CN112442596A - Method for separating and recovering nickel, cobalt and manganese in battery intermediate feed liquid by carboxylic acid extracting agent - Google Patents
Method for separating and recovering nickel, cobalt and manganese in battery intermediate feed liquid by carboxylic acid extracting agent Download PDFInfo
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- CN112442596A CN112442596A CN202011131786.2A CN202011131786A CN112442596A CN 112442596 A CN112442596 A CN 112442596A CN 202011131786 A CN202011131786 A CN 202011131786A CN 112442596 A CN112442596 A CN 112442596A
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- 238000000605 extraction Methods 0.000 claims abstract description 237
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 191
- 229910001868 water Inorganic materials 0.000 claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 96
- 239000012071 phase Substances 0.000 claims abstract description 96
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 81
- 239000010941 cobalt Substances 0.000 claims abstract description 81
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000012074 organic phase Substances 0.000 claims abstract description 77
- 239000011572 manganese Substances 0.000 claims abstract description 75
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 72
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 59
- 238000005406 washing Methods 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 30
- 238000007127 saponification reaction Methods 0.000 claims description 28
- 239000008346 aqueous phase Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 18
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 150000007522 mineralic acids Chemical class 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 11
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- -1 Escaid110 Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000002923 oximes Chemical class 0.000 claims description 4
- 239000012527 feed solution Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 10
- 239000000945 filler Substances 0.000 claims 3
- 239000005416 organic matter Substances 0.000 claims 1
- 239000000344 soap Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910015853 MSO4 Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, which comprises the following steps: (1) carrying out chemical impurity removal on the feed liquid to obtain a water phase 1 and iron-containing aluminum slag; (2) performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2; (3) carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel loaded organic phase and a water phase 3; (4) carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt loaded organic phase and a water phase 4; (5) and (3) enriching and separating sodium sulfate crystals in the water phase 4 obtained in the step (4) to obtain a sodium sulfate product, and treating the wastewater to reach the standard and discharging, wherein the extracting agent B used in the nickel extraction comprises a carboxylic acid extracting agent. The method provided by the invention can separate, extract and recover nickel, cobalt and manganese in the battery intermediate feed liquid containing nickel, cobalt and manganese, and the extracting agent B has high efficiency for extracting nickel, low acid and alkali consumption and low operation cost.
Description
Technical Field
The invention relates to the field of resource recovery, in particular to a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese.
Background
The nickel-cobalt-manganese ternary cathode material has good cycle performance, stable structure and high cost performance, is a novel lithium ion battery cathode material, is widely applied to the new energy automobile industry, and the required scale of the lithium ion battery is continuously enlarged, so that the quantity of the waste lithium ion batteries is increased day by day. If the waste lithium battery is discarded at will, the environment is seriously polluted, and valuable metal resources are wasted in a large amount, and the best way for solving the problem is to realize recycling of nickel, cobalt, manganese and lithium, so that the recycling of the waste lithium battery has double effects of environmental effect and market effect.
Hydrometallurgy is a scientific technology for dissolving valuable metal components in ores, concentrates, waste battery anode materials and other materials in a solution or separating out the valuable metal components in a new solid phase by using a leaching agent to separate, enrich and extract metals, has the characteristics of low energy consumption, small pollution, high resource utilization rate and the like, and is continuously concerned and developed by a plurality of researchers all the time.
CN110066925A discloses a method for recovering valuable metals from waste nickel-cobalt-manganese ternary lithium batteries, which comprises the steps of extracting and purifying a battery feed liquid by using P204, carrying out back extraction to obtain a back extraction solution containing manganese sulfate and a raffinate containing Co, Ni and Li ions, removing Cu from the back extraction solution, and then carrying out evaporation concentration and crystallization to obtain manganese sulfate; extracting Co in the raffinate by using saponified P507, and obtaining a cobalt sulfate solution after back extraction; removing Mg in the raffinate by using C272, extracting Ni in the raffinate by using P507, and performing back extraction to obtain a nickel sulfate solution; detecting the concentration of divalent Fe in the leachate, adding an oxidant to oxidize the divalent Fe into trivalent Fe, adding sodium carbonate to adjust the pH value of the leachate to 4.5-5.0, and removing Fe and Al precipitates; detecting the content of Ca and Mg, adding sodium fluoride or potassium fluoride to precipitate Ca and Mg, and filtering. The process flow is complex, the separation cost for respectively recovering nickel, cobalt and manganese elements is high, impurity metal ions such as Ca, Mg and the like are removed by adopting a precipitation method, and valuable metal entrainment loss is easily caused.
Disclosure of Invention
In view of the problems in the prior art, the invention discloses a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, wherein a carboxylic acid extracting agent B adopted by the method can efficiently extract and extract nickel, and has good separation effect with impurity ions; the environmental effect is good; the organic phase can be recycled, the operation cost is low, and the economic benefit is good.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, which comprises the following steps:
(1) carrying out chemical impurity removal on the feed liquid to obtain a water phase 1 and iron-containing aluminum slag;
(2) performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2;
(3) carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel loaded organic phase and a water phase 3;
(4) carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt loaded organic phase and a water phase 4;
(5) performing sodium sulfate crystal enrichment and separation on the water phase 4 obtained in the step (4) to obtain a sodium sulfate product, treating the wastewater to reach the standard and discharging the wastewater,
wherein the extractant B used in the method comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in formula I and is named as CPH 88:
wherein-C8H17Are all straight chain alkyl groups.
By the method, nickel, cobalt and manganese in the intermediate feed liquid of the nickel-cobalt-manganese-containing battery are separated, extracted and recycled, and a byproduct sodium sulfate is concentrated and recycled, so that the nickel extraction process is not influenced by impurity metal ions such as calcium, magnesium and the like, the extraction pH value is low, the alkali consumption can be reduced, the whole process is simple to operate and stable in process operation, and meanwhile, the extraction rate of the carboxylic acid extracting agent on Ni is more than 99.5%, and the sulfuric acid back extraction rate is more than 99.9%.
In the present invention, the concentration of the solution of sodium sulfate and/or sodium carbonate used for chemical removal of impurities in step (1) is 10 to 100g/L, for example, 10g/L, 15g/L, 20g/L, 23g/L, 27g/L, 30g/L, 33g/L, 45g/L, 50g/L, 65g/L, 70g/L, 80g/L, 90g/L, or 99g/L, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In the present invention, the equilibrium pH of the raffinate aqueous phase in the manganese extraction in step (2) is 1 to 4, and may be, for example, 1, 1.2, 1.5, 1.9, 2.0, 2.5, 2.8, 3.0, 3.1, 3.6, 3.7 or 3.9, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the volume fraction of the high-purity extractant in the extractant a for manganese extraction in the step (2) is 5 to 30%, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the recited values, and other values not recited in this range are also applicable.
In the present invention, the flow ratio of the extractant a for manganese extraction in the step (2) to the feed liquid is (0.1 to 10):1, and may be, for example, 0.1:1, 0.5:1, 1.5:1, 3.5:1, 5.5:1, 7:1 or 9.8:1, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the stirring speed for manganese extraction in step (2) is 100 to 800r/min, and may be, for example, 100r/min, 200r/min, 220r/min, 300r/min, 350r/min, 380r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min or 790r/min, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the mixing time for manganese extraction in step (2) is 5 to 30min, and may be, for example, 5min, 7min, 8min, 10min, 13min, 15min, 16min, 18min, 21min, 22min, 25min, 28min or 29min, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In the present invention, the number of stages of the multistage countercurrent fractional extraction in the manganese extraction in the step (2) is 2 to 30, and for example, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17, 18, 20, 22, 24, 26, 28, or 29 may be used, but not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
As a preferred technical solution of the present invention, the extractant a used in the impurity removal extraction in step (2) includes 1 or a combination of at least 2 of a phosphorus-type extractant, a carboxylic acid-type extractant, or an oxime-type extractant.
In the present invention, the phosphorus-type extractant includes 1 or a combination of at least 2 of P204, P507, or C272.
In the present invention, the carboxylic acid extractant includes 1 or a combination of at least 2 of BC191, BC192, BC194, or BC 196.
In the present invention, the oxime extractant includes any 1 or a combination of at least 2 of Mextral 984H, Lix63 or CP 50.
In the invention, if the feed liquid contains copper ions, oxime extractant is preferably selected to remove copper in the feed liquid in impurity removal and extraction.
In the invention, the manganese loaded organic phase in the step (2) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a manganese-containing metal ion solution and a regenerated organic phase.
Preferably, the regenerated organic phase is returned to use as extractant.
In the present invention, the pH of the aqueous phase 2 obtained by nickel extraction in step (3) is 1.9 to 5, and may be, for example, 1.9, 2.0, 2.1, 2.3, 2.4, 2.7, 3.0, 3.1, 3.4, 3.6, 3.8, 4.0, 4.2, 4.6, 4.8 or 4.9, but is not limited to the values listed, and other values not listed in this range are also applicable, and preferably 2.0 to 3.5.
As a preferable technical scheme of the invention, the metal elements in the feed liquid comprise 1-60 g/L of Ni, 1-50 g/L of Co, 1-50 g/L of Mn, less than or equal to 10g/L of Fe, less than or equal to 1g/L of Al, less than or equal to 10g/L of Cu, less than or equal to 5g/L of Zn, about 0.1-0.5 g/L of Ca and 0.1-50 g/L of Mg.
In the present invention, the concentration of Ni in the feed liquid is 1 to 60g/L, and may be, for example, 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L50g/L, 52g/L, 55g/L, 58g/L or 59g/L, etc., but not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the concentration of Co in the feed liquid is 1 to 50g/L, and may be, for example, 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 32g/L, 35g/L, 37g/L, 40g/L, 43/L, 45g/L, 47g/L or 49g/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the concentration of Mn in the feed liquid is 1 to 50g/L, and may be, for example, 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 20g/L, 23g/L, 27g/L, 32g/L, 35g/L, 37g/L, 40g/L, 43/L, 45g/L, 47g/L or 49g/L, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the concentration of Fe in the feed liquid is not more than 10g/L, and may be, for example, 10g/L, 9g/L, 8g/L, 7g/L, 6g/L, 5g/L, 4g/L or 3g/L, etc., but is not limited to the values listed above, and other values not listed above within the range are also applicable.
In the present invention, the concentration of Al in the feed liquid is not more than 1g/L, and may be, for example, 1g/L, 0.8g/L, 0.6g/L, 0.4g/L or 0.2g/L, but is not limited to the values listed above, and other values not listed in the range are also applicable.
In the present invention, the Cu concentration in the feed liquid is not more than 10g/L, and may be, for example, 10g/L, 9.5g/L, 8.7g/L, 7.4g/L, 6.6g/L, 5.6g/L, 4.3g/L or 3g/L, etc., but is not limited to the values listed above, and other values not listed in the range are also applicable.
In the present invention, the Zn concentration in the feed liquid is not more than 5g/L, and may be, for example, 5g/L, 4.3g/L, 3.5g/L, 2g/L or 1g/L, etc., but is not limited to the values listed above, and other values not listed above within the range are also applicable.
In the present invention, the Ca concentration in the feed liquid is 0.1 to 0.5g/L, and may be, for example, 0.1g/L, 0.2g/L, 0.33g/L, 0.45g/L or 0.5g/L, etc., but is not limited to the values listed above, and other values not listed in this range are also applicable.
In the present invention, the concentration of Mg in the feed liquid is 0.1 to 50g/L, and may be, for example, 0.1g/L, 10g/L, 20g/L, 30g/L, 40g/L or 50g/L, but is not limited to the values listed above, and other values not listed above in this range are also applicable.
In the invention, the nickel-nickel extractant in the step (3) is a carboxylic acid extractant, and the structural formula of the carboxylic acid extractant is as shown in formula I:
wherein-C8H17Are all straight chain alkyl groups.
In the present invention, the volume fraction of carboxylic acid in the extractant B in the step (3) is 5 to 30%, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
Preferably, the diluent of the extractant B comprises 1 or a combination of at least 2 of kerosene, Escaid110, mineral spirits, dodecane.
In the present invention, the solvent may be mineral spirit No. 200 and/or mineral spirit No. 260.
In the present invention, the dodecane may be n-dodecane or the like.
Preferably, the extractant B is saponified before use.
Preferably, the saponification is carried out using 6 to 14mol/L of an alkaline saponifier, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the alkaline saponifier comprises 1 or a combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water.
The combination may be a combination of a sodium hydroxide solution and a potassium hydroxide solution, a combination of a potassium hydroxide solution and aqueous ammonia, or the like, but is not limited to the listed combinations, and other combinations not listed in this range are also applicable.
Preferably, the nickel extraction in step (3) is a multi-stage countercurrent fractional extraction, the number of stages of the multi-stage countercurrent fractional extraction is 2 to 30, for example, 2, 3, 5, 10, 15, 20, 25 or 30, etc., but the method is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the flow ratio of the extractant B to the aqueous phase 1 in the nickel extraction in step (3) is (0.1 to 20: 1), and may be, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 13:1, 15:1, 17:1, 19:1 or 20:1, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the stirring speed in the nickel extraction in the step (3) is 100-800 r/min, such as 100r/min, 150r/min, 220r/min, 300r/min, 350r/min, 370r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min or 790r/min, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the mixing time of the nickel extraction in the step (3) is 5 to 30min, such as 5min, 10min, 15min, 20min, 25min or 30min, but not limited to the values listed, and other values not listed in the range are also applicable.
As a preferable technical scheme of the invention, the nickel loaded organic phase in the step (3) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a solution containing metal ions and a regenerated organic phase.
As a preferred technical scheme of the invention, the washing in the step (3) is multi-stage countercurrent washing.
Preferably, the number of washing stages is 2 to 20, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, 18, or 19, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the regenerated organic phase is returned to use as extractant.
In the invention, the washing of the nickel-loaded organic phase is carried out by adopting inorganic acid and/or acidified water and nickel sulfate solution; the flow ratio of the nickel-loaded organic phase to the washing is (0.1 to 10: 1), and may be, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the pH of the inorganic acid and/or acidified water is 0.1 to 2, and may be, for example, 0.1, 0.2, 0.4, 0.5, 0.7, 0.9, 1.0, 1.2, 1.5, 1.7, 1.8 or 1.9, but is not limited to the above-mentioned values, and other values not mentioned in the above range are also applicable.
In the present invention, the nickel sulfate solution is 0.5 to 20g/L, for example, 0.5g/L, 1g/L, 1.5g/L, 5g/L, 6g/L, 7g/L, 10g/L, 12g/L, 13g/L, 15g/L, 17g/L, 18g/L, 19g/L or 20g/L, etc., but not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the nickel-bearing organic phase is washed by a detergent in a multi-stage counter-current manner, and then is back-extracted by an acid solution, wherein the flow ratio of the nickel-cobalt-manganese-bearing organic phase to the acid in the back-extraction is (0.1 to 10):1, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the concentration of the inorganic acid in the stripping agent is 0.5 to 4mol/L, and may be, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L or 4mol/L, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and it is more preferable that the concentration of the stripping agent is 2 mol/L.
In the present invention, the number of the stripping stages is 3 to 10, and may be, for example, 3, 4, 5, 6, 7, 8 or 9, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
In the invention, in the step (4), the aqueous phase 3 obtained in the step (3) is subjected to cobalt extraction by using an extracting agent C, wherein the extracting agent C can be a phosphine extracting agent and a carboxylic acid extracting agent.
In the invention, the phosphine extractant is P507, and the carboxylic acid extractant is BC191, BC193, BC196 and the like.
In the present invention, the volume fraction of the extractant C is 5 to 30%, and may be, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the cobalt extraction in the step (4) may be performed using a phosphine extraction in which the aqueous phase equilibrium pH is 3 to 5, and may be, for example, 3.1, 3.4, 3.5, 3.7, 4.0, 4.3, 4.6, 4.8, or 4.9, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the cobalt extraction in step (4) may be performed using a carboxylic acid extraction in which the aqueous phase equilibrium pH is 5 to 7.8, and may be, for example, 5.1, 5.4, 5.5, 5.7, 6.0, 6.3, 7.0, 7.4, or 7.8, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the extractant C is saponified before use, and the saponifying agent includes 1 or at least 2 combinations of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution, and aqueous ammonia, and the combinations may be a combination of sodium hydroxide solution and potassium hydroxide solution, a combination of potassium hydroxide solution and aqueous ammonia, and the like, but are not limited to the combinations listed, and other combinations not listed are also applicable within the scope.
Preferably, the saponification is carried out using 6 to 14mol/L of an alkaline saponifier, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the cobalt extraction in the step (4) is a multistage countercurrent fractional extraction, the number of stages of the multistage countercurrent extraction is 2 to 30, and for example, may be 2, 3, 5, 10, 15, 20, 25 or 30, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the flow ratio of the extractant C to the aqueous phase 3 in the nickel extraction in the step (4) is (0.1 to 20: 1), and may be, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 13:1, 15:1, 17:1, 19:1 or 20:1, but is not limited to the above-mentioned values, and other values not mentioned in this range are also applicable.
In the present invention, the stirring speed in the cobalt extraction in the step (4) is 100 to 800r/min, and may be, for example, 100r/min, 150r/min, 220r/min, 300r/min, 350r/min, 370r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min, 790r/min, or the like, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the mixing time for cobalt extraction in step (4) is 5 to 30min, for example, 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
As a preferable technical scheme of the invention, the cobalt loaded organic phase in the step (4) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a metal ion-containing solution and a regenerated organic phase.
As a preferred technical scheme of the invention, the washing in the step (4) is multi-stage countercurrent washing.
Preferably, the number of washing stages is 2 to 20, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, 18, or 19, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the regenerated organic phase is returned to use as extractant.
In the invention, the washing of the cobalt-loaded organic phase is carried out by adopting inorganic acid and/or acidified water and cobalt sulfate solution; the flow ratio of the nickel-loaded organic phase to the washing is (0.1 to 10: 1), and may be, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the pH of the inorganic acid and/or acidified water is 0.1 to 2, and may be, for example, 0.1, 0.2, 0.4, 0.5, 0.7, 0.9, 1.0, 1.2, 1.5, 1.7, 1.8 or 1.9, but is not limited to the above-mentioned values, and other values not mentioned in the above range are also applicable.
In the present invention, the cobalt sulfate solution is 0.5 to 20g/L, for example, 0.5g/L, 1g/L, 1.5g/L, 5g/L, 6g/L, 7g/L, 10g/L, 12g/L, 13g/L, 15g/L, 17g/L, 18g/L, 19g/L or 20g/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the nickel-bearing organic phase is washed with a detergent in a multi-stage counter-current manner, and then is back-extracted with an acid solution, wherein the flow ratio of the cobalt-bearing organic phase to the acid in the back-extraction is (0.1 to 10):1, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the present invention, the concentration of the inorganic acid in the stripping agent is 0.5 to 4mol/L, and may be, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L or 4mol/L, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and it is more preferable that the concentration of the stripping agent is 2 mol/L.
In the present invention, the number of the stripping stages is 3 to 10, and may be, for example, 3, 4, 5, 6, 7, 8 or 9, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
As the preferred technical scheme of the invention, the reaction equipment for manganese extraction, nickel extraction and cobalt extraction is a mixer-settler.
As a preferable technical scheme of the invention, the water phase 4 in the step (5) is subjected to oil removal and crystallization sequentially to obtain sodium sulfate crystals.
Preferably, the crystallization is by MVR evaporation.
In the invention, the oil removal is realized by adopting a conventional oil removal method in the prior art, and the oil-water separation is realized.
As a preferred technical scheme of the invention, the method comprises the following steps:
characterized in that the method comprises the following steps:
(1) chemically removing impurities from the feed liquid by using sodium sulfate and/or sodium carbonate to obtain a water phase 1 and iron-containing aluminum slag liquid, and performing filter pressing on the slag liquid to obtain iron-containing aluminum slag;
(2) performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese-loaded organic phase and a water phase 2, wherein the extractant A comprises 1 or at least 2 of phosphorus type extractants, carboxylic acid extractants or oxime extractants; the volume fraction of the extracting agent A is 5-30%; the manganese extraction comprises single-stage extraction or multi-stage countercurrent extraction; the flow ratio of an extracting agent A used in the manganese extraction to the feed liquid is (0.1-10): 1; the stirring speed in the manganese extraction is 100-800 r/min; the mixing time in the manganese extraction is 5-30 min; the device for impurity removal and extraction is a mixer-settler; the manganese extraction is multi-stage countercurrent fractional extraction, the number of stages is 2-30, manganese-loaded organic is washed and then is subjected to back extraction by using a back extractant, a manganese-rich solution and regenerated organic are obtained, the regenerated organic is recycled, and the cost is reduced.
(3) Carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel-loaded organic phase and a water phase 3, wherein the extractant B used in the nickel-loaded organic phase comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in formula I and is named as CPH 88:
wherein-C8H17Are all straight chain alkyl groups. The volume fraction of the extracting agent B is 5-30%, the diluent of the extracting agent B comprises 1 or the combination of at least 2 of solvent naphtha, kerosene, Escaid110 and dodecane, the extracting agent B is saponified by using 6-14 mol/L alkaline saponifying agent comprising 1 or the combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water before use, the volume ratio of the extracting agent B to the water phase 1 in the nickel extraction is (0.1-20): 1, and the stirring speed in the nickel extraction is 1The degree is 100-800 r/min, the mixing time in the nickel extraction in the step (3) is 5-30 min, the extraction equipment used in the nickel extraction is a mixer-settler, the water phase equilibrium pH value of the nickel extraction is 1.9-5, the multistage countercurrent fractional extraction is of 2-30 stages, 0.5-4 mol/L inorganic acid comprises any one or the combination of at least two of hydrochloric acid, nitric acid or sulfuric acid is used for the back extraction, the stage number of the back extraction is of 3-10 stages, the volume ratio of the back extractant to the nickel loaded organic phase is 1 (0.1-10), the step of washing the nickel loaded organic phase obtained in the step (3) is further included before the back extraction, the washing stage number is of 2-20 stages, the washing comprises the washing of inorganic acid and/or acidified water and nickel sulfate solution, the nickel loaded organic phase is subjected to the back extraction by using the back extractant after the washing, the obtained sulfuric acid solution and the regenerated organic are recycled, so that the cost is reduced.
(4) Performing cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt-loaded organic phase and a water phase 4, wherein the extractant used in the step (3) can be carboxylic acid extractants BC191, BC193 and BC196, and can also be a phosphorus extractant P507, the equipment used in the cobalt extraction is a mixed clarifying tank, before extraction, the extractant C is saponified by using an alkaline compound, the alkaline saponifying agent comprises 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water, the concentration range of the alkaline saponifying agent is 6-14 mol/L, the saponified organic phase and the water phase are contacted step by step, the volume ratio of the extractant C to the water phase 1 in the cobalt extraction is (0.1-20): 1, the stirring speed is controlled at 100-800 r/min, the cobalt extraction mixing time is 5-30 min, and the loaded cobalt extraction is washed and back-extracted, the obtained cobalt sulfate solution and the regenerated organic are recycled, so that the cost is reduced.
In the step, the extractant C is different due to the water phase equilibrium pH required to be controlled by using different types of extractants, for example, when a phosphine extractant is used in cobalt extraction, the water phase equilibrium pH is 3-5, and the water phase equilibrium pH in carboxylic acid extraction is 5-7.8 in cobalt extraction.
(5) And (4) sequentially removing oil and crystallizing the water phase 4 obtained in the step (4) to obtain sodium sulfate crystals, treating the wastewater, and discharging the wastewater after reaching the standard, wherein the crystallization mode is MVR evaporation.
In the present invention, the multi-stage countercurrent fractional extraction is one of the extraction and separation methods, and the water phase and the organic phase containing the extracted substance respectively flow into the two ends of the extractor and flow in opposite directions to perform continuous multi-stage stirring contact layering to achieve the separation purpose.
In the present invention, the reaction equation of the relevant process is as follows:
saponification of carboxylic acid extractant: HA(org)+NaOH→NaA(org)+H2O
Extracting with carboxylic acid extractant: 2NaA(org)+MSO4→MA2(org)+Na2SO4
Sulfuric acid back extraction: MA (MA)2(org)+H2SO4→2HA(org)+MSO4
Wherein: m is Fe3+、Cu2+、Al3+、Zn2+、Ni2+、Co2+、Mn2+And the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method provided by the invention, the carboxylic acid extractant CPH88 is utilized to carry out pre-extraction on the metal nickel, the extractant has a good nickel metal ion separation effect, the influence of impurity metal ions such as calcium and magnesium can be reduced, and the extraction is carried out at a low saponification rate, so that the acid-base consumption is reduced.
Drawings
FIG. 1 is a schematic diagram of the recovery process in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This embodiment provides a method for recovering nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, as shown in fig. 1.
The feed liquid in the embodiment is a battery intermediate feed liquid containing nickel, cobalt and manganese, the pH value of the feed liquid is 3.0, and the feed liquid comprises the following components:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 0.001 | 0.001 | 0.34 | 0.3 | 42 | 27 | 23 | 0.4 | 0.2 |
In this example, P204 was selected as the extractant for manganese extraction, the volume fraction was 25%, the diluent was sulfonated kerosene, 10mol/L NaOH solution was used for saponification, the degree of saponification was 42%, the flow ratio of the saponified organic phase to the aqueous phase was 2.5: 1, a reaction device uses a mixer-settler, the mixing time is 5min, the stirring speed is 200r/min, the designed extraction stage number is 10 stages, the washing stage number is 6 stages, the carried metallic elements such as nickel and cobalt are washed off, the washing residual liquid is merged into the water phase 2, the back extraction stage number is 4 stages, and the back extraction agent is 2.5mol/L sulfuric acid. Obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out the next nickel extraction on the obtained water phase 2.
Nickel extraction was performed on aqueous phase 2, in this example, CPH88 was used as the extractant, CPH88 volume fraction was 25%, escalid 110 was used as the diluent, 10mol/L NaOH solution was used for saponification, degree of saponification was 30%, flow ratio of saponified organic phase to aqueous phase 2 was 4: setting the mixing time of a mixing chamber to be 10min, setting the stirring speed to be 200r/min, using a mixer-settler as reaction equipment, designing the extraction stage number to be 5 stages, controlling the equilibrium pH value of an extraction water phase to be 2-4, washing the extraction water phase to be 6 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 3, performing back extraction on the extraction liquid to be 6 stages, and selecting 2.0mol/L sulfuric acid as a back extraction agent. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on aqueous phase 3. in this example, BC191 was used as the extractant, the BC191 volume fraction was 25%, Escaid110 was used as the diluent, 10mol/L NaOH solution was used for saponification, the degree of saponification was 40%, the flow ratio of saponified organic phase to aqueous phase 2 was 2:1, setting the mixing time of a mixing chamber to be 8min, setting the stirring speed to be 200r/min, using a mixer-settler as reaction equipment, designing the extraction stage number to be 7, controlling the balance pH value of an extraction water phase to be 5-6.5, washing the extraction water phase to be 10 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 4, performing back extraction to be 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, setting the volume of cobalt-loaded organic and washing liquid or back extraction liquid to be 10:1, obtaining a cobalt sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and performing next-step sodium sulfate precipitation on an obtained water phase.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the contents of iron, aluminum, zinc and copper in the water phase after the manganese extraction are less than 0.001g/L, the extraction rates of Ni, Co and Mn are respectively 99.8%, 99.7% and 99.6%, and the back extraction rates are respectively 99.8%, 99.8% and 99.6%.
Example 2
The feed liquid in the embodiment is a battery intermediate feed liquid containing nickel, cobalt and manganese, the pH value of the feed liquid is 2.0, and the feed liquid comprises the following components:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 1.2 | 1.0 | 0.20 | 0.01 | 48 | 22 | 27 | 0.36 | 0.48 |
In the embodiment, 20g/L of sodium carbonate is used for chemical impurity removal and iron and aluminum impurity removal, and the obtained water phase 1 is used for manganese extraction and iron and aluminum-containing slag.
In this example, P204 was selected as the extractant to perform manganese extraction on aqueous phase 1, the volume fraction was 25%, the diluent was sulfonated kerosene, 26% ammonia water solution was used for saponification, the degree of saponification was 30%, and the flow ratio of the saponified organic phase to the aqueous phase was 2:1, a reaction device uses a mixer-settler, the mixing time is 5min, the stirring speed is 300r/min, the designed extraction stage number is 8 stages, the washing stage number is 6 stages, the carried metallic elements such as nickel and cobalt are washed off, the washing residual liquid is merged into the water phase 2, the back extraction stage number is 4 stages, and the back extraction agent is 2.5mol/L sulfuric acid. Obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out the next nickel extraction on the obtained water phase 2.
Performing nickel extraction on the water phase 2, in the embodiment, using CPH88 as an extractant, the CPH88 volume fraction being 25%, using sulfonated kerosene as a diluent, using 26% ammonia water solution for saponification, the saponification degree being 45%, the flow ratio of a saponified organic phase to the water phase 2 being 5:1, setting the mixing time of a mixing chamber to be 10min, the stirring speed to be 300r/min, using a mixing clarification tank as a reaction device, designing the extraction stage number to be 7 stages, controlling the equilibrium pH value of the extraction water phase to be 2-4, washing 8 stages, washing off entrained metal elements such as cobalt, calcium, magnesium and the like, merging the washing raffinate into the water phase 3, performing back extraction to 6 stages, and selecting 2.0mol/L sulfuric acid as a back extractant. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on aqueous phase 3, in this example, BC196 was used as the extractant, the BC196 volume fraction was 25%, sulfonated kerosene was used as the diluent, 26% aqueous ammonia solution was used for saponification, the degree of saponification was 30%, the flow ratio of the saponified organic phase to aqueous phase 2 was 2:1, setting the mixing time of a mixing chamber to be 8min, setting the stirring speed to be 200r/min, using a mixer-settler as reaction equipment, designing the extraction stage number to be 7, controlling the balance pH value of an extraction water phase to be 6-7, washing the extraction water phase to be 10 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing raffinate into a water phase 4, performing back extraction to be 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, setting the volume of cobalt-loaded organic and washing liquid or back extraction liquid to be 10:1, obtaining a cobalt sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and performing next sodium sulfate precipitation on an obtained water phase 3.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the contents of iron and aluminum in the water phase after chemical impurity removal are less than 0.3g/L, the contents of iron, aluminum, zinc and copper in the water phase after manganese extraction are less than 0.001g/L, the extraction rates of Ni, Co and Mn are respectively 99.6%, 99.7% and 99.9%, and the back extraction rates are respectively 99.8%, 99.8% and 99.9%.
Example 3
This embodiment provides a method for recovering nickel, cobalt, and manganese from a nickel, cobalt, and manganese-containing feed liquid, where the feed liquid in this embodiment is a nickel, cobalt, and manganese-containing battery intermediate feed liquid, and the pH of the feed liquid is 5.2, and the components are as follows:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 0.001 | 0.001 | 0.001 | 0.001 | 40 | 27 | 23 | 0.30 | 0.56 |
In this example, P204 was selected as the extractant to perform manganese extraction on aqueous phase 1, the volume fraction was 25%, the diluent was solvent oil No. 260, the slurry magnesium oxide solution was used to perform saponification, the degree of saponification was 34%, and the flow ratio of the saponified organic phase to the aqueous phase was 2:1, a reaction device uses a mixer-settler, the mixing time is 10min, the stirring speed is 500r/min, the designed extraction stage number is 10 stages, the washing stage is 12 stages, the carried metallic elements such as nickel and cobalt are washed off, the washing residual liquid is merged into the water phase 2, the back extraction stage is 4 stages, and the back extractant is 2.0mol/L sulfuric acid. Obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out the next nickel extraction on the obtained water phase 2.
Performing nickel extraction on the water phase 2, in the embodiment, using CPH88 as an extractant, CPH88 volume fraction of 25%, using 260 # solvent oil as a diluent, using a pulpy magnesium oxide solution to perform saponification, saponification degree of 30%, flow ratio of a saponified organic phase to the water phase 2 of 4:1, setting mixing time of a mixing chamber to be 5min, stirring speed to be 500r/min, using a mixing clarification tank as reaction equipment, designing extraction stage number to be 10 stages, controlling the equilibrium pH value of the extracted water phase to be 2-3, washing 12 stages, washing off entrained metal elements such as cobalt, calcium, magnesium and the like, merging the washing raffinate into the water phase 3, and performing back extraction on 6 stages, wherein the back extractant is 2.0mol/L sulfuric acid. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on aqueous phase 3. in this example, BC196 was used as the extractant, BC196 volume fraction was 25%, No. 260 mineral spirit was used as the diluent, slurry magnesium oxide solution was used for saponification, degree of saponification was 25%, flow ratio of saponified organic phase to aqueous phase 2 was 3:1, setting the mixing time of a mixing chamber to be 7min, setting the stirring speed to be 500r/min, using a mixer-settler as reaction equipment, designing the extraction stage number to be 10 stages, controlling the balance pH value of an extraction water phase to be 6-7, washing 16 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 4, performing back extraction for 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, setting the volume of cobalt-loaded organic and washing liquid or back extraction liquid to be 10:1, obtaining a cobalt sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and performing next step of sodium sulfate precipitation on an obtained water phase 3.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the content of iron, aluminum, zinc and copper in the water phase is about 0.001g/L, the purity of manganese extraction is more than 97%, the extraction rates of Ni, Co and Mn are respectively 99.4%, 99.2% and 99.8%, and the back extraction rates are respectively 99.8%, 99.8% and 99.9%.
Example 4
The difference from the embodiment 2 is that the average pH of the water phase 3 is controlled to be 1.9, the extraction rates of Ni, Co and Mn are respectively 99.9%, 99.7% and 99.9%, the back extraction rate is more than 99.5%, the extraction series and the alkali consumption are reduced, and the advantage of efficiently extracting nickel by CPH88 with low pH is realized.
Example 5
The difference from the embodiment 1 is that the extractant for extracting manganese is changed from P204 to C272, the extraction rates of Ni, Co and Mn are respectively 99.9%, 99.9% and 99.9%, and the back extraction rate is more than 99.5%.
Comparative example 1
The difference from example 1 is only that the equilibrium pH of the aqueous phase of cobalt extraction is controlled to 7.6 and the impurity content of Co is not up to standard.
Comparative example 2
The only difference from example 3 is that the extractant CPH88 in the nickel extraction is replaced by an equal amount of P507, and the nickel cannot achieve the extraction separation.
From the results of the above examples and comparative examples, it is clear that the method provided by the present invention can realize the effect of the impurity metal ions such as calcium and magnesium in the nickel extraction process by efficiently separating nickel in advance by utilizing the advantage of extracting nickel with low acid by using the extractant CPH88, and reduce the separation cost of separately recovering nickel, cobalt and manganese and the extraction and purification cost of the impurity metal ions by using carboxylic acids to extract BC196, BC191 and the like in the cobalt extraction process.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese is characterized by comprising the following steps:
(1) carrying out chemical impurity removal on the feed liquid to obtain a water phase 1 and iron-containing aluminum slag;
(2) performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2;
(3) carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel loaded organic phase and a water phase 3;
(4) carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt loaded organic phase and a water phase 4;
(5) performing sodium sulfate crystal enrichment and separation on the water phase 4 obtained in the step (4) to obtain a sodium sulfate product, treating the wastewater to reach the standard and discharging the wastewater,
wherein the extractant B used in the method comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in formula I and is named as CPH 88:
wherein-C8H17Are all straight chain alkyl groups.
2. The method of claim 1, wherein the metallic elements in the feed solution comprise: 1-60 g/L of Ni, 1-50 g/L of Co, 1-50 g/L of Mn, less than or equal to 10g/L of Fe, less than or equal to 1g/L of Al, less than or equal to 10g/L of Cu, less than or equal to 5g/L of Zn, 0.1-0.5 g/L of Ca and 0.1-50 g/L of Mg.
3. The method of claim 1 or 2, wherein the iron and aluminum remover is a sodium sulfate and/or sodium carbonate solution, preferably the iron and aluminum remover is a sodium carbonate solution, and further preferably the concentration of the sodium carbonate is 10-100 g/L.
4. The method of claims 1 to 3, wherein the extractant A used in the manganese extraction in the step (2) comprises 1 or a combination of at least 2 of a phosphorus-type extractant, a carboxylic acid-type extractant or an oxime-type extractant;
preferably, the carboxylic acid extractant comprises 1 or a combination of at least 2 of BC191, BC192, BC194, or BC 196;
preferably, the phosphorus-type extractant includes 1 or a combination of at least 2 of P204 or C272;
preferably, the volume fraction of the extracting agent A is 5-30%;
preferably, the diluent of the extractant a comprises 1 or a combination of at least 2 of mineral spirit, kerosene, Escaid110, hexane, heptane, dodecane;
preferably, the extractant a is saponified before use;
preferably, the saponification is carried out by using an alkaline saponifying agent of 6-14 mol/L;
preferably, the alkaline saponifier comprises 1 or a combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water.
5. The method according to any one of claims 1 to 4, wherein the flow ratio of the extracting agent A used in the manganese extraction in the step (2) to the feed liquid is (0.1-10): 1;
preferably, the manganese extraction mode in the step (2) comprises single-stage extraction or multi-stage countercurrent fractional extraction;
preferably, the multistage countercurrent fractional extraction in the step (2) has 2-30 stages;
preferably, the stirring speed in the manganese extraction in the step (2) is 100-800 r/min;
preferably, the stirring and mixing time in the step (2) is 5-30 min;
preferably, the extraction equipment used in the manganese extraction in the step (2) is a mixer settler and a tower type filler extractor, and further preferably, the extraction equipment used in the impurity removal extraction in the step (2) is a mixer settler.
6. The process according to any one of claims 1 to 5, wherein the volume fraction of the extractant B is 5 to 30%;
preferably, the diluent of the extractant B comprises 1 or at least 2 combinations of solvent naphtha, kerosene, Escaid110, hexane, heptane and dodecane, and the kerosene is further optimized to be sulfonated kerosene;
preferably, the extractant B is saponified before use;
preferably, the saponification is carried out with an alkaline saponifier;
preferably, the alkaline saponifier comprises 1 or a combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water;
preferably, the concentration range of the alkaline saponifier is 6-14 mol/L;
preferably, the saponification degree of the extractant B is 5-60%.
7. The method of any one of claims 1 to 6, wherein the volume ratio of the extractant B to the aqueous phase 1 in the nickel extraction in step (3) is (0.1-20): 1;
preferably, the nickel extraction in the step (3) is multi-stage countercurrent fractional extraction;
preferably, the number of stages of the multistage countercurrent fractional extraction in the step (3) is 2-30 stages;
preferably, the stirring speed in the nickel extraction in the step (3) is 100-800 r/min;
preferably, the mixing time in the nickel extraction in the step (3) is 5-30 min;
preferably, the equilibrium pH of the water phase in the nickel extraction in the step (3) is 1.9-5;
preferably, the extraction equipment used in the nickel extraction in the step (3) is a mixer settler and a tower type filler extractor, and further preferably, the extraction equipment used in the nickel extraction in the step (3) is a mixer settler.
8. The method of any one of claims 1 to 7, wherein the cobalt extraction in step (4) is carried out by multistage countercurrent fractional extraction using extractant C;
preferably, the extractant C comprises a phosphorus-type extractant or a carboxylic acid-type extractant;
preferably, the phosphorus-based extractant comprises P507;
preferably, the carboxylic acid extractant comprises 1 or a combination of at least 2 of BC191, BC193, or BC 196.
9. The process of any one of claims 1 to 8, wherein the volume fraction of extractant C is 5 to 30%;
preferably, the diluent of the extractant C comprises 1 or a combination of at least 2 of mineral spirit, kerosene, Escaid110, hexane, heptane, dodecane, further optimally, the kerosene is sulfonated kerosene;
preferably, the extractant C is saponified before use;
preferably, the saponification is carried out with an alkaline saponifier;
preferably, the alkaline saponifier comprises 1 or a combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water;
preferably, the concentration range of the alkaline saponifier is 6-14 mol/L;
preferably, the saponification degree of the extractant C is 5-60%;
preferably, the alkaline saponifier is 10mol/L sodium hydroxide;
preferably, the volume ratio of the extractant C to the water phase 1 in the cobalt extraction in the step (4) is (0.1-20): 1;
preferably, the stirring speed in the cobalt extraction in the step (4) is 100-800 r/min;
preferably, the mixing time in the cobalt extraction in the step (4) is 5-30 min;
preferably, the water phase balance pH in the phosphorus-type extraction used in the cobalt extraction in the step (4) is 3-5;
preferably, the water phase in the carboxylic acid extraction used for cobalt extraction in the step (4) has an equilibrium pH of 5-7.8;
preferably, the extraction equipment used in the cobalt extraction in the step (4) is a mixer settler and a tower type filler extractor, and further preferably, the extraction equipment used in the nickel extraction in the step (4) is a mixer settler;
preferably, the multistage countercurrent fractional extraction in the step (4) has 2-30 stages.
10. The separation process according to any one of claims 1 to 9, wherein the stripping agent used for the loaded organic phase stripping comprises an inorganic acid;
preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof;
preferably, the concentration of the inorganic acid in the stripping agent is 0.5-4 mol/L, and further preferably, the concentration of the stripping agent is 2 mol/L.
11. The separation method according to any one of claims 1 to 10, wherein the number of stripping stages is 3 to 10;
preferably, the flow ratio of the stripping agent to the loaded organic phase is 1 (0.1-15);
preferably, the loaded organic phase is washed before the loaded organic phase reverse extraction;
preferably, the washing stages are 2-20 stages;
preferably, the washing comprises washing with mineral acid and/or acidified water, nickel sulfate, cobalt sulfate solution;
preferably, the pH value of the inorganic acid and/or the acidified water is 0.1-2;
preferably, the solution of nickel sulfate and cobalt sulfate is 0.5-20 g/L.
12. The method according to any one of claims 1 to 11, wherein the aqueous phase 4 is subjected to oil removal and crystallization in sequence in the step (5) to obtain a sodium sulfate product;
preferably, the crystallization is by MVR evaporation.
13. The method according to any one of claims 1 to 12, characterized in that it comprises the following steps:
(1) chemically removing impurities from the feed liquid by using sodium sulfate and/or sodium carbonate to obtain a water phase 1 and iron-containing aluminum slag liquid, and performing filter pressing on the slag liquid to obtain iron-containing aluminum slag;
(2) performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese-loaded organic phase and a water phase 2, wherein the extractant A comprises 1 or at least 2 of phosphorus type extractants, carboxylic acid extractants or oxime extractants; the volume fraction of the extracting agent A is 5-30%; the manganese extraction comprises single-stage extraction or multi-stage countercurrent extraction; the flow ratio of an extracting agent A used in the manganese extraction to the feed liquid is (0.1-10): 1; the stirring speed in the manganese extraction is 100-800 r/min; the mixing time in the manganese extraction is 5-30 min; the manganese extraction equipment is optimized to be a mixer-settler; the manganese extraction is multi-stage countercurrent fractional extraction, the stage number is 2-30, and the manganese-loaded organic matter is subjected to back extraction to obtain a crude manganese solution;
(3) carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel-loaded organic phase and a water phase 3, and washing and back-extracting the nickel-loaded organic phase to obtain a nickel sulfate solution, wherein the extractant B used in the process comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in formula I and is named as CHP 88:
wherein-C8H17The volume fraction of the extractant B is 5-30%, the diluent of the extractant B comprises 1 or a combination of at least 2 of solvent naphtha, kerosene, Escaid110, hexane, heptane and dodecane, and 6-14 mol/L alkaline soap is used before the extractant B is usedThe agent comprises 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water for saponification, the volume ratio of the extractant B to the water phase 2 in the nickel extraction is (0.1-20): 1, the stirring speed in the nickel extraction is 100-800 r/min, the mixing time in the nickel extraction in the step (3) is 5-30 min, the extraction equipment used in the nickel extraction is a mixing clarifying tank, the multistage countercurrent fractional extraction is 2-30 stages, the back extraction uses 0.5-4 mol/L inorganic acid comprising any one or combination of at least two of hydrochloric acid, nitric acid or sulfuric acid, the back extraction stage is 3-10 stages, and the volume ratio of the back extraction agent to the loaded organic phase is 1 (0.1-15); before the back extraction, the method further comprises the step of washing the loaded organic phase obtained in the step (3), wherein the washing stages are 2-20 stages, and the washing comprises washing with inorganic acid and/or acidified water and a nickel sulfate solution;
(4) performing cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt-loaded organic phase and a water phase 4, washing and back-extracting the cobalt-loaded organic phase to obtain a cobalt sulfate solution, wherein the extractant C comprises a phosphorus type extractant or a carboxylic acid type extractant, the volume concentration of the extractant C in the extracted organic phase is 5-30%, a diluent of the extractant C comprises 1 or at least 2 of solvent naphtha, kerosene, Escaid110, hexane, heptane and dodecane, an alkaline saponifier used before the extractant C is 6-14 mol/L comprises 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water, the volume ratio of the extractant C to the water phase 3 in the cobalt extraction is (0.1-20): 1, and the stirring speed in the cobalt extraction is 100-800 r/min, the mixing time in the extraction is 5-30 min, the extraction equipment used in the cobalt extraction is a mixer-settler, the multistage countercurrent fractional extraction has 2-30 stages, the back extraction uses 0.5-4 mol/L inorganic acid comprising any one or the combination of at least two of hydrochloric acid, nitric acid or sulfuric acid, the back extraction has 3-10 stages, and the volume ratio of the back extraction agent to the loaded organic phase is 1 (0.1-15); before the back extraction, the step of washing the loaded organic phase obtained in the step (3) is also included, the number of washing stages is 2-20, and the washing includes washing with inorganic acid and/or acidified water and cobalt sulfate solution;
(5) and (4) sequentially removing oil and crystallizing the water phase 4 obtained in the step (4) to obtain sodium sulfate crystals, treating the wastewater, and discharging the wastewater after reaching the standard, wherein the crystallization mode is MVR evaporation.
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