CN112538569B - Method for separating nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese - Google Patents
Method for separating nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 56
- 239000011572 manganese Substances 0.000 title claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 47
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 46
- 239000010941 cobalt Substances 0.000 title claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000605 extraction Methods 0.000 claims abstract description 117
- 239000012074 organic phase Substances 0.000 claims abstract description 66
- 238000005406 washing Methods 0.000 claims abstract description 40
- 239000008346 aqueous phase Substances 0.000 claims abstract description 25
- 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 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 150000001735 carboxylic acids Chemical class 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- -1 escaid110 Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000015096 spirit Nutrition 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 18
- 239000011575 calcium Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 58
- 239000000243 solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating nickel, cobalt and manganese from a feed liquid containing nickel, cobalt and manganese, which comprises the following steps: (1) Carrying out first extraction on the feed liquid by adopting a first extractant to obtain a first aqueous phase and a first organic phase; (2) Performing second extraction on the first aqueous phase obtained in the step (1) by adopting a second extractant to obtain a second organic phase and a second aqueous phase with the pH value of 4.5-6.5; (3) Washing and back-extracting the second organic phase obtained in the step (2) sequentially to obtain a solution containing nickel, cobalt and manganese; wherein the second extractant includes a carboxylic acid extractant. The method provided by the invention can realize synchronous extraction and recovery of nickel, cobalt and manganese in the battery feed liquid containing nickel, cobalt and manganese, and effectively separate the nickel, cobalt and manganese from impurity ions such as calcium, magnesium and the like.
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 nickel-cobalt-manganese-containing feed liquid.
Background
The nickel-cobalt-manganese ternary anode material has good cycle performance, stable structure and high cost performance, and is a novel lithium ion battery anode material. Along with the rapid development of electric automobiles, the demand scale of lithium ion batteries is continuously enlarged, the number of waste lithium ion batteries is also increased year by year, valuable metals in the positive electrode materials of the waste lithium batteries are recovered, and the method has good environmental protection and economic benefits.
Hydrometallurgy is a scientific technology for separating, enriching and extracting metal by 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, and has the characteristics of low energy consumption, small pollution, high resource utilization rate and the like, and is continuously focused by a plurality of researchers for a long time.
CN105483382a discloses a method for synchronously recovering nickel, cobalt and manganese from nickel, cobalt and manganese-containing waste residues, which comprises the steps of adding oxidizing agents such as hypochlorite or nitric acid, adjusting the pH value to be 5.0-5.5, removing Fe and Al in the leaching solution, and obtaining raffinate after removing Fe and Al; then adopting a Mextral984H or CP50 extractant to adjust the pH value to be 2.0-2.5, and removing Cu in the raffinate; then P507 and kerosene are used as diluents, the pH value=2.0-2.3 is regulated, zn and a small amount of Mn in the raffinate are extracted and removed, dilute sulfuric acid is adopted for washing, sulfuric acid is adopted for back extraction of an organic phase containing Zn and a small amount of Mn, back extraction liquid containing Zn and a small amount of Mn is obtained, and the Zn and Mn in the back extraction liquid are extracted and separated by P204; and finally, synchronously extracting Ni, co and Mn by adopting a tributyl phosphate and neodecanoic acid mixed extractant to obtain an organic phase containing Ni, co and Mn, washing the organic phase with dilute sulfuric acid to remove calcium and magnesium impurities, and carrying out back extraction by adopting sulfuric acid to obtain a nickel-cobalt-manganese mixed solution.
Patent CN109449523a discloses a comprehensive recovery method of waste lithium ion batteries, which comprises the steps of firstly adjusting the pH=4.2-4.5 of feed liquid, extracting the feed liquid by using P204 to obtain P204 raffinate and a loaded organic phase, and back-extracting the loaded organic phase by using sulfuric acid to obtain manganese sulfate; adjusting the pH value of the P204 raffinate to be 4.5-5, extracting the P204 raffinate by using C272 to obtain C272 raffinate and a loaded organic phase, and back-extracting the C272 loaded organic phase by using sulfuric acid to obtain a cobalt sulfate solution; adjusting the pH value of the C272 raffinate to be=5-5.5, extracting Ni from the raffinate by using P507, and stripping the loaded organic phase by using sulfuric acid to obtain a nickel sulfate solution by using the P507.
The extraction process is complex, the process is easy to operate and unstable by adopting the mixed extractant to synchronously extract nickel, cobalt and manganese, and P507/P204/C272 is used for separating nickel, cobalt and manganese, but in the aspect of recycling the anode material of the lithium ion battery, nickel, cobalt and manganese cannot be synchronously extracted, and the process for respectively recycling nickel, cobalt and manganese has high cost, high back extraction acidity and serious pollution.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a method for separating nickel, cobalt and manganese from a feed liquid containing nickel, cobalt and manganese, and the carboxylic acid extractant adopted by the invention can synchronously extract nickel, cobalt and manganese, and has high extraction efficiency and good separation effect with impurity ions; the water solubility is low, and the environment is friendly; the organic phase can be recycled, the operation cost is low, and good economic benefits are achieved.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for separating nickel, cobalt and manganese from a feed liquid containing nickel, cobalt and manganese, which comprises the following steps:
(1) Carrying out first extraction on the feed liquid by adopting a first extractant to obtain a first aqueous phase and a first organic phase;
(2) Performing second extraction on the first aqueous phase obtained in the step (1) by adopting a second extractant to obtain a second organic phase and a second aqueous phase with the pH value of 4.5-6.5;
(3) Washing and back-extracting the second organic phase obtained in the step (2) sequentially to obtain a solution containing nickel, cobalt and manganese;
wherein the second extractant comprises a carboxylic acid extractant; the carboxylic acid extractant has a structure shown in a formula I:
i
In the formula I, R 1 Is C 3 ~C 9 Straight-chain alkyl, R 2 Is C 3 ~C 9 Straight chain alkyl or C 3 ~C 9 Branched alkyl groups.
The method provided by the invention realizes synchronous extraction and recovery of nickel, cobalt and manganese in the nickel, cobalt and manganese-containing battery feed liquid, is not influenced by impurity metal ions such as calcium, magnesium and the like, has simple operation and stable process operation, and reduces the separation cost for respectively recovering nickel, cobalt and manganese and the extraction and purification cost of the impurity metal ions. Meanwhile, the impurity removal rate of the carboxylic acid extractant and the extraction rate of Ni, co and Mn are both more than 99.5%, and the sulfuric acid back extraction rate is more than 99.5%.
In the present invention, the pH of the second aqueous phase obtained by the second extraction in step (2) is 4.5 to 6.5, and may be, for example, 4.5, 4.6, 4.8, 5.2, 5.4, 5.6, 6.2, 6.3, 6.4 or 6.5, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the volume fraction of the carboxylic acid in the second extractant is 5 to 30%, for example, 5%, 10%, 15%, 20%, 25% or 30%, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferred technical scheme of the invention, the metal elements in the feed liquid comprise: li 1-16g/L, ni 1-50g/L, co 1-26g/L, mn1-30g/L, fe less than or equal to 10g/L, al less than or equal to 1g/L, cu less than or equal to 10g/L, zn less than or equal to 5g/L, ca 0.1-0.5g/L and Mg 0.1-50g/L.
In the present invention, the concentration of Li in the feed liquid is 1 to 16g/L, and for example, 1g/L, 5g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, etc., but the concentration is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
In the present invention, the concentration of Ni in the feed liquid is 1 to 50g/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/L, 50g/L, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the concentration of Co in the feed solution is 1 to 26g/L, and for example, it may be 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 22g/L, 23g/L, 24g/L, 25g/L, 26g/L, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the concentration of Mn in the feed liquid is 1 to 30g/L, and for example, 1g/L, 5g/L, 10g/L, 20g/L, 30g/L, or the like may be used, but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
In the present invention, the concentration of Fe in the feed solution may be 10g/L, 9g/L, 8g/L, 7g/L, 6g/L, 5g/L, 4g/L, 3g/L, or the like, for example, but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the Al concentration in the feed liquid may be 1g/L, 0.8g/L, 0.6g/L, 0.4g/L, 0.2g/L, or the like, for example, but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the Cu concentration in the feed solution is 10g/L or less, for example, 10g/L, 9g/L, 8g/L, 7g/L, 6g/L, 5g/L, 4g/L, 3g/L, or the like, but the Cu concentration is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
In the present invention, the Zn concentration in the feed liquid is 5g/L or less, for example, 5g/L, 4g/L, 3g/L, 2g/L, or 1g/L, etc., but the Zn concentration is not limited to the recited values, and other values not recited in the range are equally applicable.
In the present invention, the Ca concentration in the feed solution is 0.1 to 0.5g/L, and may be, for example, 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, or 0.5g/L, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In the present invention, the concentration of Mg in the feed liquid is 0.1 to 50g/L, and for example, it may be 0.1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
As a preferred embodiment of the present invention, the first extractant in step (1) includes 1 or a combination of at least 2 of a phosphorus extractant, a carboxylic acid extractant, or an oxime 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 oxime extractant includes any 1 or a combination of at least 2 of Mextral984H, lix or CP 50.
Preferably, the carboxylic acid extractant has a structure represented by formula I:
i
In the formula I, R 1 Is C 3 ~C 9 Straight-chain alkyl, R 2 Is C 3 ~C 9 Straight chain alkyl or C 3 ~C 9 Branched alkyl groups.
Preferably, the carboxylic acid extractant is a mixture of 1 or at least 2 carboxylic acids.
Preferably, the volume fraction of the first extractant is 5-30%, for example, 5%, 10%, 15%, 20%, 25% or 30%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the diluent of the first extractant comprises 1 or a combination of at least 2 of solvent naphtha, kerosene, escaid110, hexane, heptane, dodecane.
The combination may be a combination of solvent oil and kerosene, a combination of Escaid110 and hexane, or a combination of heptane and dodecane, etc., but is not limited to the recited combinations, and other non-recited combinations are equally applicable within this range.
In the present invention, the solvent may be No. 200 solvent oil and/or No. 260 solvent oil.
Preferably, the first extractant is saponified prior to use.
Preferably, the saponification is carried out with 6-14mol/L of lye, for example 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc., but not limited to the values recited, other values not recited in this range are equally applicable.
Preferably, the lye comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or aqueous ammonia.
The combination may be a combination of sodium hydroxide solution and potassium hydroxide solution, a combination of potassium hydroxide solution and aqueous ammonia, or the like, but is not limited to the recited combination, and other combinations not recited in the range are equally applicable.
As a preferred embodiment of the present invention, the first extraction in step (1) comprises single-stage extraction or multistage countercurrent extraction.
Preferably, the volume ratio of the first extractant to the feed liquid in step (1) is (0.1-10): 1, for example, it may be 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, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the stirring speed in the first extraction in the step (1) is 100-250r/min, for example, 100r/min, 150r/min, 200r/min or 250r/min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the mixing time in the first extraction in the step (1) is 5-30min, for example, may be 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the multistage countercurrent extraction has a stage number of 2-30, for example, 2, 3, 5, 10, 15, 20, 25 or 30, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present invention, the volume fraction of the second extractant is 5 to 30%, for example, 5%, 10%, 15%, 20%, 25% or 30%, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the carboxylic acid-based extractant in the second extractant is a mixture of 1 or at least 2 carboxylic acids.
Preferably, the diluent of the second extractant comprises 1 or a combination of at least 2 of solvent naphtha, kerosene, escaid110, hexane, heptane, dodecane.
The combination may be a combination of solvent oil and kerosene, a combination of Escaid110 and hexane, or a combination of heptane and dodecane, etc., but is not limited to the recited combinations, and other non-recited combinations are equally applicable within this range.
In the present invention, the solvent may be No. 200 solvent oil and/or No. 260 solvent oil.
In the present invention, the dodecane may be n-dodecane or the like.
Preferably, the second extractant is saponified prior to use.
Preferably, the saponification is carried out with 6-14mol/L of lye, for example 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc., but not limited to the values recited, other values not recited in this range are equally applicable.
Preferably, the lye comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or aqueous ammonia.
The combination may be a combination of sodium hydroxide solution and potassium hydroxide solution, a combination of potassium hydroxide solution and aqueous ammonia, or the like, but is not limited to the recited combination, and other combinations not recited in the range are equally applicable. As a preferred technical scheme of the invention, the second extraction in the step (2) is multistage countercurrent extraction.
Preferably, the volume ratio of the second extractant to the first aqueous phase in step (2) is (0.1-10): 1, for example, it may be 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, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the stirring speed in the second extraction in the step (2) is 100-250r/min, for example, 100r/min, 150r/min, 200r/min or 250r/min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the mixing time in the second extraction in the step (2) is 5-30min, for example, may be 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the number of stages of the multistage countercurrent extraction in the second extraction is 5 to 30, for example, 5, 10, 15, 20, 25 or 30, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the first organic phase in the step (1) is subjected to multi-stage countercurrent washing and then back extraction to obtain a solution containing metal ions and a regenerated organic phase.
Preferably, the number of steps of the washing is 2 to 8, and may be, for example, 2, 3, 4, 5, 6, 7 or 8, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the regenerated organic phase is returned for use as an extractant.
In the invention, the first organic phase is subjected to acid multistage countercurrent washing, then is subjected to back extraction by adopting an acid solution, and is concentrated and crystallized after degreasing to obtain a mixed solution containing iron, copper, zinc, calcium, aluminum and the like, the organic phase is returned to a saponification process for recycling, and the washing and the back extraction adopt acid comprising hydrochloric acid and/or sulfuric acid. The volume ratio of the acid used in the regenerated organic phase and the washing or stripping is (1-10): 1, for example, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., and other non-enumerated values within this range are equally applicable, and the stripping uses hydrochloric acid concentration of 1-6 mol/L, for example, 1mol/L, 1.5 mol/L, 2mol/L, 2.5mol/L, 3mol/L, 4mol/L, 5mol/L or 6mol/L, etc., but not limited to, other non-enumerated values within this range are equally applicable, and the stripping uses sulfuric acid concentration of 0.5-3mol/L, for example, 0.5 mol/L, 1mol/L, 2mol/L, 2.5mol/L or 3mol/L, etc., but not limited to the enumerated values within this range are equally applicable.
As a preferable technical scheme of the invention, the second water phase in the step (2) is subjected to oil removal and crystallization in sequence 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 embodiment of the present invention, the washing in the step (3) is multistage countercurrent washing.
Preferably, the number of steps of the washing is 2 to 8, and may be, for example, 2, 3, 4, 5, 6, 7 or 8, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In the invention, the washing and back extraction of the second organic phase is performed by sulfuric acid and/or hydrochloric acid; the volume ratio of the second organic phase to the wash stripping is (1-10): 1, for example, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., and other non-enumerated values within this range are equally applicable, and the stripping is carried out with a hydrochloric acid concentration of 1-6 mol/L, for example, but not limited to, 1mol/L, 1.5 mol/L, 2mol/L, 2.5mol/L, 3mol/L, 4mol/L, 5mol/L or 6mol/L, etc., and other non-enumerated values within this range are equally applicable, and the sulfuric acid concentration used for stripping is 0.5-3mol/L, for example, 0.5 mol/L, 1mol/L, 2mol/L, 2.5mol/L or 3/L, etc., but not limited to the enumerated values within this range are equally applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Carrying out first extraction on the feed liquid by adopting a first extractant to obtain a first aqueous phase and a first organic phase; wherein the first extractant comprises 1 or a combination of at least 2 of a phosphorus extractant, a carboxylic acid extractant, or an oxime extractant; the carboxylic acid extractant has a structure shown in a formula I:
i
In the formula I, R 1 Is C 3 ~C 9 Straight-chain alkyl, R 2 Is C 3 ~C 9 Straight chain alkyl or C 3 ~C 9 Branched alkyl; the volume fraction of the first extractant is 5-30%; the first extraction comprises single-stage extraction or multistage countercurrent extraction; the volume ratio of the first extractant to the feed liquid is (0.1-10): 1; the stirring speed in the first extraction is 100-250r/min; the mixing time in the first extraction is 5-30min; the number of stages of the multistage countercurrent extraction is 2-30;
(2) Performing second extraction on the first aqueous phase obtained in the step (1) by adopting a second extractant to obtain a second organic phase and a second aqueous phase with the pH value of 4.5-6.5; wherein the second extractant comprises a carboxylic acid extractant; the carboxylic acid extractant has a structure shown in a formula I:
i
In the formula I, R 1 Is C 3 ~C 9 Straight-chain alkyl, R 2 Is C 3 ~C 9 Straight chain alkyl or C 3 ~C 9 Branched alkyl; the volume fraction of the second extractant is 5-30%; the second extraction is multistage countercurrent extraction; the volume ratio of the second extractant to the first aqueous phase is (0.1-10): 1; the stirring speed in the second extraction is 100-250r/min; the mixing time in the second extraction is 5-30min; multistage countercurrent extraction in the second extractionThe number of the stages is 5-30;
(3) Washing and back-extracting the second organic phase obtained in the step (2) sequentially to obtain a solution containing nickel, cobalt and manganese; wherein the washing is multistage countercurrent washing; the washing stage number is 2-8.
In the present invention, the pH of the first extraction may be selected by referring to the impurity ions removed in the first extraction in the prior art, for example, when P204 is used, the pH of the first extraction is 2.5 to 3.5, and when oxime extractant is used, the pH of the first extraction is 2 to 2.5, because the pH of the first extraction may have different pH operating ranges due to different extractants.
In the invention, the extractant obtained by back extraction of the second organic phase can be returned to the extraction operation after saponification.
In the present invention, the carboxylic acid extractant may be a mixture of one or more carboxylic acids, for example, a first extractant BC196 (a compound corresponding to m=8, n=8 in the general formula), a first extractant BC191 (a compound corresponding to m=8, n=10 in the general formula), a mixture of the first extractants BC196 and BC191, and a first extractant BC194 (a compound corresponding to m=6, n=6 in the general formula).
In the invention, countercurrent extraction is one of extraction and separation methods, and the aqueous phase and the organic phase containing the extracted matter flow into the extractor from two ends respectively and flow in opposite directions, and are subjected to continuous multistage stirring, contact and layering to achieve the purpose of separation.
In the present invention, the reaction equation of the related process is as follows:
saponification of carboxylic acid extractant: HA (HA) (org) +NaOH→NaA (org) +H 2 O
Extracting with carboxylic acid extractant: 2NaA (org) +MSO 4 →MA 2(org) +Na 2 SO 4
Sulfuric acid back extraction: MA (MA) 2(org) +H 2 SO 4 →2HA (org) +MSO 4
Wherein: m is Fe 3+ 、Cu 2+ 、Al 3+ 、Zn 2+ 、Ni 2+ 、Co 2+ 、Mn 2+ Isojin (a. K)Belongs to the field of technology.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method provided by the invention has good separation effect on metal ions, realizes synchronous extraction and recovery of nickel, cobalt and manganese in the nickel-cobalt-manganese-containing battery feed liquid by utilizing the coupling effect between the extractant and the extraction pH value, is not influenced by impurity metal ions such as calcium, magnesium and the like, is simple to operate, reduces the separation cost of respectively recovering nickel, cobalt and manganese and the extraction and purification cost of impurity metal ions, and in addition, the adopted carboxylic acid extractant has small water solubility and can be recycled. (2) The recovery method provided by the invention has the impurity removal rate of more than or equal to 99.5%, the nickel-cobalt-manganese extraction rate of more than or equal to 99%, and the sulfuric acid stripping rate of more than or equal to 99.5%.
Drawings
FIG. 1 is a schematic diagram of the recovery method in example 1 of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
This example provides a method for separating nickel, cobalt and manganese from a nickel, cobalt and manganese containing feed liquid, as shown in fig. 1.
The feed liquid in this embodiment is a battery feed liquid containing nickel, cobalt and manganese, and the pH value of the feed liquid is 4.46, and the components are as follows:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg | Li |
| Content (g/L) | 0.001 | 0.001 | 0.5 | 0.8 | 46 | 22 | 20 | 0.4 | 0.3 | 9 |
In the embodiment, a saponified Mextral984H extractant (volume fraction is 15%, diluent is No. 260 solvent oil, saponifier is 8mol/L NaOH solution) is adopted to extract copper in the feed liquid before the first extraction, the extraction stage number is 1, the volume ratio of an organic phase to the feed liquid is 0.25:1, the mixing time is 20min, the stirring speed is 120r/min, the standing is 10min, the experimental temperature is 25 ℃ at the conventional temperature, the pH of the aqueous phase is controlled to be 2.5, the loaded copper organic phase and the feed liquid after copper removal are respectively obtained after phase separation, the loaded copper organic phase is subjected to 2-stage countercurrent washing by adopting dilute sulfuric acid with pH of 1, then back extraction is carried out for 2 times by adopting 2mol/L sulfuric acid, the volume of the first organic phase and the washing liquid or the back extraction liquid is 10:1, and then concentrated crystallization is obtained after the copper sulfate solution is deoiled.
In this example, C272 was used as the extractant for the first extraction, the volume fraction was 15%, the diluent was No. 260 solvent oil, and saponification was performed with 8mol/L NaOH solution.
The method comprises the steps of carrying out multistage countercurrent extraction on copper-removed feed liquid by using saponified C272, carrying out extraction stage number 3, wherein the volume ratio of an organic phase to the copper-removed feed liquid is 0.1:1, the mixing time is 20min, the stirring speed is 120r/min, the experimental temperature is 25 ℃ of conventional temperature, respectively obtaining a first organic phase and a first aqueous phase with pH value of 2.8 after phase separation, carrying out 4-stage countercurrent washing on the first organic phase by using dilute sulfuric acid with pH value of 1, carrying out back extraction 2 times by using 2mol/L sulfuric acid, and concentrating and crystallizing after the volume ratio of the first organic phase to the washing liquid or the back extraction liquid is 5:1, so as to obtain zinc sulfate solution for degreasing, and recycling the organic phase in a saponification process.
Performing multistage countercurrent extraction on the first water phase by adopting saponified BC191 (volume fraction is 25%, diluent is 260 # solvent oil, saponifying agent is 8mol/L NaOH solution), extracting the first water phase for 15 stages, wherein the volume ratio of the organic phase to the first water phase is 10:1, mixing time is 20min, stirring speed is 120r/min, standing is 10min, experimental temperature is 25 ℃ at conventional temperature, a second organic phase and a second water phase with pH value of 5.5 are respectively obtained, performing 5 stages of countercurrent washing on the second organic phase by adopting dilute sulfuric acid with pH value of 1, performing back extraction for 6 times by adopting sulfuric acid with concentration of 2mol/L, and the volume of the second organic phase and washing solution or back extraction solution is 3:1, thus obtaining the nickel-rich, cobalt-manganese solution.
The impurity removal rate in this example was 99.7%, and the extraction rates of Ni, co and Mn were 99.8%, 99.7% and 99.6%, respectively, and the stripping rates were 99.8%, 99.7% and 99.7%.
Example 2
The embodiment provides a method for separating nickel, cobalt and manganese from a nickel, cobalt and manganese containing feed liquid, wherein the feed liquid in the embodiment is a nickel, cobalt and manganese containing battery feed liquid, the pH value of the feed liquid is 2.59, and the components are as follows:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg | Li |
| Content (g/L) | 0.01 | 0.01 | 0.3 | 0.6 | 48 | 22 | 18 | 0.5 | 0.5 | 10 |
In this example BC196 was used as the extractant with a volume fraction of 25% and Escaid110 as the diluent and saponified with 6mol/L NaOH solution.
Performing 13-level countercurrent extraction on the nickel-cobalt-manganese-containing feed liquid by using saponified BC196, wherein the volume ratio of the extractant to the battery feed liquid is 0.2:1, the mixing time is 10min, the stirring speed is 150r/min, the experimental temperature is 25 ℃, a first organic phase and a first aqueous phase with the pH value of 4.5 are respectively obtained after phase separation, 8-level countercurrent washing is performed on the first organic phase by using dilute sulfuric acid with the pH value of 1.5, then back extraction is performed for 3 times by using 2.5mol/L sulfuric acid, the volume of the first organic phase and the washing solution or back extraction solution is 10:1, and the concentrated crystallization is performed after the oil removal of the mixed solution of ferric sulfate, copper sulfate, zinc sulfate, aluminum sulfate, calcium sulfate and the like, and the organic phase returns to the saponification procedure for recycling.
Performing multistage countercurrent extraction on the first water phase by using saponified BC196, performing extraction stages at 10 stages, wherein the volume ratio of the organic phase to the first water phase is 9:1, the mixing time is 10min, the stirring speed is 150r/min, the standing is performed for 15min, the experimental temperature is 25 ℃, the second organic phase and the second water phase with the pH value of 6.0 are respectively obtained, 7-stage countercurrent washing is performed on the second organic phase by using dilute sulfuric acid with the pH value of 1.5, and then back extraction is performed for 5 times by using sulfuric acid with the concentration of 2.5mol/L, wherein the volume ratio of the second organic phase to the washing solution or the back extraction solution is 2:1, so that the nickel, cobalt and manganese-rich solution is obtained.
The impurity removal rate in this example was 99.6%, and the extraction rates of Ni, co and Mn were 99.8%, 99.8% and 99.7%, respectively, and the stripping rates were 99.8%, 99.7 and 99.8%, respectively.
Example 3
The embodiment provides a method for separating nickel, cobalt and manganese from a nickel, cobalt and manganese containing feed liquid, wherein the feed liquid in the embodiment is a nickel, cobalt and manganese containing battery feed liquid, the pH value of the feed liquid is 4.3, and the components are as follows:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg | Li |
| Content (g/L) | 0.001 | 0.001 | 0.5 | 0.7 | 48 | 24 | 20 | 0.5 | 0.5 | 10 |
In the embodiment, the saponified CP50 extractant (the volume fraction is 20%, the diluent is sulfonated kerosene, the saponifying agent is 10mol/L ammonia water solution) is adopted to extract copper in the feed liquid before the first extraction, the extraction stage number is 1, the mixing time is 8min, the stirring speed is 200r/min, the rest is 20min, the experimental temperature is 20 ℃, the pH of the aqueous phase is controlled to be 2.5, the loaded copper organic phase and the feed liquid after copper removal are respectively obtained after phase separation, the loaded copper organic phase is subjected to 2-stage countercurrent washing by adopting dilute sulfuric acid with the pH of 1, the back extraction is carried out for 2 times by adopting 2mol/L sulfuric acid, the volume of the first organic phase and the washing liquid or the back extraction liquid is 10:1, and the concentrated crystallization is obtained after the copper sulfate solution is deoiled.
In the first extraction in this example, P204 was used as the extractant, the volume fraction was 20%, the diluent was sulfonated kerosene, and 10mol/L ammonia was usedWater and its preparation methodThe solution was saponified.
The method comprises the steps of carrying out 7-level countercurrent extraction on copper-removed feed liquid containing nickel, cobalt and manganese by using saponified P204, wherein the volume ratio of an extracting agent to the copper-removed feed liquid is 0.25:1, the mixing time is 5min, the stirring speed is 200r/min, the experimental temperature is 20 ℃, a first organic phase and a first aqueous phase with a pH value of 2 are respectively obtained after phase separation, 4-level countercurrent washing is carried out on the first organic phase by using hydrochloric acid with the pH value of 1, then back extraction is carried out 2 times by using 4mol/L hydrochloric acid, the volume of the first organic phase is 10:1, and the mixed solution of calcium chloride, zinc chloride and the like is obtained for degreasing, then concentrated crystallization is carried out, and the organic phase is returned to a saponification process for recycling.
The BC194 (30% by volume, escaid110 as diluent and 10mol/L ammonia as saponifier) after saponification is adoptedWater and its preparation methodSolution) carrying out second extraction on the first water phase, carrying out multistage countercurrent extraction on the extraction stage number 7, wherein the volume ratio of the BC194 extractant to the first water phase is 8:1, the mixing time is 8min, the stirring speed is 200r/min, the experimental temperature is 20 ℃, respectively obtaining a second organic phase and a second water phase with the pH value of 6.5, carrying out 8-stage countercurrent washing on the second organic phase by sulfuric acid with the pH value of 1, carrying out back extraction on the second organic phase by 2mol/L sulfuric acid for 6 times, and the volume of the second organic phase and the washing solution or the back extraction solution is 2:1, thus obtaining the nickel, cobalt and manganese-rich solution.
The impurity removal rate in this example was 99.6%, and the extraction rates of Ni, co and Mn were 99.8%, 99.6% and 99.5%, respectively, and the stripping rates were 99.7%, 99.6% and 99.7%, respectively.
Example 4
The difference from example 1 is only that the pH of the second aqueous phase is controlled to 7, the impurity removal rate in this example is 99.5%, the extraction rates of Ni, co and Mn are 99.9%, 99.8% and 99.8%, respectively, and the stripping rates are 99.7%, 99.6% and 99.6%, respectively. The washing process increases and the washing cost increases.
Comparative example 1
The only difference from example 1 is that the pH of the second aqueous phase obtained by the second extraction is controlled to be 4, and the single-stage extraction rates of Ni, co and Mn are all less than 10%.
Comparative example 2
The only difference from example 1 is that the extractant in the second extraction was replaced by an equal amount of P507 and the nickel cobalt manganese could not be extracted simultaneously.
Comparative example 3
The difference from example 1 is only that the extractant in the second extraction was replaced with carboxylic acid extractant CA-12, the impurity removal rate was 99.3%, the extraction rates of Ni, co and Mn were 98.8%, 98.2% and 97.4%, respectively, and the stripping rates were 99.4%, 99.3% and 99.4%, respectively.
According to the method provided by the invention, the nickel, cobalt and manganese in the leaching solution of the positive electrode material of the waste lithium ion battery are synchronously extracted and recovered by utilizing the coupling effect between the extracting agent and the extraction pH value, and the method is free from the influence of impurity metal ions such as calcium, magnesium and the like, is simple to operate, and reduces the separation cost for respectively recovering nickel, cobalt and manganese and the extraction and purification cost for impurity metal ions. Meanwhile, the impurity removal rate of the carboxylic acid extractant is more than or equal to 99.5%, and the sulfuric acid back extraction rate is more than or equal to 99.5%.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A method for separating nickel, cobalt and manganese from a feed liquid containing nickel, cobalt and manganese, which is characterized by comprising the following steps:
(1) Carrying out first extraction on the feed liquid by adopting a first extractant to obtain a first aqueous phase and a first organic phase; wherein the first extractant comprises 1 or a combination of at least 2 of a phosphorus extractant, a carboxylic acid extractant, or an oxime extractant; the volume fraction of the first extractant is 5-30%; the first extraction comprises single-stage extraction or multistage countercurrent extraction; the volume ratio of the first extractant to the feed liquid is (0.1-10): 1; the stirring speed in the first extraction is 100-250r/min; the mixing time in the first extraction is 5-30min; the number of stages of the multistage countercurrent extraction is 2-30;
(2) Performing second extraction on the first aqueous phase obtained in the step (1) by adopting a second extractant to obtain a second organic phase and a second aqueous phase with the pH value of 4.5-6.5; the volume fraction of the second extractant is 5-30%; the second extraction is multistage countercurrent extraction; the volume ratio of the second extractant to the first aqueous phase is (0.1-10): 1; the stirring speed in the second extraction is 100-250r/min; the mixing time in the second extraction is 5-30min; the number of stages of the multistage countercurrent extraction in the second extraction is 5-30;
(3) Washing and back-extracting the second organic phase obtained in the step (2) sequentially to obtain a solution containing nickel, cobalt and manganese; the washing is multistage countercurrent washing; the washing stage number is 2-8;
wherein the second extractant comprises a carboxylic acid extractant; the carboxylic acid extractant has a structure shown in a formula I:
in the formula I, R 1 Is C 3 ～C 9 Straight-chain alkyl, R 2 Is C 3 ～C 9 Straight chain alkyl or C 3 ～C 9 Branched alkyl; the carboxylic acid extractant is a mixture of 1 or at least 2 carboxylic acids;
the metal elements in the feed liquid comprise: li 1-16g/L, ni 1-50g/L, co 1-26g/L, mn1-30g/L, fe less than or equal to 10g/L, al less than or equal to 1g/L, cu less than or equal to 10g/L, zn less than or equal to 5g/L, ca 0.1-0.5g/L and Mg 0.1-50g/L.
2. The method of claim 1, wherein the diluent of the first and second extractants comprises 1 or a combination of at least 2 of mineral spirits, kerosene, escaid110, hexane, heptane, dodecane.
3. The method of claim 1, wherein the first extractant and the second extractant are saponified prior to use.
4. The method of claim 3, wherein the saponification is performed with 6-14mol/L lye.
5. The method of claim 4, wherein the lye comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution, or aqueous ammonia.
6. The process of claim 1 wherein the first organic phase of step (1) is subjected to a multistage countercurrent washing followed by stripping to provide a metal ion containing solution and a regenerated organic phase.
7. The method of claim 6, wherein the washing is performed in a number of stages ranging from 2 to 8.
8. The process of claim 6, wherein the regenerated organic phase is returned for use as an extractant.
9. The method of claim 1, wherein the second aqueous phase of step (2) is subjected to degreasing and crystallization in sequence to obtain sodium sulfate crystals.
10. The method of claim 9, wherein the crystallization is by MVR evaporation.
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| CN114134322B (en) * | 2020-09-04 | 2023-03-14 | 苏州博萃循环科技有限公司 | Method for separating copper and manganese from copper-manganese-calcium-zinc-containing mixed solution |
| CN112575193A (en) * | 2020-11-24 | 2021-03-30 | 北京博萃循环科技有限公司 | Method for separating copper and manganese and application thereof |
| CN112457188B (en) * | 2020-11-24 | 2022-07-08 | 苏州博萃循环科技有限公司 | Carboxylic acid compound and preparation method and application thereof |
| CN113443664B (en) * | 2021-07-22 | 2023-03-24 | 四川顺应动力电池材料有限公司 | Method for producing nickel cobalt manganese sulfate by using nickel cobalt manganese hydroxide raw material |
| CN114085994A (en) * | 2021-11-09 | 2022-02-25 | 苏州博萃循环科技有限公司 | Method for recovering valuable metal from waste nickel-hydrogen battery |
| CN114317961B (en) * | 2021-12-30 | 2023-06-02 | 重庆康普化学工业股份有限公司 | Co-extraction system for nickel-cobalt co-extraction and co-extraction method thereof |
| CN117004830B (en) * | 2023-09-28 | 2023-12-08 | 上海稀固科技有限公司 | Method for recovering nickel from nickel-containing iron material liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378262A (en) * | 1994-03-22 | 1995-01-03 | Inco Limited | Process for the extraction and separation of nickel and/or cobalt |
| JP2016060926A (en) * | 2014-09-16 | 2016-04-25 | ソルベイ日華株式会社 | Separation method of metal |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN108504868A (en) * | 2018-05-15 | 2018-09-07 | 中国科学院过程工程研究所 | A kind of method of lithium metal in recycling waste and old lithium ion battery |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
-
2020
- 2020-11-24 CN CN202011335222.0A patent/CN112538569B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378262A (en) * | 1994-03-22 | 1995-01-03 | Inco Limited | Process for the extraction and separation of nickel and/or cobalt |
| JP2016060926A (en) * | 2014-09-16 | 2016-04-25 | ソルベイ日華株式会社 | Separation method of metal |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN108504868A (en) * | 2018-05-15 | 2018-09-07 | 中国科学院过程工程研究所 | A kind of method of lithium metal in recycling waste and old lithium ion battery |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 无.RN1987774-88-8等.《REG,STN ON THE WEB》.2016, * |
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