CN114614136B - Method for preparing dihydrate ferric phosphate and ternary positive electrode material from laterite nickel ore - Google Patents
Method for preparing dihydrate ferric phosphate and ternary positive electrode material from laterite nickel ore Download PDFInfo
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- CN114614136B CN114614136B CN202210348768.2A CN202210348768A CN114614136B CN 114614136 B CN114614136 B CN 114614136B CN 202210348768 A CN202210348768 A CN 202210348768A CN 114614136 B CN114614136 B CN 114614136B
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- nickel
- laterite
- nickel ore
- nitric acid
- leaching
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 34
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 34
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910001710 laterite Inorganic materials 0.000 title claims abstract description 20
- 239000011504 laterite Substances 0.000 title claims abstract description 20
- -1 dihydrate ferric phosphate Chemical class 0.000 title abstract description 6
- 239000007774 positive electrode material Substances 0.000 title description 11
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000002386 leaching Methods 0.000 claims abstract description 69
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 60
- 239000000706 filtrate Substances 0.000 claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 37
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000005336 cracking Methods 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000197 pyrolysis Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 13
- 239000011651 chromium Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910017061 Fe Co Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- VVPNOTYZCXWJCH-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) hexanitrate Chemical compound [Mn++].[Co++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VVPNOTYZCXWJCH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000036573 scar formation Effects 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of recycling of nickel ore materials, in particular to a method for preparing ferric phosphate dihydrate and ternary anode materials from laterite nickel ores. The method for preparing the dihydrate ferric phosphate and the ternary anode material from the laterite nickel ore comprises the following steps: mixing laterite nickel ore with nitric acid solution for acid leaching treatment, and carrying out solid-liquid separation to obtain leaching residues and leaching liquid; mixing the leaching solution and the phosphoric acid solution under the heating condition, and carrying out solid-liquid separation to obtain ferric phosphate dihydrate and primary filtrate; removing iron element, chromium element, aluminum element, calcium element and magnesium element from the primary filtrate, and carrying out solid-liquid separation to obtain a nickel-cobalt-manganese mixed solution; and mixing the nickel-cobalt-manganese mixed solution with soluble nickel salt, cobalt salt, manganese salt and lithium salt, and then performing cracking and sintering to obtain the ternary anode material. The method can efficiently separate nickel and cobalt from iron, efficiently recycle the iron in the laterite-nickel ore, greatly reduce the waste of iron resources and realize the high-value comprehensive utilization of the laterite-nickel ore.
Description
Technical Field
The invention relates to the technical field of recycling of nickel ore materials, in particular to a method for preparing ferric phosphate dihydrate and ternary anode materials from laterite nickel ores.
Background
Under the pulling of the growth of new energy automobiles, the consumption of the ternary power battery is rapidly increased, so that a great deal of demands on nickel resources are driven. Nickel ore resources mainly comprise nickel sulfide ores and laterite nickel ores, and the nickel sulfide ores are mined for nearly one hundred years, so that the resources are reduced. In order to meet the requirement of new energy materials on nickel, people have to pay attention to laterite-nickel ores with rich nickel resource reserves.
Laterite nickel ore is an important nickel cobalt resource. Laterite nickel ores are mainly divided into three types according to occurrence states: brown iron type, magnesium type, and transition type. The traditional process of treating the brown iron type laterite-nickel ore is a high-pressure acid leaching process. The traditional pressure acid leaching technology adopts sulfuric acid treatment under the conditions of high temperature (245-270 ℃) and high pressure (4-5 MPa), and has the defects of complex technology, high equipment requirement, high investment, high operation cost, serious scar formation of a pressure kettle, incapability of realizing comprehensive utilization of leached slag due to low iron and high sulfur, and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore, which can efficiently separate nickel from cobalt and iron, efficiently recycle iron in the laterite-nickel ore, greatly reduce waste of iron resources and realize high-value comprehensive utilization of the laterite-nickel ore; the ternary anode material is directly prepared by spraying, cracking and sintering nitrate solutions of nickel, cobalt and manganese.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the method for preparing the ferric phosphate dihydrate and the ternary anode material from the laterite-nickel ore comprises the following steps:
(a) Mixing laterite nickel ore with nitric acid solution for acid leaching treatment, and obtaining leaching slag and leaching liquid after solid-liquid separation; mixing the leaching solution and the phosphoric acid solution under the heating condition, and carrying out solid-liquid separation to obtain ferric phosphate dihydrate and primary filtrate;
(b) Mixing the primary filtrate with an alkaline regulator to precipitate iron element, chromium element and aluminum element in the primary filtrate, carrying out solid-liquid separation to obtain secondary filtrate, mixing the secondary filtrate with ammonium fluoride to precipitate calcium element and magnesium element, and carrying out solid-liquid separation to obtain nickel-cobalt-manganese mixed solution; and mixing the nickel-cobalt-manganese mixed solution with soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble lithium salt, and then performing cracking and sintering to obtain the ternary anode material.
In one embodiment, the laterite-nickel ore includes at least one of limonite, transition ore, and saprolite ore.
In one embodiment, the laterite nickel ore has a particle size of less than 2mm.
In one embodiment, the mass ratio of the nitric acid in the nitric acid solution to the laterite-nickel ore is (1.4-2.0): 1.
In one embodiment, the mass content of the laterite-nickel ore in the mixture of the laterite-nickel ore and the nitric acid solution is 20-30%; in the nitric acid solution, the mass content of nitric acid is 10% -90%.
In one embodiment, the acid leaching treatment is performed at a temperature of 80 to 110 ℃ for a time of 2 to 6 hours.
In one embodiment, the molar ratio of phosphoric acid to elemental iron in the mixed liquor of the leachate and the phosphoric acid solution is 1:1.
In one embodiment, the mass content of phosphoric acid in the phosphoric acid solution is 80% -88%;
in one embodiment, the heating temperature of the mixture under heating conditions is 50 to 90 ℃ and the heating time is 4 to 8 hours.
In one embodiment, the reaction is stopped when the leachate and phosphoric acid solution are mixed under heating until the D50 particle size of the precipitate is 3 to 5 μm.
In one embodiment, the primary filtrate in step (a) is distilled under reduced pressure, and the azeotrope of nitric acid and water is collected and recycled to the acid leaching process; the remaining liquid after distillation under reduced pressure is subjected to the operation of step (b).
In one embodiment, the primary filtrate in step (a) is mixed with a nitric acid solution and then subjected to an acid leaching treatment; repeating the step (a) for 1-3 times, carrying out reduced pressure distillation on the filtrate obtained in the last time, and collecting the azeotrope of nitric acid and water; carrying out the operation of the step (b) on the residual liquid after the reduced pressure distillation; the filtrate obtained by acid leaching treatment and the nitric acid solution are mixed according to the volume ratio of (0.9-1.1), and the mass content of nitric acid in the nitric acid solution is 65-70%.
In one embodiment, the precipitating the iron element, chromium element and aluminum element in the primary filtrate specifically includes: and adding the alkaline regulator into the primary filtrate to gradually increase the pH value of the mixed solution to 5.0.
In one embodiment, the primary filtrate and alkaline modifier are mixed at a temperature of 50 to 90 ℃ for a time of 1.5 to 2.5 hours.
In one embodiment, the alkaline modifier comprises at least one of lithium carbonate, ammonium bicarbonate, ammonium carbonate, and aqueous ammonia.
In one embodiment, the nickel cobalt manganese mixed solution is mixed with soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble lithium salt in a molar ratio of 1.05: (0.5-0.8): (0.1-0.2): (0.1-0.3).
In one embodiment, the temperature of the cleavage is 500 to 700 ℃;
in one embodiment, the off-gas from the cracking is used to produce nitric acid and is recycled to the acid leaching process.
In one embodiment, the sintering temperature is 860-980 ℃ and the sintering time is 12-24 hours.
Compared with the prior art, the invention has the beneficial effects that:
The method can efficiently separate nickel and cobalt from iron, efficiently recycle iron in the laterite-nickel ore, greatly reduce the waste of iron resources, and realize high-value comprehensive utilization of the laterite-nickel ore; the ternary precursor is directly prepared by spraying and cracking nitrate solutions of nickel, cobalt and manganese, the nickel, cobalt and manganese in the leaching solution are not required to be separated, mixed Hydroxide (MHP) and sulfate are not required to be prepared, the intermediate flow is greatly reduced, and the processing cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of iron phosphate dihydrate according to example 1 of the present invention;
FIG. 2 is an SEM image of ternary monocrystalline material of NCM523 in example 1 of the present invention;
FIG. 3 is a flow chart of a method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore in the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect, the invention relates to a method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore, comprising the following steps:
(a) Mixing laterite nickel ore with nitric acid solution for acid leaching treatment, and obtaining leaching slag and leaching liquid after solid-liquid separation; mixing the leaching solution and the phosphoric acid solution under the heating condition, and carrying out solid-liquid separation to obtain ferric phosphate dihydrate and primary filtrate;
(b) Mixing the primary filtrate with an alkaline regulator to precipitate iron element, chromium element and aluminum element in the primary filtrate, carrying out solid-liquid separation to obtain secondary filtrate, mixing the secondary filtrate with ammonium fluoride to precipitate calcium element and magnesium element, and carrying out solid-liquid separation to obtain nickel-cobalt-manganese mixed solution; and mixing the nickel-cobalt-manganese mixed solution with soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble lithium salt, and then performing cracking and sintering to obtain the ternary anode material.
According to the invention, nitric acid is used as a low-temperature normal-pressure leaching agent, and ferrous iron in laterite-nickel ore is oxidized into ferric iron due to strong oxidizing property of nitric acid, and phosphoric acid or phosphate is used for precipitation to obtain an iron phosphate precursor. After the subsequent impurity removal of iron, chromium, aluminum, calcium and magnesium, a high-purity nickel cobalt manganese nitrate solution is obtained, a proper amount of nickel, cobalt and manganese soluble salts and lithium salts are added into the obtained nickel cobalt manganese nitrate solution according to the proportion of target components, a precursor solution is obtained, a ternary precursor is obtained by a spray pyrolysis method of the precursor solution, and the ternary monocrystalline anode material is obtained after sintering.
In one embodiment, the laterite-nickel ore includes at least one of limonite, transition ore, and saprolite ore.
In one embodiment, the laterite nickel ore has a particle size of less than 2mm. The particle size of the laterite nickel ore includes, but is not limited to, 0.1mm, 0.2mm, 0.5mm, 0.7mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.5mm, 1.7mm, or 1.9mm.
In one embodiment, the mass ratio of the nitric acid in the nitric acid solution to the laterite-nickel ore is (1.4-2.0): 1. The mass ratio of nitric acid in the nitric acid solution to the laterite nickel ore includes, but is not limited to, 1.5: 1. 1.6:1, 1.7:1, 1.8:1, or 1.9:1.
In one embodiment, the mass content of the laterite-nickel ore in the mixture of the laterite-nickel ore and the nitric acid solution is 20-30%; in the nitric acid solution, the mass content of nitric acid is 10% -90%. In one embodiment, the mass content of laterite nickel ore includes, but is not limited to, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, or 29%. The mass content of nitric acid in the nitric acid solution includes, but is not limited to, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 85%.
The invention is beneficial to improving the leaching rate of metal elements in the laterite-nickel ore by adopting nitric acid and laterite-nickel ore with proper mass ratio.
In one embodiment, the acid leaching treatment is performed at a temperature of 80 to 110 ℃ for a time of 2 to 6 hours. In one embodiment, the temperature of the acid leaching treatment includes, but is not limited to, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or 105 ℃. The time for the acid leaching treatment includes, but is not limited to, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or 5.5 hours. The leaching rate of the metal element is improved by adopting proper acid leaching treatment temperature and time.
In one embodiment, the molar ratio of phosphoric acid to elemental iron in the mixed liquor of the leachate and the phosphoric acid solution is 1:1.
In one embodiment, the phosphoric acid solution has a mass content of 80% to 88%. Specifically, 81%, 82%, 83%, 84%, 85%, 86% or 87% may be used.
In one embodiment, the heating temperature of the mixture under heating conditions is 50 to 90 ℃ and the heating time is 4 to 8 hours. In one embodiment, the heating temperature of the mixing under heating conditions includes, but is not limited to, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or 85 ℃. Heating times include, but are not limited to, 4.5h, 5h, 5.5h, 6h, 6.6h, 7h, or 7.5h.
In one embodiment, the reaction is stopped when the leachate and phosphoric acid solution are mixed under heating until the D50 particle size of the precipitate is 3 to 5 μm.
In the invention, the primary filtrate contains excessive nitric acid, and the recycling treatment can be carried out in the following two ways:
In one embodiment, the primary filtrate in step (a) is distilled under reduced pressure, and the azeotrope of nitric acid and water is collected and recycled to the acid leaching process; the remaining liquid after distillation under reduced pressure is subjected to the operation of step (b).
In another embodiment, the primary filtrate in step (a) is mixed with a nitric acid solution and then subjected to an acid leaching treatment; repeating the step (a) for 1-3 times, carrying out reduced pressure distillation on the filtrate obtained in the last time, and collecting the azeotrope of nitric acid and water; carrying out the operation of the step (b) on the residual liquid after the reduced pressure distillation; the filtrate obtained by acid leaching treatment and the nitric acid solution are mixed according to the volume ratio of (0.9-1.1), and the mass content of nitric acid in the nitric acid solution is 65-70%.
In one embodiment, the precipitating the iron element, chromium element and aluminum element in the primary filtrate specifically includes: and adding the alkaline regulator into the primary filtrate to gradually increase the pH value of the mixed solution to 5.0. Wherein, the pH value is 2.0-3.0, and residual iron and chromium are mainly hydrolyzed and precipitated, and aluminum in the solution with the pH value of 4.0-5.0 is hydrolyzed and precipitated.
In one embodiment, the primary filtrate and alkaline modifier are mixed at a temperature of 50 to 90 ℃ for a time of 1.5 to 2.5 hours. In one embodiment, the temperature at which the primary filtrate and alkaline modifier are mixed includes, but is not limited to 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃ for a period of time of 1.5 hours, 2 hours or 2.5 hours.
In one embodiment, the alkaline modifier comprises at least one of lithium carbonate, ammonium bicarbonate, ammonium carbonate, and aqueous ammonia.
In one embodiment, the nickel cobalt manganese mixed solution is mixed with soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble lithium salt in a molar ratio of 1.05: (0.5-0.8): (0.1-0.2): (0.1-0.3). In one embodiment, the molar ratio of lithium element, nickel element, cobalt element and manganese element is 1.05:0.5:0.2: and 0.3, obtaining the NCM523 ternary positive electrode material. In one embodiment, the molar ratio of lithium element, nickel element, cobalt element and manganese element is 1.05:0.8:0.1:0.1 to obtain NCM811 ternary positive electrode material.
In one embodiment, the soluble nickel salt, soluble cobalt salt, soluble manganese salt, and soluble lithium salt are nitrate or acetate salts, respectively, of nickel, cobalt, manganese, lithium.
In one embodiment, the temperature of the cleavage is 500 to 700 ℃. In one embodiment, the temperature of the cleavage includes, but is not limited to, 520 ℃, 550 ℃, 570 ℃, 600 ℃, 620 ℃, 650 ℃, 670 ℃, or 690 ℃.
In one embodiment, the off-gas from the cracking is used to produce nitric acid and is recycled to the acid leaching process.
In one embodiment, the sintering temperature is 860-980 ℃ and the sintering time is 12-24 hours. In one embodiment, the sintering temperature includes, but is not limited to 870 ℃, 880 ℃, 900 ℃, 920 ℃, 950 ℃, 960 ℃, 970 ℃, or 980 ℃.
Further description will be provided below in connection with specific examples.
FIG. 1 is an SEM image of iron phosphate dihydrate according to example 1 of the present invention. Fig. 2 is an SEM image of NCM523 ternary single crystal material in example 1 of the present invention. FIG. 3 is a flow chart of a method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore in the invention.
Example 1
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore comprises the following steps:
(1) Stirring laterite nickel ore powder with the particle size smaller than 2mm and nitric acid solution (the mass content of nitric acid is 50%) in a mixing kettle, wherein the solid content is 20%, conveying the slurry into a leaching reaction kettle, keeping the temperature at 95 ℃, leaching for 4 hours, wherein the content of each element in the leaching solution is shown in a table 1, carrying out solid-liquid separation on the mixed slurry by adopting a filter press, treating insoluble substances as slag after washing, and transferring the leaching solution into an iron phosphate reaction kettle;
Table 1 contents of elements of leachate in example 1
| Element(s) | Ni | Fe | Co | Mn | Al | Mg | Ca | Cr |
| Laterite nickel content (wt.%) | 1.63 | 30.5 | 0.09 | 0.53 | 2.8 | 6.6 | 0.2 | 1.4 |
| Leachate content (g/L) | 7.56 | 123.83 | 0.28 | 1.89 | 8.69 | 30.3 | 0.56 | 1.43 |
| Leaching rate | 95％ | 89％ | 86％ | 85％ | 69％ | 87％ | 75％ | 29％ |
(2) Adding a phosphoric acid solution (the mass content of phosphoric acid is 85%) into the ferric phosphate reaction kettle with the leaching liquid in the step (1), wherein the molar ratio of phosphoric acid to iron element in the solution is 1:1, keeping the temperature at 70 ℃ and stirring for 5 hours, stopping the reaction when the particle size of the generated precipitate is 3.0-5.0 mu m by sampling and detecting, and filtering and separating to obtain ferric phosphate dihydrate and primary filtrate; washing and drying the dihydrate ferric phosphate precipitate, and can be used for producing lithium iron phosphate; the iron phosphate dihydrate has spherical aggregate morphology (figure 1), P/Fe ratio of more than 0.96 and high purity.
(3) Distilling the primary filtrate in the step (2) under reduced pressure, collecting an azeotrope of nitric acid and water, and recycling the azeotrope to the acid leaching treatment in the step (1); adding ammonium bicarbonate into the residual liquid after reduced pressure distillation to gradually increase the pH value of the filtrate to 5.0, wherein the pH value is 2.0-3.0, and the residual iron element and chromium element are mainly hydrolyzed and precipitated, and aluminum in the solution with the pH value of 4.0-5.0 is hydrolyzed and precipitated; controlling the temperature to 80 ℃ and the time to 2.0h, and carrying out solid-liquid separation after the reaction is finished to obtain secondary filtrate; then adding ammonium fluoride into the secondary filtrate, precipitating calcium element and magnesium element, and carrying out solid-liquid separation to obtain the nickel-cobalt-manganese mixed solution with high purity.
(4) Adding nickel nitrate, manganese nitrate, cobalt nitrate and lithium nitrate into the nickel-cobalt-manganese mixed solution obtained in the step (3), and adjusting the molar ratio of the target components NCM523 and Li, ni, co, mn to be 1.05:0.5:0.2:0.3, spraying the precursor solution into a cracking furnace, wherein the cracking temperature is 630 ℃, carrier gas is compressed air, waste gas generated by cracking enters a nitric acid recovery system for treatment, the generated precursor powder is collected and can be used for sintering at the later stage, the obtained NCM523 ternary precursor is compact spherical particles, the fluidity is good, the NCM523 ternary precursor is filled into a sagger, sintering is carried out in a muffle furnace or a roller kiln at 950 ℃ for 14 hours, and the atmosphere is air, so that the NCM523 ternary anode material with single crystal morphology can be obtained (as shown in figure 2).
Example 2
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore comprises the following steps:
(1) Stirring laterite nickel ore powder with the particle size smaller than 2mm and nitric acid solution (the mass content of nitric acid is 50%) in a mixing kettle, wherein the solid content is 20%, conveying the slurry into a leaching reaction kettle, keeping the temperature at 95 ℃, leaching for 4 hours, wherein the content of each element in the leaching solution is shown in a table 2, the leaching rate of nickel element reaches 95%, carrying out solid-liquid separation on the mixed slurry by adopting a filter press, treating insoluble substances as slag after washing, and transferring the leaching solution into an iron phosphate reaction kettle;
TABLE 2 example 2 contents of elements in leachate
| Element(s) | Ni | Fe | Co | Mn | Al | Mg | Ca | Cr |
| Content (g/L) | 7.56 | 123.83 | 0.28 | 1.89 | 8.69 | 30.3 | 0.56 | 1.43 |
| Leaching rate | 95％ | 89％ | 86％ | 85％ | 69％ | 87％ | 75％ | 29％ |
(2) Adding a phosphoric acid solution (the mass content of phosphoric acid is 85%) into the ferric phosphate reaction kettle with the leaching liquid in the step (1), wherein the molar ratio of phosphoric acid to iron element in the solution is 1:1, keeping the temperature at 70 ℃ and stirring for 5 hours, stopping the reaction when the particle size of the generated precipitate is 3.0-5.0 mu m by sampling and detecting, and filtering and separating to obtain ferric phosphate dihydrate and primary filtrate; washing and drying the dihydrate ferric phosphate precipitate, and can be used for producing lithium iron phosphate; the morphology of the dihydrate ferric phosphate spherical aggregate is that the P/Fe ratio is more than 0.96, and the purity is high.
(3) The primary filtrate contains unreacted nitric acid during leaching and nitric acid generated during ferric phosphate precipitation, the primary filtrate is mixed into the leaching slurry in the step (1) and is mixed with 67% of nitric acid solution by mass to be used as leaching solution, and the volume ratio of the primary filtrate to the nitric acid solution is 1:1, maintaining the temperature at 80 ℃ and leaching for 4 hours, wherein the components of the filtrate obtained after solid-liquid separation of the leached slurry are shown in table 3:
TABLE 3 leaching of the components of the slurry after solid-liquid separation (secondary leaching)
| Element(s) | Ni | Fe | Co | Mn | Al | Mg | Ca | Cr |
| Content (g/L) | 11.52 | 135.83 | 0.41 | 3.40 | 12.62 | 50.52 | 0.84 | 2.26 |
(4) Adding ammonium carbonate into the filtrate obtained after solid-liquid separation of the leached slurry in the step (3), and gradually increasing the pH value of the filtrate to 5.0, wherein the pH value is 2.0-3.0, and the residual iron element and chromium element are mainly hydrolyzed and precipitated, and aluminum in the solution with the pH value of 4.0-5.0 is hydrolyzed and precipitated; controlling the temperature to 80 ℃ and the time to 2.0h, and carrying out solid-liquid separation after the reaction is finished to obtain secondary filtrate; then adding ammonium fluoride into the secondary filtrate, precipitating calcium element and magnesium element, and carrying out solid-liquid separation to obtain the nickel-cobalt-manganese mixed solution with high purity.
(5) Adding nickel acetate, manganese acetate, cobalt acetate and lithium acetate into the nickel-cobalt-manganese mixed solution obtained in the step (3), and adjusting the molar ratio of the target components NCM523 and Li, ni, co, mn to be 1.05:0.8:0.1:0.1, spraying a precursor solution into a cracking furnace, wherein the cracking temperature is 550 ℃, carrier gas is compressed air, waste gas generated by cracking enters a nitric acid recovery system for treatment, the generated precursor powder is collected and can be used for sintering at the later stage, the obtained NCM523 ternary precursor is compact spherical particles, the fluidity is good, the NCM811 ternary precursor is filled into a sagger, sintering is carried out in a muffle furnace or a roller kiln at 880 ℃ for 16 hours, and the atmosphere is air, so that the NCM523 ternary anode material with single crystal morphology can be obtained.
Example 3
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore comprises the steps of (1) keeping the temperature at 80 ℃ and leaching for 6 hours; in the step (2), the temperature is kept at 50 ℃ and the stirring time is 8 hours; in the step (3), the temperature is controlled to be 50 ℃ and the time is controlled to be 2.5 hours; other conditions were the same as in example 1.
Example 4
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore comprises the steps of (1) keeping the temperature at 110 ℃ and leaching for 2 hours; in the step (2), the temperature is kept at 90 ℃ and the stirring time is 4 hours; in the step (3), the temperature is controlled to be 90 ℃ and the time is controlled to be 1.5h; other conditions were the same as in example 1.
Comparative example 1
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore is provided, wherein in the step (1), the leaching time is 1.5h while the temperature is kept at 60 ℃, and other conditions are the same as in example 1.
Comparative example 2
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore is provided, wherein in the step (2), the temperature is kept at 40 ℃, the stirring time is 3.5 hours, and other conditions are the same as those in the example 1.
Comparative example 3
A method for preparing a ternary positive electrode material of ferric phosphate dihydrate and nickel cobalt manganese by comprehensively utilizing laterite-nickel ore comprises the steps of (3) controlling the temperature to be 45 ℃ and the time to be 1h; other conditions were the same as in example 1.
Test examples
1. The leaching rate results of the main elements (nickel element, iron element, cobalt element and manganese element) in the examples and comparative examples are shown in table 4.
TABLE 4 leaching rate results of Nickel element, iron element, cobalt element and manganese element
2. The purity of the iron phosphate dihydrate and the purity of the nickel cobalt manganese mixed solution in examples and comparative examples are shown in table 5.
TABLE 5 purity of iron phosphate dihydrate and purity of Nickel cobalt manganese Mixed solution
From the above, the temperature in the step (1) is Shi Tie, the leaching rate of nickel, cobalt and manganese is increased, but the volatilization of nitric acid is increased when the temperature is too high, the corrosion to equipment is increased, and the proper temperature is 90 ℃; in the step (2), the temperature is increased, the yield and purity of ferric phosphate dihydrate are increased, the recovery rate of iron element is increased, the content of main impurity element chromium is reduced, and the optimal temperature range is 80-90 ℃; and step (3) is to remove impurity elements such as iron, chromium and aluminum in the secondary filtrate, and the impurity removal efficiency can be improved by properly increasing the temperature, so that the purity of the nickel-cobalt-manganese mixed solution is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The method for preparing the ferric phosphate dihydrate and the ternary anode material from the laterite-nickel ore is characterized by comprising the following steps of:
(a) Mixing laterite nickel ore with nitric acid solution for acid leaching treatment, and obtaining leaching slag and leaching liquid after solid-liquid separation; mixing the leaching solution and the phosphoric acid solution under the heating condition, and carrying out solid-liquid separation to obtain ferric phosphate dihydrate and primary filtrate;
(b) Mixing the primary filtrate with an alkaline regulator to precipitate iron element, chromium element and aluminum element in the primary filtrate, carrying out solid-liquid separation to obtain secondary filtrate, mixing the secondary filtrate with ammonium fluoride to precipitate calcium element and magnesium element, and carrying out solid-liquid separation to obtain nickel-cobalt-manganese mixed solution; mixing the nickel-cobalt-manganese mixed solution with soluble nickel salt, soluble cobalt salt, soluble manganese salt and soluble lithium salt, and then cracking and sintering to obtain a ternary anode material;
Distilling the primary filtrate in the step (a) under reduced pressure, collecting an azeotrope of nitric acid and water, and recycling the azeotrope to the acid leaching treatment; carrying out the operation of the step (b) on the residual liquid after the reduced pressure distillation;
Or mixing the primary filtrate in the step (a) with a nitric acid solution, and then carrying out acid leaching treatment; repeating the step (a) for 1-3 times, carrying out reduced pressure distillation on the filtrate obtained in the last time, and collecting the azeotrope of nitric acid and water; carrying out the operation of the step (b) on the residual liquid after the reduced pressure distillation; mixing filtrate obtained by acid leaching treatment and nitric acid solution according to the volume ratio of (0.9-1.1), wherein the mass content of nitric acid in the nitric acid solution is 65% -70%;
the alkaline regulator comprises at least one of lithium carbonate, ammonium bicarbonate, ammonium carbonate and ammonia water;
The method for precipitating the iron element, the chromium element and the aluminum element in the primary filtrate specifically comprises the following steps: and adding the alkaline regulator into the primary filtrate to gradually increase the pH value of the mixed solution to 5.0.
2. The method for producing iron phosphate dihydrate and ternary anode material from laterite-nickel ore according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The laterite-nickel ore comprises at least one of limonite, transition ore and saprolite ore;
(2) The particle size of the laterite-nickel ore is smaller than 2mm.
3. The method for producing iron phosphate dihydrate and ternary anode material from laterite-nickel ore according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The mass ratio of the nitric acid in the nitric acid solution to the laterite-nickel ore is (1.4-2.0) 1;
(2) The mass content of the laterite-nickel ore in the mixture of the laterite-nickel ore and the nitric acid solution is 20% -30%; in the nitric acid solution, the mass content of nitric acid is 10% -90%.
4. A method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore according to any one of claims 1-3, characterized in that the temperature of the acid leaching treatment is 80-110 ℃, and the time of the acid leaching treatment is 2-6 h.
5. The method for producing iron phosphate dihydrate and ternary anode material from laterite-nickel ore according to claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) In the mixed solution of the leaching solution and the phosphoric acid solution, the molar ratio of phosphoric acid to iron element is 1:1;
(2) In the phosphoric acid solution, the mass content of phosphoric acid is 80% -88%;
(3) The heating temperature of the mixture under the heating condition is 50-90 ℃ and the heating time is 4-8 h;
(4) And mixing the leaching solution and the phosphoric acid solution under the heating condition until the D50 particle size of the precipitate is 3-5 mu m, and stopping the reaction.
6. The method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore according to claim 1, wherein the temperature of mixing the primary filtrate and the alkaline regulator is 50-90 ℃ for 1.5-2.5 h.
7. The method for preparing ferric phosphate dihydrate and ternary anode material from laterite-nickel ore according to claim 1, wherein the molar ratio of lithium element, nickel element, cobalt element and manganese element in the mixture of the nickel-cobalt-manganese mixed solution and the soluble nickel salt, the soluble cobalt salt, the soluble manganese salt and the soluble lithium salt is 1.05: (0.5-0.8): (0.1-0.2): (0.1-0.3).
8. The method for producing iron phosphate dihydrate and ternary anode material according to claim 1 or 7, characterized by comprising at least one of the following features (1) to (3):
(1) The cracking temperature is 500-700 ℃;
(2) The waste gas generated by the pyrolysis is used for preparing nitric acid and is recycled for the acid leaching treatment;
(3) The sintering temperature is 860-980 ℃, and the sintering time is 12-24 h.
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