WO2022166476A1 - Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, and application - Google Patents
Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, and application Download PDFInfo
- Publication number
- WO2022166476A1 WO2022166476A1 PCT/CN2021/142334 CN2021142334W WO2022166476A1 WO 2022166476 A1 WO2022166476 A1 WO 2022166476A1 CN 2021142334 W CN2021142334 W CN 2021142334W WO 2022166476 A1 WO2022166476 A1 WO 2022166476A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- iron
- iron phosphate
- iron powder
- phosphate
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 36
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000011268 mixed slurry Substances 0.000 claims abstract description 10
- 239000005955 Ferric phosphate Substances 0.000 claims description 19
- 229940032958 ferric phosphate Drugs 0.000 claims description 19
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical group [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 239000007790 solid phase Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 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
- 238000012360 testing method Methods 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- CKRORYDHXIRZCH-UHFFFAOYSA-N phosphoric acid;dihydrate Chemical compound O.O.OP(O)(O)=O CKRORYDHXIRZCH-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Definitions
- the invention belongs to the technical field of nickel-iron hydrometallurgy, and in particular relates to a method and application for extracting nickel from nickel-containing iron powder and preparing iron phosphate.
- Nickel ore widely existing in nature is mainly divided into nickel sulfide ore and nickel oxide ore. Due to the high iron content in nickel ore, nickel-iron alloy can be obtained after smelting, which is mainly used to manufacture stainless steel. In recent years, the rapid increase in the production of stainless steel has also stimulated the rapid increase in the global demand for nickel. Nickel is a non-renewable resource. Due to continuous mining and application, nickel resources have been increasingly exhausted. Therefore, the use of secondary nickel in nickel-iron alloys has been adopted. Conversion to primary nickel that can be used in cathode materials is a growing trend.
- power battery cathode materials mainly include lithium iron phosphate, ternary materials, lithium manganate, etc.
- ternary power batteries are relatively poor in safety performance, but have high energy density, which is one of the development directions of future power batteries.
- ternary cathode materials accounted for 47.6% of the sales of cathode materials in China in 2019, becoming the cathode material with the highest market share.
- the battery needs a better metal-nickel, and increasing the nickel content in the ternary material can improve the energy density of the battery, reduce the raw materials and make the lithium battery The battery life has been improved again. Therefore, the ternary cathode material is developing in the direction of high nickelization.
- ferronickel material which involves the process of adding oxidant and strengthening agent to ferronickel powder in a sulfuric acid system for oxidative leaching to obtain a nickel sulfate solution and a solid phase containing iron oxide.
- This method does not generate hydrogen during the reaction process, which solves some safety problems, but this process requires high-pressure oxygen immersion, and the production cost and equipment maintenance cost are high, which is not suitable for promotion.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
- the present invention proposes a method and application for extracting nickel from nickel-containing iron powder and preparing iron phosphate, using mixed acid to pickle the nickel-containing iron powder, and adding mixed acid by proportioning with the content of iron and nickel in the raw material, Nickel can enter the solution in the form of ions, and iron exists in the solid phase in the form of iron phosphate, which not only realizes the extraction of nickel from the nickel-containing iron powder, but also prepares nickel and iron into products with higher utilization value.
- the process is simple, the energy consumption is low, the cost is also low, and at the same time, it has great economic benefits.
- a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate comprising the steps:
- the acid solution is phosphoric acid and sulfuric acid.
- the sulfuric acid and phosphoric acid are prepared according to the iron content and nickel content in the nickel-containing iron powder.
- the concentration of the phosphoric acid is 10-19 mol/L; the liquid-solid ratio of the phosphoric acid to the nickel-containing iron powder is 0.2-5 mL/g.
- the concentration of the phosphoric acid is 12-14 mol/L; the liquid-solid ratio of the phosphoric acid to the nickel-containing iron powder is 0.5-3 mL/g.
- the concentration of the sulfuric acid is 0.5-10 mol/L; the liquid-solid ratio of the sulfuric acid to the nickel-containing iron powder is 0.5-10 mL/g.
- the concentration of the sulfuric acid is 1-5 mol/L; the liquid-solid ratio of the sulfuric acid to the nickel-containing iron powder is 1-8 mL/g.
- the nickel-containing iron powder is the nickel-iron block obtained by smelting nickel ore (latterite nickel ore and nickel sulfide ore), and the powdery material obtained by the air atomization method , the particle size is 1 ⁇ 900 ⁇ m, the nickel content in the nickel-containing iron powder is 10 ⁇ 40%, the iron content is 60 ⁇ 85%, and the total impurity content is less than 2%, such as: Co: 0.34%, Mn: 0.09%, Si : 0.27%, Cr: 0.05%, Ca: 0.006%, Mg: 0.004%, Cu: 0.03%, S: 0.21%, P: 0.03%.
- the heating temperature is 30-100° C.
- the stirring time is 1-6 h.
- the heating temperature is 50-90° C.
- the stirring time is 2-5 h.
- the oxidant is one or more of oxygen, air, hydrogen peroxide, ozone or sodium hypochlorite. Since the iron ions in the leaching solution may be ferrous iron or a mixture of ferrous iron and ferric iron, an oxidizing agent is required to oxidize it to ferric iron.
- the feeding amount when the oxidant is oxygen, air, and ozone, the feeding amount is 0.5-2.0 L/min; when the oxidant is hydrogen peroxide or sodium hypochlorite, the amount of the oxidant and the mixed slurry is The volume ratio is (0.05-0.5):1.
- step (2) the heating temperature is 20-100° C., and the stirring time is 1-20 h.
- step (2) the heating temperature is 40-90° C., and the stirring time is 2-15 h.
- step (2) a step of adding a precipitating agent is included before the heating, and the precipitating agent is titanium dioxide, aluminum hydroxide, aluminum oxide, anhydrous iron phosphate or dihydrate phosphoric acid One or more kinds of iron; the solid-liquid ratio of the precipitating agent and the mixed slurry is 1-500 g/L.
- the precipitation agent can overcome certain energy barriers in the process of iron phosphate precipitation, thereby preparing iron phosphate products.
- the solid-to-liquid ratio of the precipitant to the mixed slurry is 10-200 g/L.
- step (2) the iron phosphate is washed, filtered and dried to obtain the iron phosphate after removal of impurities.
- step (2) the washing is pulping washing with water, the liquid-solid ratio of water to iron phosphate is 1-20:1 mL/g, and the washing time is 0.5-5 h.
- the liquid-solid ratio of water to iron phosphate is 1-10:1 mL/g, and the washing time is 1-3 hours.
- the drying temperature is 60-120°C.
- the drying temperature is 90-110°C.
- the neutralizing agent is one or more of sodium carbonate, calcium carbonate, ammonium carbonate, potassium hydroxide or sodium hydroxide.
- step (4) the process of adding the neutralizing agent is to prepare the neutralizing agent into a solution or slurry, and add it to the nickel sulfate solution to adjust the pH to 3 ⁇ 6.
- step (4) in step (4), the heating temperature is 30-100° C., and the stirring time is 1-10 h.
- step (4) in step (4), the heating temperature is 50-80° C., and the stirring time is 2-6 h.
- the invention also proposes the application of the method in preparing power battery.
- the mixed acid is used to pickle the nickel-containing iron powder, and the mixed acid is added in proportion to the content of iron and nickel in the raw material, so that the nickel can enter the solution in the form of ions, and the iron exists in the solid phase in the form of iron phosphate, which can effectively
- the nickel and iron in the solid phase are separated to obtain nickel sulfate solution and battery-grade iron phosphate products.
- Nickel sulfate is one of the indispensable materials in ternary materials
- iron phosphate is further used as a precursor of lithium iron phosphate to prepare phosphoric acid.
- the iron-lithium cathode material not only realizes the extraction of nickel from the nickel-containing iron powder, but also prepares nickel and iron into products with higher utilization value.
- the method has the advantages of simple process, low energy consumption and low cost. Great economic benefits, suitable for industrial production and application.
- FIG. 1 is a process flow diagram of the present invention for extracting nickel from nickel-containing iron powder and preparing iron phosphate.
- Fig. 1 is the process flow diagram that the present invention extracts nickel from nickel-containing iron powder and prepares iron phosphate, as can be seen from the figure, to nickel-containing iron powder, add sulfuric acid and phosphoric acid heating and stirring for a period of time, then add oxidant heating and stirring, filter Ferric phosphate and nickel sulfate solutions can be obtained, a neutralizing agent is added to the nickel sulfate solution, heated and stirred, and impurity precipitates are removed by filtration to obtain a relatively pure nickel sulfate solution.
- the process is simple, low in energy consumption, and low in cost.
- a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate comprising the following steps:
- ferric phosphate was washed with water at a liquid-solid ratio of 5:1 mL/g for 1 h, and after filtration, the ferric phosphate was dried at 105°C to obtain a ferric phosphate product;
- a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate comprising the following steps:
- ferric phosphate was washed with water at a liquid-solid ratio of 10:1 mL/g for 2 hours, and after filtration, the ferric phosphate was dried at 90°C to obtain a ferric phosphate product;
- a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate comprising the following steps:
- ferric phosphate was washed with water at a liquid-solid ratio of 8:1 mL/g for 0.5 h, and after filtration, the ferric phosphate was dried at 105°C to obtain a ferric phosphate product;
- a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate comprising the following steps:
- ferric phosphate was washed with water for 1 h at a liquid-solid ratio of 12:1 mL/g, and after filtration, the ferric phosphate was dried at 100° C. to obtain a ferric phosphate product;
- each physical and chemical index of the iron phosphate obtained by the preparation method of the present invention meets the standard of the lithium iron phosphate positive electrode material.
- Example 1 35891.5 1.07 343.2 53.9 0.139 0.229
- Example 2 28455.8 2.73 456.6 87.2 0.189 0.357
- Example 3 10652.6 10.72 212.6 67.9 0.155 0.582
- Ca Mg P Cr Zn Si Example 1 16.7 1.56 1.75 0.138 1.142 73.9
- Example 2 13.9 0.98 2.15 0.112 0.997 57.2
- Example 3 20.5 1.12 2.67 0.145 1.102 65.8
- the impurity content of the nickel sulfate solution obtained by the preparation method of the present invention is relatively low, and the impurity (excluding Co, Mn) content in the nickel sulfate solution after impurity removal is less than 100 ⁇ m.
- Table 3 The iron phosphate synthesis lithium iron phosphate powder of the embodiment 1-3 of table 3 compares table of compaction density and electrical property test result
- the compacted density and electrical properties of the lithium iron phosphate powder synthesized by the iron phosphate obtained in the present invention have all reached the use standard of iron phosphate for lithium iron phosphate, and can be directly used as the precursor produced by lithium iron phosphate.
- the reaction is mainly based on the reaction of iron and phosphoric acid to obtain ferrous dihydrogen phosphate, nickel and sulfuric acid to obtain nickel sulfate, and then the oxidizing agent is used to dissolve the ferrous phosphate.
- iron phosphate is obtained under the action of the precipitating agent, and the trace impurities in the nickel sulfate solution can be discharged as slag after the impurity removal by the neutralizing agent, thereby preparing a nickel sulfate solution with a lower impurity content,
- the reagents used in this method are all readily available, the operation is simple, the Fe/P of the prepared iron phosphate product is between 0.96 and 1, and the content of impurities (excluding Co and Mn) in the nickel sulfate solution after impurity removal is less than 100 pm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed are a method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, and an application. The method comprises the following steps: (1) adding sulfuric acid and phosphoric acid into nickel-containing iron powder, and performing heating and stirring to obtain a mixed slurry; (2) adding an oxidant into the mixed slurry, performing heating and stirring, and filtering to obtain iron phosphate and a nickel sulfate solution; (3) washing, filtering, and drying the iron phosphate to obtain an iron phosphate product; and (4) adding a neutralizer into the nickel sulfate solution, performing heating and stirring, and filtering to obtain a nickel sulfate solution subjected to impurity removal. In the present invention, an acid mixture is used to perform acid leaching on the nickel-containing iron powder, and because the acid mixture is added in proportion to the content of iron and nickel in raw materials, nickel can enter the solution in ionic form, and iron is present in a solid phase in an iron phosphate form, so that nickel and iron in the solid phase can be effectively separated. The process is simple, the energy consumption is low, and the cost is also low; meanwhile, the present invention has great economic benefit and is suitable for industrial production and application.
Description
本发明属于镍铁湿法冶金技术领域,具体涉及一种从含镍铁粉中提取镍并制备磷酸铁的方法和应用。The invention belongs to the technical field of nickel-iron hydrometallurgy, and in particular relates to a method and application for extracting nickel from nickel-containing iron powder and preparing iron phosphate.
自然界广泛存在的镍矿主要分为硫化镍矿和氧化镍矿,由于镍矿中铁含量较高,通过冶炼后可得到镍铁合金,主要用于制造不锈钢。近年来,不锈钢的产量迅速增加,也刺激了全球镍需求的急速上升,而镍是不可再生资源,由于不断的开采和应用,镍资源已经日益枯竭,因此,采取将镍铁合金中的二级镍转化成可以用于正极材料中的一级镍是一种发展趋势。Nickel ore widely existing in nature is mainly divided into nickel sulfide ore and nickel oxide ore. Due to the high iron content in nickel ore, nickel-iron alloy can be obtained after smelting, which is mainly used to manufacture stainless steel. In recent years, the rapid increase in the production of stainless steel has also stimulated the rapid increase in the global demand for nickel. Nickel is a non-renewable resource. Due to continuous mining and application, nickel resources have been increasingly exhausted. Therefore, the use of secondary nickel in nickel-iron alloys has been adopted. Conversion to primary nickel that can be used in cathode materials is a growing trend.
目前动力电池正极材料主要包括磷酸铁锂、三元材料、锰酸锂等,其中,三元动力电池尽管在安全性能上相对差一点,但能量密度高,是未来动力电池发展的方向之一。随着三元动力电池的技术进步,导致成本下降和市场认可度提高,2019年三元正极材料在中国正极材料销量的占比达到47.6%,成为市场份额最高的正极材料。与此同时,近几年随着锂电池技术的不断改良进步,逐渐发现电池需要更优质的金属—镍,提高三元材料中的镍含量,能提升电池能量密度,减少原材料的同时让锂电池的续航能力再度提高。因此,三元正极材料又向高镍化方向发展。At present, power battery cathode materials mainly include lithium iron phosphate, ternary materials, lithium manganate, etc. Among them, ternary power batteries are relatively poor in safety performance, but have high energy density, which is one of the development directions of future power batteries. With the technological progress of ternary power batteries, which has led to a decrease in cost and an increase in market recognition, ternary cathode materials accounted for 47.6% of the sales of cathode materials in China in 2019, becoming the cathode material with the highest market share. At the same time, with the continuous improvement and progress of lithium battery technology in recent years, it is gradually found that the battery needs a better metal-nickel, and increasing the nickel content in the ternary material can improve the energy density of the battery, reduce the raw materials and make the lithium battery The battery life has been improved again. Therefore, the ternary cathode material is developing in the direction of high nickelization.
相关公开了一种镍铁材料的湿法处理工艺,其中涉及到的工艺是将镍铁粉在硫酸体系中加入氧化剂和强化剂进行氧化浸出,得到硫酸镍溶液和含氧化铁固相。此方法在反应过程中没有氢气产生,解决了一些安全问题,但此工艺需要采用高压氧浸,生产成本和设备维护成本较高,不适于推广。Relatedly disclosed is a wet treatment process of ferronickel material, which involves the process of adding oxidant and strengthening agent to ferronickel powder in a sulfuric acid system for oxidative leaching to obtain a nickel sulfate solution and a solid phase containing iron oxide. This method does not generate hydrogen during the reaction process, which solves some safety problems, but this process requires high-pressure oxygen immersion, and the production cost and equipment maintenance cost are high, which is not suitable for promotion.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种从含镍铁粉中提取镍并制备磷酸铁的方法和应用,使用混酸对含镍铁粉进行酸浸,通过与原料中铁和镍的含量进行配比添加混酸,可将镍以离子形式进入溶液,铁以磷酸铁的形式存在固相中,既实现了含镍铁粉中镍的提取,又分别将镍和铁制备成了利用价值较高的产品,该方法工艺简单,能耗低,成本也较低,同时具有较大经济效益。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method and application for extracting nickel from nickel-containing iron powder and preparing iron phosphate, using mixed acid to pickle the nickel-containing iron powder, and adding mixed acid by proportioning with the content of iron and nickel in the raw material, Nickel can enter the solution in the form of ions, and iron exists in the solid phase in the form of iron phosphate, which not only realizes the extraction of nickel from the nickel-containing iron powder, but also prepares nickel and iron into products with higher utilization value. The process is simple, the energy consumption is low, the cost is also low, and at the same time, it has great economic benefits.
一种从含镍铁粉中提取镍并制备磷酸铁的方法,包括如下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the steps:
(1)向含镍铁粉加入酸液,加热搅拌,得到混合浆料;(1) adding acid solution to nickel-containing iron powder, heating and stirring to obtain mixed slurry;
(2)向所述混合浆料添加氧化剂,加热搅拌,过滤得到磷酸铁和硫酸镍溶液;(2) adding an oxidant to the mixed slurry, heating and stirring, and filtering to obtain iron phosphate and nickel sulfate solution;
(3)向所述硫酸镍溶液添加中和剂进行加热搅拌,过滤得到除杂后的硫酸镍溶液;(3) add neutralizer to described nickel sulfate solution and carry out heating and stirring, filter to obtain the nickel sulfate solution after removing impurities;
其中,所述酸液为磷酸和硫酸。所述硫酸与磷酸是根据含镍铁粉中的铁含量、镍含量进行配制。Wherein, the acid solution is phosphoric acid and sulfuric acid. The sulfuric acid and phosphoric acid are prepared according to the iron content and nickel content in the nickel-containing iron powder.
在本发明的一些实施方式中,所述磷酸的浓度为10~19mol/L;所述磷酸与含镍铁粉的液固比为0.2~5mL/g。In some embodiments of the present invention, the concentration of the phosphoric acid is 10-19 mol/L; the liquid-solid ratio of the phosphoric acid to the nickel-containing iron powder is 0.2-5 mL/g.
在本发明的一些优选的实施方式中,所述磷酸的浓度为12~14mol/L;所述磷酸与含镍铁粉的液固比为0.5~3mL/g。In some preferred embodiments of the present invention, the concentration of the phosphoric acid is 12-14 mol/L; the liquid-solid ratio of the phosphoric acid to the nickel-containing iron powder is 0.5-3 mL/g.
在本发明的一些实施方式中,所述硫酸的浓度为0.5~10mol/L;所述硫酸与含镍铁粉的液固比为0.5~10mL/g。In some embodiments of the present invention, the concentration of the sulfuric acid is 0.5-10 mol/L; the liquid-solid ratio of the sulfuric acid to the nickel-containing iron powder is 0.5-10 mL/g.
在本发明的一些优选的实施方式中,所述硫酸的浓度为1~5mol/L;所述硫酸与含镍铁粉的液固比为1~8mL/g。In some preferred embodiments of the present invention, the concentration of the sulfuric acid is 1-5 mol/L; the liquid-solid ratio of the sulfuric acid to the nickel-containing iron powder is 1-8 mL/g.
在本发明的一些实施方式中,步骤(1)中,所述含镍铁粉为冶炼镍矿(红土镍矿和硫化镍矿)得到的镍铁块,经过空气雾化法制得的粉状物料,粒度为1~900μm,含镍铁粉中镍的含量为10~40%,铁的含量为60~85%,杂质总含量小于2%,如:Co:0.34%、Mn:0.09%、Si:0.27%、Cr:0.05%、Ca:0.006%、Mg:0.004%、Cu:0.03%、S:0.21%、P:0.03%。In some embodiments of the present invention, in step (1), the nickel-containing iron powder is the nickel-iron block obtained by smelting nickel ore (latterite nickel ore and nickel sulfide ore), and the powdery material obtained by the air atomization method , the particle size is 1~900μm, the nickel content in the nickel-containing iron powder is 10~40%, the iron content is 60~85%, and the total impurity content is less than 2%, such as: Co: 0.34%, Mn: 0.09%, Si : 0.27%, Cr: 0.05%, Ca: 0.006%, Mg: 0.004%, Cu: 0.03%, S: 0.21%, P: 0.03%.
在本发明的一些实施方式中,步骤(1)中,所述加热的温度为30~100℃,所述搅拌的时间为1~6h。In some embodiments of the present invention, in step (1), the heating temperature is 30-100° C., and the stirring time is 1-6 h.
在本发明的一些优选的实施方式中,步骤(1)中,所述加热的温度为50~90℃,所述搅拌的时间为2~5h。In some preferred embodiments of the present invention, in step (1), the heating temperature is 50-90° C., and the stirring time is 2-5 h.
在本发明的一些实施方式中,步骤(2)中,所述氧化剂为氧气、空气、双氧水、臭氧或次氯酸钠中的一种或几种。由于浸出液中的铁离子可能为二价铁,也可能为二价铁与三价铁的混合,因此需使用氧化剂将其氧化至三价铁。In some embodiments of the present invention, in step (2), the oxidant is one or more of oxygen, air, hydrogen peroxide, ozone or sodium hypochlorite. Since the iron ions in the leaching solution may be ferrous iron or a mixture of ferrous iron and ferric iron, an oxidizing agent is required to oxidize it to ferric iron.
在本发明的一些实施方式中,当所述氧化剂为氧气、空气、臭氧时,通入量为0.5~2.0L/min;当所述氧化剂为双氧水、次氯酸钠时,所述氧化剂与混合浆料的体积比 为(0.05-0.5):1。In some embodiments of the present invention, when the oxidant is oxygen, air, and ozone, the feeding amount is 0.5-2.0 L/min; when the oxidant is hydrogen peroxide or sodium hypochlorite, the amount of the oxidant and the mixed slurry is The volume ratio is (0.05-0.5):1.
在本发明的一些实施方式中,步骤(2)中,所述加热的温度为20~100℃,所述搅拌的时间为1~20h。In some embodiments of the present invention, in step (2), the heating temperature is 20-100° C., and the stirring time is 1-20 h.
在本发明的一些优选的实施方式中,步骤(2)中,所述加热的温度为40~90℃,所述搅拌的时间为2~15h。In some preferred embodiments of the present invention, in step (2), the heating temperature is 40-90° C., and the stirring time is 2-15 h.
在本发明的一些实施方式中,步骤(2)中,在所述加热前还包括加入沉淀剂的步骤,所述沉淀剂为二氧化钛、氢氧化铝、氧化铝、无水磷酸铁或二水磷酸铁中的一种或几种;所述沉淀剂与混合浆料的固液比为1~500g/L。沉淀剂可使磷酸铁沉淀过程中克服一定的能量壁垒,从而制备出磷酸铁产品。In some embodiments of the present invention, in step (2), a step of adding a precipitating agent is included before the heating, and the precipitating agent is titanium dioxide, aluminum hydroxide, aluminum oxide, anhydrous iron phosphate or dihydrate phosphoric acid One or more kinds of iron; the solid-liquid ratio of the precipitating agent and the mixed slurry is 1-500 g/L. The precipitation agent can overcome certain energy barriers in the process of iron phosphate precipitation, thereby preparing iron phosphate products.
在本发明的一些优选的实施方式中,所述沉淀剂与混合浆料的固液比为10~200g/L。In some preferred embodiments of the present invention, the solid-to-liquid ratio of the precipitant to the mixed slurry is 10-200 g/L.
在本发明的一些实施方式中,步骤(2)中,对所述磷酸铁进行洗涤、过滤和烘干,得到除杂后的磷酸铁。In some embodiments of the present invention, in step (2), the iron phosphate is washed, filtered and dried to obtain the iron phosphate after removal of impurities.
在本发明的一些实施方式中,步骤(2)中,所述洗涤为加水制浆洗涤,水与磷酸铁的液固比为1~20:1mL/g,洗涤的时间为0.5~5h。In some embodiments of the present invention, in step (2), the washing is pulping washing with water, the liquid-solid ratio of water to iron phosphate is 1-20:1 mL/g, and the washing time is 0.5-5 h.
在本发明的一些优选的实施方式中,水与磷酸铁的液固比为1~10:1mL/g,洗涤的时间为1~3h。In some preferred embodiments of the present invention, the liquid-solid ratio of water to iron phosphate is 1-10:1 mL/g, and the washing time is 1-3 hours.
在本发明的一些实施方式中,步骤(3)中,所述烘干的温度为60~120℃。In some embodiments of the present invention, in step (3), the drying temperature is 60-120°C.
在本发明的一些优选的实施方式中,步骤(3)中,所述烘干的温度为90~110℃。In some preferred embodiments of the present invention, in step (3), the drying temperature is 90-110°C.
在本发明的一些实施方式中,步骤(4)中,所述中和剂为碳酸钠、碳酸钙、碳酸铵、氢氧化钾或氢氧化钠中的一种或几种。In some embodiments of the present invention, in step (4), the neutralizing agent is one or more of sodium carbonate, calcium carbonate, ammonium carbonate, potassium hydroxide or sodium hydroxide.
在本发明的一些实施方式中,步骤(4)中,所述添加中和剂的过程为,将中和剂配制成溶液或浆料,添加到所述硫酸镍溶液中使其pH调至3~6。In some embodiments of the present invention, in step (4), the process of adding the neutralizing agent is to prepare the neutralizing agent into a solution or slurry, and add it to the nickel sulfate solution to adjust the pH to 3 ~6.
在本发明的一些实施方式中,步骤(4)中,所述加热的温度为30~100℃,所述搅拌的时间为1~10h。In some embodiments of the present invention, in step (4), the heating temperature is 30-100° C., and the stirring time is 1-10 h.
在本发明的一些优选的实施方式中,步骤(4)中,所述加热的温度为50~80℃,所述搅拌的时间为2~6h。In some preferred embodiments of the present invention, in step (4), the heating temperature is 50-80° C., and the stirring time is 2-6 h.
本发明还提出所述的方法在制备动力电池中的应用。The invention also proposes the application of the method in preparing power battery.
根据本发明的一种优选的实施方式,至少具有以下有益效果:According to a preferred embodiment of the present invention, it has at least the following beneficial effects:
本发明使用混酸对含镍铁粉进行酸浸,通过与原料中铁和镍的含量进行配比添加混酸,可将镍以离子形式进入溶液,铁以磷酸铁的形式存在固相中,可以有效地将固相中的镍和铁分离,得到硫酸镍溶液和电池级磷酸铁产品,硫酸镍为三元材料中不可或缺的材料之一,磷酸铁则进一步作为磷酸铁锂的前驱体制备出磷酸铁锂正极材料,既实现了含镍铁粉中镍的提取,又分别将镍和铁制备成了利用价值较高的产品,该方法工艺简单,能耗低,成本也较低,同时具有较大经济效益,适于工业化生产和应用。In the invention, the mixed acid is used to pickle the nickel-containing iron powder, and the mixed acid is added in proportion to the content of iron and nickel in the raw material, so that the nickel can enter the solution in the form of ions, and the iron exists in the solid phase in the form of iron phosphate, which can effectively The nickel and iron in the solid phase are separated to obtain nickel sulfate solution and battery-grade iron phosphate products. Nickel sulfate is one of the indispensable materials in ternary materials, and iron phosphate is further used as a precursor of lithium iron phosphate to prepare phosphoric acid. The iron-lithium cathode material not only realizes the extraction of nickel from the nickel-containing iron powder, but also prepares nickel and iron into products with higher utilization value. The method has the advantages of simple process, low energy consumption and low cost. Great economic benefits, suitable for industrial production and application.
下面结合附图和实施例对本发明做进一步的说明,其中:The present invention will be further described below in conjunction with the accompanying drawings and embodiments, wherein:
图1为本发明从含镍铁粉中提取镍并制备磷酸铁的工艺流程图。1 is a process flow diagram of the present invention for extracting nickel from nickel-containing iron powder and preparing iron phosphate.
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
图1是本发明从含镍铁粉中提取镍并制备磷酸铁的工艺流程图,从图中可以看出,向含镍铁粉加入硫酸和磷酸加热搅拌一段时间,再加入氧化剂加热搅拌,过滤即可得到磷酸铁和硫酸镍溶液,向硫酸镍溶液加入中和剂加热搅拌,过滤除去杂质沉淀,即可得到较为纯净的硫酸镍溶液,该工艺简单,能耗低,成本也较低。Fig. 1 is the process flow diagram that the present invention extracts nickel from nickel-containing iron powder and prepares iron phosphate, as can be seen from the figure, to nickel-containing iron powder, add sulfuric acid and phosphoric acid heating and stirring for a period of time, then add oxidant heating and stirring, filter Ferric phosphate and nickel sulfate solutions can be obtained, a neutralizing agent is added to the nickel sulfate solution, heated and stirred, and impurity precipitates are removed by filtration to obtain a relatively pure nickel sulfate solution. The process is simple, low in energy consumption, and low in cost.
实施例1Example 1
一种从含镍铁粉中提取镍并制备磷酸铁的方法,包括以下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the following steps:
(1)分别配制2mol/L的硫酸和14mol/L的磷酸,备用;(1) prepare the sulfuric acid of 2mol/L and the phosphoric acid of 14mol/L respectively, standby;
(2)称量50g含镍铁粉,其中,铁含量为64.13%,镍含量为35.67%,加入37mL的上述磷酸,再加入250mL的上述硫酸,将浆料水浴加热至80℃,搅拌时间为3h;(2) Weighing 50g of nickel-containing iron powder, wherein the iron content is 64.13% and the nickel content is 35.67%, add 37mL of the above phosphoric acid, then add 250mL of the above-mentioned sulfuric acid, and heat the slurry water bath to 80°C, and the stirring time is 3h;
(3)添加50mL双氧水,搅拌1h,再添加7g的氢氧化铝和磷酸铁于溶液中,加热升温至90℃,搅拌10h,过滤得到磷酸铁和硫酸镍溶液;(3) Add 50 mL of hydrogen peroxide, stir for 1 h, then add 7 g of aluminum hydroxide and iron phosphate to the solution, heat to 90 ° C, stir for 10 h, and filter to obtain iron phosphate and nickel sulfate solution;
(4)将磷酸铁以液固比5:1mL/g加水制浆洗涤1h,过滤后将磷酸铁在105℃下烘干得到磷酸铁产品;(4) ferric phosphate was washed with water at a liquid-solid ratio of 5:1 mL/g for 1 h, and after filtration, the ferric phosphate was dried at 105°C to obtain a ferric phosphate product;
(5)向硫酸镍溶液添加浓度为25%碳酸钠溶液调节pH至4.5左右,加热至80℃, 搅拌3h,过滤得到杂质含量较低的硫酸镍溶液。(5) Add sodium carbonate solution with a concentration of 25% to the nickel sulfate solution to adjust pH to about 4.5, heat to 80° C., stir for 3 hours, and filter to obtain a nickel sulfate solution with low impurity content.
实施例2Example 2
一种从含镍铁粉中提取镍并制备磷酸铁的方法,包括以下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the following steps:
(1)分别配制1.5mol/L的硫酸和13.5mol/L的磷酸,备用;(1) prepare the sulfuric acid of 1.5mol/L and the phosphoric acid of 13.5mol/L respectively, standby;
(2)称量100g含镍铁粉,其中,铁含量为69.28%,镍含量为30.29%,加入85mL的上述磷酸,再加入520mL的上述硫酸,将浆料水浴加热至85℃,搅拌时间为4h;(2) Weighing 100g of nickel-containing iron powder, wherein the iron content is 69.28% and the nickel content is 30.29%, 85 mL of the above phosphoric acid is added, and 520 mL of the above sulfuric acid is added, and the slurry water bath is heated to 85 ℃, and the stirring time is 4h;
(3)添加40mL双氧水,同时通入2h曝气氧气,再添加15g的二氧化钛和二水磷酸铁于溶液中,加热升温至80℃,搅拌8h,过滤得到磷酸铁和硫酸镍溶液;(3) adding 40mL hydrogen peroxide, feeding 2h aeration oxygen at the same time, adding 15g titanium dioxide and ferric phosphate dihydrate to the solution, heating to 80°C, stirring for 8h, and filtering to obtain ferric phosphate and nickel sulfate solution;
(4)将磷酸铁以液固比10:1mL/g加水制浆洗涤2h,过滤后将磷酸铁在90℃下烘干得到磷酸铁产品;(4) ferric phosphate was washed with water at a liquid-solid ratio of 10:1 mL/g for 2 hours, and after filtration, the ferric phosphate was dried at 90°C to obtain a ferric phosphate product;
(5)向硫酸镍溶液添加浓度为15%碳酸钠溶液调节pH至4.0左右,加热至85℃,搅拌2h,过滤得到杂质含量较低的硫酸镍溶液。(5) Add sodium carbonate solution with a concentration of 15% to the nickel sulfate solution to adjust the pH to about 4.0, heat to 85° C., stir for 2 hours, and filter to obtain a nickel sulfate solution with low impurity content.
实施例3Example 3
一种从含镍铁粉中提取镍并制备磷酸铁的方法,包括以下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the following steps:
(1)分别配制2.5mol/L的硫酸和14.5mol/L的磷酸,备用;(1) respectively prepare the sulfuric acid of 2.5mol/L and the phosphoric acid of 14.5mol/L, standby;
(2)称量100g含镍铁粉,其中,铁含量为85.42%,镍含量为13.95%,加入95mL的上述磷酸,再加入200mL的上述硫酸,将浆料水浴加热至75℃,搅拌时间为6h;(2) Weighing 100g of nickel-containing iron powder, wherein the iron content is 85.42% and the nickel content is 13.95%, add 95mL of the above phosphoric acid, then add 200mL of the above-mentioned sulfuric acid, heat the slurry water bath to 75°C, and the stirring time is 6h;
(3)添加100mL双氧水,搅拌0.5h,再添加20g氧化铝和二氧化钛于溶液中,加热升温至85℃,搅拌6h,过滤得到磷酸铁和硫酸镍溶液;(3) Add 100 mL of hydrogen peroxide, stir for 0.5 h, then add 20 g of alumina and titanium dioxide to the solution, heat up to 85°C, stir for 6 h, and filter to obtain iron phosphate and nickel sulfate solution;
(4)将磷酸铁以液固比8:1mL/g加水制浆洗涤0.5h,过滤后将磷酸铁在105℃下烘干得到磷酸铁产品;(4) ferric phosphate was washed with water at a liquid-solid ratio of 8:1 mL/g for 0.5 h, and after filtration, the ferric phosphate was dried at 105°C to obtain a ferric phosphate product;
(5)向硫酸镍溶液添加浓度为5%氢氧化钠溶液调节pH至5.0左右,加热至70℃,搅拌4h,过滤得到杂质含量较低的硫酸镍溶液。(5) Add sodium hydroxide solution with a concentration of 5% to the nickel sulfate solution to adjust pH to about 5.0, heat to 70° C., stir for 4 hours, and filter to obtain a nickel sulfate solution with low impurity content.
实施例4Example 4
一种从含镍铁粉中提取镍并制备磷酸铁的方法,包括以下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the following steps:
(1)分别配制3.0mol/L的硫酸和14mol/L的磷酸,备用;(1) prepare the sulfuric acid of 3.0mol/L and the phosphoric acid of 14mol/L respectively, standby;
(2)称量100g含镍铁粉,其中,铁含量为83.29%,镍含量为15.99%,加入110mL的上述磷酸,再加入170mL的上述硫酸,将浆料水浴加热至80℃,搅拌时间为5h;(2) Weigh 100g of nickel-containing iron powder, wherein the iron content is 83.29% and the nickel content is 15.99%, add 110 mL of the above phosphoric acid, and then add 170 mL of the above-mentioned sulfuric acid, and heat the slurry water bath to 80 ° C, and the stirring time is 5h;
(3)添加65mL次氯酸钠,搅拌2h,再添加20g氢氧化铝和二水磷酸铁于溶液中,加热升温至90℃,搅拌8h,过滤得到磷酸铁和硫酸镍溶液;(3) Add 65mL of sodium hypochlorite, stir for 2h, then add 20g of aluminum hydroxide and ferric phosphate dihydrate to the solution, heat to 90°C, stir for 8h, and filter to obtain ferric phosphate and nickel sulfate solution;
(4)将磷酸铁以液固比12:1mL/g加水制浆洗涤1h,过滤后将磷酸铁在100℃下烘干得到磷酸铁产品;(4) ferric phosphate was washed with water for 1 h at a liquid-solid ratio of 12:1 mL/g, and after filtration, the ferric phosphate was dried at 100° C. to obtain a ferric phosphate product;
(5)向硫酸镍溶液添加碳酸钙溶液调节pH至5.5左右,加热至75℃,搅拌4h,过滤得到杂质含量较低的硫酸镍溶液。(5) adding calcium carbonate solution to the nickel sulfate solution to adjust the pH to about 5.5, heating to 75° C., stirring for 4 hours, and filtering to obtain a nickel sulfate solution with a lower impurity content.
试验例Test example
取上述实施例1~3制得的磷酸铁成品进行理化指标检测,结果如下表1所示:Get the ferric phosphate finished product that above-mentioned embodiment 1~3 makes and carry out physical and chemical index detection, the result is as shown in table 1 below:
表1本发明实施例1-3制备的磷酸铁理化指标检测结果Table 1 Physicochemical index detection results of iron phosphate prepared by Example 1-3 of the present invention
从表1可以看出,采用本发明的制备方法得到的磷酸铁的各项理化指标均符合磷酸铁锂正极材料的标准。As can be seen from Table 1, each physical and chemical index of the iron phosphate obtained by the preparation method of the present invention meets the standard of the lithium iron phosphate positive electrode material.
取上述实施例1~3制得的硫酸镍溶液进行杂质含量分析,结果如下表2所示:Get the nickel sulfate solution that above-mentioned embodiment 1~3 makes and carry out impurity content analysis, the result is as shown in following table 2:
表2本发明实施例1~3制备的硫酸镍溶液杂质元素分析(mg/L)Table 2 Analysis (mg/L) of impurities in nickel sulfate solution prepared in Examples 1 to 3 of the present invention
NiNi | FeFe | CoCo | MnMn | CuCu | AlAl | |
实施例1Example 1 | 35891.535891.5 | 1.071.07 | 343.2343.2 | 53.953.9 | 0.1390.139 | 0.2290.229 |
实施例2Example 2 | 28455.828455.8 | 2.732.73 | 456.6456.6 | 87.287.2 | 0.1890.189 | 0.3570.357 |
实施例3Example 3 | 10652.610652.6 | 10.7210.72 | 212.6212.6 | 67.967.9 | 0.1550.155 | 0.5820.582 |
CaCa | MgMg | PP | CrCr | ZnZn | SiSi | |
实施例1Example 1 | 16.716.7 | 1.561.56 | 1.751.75 | 0.1380.138 | 1.1421.142 | 73.973.9 |
实施例2Example 2 | 13.913.9 | 0.980.98 | 2.152.15 | 0.1120.112 | 0.9970.997 | 57.257.2 |
实施例3Example 3 | 20.520.5 | 1.121.12 | 2.672.67 | 0.1450.145 | 1.1021.102 | 65.865.8 |
从表2可以看出,采用本发明的制备方法得到的硫酸镍溶液的杂质含量较低,除杂后的硫酸镍溶液中杂质(不包含Co、Mn)含量小于100pm。As can be seen from Table 2, the impurity content of the nickel sulfate solution obtained by the preparation method of the present invention is relatively low, and the impurity (excluding Co, Mn) content in the nickel sulfate solution after impurity removal is less than 100 μm.
取上述实施例1~3制得的磷酸铁按照常规方法制备成磷酸铁锂,对制得的磷酸铁锂的电性能进行检测,结果如表3所示:Get the iron phosphate that the above-mentioned embodiment 1~3 obtains and prepare into lithium iron phosphate according to the conventional method, the electrical property of the obtained lithium iron phosphate is detected, the result is as shown in Table 3:
表3实施例1-3的磷酸铁合成磷酸铁锂粉末压实密度及电性能检测结果对比表Table 3 The iron phosphate synthesis lithium iron phosphate powder of the embodiment 1-3 of table 3 compares table of compaction density and electrical property test result
从表3可以看出,本发明得到的磷酸铁合成的磷酸铁锂粉末的压实密度及电性能均达到了磷酸铁锂用磷酸铁的使用标准,可以直接作为磷酸铁锂生产的前驱体。As can be seen from Table 3, the compacted density and electrical properties of the lithium iron phosphate powder synthesized by the iron phosphate obtained in the present invention have all reached the use standard of iron phosphate for lithium iron phosphate, and can be directly used as the precursor produced by lithium iron phosphate.
采用本发明实施例的方法对含镍铁粉中的镍进行提取,可以有效的将镍、铁分离,同时得到经济效益较大的两种产品。本发明在使用硫酸、磷酸的混酸对含镍铁粉进行溶解时,主要是根据其中的铁和磷酸反应得到磷酸二氢亚铁,镍和硫酸得到硫酸镍来进行,再使用氧化剂对亚铁进行氧化,同时在沉淀剂的作用下得到磷酸铁,而硫酸镍溶液中存在的微量杂质经过中和剂的除杂后,均能以渣相排出,从而制备出杂质含量较低的硫酸镍溶液,此方法中所用试剂均易得,操作简单,制备出的磷酸铁产品的Fe/P在0.96~1之间,除杂后的硫酸镍溶液中杂质(不包含Co、Mn)含量小于100pm。Using the method of the embodiment of the present invention to extract the nickel in the nickel-containing iron powder can effectively separate the nickel and the iron, and simultaneously obtain two products with greater economic benefits. In the present invention, when the mixed acid of sulfuric acid and phosphoric acid is used to dissolve the nickel-containing iron powder, the reaction is mainly based on the reaction of iron and phosphoric acid to obtain ferrous dihydrogen phosphate, nickel and sulfuric acid to obtain nickel sulfate, and then the oxidizing agent is used to dissolve the ferrous phosphate. At the same time, iron phosphate is obtained under the action of the precipitating agent, and the trace impurities in the nickel sulfate solution can be discharged as slag after the impurity removal by the neutralizing agent, thereby preparing a nickel sulfate solution with a lower impurity content, The reagents used in this method are all readily available, the operation is simple, the Fe/P of the prepared iron phosphate product is between 0.96 and 1, and the content of impurities (excluding Co and Mn) in the nickel sulfate solution after impurity removal is less than 100 pm.
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.
Claims (10)
- 一种从含镍铁粉中提取镍并制备磷酸铁的方法,其特征在于,包括如下步骤:A method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, comprising the steps of:(1)向含镍铁粉加入酸液,加热搅拌,得到混合浆料;(1) adding acid solution to nickel-containing iron powder, heating and stirring to obtain mixed slurry;(2)向所述混合浆料添加氧化剂,加热搅拌,过滤得到磷酸铁和硫酸镍溶液;(2) adding an oxidant to the mixed slurry, heating and stirring, and filtering to obtain iron phosphate and nickel sulfate solution;(3)向所述硫酸镍溶液添加中和剂进行加热搅拌,过滤得到除杂后的硫酸镍溶液;(3) add neutralizer to described nickel sulfate solution and carry out heating and stirring, filter to obtain the nickel sulfate solution after removing impurities;其中,所述酸液为磷酸和硫酸。Wherein, the acid solution is phosphoric acid and sulfuric acid.
- 根据权利要求1所述的方法,其特征在于,所述磷酸的浓度为10~19mol/L;所述磷酸与含镍铁粉的液固比为0.2~5mL/g。The method according to claim 1, wherein the concentration of the phosphoric acid is 10-19 mol/L; the liquid-solid ratio of the phosphoric acid to the nickel-containing iron powder is 0.2-5 mL/g.
- 根据权利要求1所述的方法,其特征在于,所述硫酸的浓度为0.5~10mol/L;所述硫酸与含镍铁粉的液固比为0.5~10mL/g。The method according to claim 1, wherein the concentration of the sulfuric acid is 0.5-10 mol/L; the liquid-solid ratio of the sulfuric acid to the nickel-containing iron powder is 0.5-10 mL/g.
- 根据权利要求1所述的方法,其特征在于,步骤(1)中,所述含镍铁粉为冶炼镍矿得到的镍铁块,经过空气雾化法制得的粉状物料,粒度为1~900μm,含镍铁粉中镍的含量为10~40%,铁的含量为60~85%。The method according to claim 1, characterized in that, in step (1), the nickel-containing iron powder is a nickel-iron nugget obtained by smelting nickel ore, and the powdery material obtained by an air atomization method has a particle size of 1- 900 μm, the content of nickel in the nickel-containing iron powder is 10-40%, and the content of iron is 60-85%.
- 根据权利要求1所述的方法,其特征在于,步骤(1)中,所述加热的温度为30~100℃,所述搅拌的时间为1~6h。The method according to claim 1, characterized in that, in step (1), the heating temperature is 30-100° C., and the stirring time is 1-6 h.
- 根据权利要求1所述的方法,其特征在于,步骤(2)中,所述氧化剂为氧气、空气、双氧水、臭氧或次氯酸钠中的一种或几种;步骤(2)中,所述加热的温度为20~100℃,所述搅拌的时间为1~20h。The method according to claim 1, wherein in step (2), the oxidant is one or more of oxygen, air, hydrogen peroxide, ozone or sodium hypochlorite; in step (2), the heated The temperature is 20~100°C, and the stirring time is 1~20h.
- 根据权利要求1所述的方法,其特征在于,步骤(2)中,对所述磷酸铁进行洗涤、过滤和烘干,得到除杂后的磷酸铁。The method according to claim 1, characterized in that, in step (2), the iron phosphate is washed, filtered and dried to obtain the iron phosphate after removal of impurities.
- 根据权利要求1所述的方法,其特征在于,步骤(2)中,在所述加热前还包括加入沉淀剂的步骤,所述沉淀剂为二氧化钛、氢氧化铝、氧化铝、无水磷酸铁或二水磷酸铁中的一种或几种;所述沉淀剂与混合浆料的固液比为1~500g/L。The method according to claim 1, characterized in that, in step (2), before the heating, it further comprises the step of adding a precipitating agent, and the precipitating agent is titanium dioxide, aluminum hydroxide, aluminum oxide, anhydrous iron phosphate Or one or more of ferric phosphate dihydrate; the solid-liquid ratio of the precipitant to the mixed slurry is 1-500 g/L.
- 根据权利要求1所述的方法,其特征在于,步骤(3)中,所述中和剂为碳酸钠、碳酸钙、碳酸铵、氢氧化钾或氢氧化钠中的一种或几种;步骤(3)中,所述加热的温度为30~100℃,所述搅拌的时间为1~10h。The method according to claim 1, wherein, in step (3), the neutralizing agent is one or more of sodium carbonate, calcium carbonate, ammonium carbonate, potassium hydroxide or sodium hydroxide; step In (3), the heating temperature is 30-100° C., and the stirring time is 1-10 h.
- 权利要求1-9任一项所述的方法在制备动力电池中的应用。Application of the method of any one of claims 1-9 in preparing power batteries.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110152830.6 | 2021-02-04 | ||
CN202110152830.6A CN113025822B (en) | 2021-02-04 | 2021-02-04 | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate and application |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022166476A1 true WO2022166476A1 (en) | 2022-08-11 |
Family
ID=76459888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/142334 WO2022166476A1 (en) | 2021-02-04 | 2021-12-29 | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, and application |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN113025822B (en) |
WO (1) | WO2022166476A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117003212A (en) * | 2023-08-07 | 2023-11-07 | 上海天汉环境资源有限公司 | Preparation method of battery grade material |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113025822B (en) * | 2021-02-04 | 2022-08-16 | 湖南邦普循环科技有限公司 | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate and application |
CN113578235B (en) * | 2021-07-30 | 2023-05-12 | 福建常青新能源科技有限公司 | Nickel sulfate solution production device |
CN113666351B (en) * | 2021-08-31 | 2023-12-12 | 广东邦普循环科技有限公司 | Method for preparing ferric phosphate by recycling ferronickel slag |
CN113753872A (en) * | 2021-09-15 | 2021-12-07 | 广东邦普循环科技有限公司 | Comprehensive utilization method of iron-containing minerals |
CN113942986B (en) * | 2021-09-27 | 2023-06-16 | 荆门市格林美新材料有限公司 | Method for recycling nickel and iron from nickel-iron alloy |
CN113860397B (en) * | 2021-10-22 | 2022-08-26 | 江西佳纳能源科技有限公司 | Preparation method of nickel sulfate |
CN116409762A (en) * | 2021-12-29 | 2023-07-11 | 荆门市格林美新材料有限公司 | Method for preparing battery material by utilizing nickel-iron alloy |
CN114574713B (en) * | 2022-02-28 | 2023-03-31 | 中南大学 | Method for separating iron and nickel and cobalt from nickel and cobalt acid leaching solution containing high-concentration iron ions |
CN114933291A (en) * | 2022-04-08 | 2022-08-23 | 四川顺应动力电池材料有限公司 | Method for preparing high-purity lithium iron phosphate by using nickel-iron alloy |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
CN102212690A (en) * | 2011-06-08 | 2011-10-12 | 广西银亿科技矿冶有限公司 | Method for purifying lateritic nickel ore leach liquor |
CN102212698A (en) * | 2011-05-19 | 2011-10-12 | 江门市芳源环境科技开发有限公司 | Method for recovering nickel sulfate through comprehensive treatment of nickel-containing waste |
KR101191042B1 (en) * | 2011-12-27 | 2012-10-15 | 강호길 | Process for making high purified nickel sulfate from nickel concentrates, nickel matte |
CN106829907A (en) * | 2017-03-31 | 2017-06-13 | 广东佳纳能源科技有限公司 | A kind of method that nickel-contained pig iron prepares nickel sulfate solution and battery-grade iron phosphate |
CN110342590A (en) * | 2019-08-19 | 2019-10-18 | 中南大学 | A kind of method that normal pressure decomposition converter mattes prepare nickel sulfate |
CN113025822A (en) * | 2021-02-04 | 2021-06-25 | 湖南邦普循环科技有限公司 | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate and application |
-
2021
- 2021-02-04 CN CN202110152830.6A patent/CN113025822B/en active Active
- 2021-12-29 WO PCT/CN2021/142334 patent/WO2022166476A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
CN102212698A (en) * | 2011-05-19 | 2011-10-12 | 江门市芳源环境科技开发有限公司 | Method for recovering nickel sulfate through comprehensive treatment of nickel-containing waste |
CN102212690A (en) * | 2011-06-08 | 2011-10-12 | 广西银亿科技矿冶有限公司 | Method for purifying lateritic nickel ore leach liquor |
KR101191042B1 (en) * | 2011-12-27 | 2012-10-15 | 강호길 | Process for making high purified nickel sulfate from nickel concentrates, nickel matte |
CN106829907A (en) * | 2017-03-31 | 2017-06-13 | 广东佳纳能源科技有限公司 | A kind of method that nickel-contained pig iron prepares nickel sulfate solution and battery-grade iron phosphate |
CN110342590A (en) * | 2019-08-19 | 2019-10-18 | 中南大学 | A kind of method that normal pressure decomposition converter mattes prepare nickel sulfate |
CN113025822A (en) * | 2021-02-04 | 2021-06-25 | 湖南邦普循环科技有限公司 | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate and application |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117003212A (en) * | 2023-08-07 | 2023-11-07 | 上海天汉环境资源有限公司 | Preparation method of battery grade material |
CN117003212B (en) * | 2023-08-07 | 2024-04-05 | 上海天汉环境资源有限公司 | Preparation method of battery grade material |
Also Published As
Publication number | Publication date |
---|---|
CN113025822B (en) | 2022-08-16 |
CN113025822A (en) | 2021-06-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022166476A1 (en) | Method for extracting nickel from nickel-containing iron powder and preparing iron phosphate, and application | |
WO2022166023A1 (en) | Method for resource recycling of nickel-iron alloy and use thereof | |
CN106829907B (en) | A kind of method that nickel-contained pig iron prepares nickel sulfate solution and battery-grade iron phosphate | |
CN112158894A (en) | Method for recovering anode material of waste lithium battery | |
CN109052492B (en) | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution | |
CN112093785A (en) | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery | |
CN114394582B (en) | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag | |
CN107699714B (en) | A method of manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide | |
CN109626350A (en) | A kind of method that waste lithium iron phosphate battery positive plate prepares battery-grade iron phosphate | |
CN112723330B (en) | Preparation method and application of iso-phospho-ferromanganese iron phosphate | |
CN113912033A (en) | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction | |
CN112267023B (en) | Two-stage defluorination method for fluorine-containing material | |
CN115448279B (en) | Method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag | |
CN115074540B (en) | Comprehensive recovery method for valuable components of waste power battery | |
WO2023029573A1 (en) | Method for extracting lithium from waste lithium battery | |
CN114249313A (en) | Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder | |
CN115092902A (en) | Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag | |
CN112342383B (en) | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste | |
CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
CN115947323A (en) | Method for extracting lithium from waste lithium iron phosphate and preparing iron phosphate | |
CN115709979A (en) | Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material | |
WO2022205534A1 (en) | Preparation method for electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery | |
WO2024130856A1 (en) | Low-copper-aluminum lithium iron phosphate black powder, and preparation method therefor | |
CN117545714A (en) | Reuse method of ferrophosphorus slag | |
CN118206092A (en) | Recycling method and application of waste lithium iron phosphate lithium extraction slag |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21924469 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21924469 Country of ref document: EP Kind code of ref document: A1 |