 前記(2)炭酸化工程後の固液分離工程で得られる液分にpH調整と固液分離を行い、溶存している炭酸と多価金属を除去した溶液を得る工程、および、得られた溶液を前記濃縮晶析工程へ導入する請求項2~4の何れかに記載の硫酸ニッケル水溶液の製造方法。
- 前記濃縮晶析工程における操作温度を40℃以上とする請求項2~5の何れかに記載の硫酸ニッケル水溶液の製造方法。
- 前記冷却晶析工程における操作温度を濃縮晶析工程の操作温度より20℃以上低い温度とする請求項3~6の何れかに記載の硫酸ニッケル水溶液の製造方法。
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JP2010229534A (ja) * | 2009-03-30 | 2010-10-14 | Nippon Mining & Metals Co Ltd | ニッケルとリチウムの分離回収方法 |
CN102115125A (zh) * | 2010-12-30 | 2011-07-06 | 何云 | 用含锰废液制备碳酸盐和硫酸锂混合产品的方法 |
JP2014144877A (ja) * | 2013-01-25 | 2014-08-14 | Sumitomo Metal Mining Co Ltd | 高純度硫酸ニッケルの製造方法、及びニッケルを含む溶液からの不純物元素除去方法 |
JP2016056434A (ja) * | 2014-09-12 | 2016-04-21 | 住友金属鉱山株式会社 | ニッケルスラッジからのニッケルの分離方法 |
CN109706318A (zh) * | 2018-12-28 | 2019-05-03 | 池州西恩新材料科技有限公司 | 一种含镍钴锰锂废正极材料的资源化回收方法 |
CN109734107A (zh) * | 2018-12-28 | 2019-05-10 | 池州西恩新材料科技有限公司 | 一种锂电池废正极材料的资源化回收方法 |
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