CN114394582A - Method for regenerating iron phosphate from phosphorus iron slag after lithium extraction - Google Patents
Method for regenerating iron phosphate from phosphorus iron slag after lithium extraction Download PDFInfo
- Publication number
- CN114394582A CN114394582A CN202210105958.1A CN202210105958A CN114394582A CN 114394582 A CN114394582 A CN 114394582A CN 202210105958 A CN202210105958 A CN 202210105958A CN 114394582 A CN114394582 A CN 114394582A
- Authority
- CN
- China
- Prior art keywords
- slag
- iron
- solution
- phosphorus
- regenerating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002893 slag Substances 0.000 title claims abstract description 58
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 50
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000000605 extraction Methods 0.000 title claims abstract description 24
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 18
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 15
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 238000000909 electrodialysis Methods 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 229920001429 chelating resin Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 11
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000011069 regeneration method Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- 239000000047 product Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical group OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- C01B25/18—Phosphoric acid
- C01B25/185—Preparation neither from elemental phosphorus or phosphoric anhydride nor by reacting phosphate-containing material with an acid, e.g. by reacting phosphate-containing material with an ion-exchange resin or an acid salt used alone
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction, belonging to the technical field of waste resource recycling and lithium ion battery materials, which mainly comprises the following steps: alkaline aluminum removal, reduction roasting and acid leaching, coprecipitation to produce iron phosphate, and bipolar membrane electrodialysis to regenerate acid and alkali. The method realizes the regeneration of the ferro-phosphorus slag into the ferric phosphate product on the premise of reducing the use amount of acid and alkali and protecting the environment.
Description
Technical Field
The invention belongs to the technical field of waste resource recycling and lithium ion battery materials, and particularly relates to a method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction.
Background
The development of new energy automobiles has become a national strategy in countries around the world. The output and sales of new energy automobiles in China account for more than 50% of the world, and by the end of 6 months in 2021, the inventory of new energy automobiles in China reaches 603 thousands, the sales of new energy automobiles in 2025 break through 800 thousands, and the loading capacity of power batteries reaches 406 GWh. Because of the advantages of relatively low price, higher safety and the like, the lithium iron phosphate battery has an increasing share in power batteries, and the ratio of the lithium iron phosphate battery reaches 62% in 2020. The limited service life of the lithium ion battery inevitably causes a great deal of retirement of the power lithium ion battery, and the retirement amount of the power lithium ion battery in China is expected to exceed 134GWh (over 80 ten thousand tons) in 2025, and the market planning is over 300 million yuan and is in a trend of increasing year by year.
In the waste lithium iron phosphate battery, the mass ratio of lithium iron phosphate is 30-35%, the ratio of copper foil to aluminum foil is about 10%, and the contents of valuable metal elements Li, Fe, Cu and Al far exceed the contents of the valuable metal elements in natural minerals, so that the waste of valuable resources is greatly caused by random stacking, and the waste lithium iron phosphate battery is inconsistent with the national green sustainable development strategy.
At present, waste lithium iron phosphate is mainly treated by a wet process, the main procedures comprise battery discharging, disassembling, crushing and sorting to obtain black powder, and valuable elements are recycled and reused by operations such as leaching, element separation and purification, product regeneration and the like. The recovery value of lithium is high, and the process for recovering lithium in waste lithium iron phosphate into high-value lithium carbonate or lithium hydroxide products is mature. However, at present, the disposal of the phosphorus-iron slag forms low-end products of phosphate fertilizer and iron oxide red, or the phosphorus-iron slag is directly dumped, and although reports of regeneration of iron phosphate exist, the related processes have the problems of poor applicability, high cost and the like, and the development of a green and efficient regeneration technology of the phosphorus-iron slag is urgently needed.
In addition, only a few technologies relate to the recovery of the phosphorus iron slag, such as CN110683528A and CN 111646447a, wherein CN110683528A only aims at pure iron phosphate waste, and has poor adaptability to raw materials, and no description is made on slag after lithium extraction from waste lithium iron phosphate battery powder. For CN 111646447A, the ferrophosphorus slag is not reduced by a reducing agent, and phosphorus and iron in the ferrophosphorus slag mainly exist as ferric orthophosphate. According to thermodynamic calculation and experiments, the leaching pH value of ferric orthophosphate is lower than-2, and the leaching pH value of ferrous phosphate is only about 1-2, so that the dosage of acid is particularly large, a large amount of alkali is consumed during ferric phosphate precipitation, and a large amount of high-salt wastewater is generated.
Disclosure of Invention
The invention aims to provide a method for regenerating iron phosphate from ferrophosphorus slag after lithium extraction, which realizes the regeneration of the ferrophosphorus slag into iron phosphate products on the premise of reducing the use amount of acid and alkali and being green and environment-friendly.
In order to achieve the technical effects, the invention provides the following technical scheme:
a method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction comprises the following steps:
s1, mixing the ferrophosphorus slag after lithium extraction with water, adding alkali liquor, after the reaction is finished, carrying out solid-liquid separation, and washing the slag after solid-liquid separation to obtain slag A.
S2, drying the slag A, mixing the slag A with a reducing agent, and roasting the mixture in a reducing atmosphere to obtain slag B.
S3, mixing the residue B with water, pulping, adding acid liquor for leaching, and after the reaction is finished, carrying out solid-liquid separation to obtain a solution A.
S4, adding a proper amount of iron powder into the solution A, removing copper by replacing the iron powder, and performing solid-liquid separation after the reaction is finished to obtain a solution B.
S5, supplementing a phosphorus source or an iron source into the solution B to obtain a raw material solution, adding hydrogen peroxide and ammonia water into the raw material solution to perform coprecipitation reaction, performing solid-liquid separation after the reaction is finished to obtain ferric phosphate dihydrate and a solution C, and sintering the ferric phosphate dihydrate to obtain the ferric phosphate.
S6, removing iron and other impurity element ions from the solution C by using chelating resin to obtain a solution D.
S7 electrolyzing the solution D by using bipolar membrane electrodialysis to obtain acid liquor and alkali liquor, and respectively returning to the leaching in S3 and the coprecipitation in S5 for use.
The phosphorus-iron slag is phosphorus-iron slag obtained after lithium extraction from waste lithium iron phosphate batteries or other phosphorus-iron slag (such as waste slag in iron phosphate production).
In the invention, the alkali liquor in the step S1 is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide, the reaction temperature is 40-90 ℃, the reaction time is 1-3 hours, and the addition amount is 1-5 times of the theoretical amount. The method of step S1 is to remove aluminum from the ferrophosphorus slag, and whether step S1 is required may be adjusted according to the content of aluminum in the raw ferrophosphorus slag.
In the invention, the reducing agent in the step S2 is one or more of glucose, negative electrode powder, coke powder and charcoal powder, preferably glucose, the roasting temperature is 300-800 ℃, the addition amount of the reducing agent is 1-3 times of the theoretical amount, and the roasting time is 0.5-5 hours. According to the formula Fe-P-H2And in an O-series potential-pH diagram, the acidity value required by ferric iron leaching is far higher than that required by ferrous iron leaching, and the slag B obtained in the step S2 is easier to leach under low acidity, so that the high leaching rate of the medium-strong acid to the phosphorus-iron slag is ensured.
In the invention, the acid solution in the step S3 is one or more of phosphoric acid, hydrochloric acid and sulfuric acid, preferably phosphoric acid, the solid-to-liquid ratio is 1: 3-10, the leaching temperature is 20-95 ℃, the reaction time is 1-6 h, and the degree of reduction of the residue B is related to the acidity (i.e. the acid addition) required during leaching.
In the invention, the adding amount of the iron powder in the step S4 is 1-3 times of the theoretical amount, the reaction time is 1-6 hours, the impurity element copper in the solution a is removed by adopting an iron powder displacement copper removal mode, the iron powder is ultrafine reducing iron powder, the adding amount of the iron powder is related to the leached acidity and the copper content in the solution a, and the possible reaction equation is as follows:
Fe+Cu2+＝Fe2++Cu
Fe+2H+＝Fe2++H2
in the invention, the addition amount of the ammonia water in the step S5 is determined according to the pH value, the pH value during precipitation is 0.5-2.5, the reaction temperature is 40-80 ℃, and the addition amount of the hydrogen peroxide is 1-3 times of the theoretical amount.
In the invention, the bipolar membrane electrolysis in the step S7 adopts constant current electrolysis, the current density is 200-800A/m 2, the acid chamber receiving liquid is pure water or dilute acid solution, the alkali chamber receiving liquid is pure water or ammonia water solution, and the osmotic pressure difference between adjacent polar chambers cannot exceed 8 times.
Compared with the prior art, the invention has the following technical effects:
(1) according to the invention, through the use of bipolar membrane electrodialysis, acid and alkali are regenerated through electrolysis, so that the use amount of the acid and alkali is greatly reduced, meanwhile, the treatment of the solution after iron phosphate coprecipitation is avoided, the environment-friendly treatment pressure and cost are reduced, and the cyclic utilization of resources is increased.
(2) The raw materials of the invention have strong applicability, and compared with the ultra-high acidity leaching condition required by the leaching of the ferric orthophosphate slag, the invention greatly reduces the acid amount required by leaching by reducing roasting and simultaneously reduces the using amount of ammonia water during coprecipitation.
(3) The full components of the ferrophosphorus are recovered, the recovery rate is high, and the low-value byproducts are few.
Drawings
FIG. 1 is a process flow chart of the regeneration of iron phosphate from iron phosphate slag after lithium extraction.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction comprises the following steps:
mixing the lithium-extracted ferrophosphorus slag and pure water according to a solid-to-liquid ratio of 1:5, mixing, adding a sodium hydroxide solution with 2 times of the theoretical amount into the slurry, reacting for 1 hour, filtering and washing the solid to obtain slag A.
And (3) drying the slag A in a vacuum drying oven, adding 2 times of theoretical amount of glucose, uniformly mixing, and roasting in a tubular furnace for 2 hours to obtain slag B.
Mixing the slag B and a dilute phosphoric acid solution according to the mass ratio of 1:6, stirring and leaching for 2 hours at 80 ℃ to obtain a solution A, and adjusting the phosphorus-iron ratio to be 1.1:1 to obtain a solution B.
Dropwise adding 6 vol% hydrogen peroxide into the solution B at 60 ℃, adjusting the pH value of the solution to 2 by using ammonia water for coprecipitation, and carrying out solid-liquid separation to obtain ferric phosphate dihydrate and precipitated liquid, wherein the ferric phosphate dihydrate is roasted in a muffle furnace at 600 ℃ for 4 hours to obtain ferric phosphate, and the precipitated liquid enters chelate resin for impurity removal.
Performing bipolar membrane electrodialysis electrolysis by using the solution obtained after the chelating resin is subjected to impurity removal as a raw material solution, wherein the current density is 400A/m2The acid chamber receiving solution is a low-concentration phosphoric acid solution, the alkali chamber receiving solution is a low-concentration ammonia water solution, and the polar solution is an ammonium dihydrogen phosphate solution. The acid chamber after electrolysis is phosphoric acid solution, the alkali chamber is ammonia water, and the acid chamber and the alkali chamber can both return to the leaching section and the iron phosphate precipitation section for continuous use. The ingredients of the synthesized iron phosphate are specifically shown in table 1.
Example 2
A method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction comprises the following steps:
and mixing the ferrophosphorus slag after lithium extraction with charcoal powder 2 times of theoretical amount, and roasting in a tubular furnace for two hours to obtain slag A.
And (3) mixing the slag A with water according to the mass ratio of 1:3, adding sulfuric acid, and leaching for 2 hours at 25 ℃ to obtain a solution A.
Adding iron powder 2 times of theory into the solution A to remove copper by replacement, and filtering to obtain a solution B.
Adding ammonium dihydrogen phosphate to adjust the phosphorus-iron ratio to be 1:1, then adding hydrogen peroxide and ammonia water to perform coprecipitation, and performing solid-liquid separation to obtain ferric phosphate dihydrate and a precipitated liquid, wherein the ferric phosphate dihydrate is roasted in a muffle furnace at 600 ℃ for 4 hours to obtain ferric phosphate, and the precipitated liquid enters chelate resin to remove impurities.
And (3) performing bipolar membrane electrodialysis electrolysis by taking the solution obtained after the impurity removal of the chelate resin as a raw material solution, wherein the solution received by an acid chamber is a low-concentration sulfuric acid solution, the solution received by an alkali chamber is a low-concentration ammonia water solution, the electrode chamber adopts an ammonium sulfate solution, the alkali chamber is an ammonia water solution after electrolysis, and the acid chamber is a sulfuric acid-phosphoric acid mixed solution mainly containing sulfuric acid and respectively returns acid leaching and coprecipitation of ferric phosphate dihydrate. The ingredients of the synthesized iron phosphate are specifically shown in table 1.
Table 1 composition table of synthetic iron phosphate
As can be seen from table 1, the iron phosphate product composition produced by the present invention meets the industry standard for iron phosphate for batteries.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. A method for regenerating iron phosphate from phosphorus and iron slag after lithium extraction is characterized by comprising the following steps:
s1, mixing the ferrophosphorus slag after lithium extraction with water, adding alkali liquor, after the reaction is finished, carrying out solid-liquid separation, and washing the slag after solid-liquid separation to obtain slag A;
s2, drying the slag A, mixing the slag A with a reducing agent, and roasting the mixture in a reducing atmosphere to obtain slag B;
s3, mixing the slag B with water, pulping, adding acid liquor for leaching, and after the reaction is finished, carrying out solid-liquid separation to obtain a solution A;
s4, adding a proper amount of iron powder into the solution A, removing copper by adopting iron powder displacement, and carrying out solid-liquid separation after the reaction is finished to obtain a solution B;
s5, supplementing a phosphorus source or an iron source into the solution B to obtain a raw material solution, adding hydrogen peroxide and ammonia water into the raw material solution to perform a coprecipitation reaction, performing solid-liquid separation after the reaction is finished to obtain ferric phosphate dihydrate and a solution C, and sintering the ferric phosphate dihydrate to obtain ferric phosphate;
s6, removing impurity element ions from the solution C by using chelating resin to obtain a solution D;
s7, electrolyzing the solution D by using bipolar membrane electrodialysis to obtain acid liquor and alkali liquor, and respectively returning to the leaching in the S3 and the coprecipitation in the S5 for use.
2. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the alkali solution in step S1 is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide.
3. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the reducing agent in step S2 is one or more of glucose, negative electrode powder, coke powder and charcoal powder.
4. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the roasting temperature in step S2 is 300-800 ℃, and the roasting time is 0.5-5 hours.
5. The method for regenerating iron phosphate from ferrophosphorus slag after lithium extraction according to claim 1, wherein the acid solution in step S3 is one or more of phosphoric acid, hydrochloric acid and sulfuric acid.
6. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the solid-to-liquid ratio in step S3 is 1: 3-10, the leaching temperature is 20-95 ℃, and the reaction time is 1-6 h.
7. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the amount of the added iron powder in step S4 is 1-3 times of the theoretical amount, and the reaction time is 1-6 hours
8. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the amount of ammonia water added in step S5 is determined according to the pH, the pH at the time of precipitation is 0.5 to 2.5, and the reaction temperature is 40 to 80 ℃.
9. The method for regenerating iron phosphate from phosphorus-iron slag after lithium extraction according to claim 1, wherein the sintering temperature of the iron phosphate dihydrate in step S5 is 400-800 ℃, and the sintering time is 1-6 hours
10. The method for regenerating iron phosphate from phosphorus and iron slag after lithium extraction according to claim 1, wherein the bipolar membrane electrolysis in step S7 is constant current electrolysis with current density of 200-800A/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210105958.1A CN114394582B (en) | 2022-01-28 | 2022-01-28 | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210105958.1A CN114394582B (en) | 2022-01-28 | 2022-01-28 | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114394582A true CN114394582A (en) | 2022-04-26 |
| CN114394582B CN114394582B (en) | 2023-10-27 |
Family
ID=81233209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210105958.1A Active CN114394582B (en) | 2022-01-28 | 2022-01-28 | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114394582B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231537A (en) * | 2022-06-27 | 2022-10-25 | 湖北虹润高科新材料有限公司 | Method for preparing iron phosphate by using iron phosphorus slag, iron phosphate and application thereof |
| CN115448279A (en) * | 2022-10-25 | 2022-12-09 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery-grade iron phosphate material by recycling phosphorus-iron slag after lithium extraction |
| CN115676792A (en) * | 2022-07-06 | 2023-02-03 | 宜宾天原锂电新材有限公司 | Method for preparing iron-based phosphate lithium battery material by using phosphorus iron slag as raw material |
| CN115974026A (en) * | 2022-12-19 | 2023-04-18 | 安徽南都华铂新材料科技有限公司 | Method for obtaining iron phosphate by treating iron phosphate slag by phosphoric acid dissolution method |
| CN116161636A (en) * | 2023-02-20 | 2023-05-26 | 湖北锂宝新材料科技发展有限公司 | Method for preparing battery-grade anhydrous ferric phosphate from lithium-extracted ferric phosphate waste residues |
| CN118083935A (en) * | 2024-04-19 | 2024-05-28 | 中国科学院过程工程研究所 | Method for recovering ferric phosphate from lithium iron phosphate extraction slag and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020057042A1 (en) * | 2018-09-21 | 2020-03-26 | 深圳市德方纳米科技股份有限公司 | Method for extracting lithium from amblygonite and preparing iron-containing phosphate |
| JP2020102370A (en) * | 2018-12-21 | 2020-07-02 | 太平洋セメント株式会社 | Method for producing nasicon-type oxide particle for lithium ion secondary battery solid electrolyte |
| CN111646447A (en) * | 2020-06-17 | 2020-09-11 | 中国科学院宁波材料技术与工程研究所 | Method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate lithium battery |
| CN113415793A (en) * | 2021-05-10 | 2021-09-21 | 北京科技大学 | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste |
| CN113896211A (en) * | 2021-10-26 | 2022-01-07 | 湖北金泉新材料有限公司 | Resource treatment method for waste lithium iron phosphate batteries |
| CN113955753A (en) * | 2021-08-24 | 2022-01-21 | 安徽南都华铂新材料科技有限公司 | Method for recovering waste lithium iron phosphate battery powder |
-
2022
- 2022-01-28 CN CN202210105958.1A patent/CN114394582B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020057042A1 (en) * | 2018-09-21 | 2020-03-26 | 深圳市德方纳米科技股份有限公司 | Method for extracting lithium from amblygonite and preparing iron-containing phosphate |
| JP2020102370A (en) * | 2018-12-21 | 2020-07-02 | 太平洋セメント株式会社 | Method for producing nasicon-type oxide particle for lithium ion secondary battery solid electrolyte |
| CN111646447A (en) * | 2020-06-17 | 2020-09-11 | 中国科学院宁波材料技术与工程研究所 | Method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate lithium battery |
| CN113415793A (en) * | 2021-05-10 | 2021-09-21 | 北京科技大学 | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste |
| CN113955753A (en) * | 2021-08-24 | 2022-01-21 | 安徽南都华铂新材料科技有限公司 | Method for recovering waste lithium iron phosphate battery powder |
| CN113896211A (en) * | 2021-10-26 | 2022-01-07 | 湖北金泉新材料有限公司 | Resource treatment method for waste lithium iron phosphate batteries |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115231537A (en) * | 2022-06-27 | 2022-10-25 | 湖北虹润高科新材料有限公司 | Method for preparing iron phosphate by using iron phosphorus slag, iron phosphate and application thereof |
| CN115231537B (en) * | 2022-06-27 | 2023-09-08 | 湖北虹润高科新材料有限公司 | Method for preparing ferric phosphate from iron-phosphorus slag, ferric phosphate and application thereof |
| CN115676792A (en) * | 2022-07-06 | 2023-02-03 | 宜宾天原锂电新材有限公司 | Method for preparing iron-based phosphate lithium battery material by using phosphorus iron slag as raw material |
| CN115448279A (en) * | 2022-10-25 | 2022-12-09 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery-grade iron phosphate material by recycling phosphorus-iron slag after lithium extraction |
| CN115448279B (en) * | 2022-10-25 | 2024-03-26 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag |
| CN115974026A (en) * | 2022-12-19 | 2023-04-18 | 安徽南都华铂新材料科技有限公司 | Method for obtaining iron phosphate by treating iron phosphate slag by phosphoric acid dissolution method |
| CN116161636A (en) * | 2023-02-20 | 2023-05-26 | 湖北锂宝新材料科技发展有限公司 | Method for preparing battery-grade anhydrous ferric phosphate from lithium-extracted ferric phosphate waste residues |
| CN116161636B (en) * | 2023-02-20 | 2024-04-05 | 湖北锂宝新材料科技发展有限公司 | Method for preparing battery-grade anhydrous ferric phosphate from lithium-extracted ferric phosphate waste residues |
| CN118083935A (en) * | 2024-04-19 | 2024-05-28 | 中国科学院过程工程研究所 | Method for recovering ferric phosphate from lithium iron phosphate extraction slag and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114394582B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112357899B (en) | Comprehensive recycling method of waste lithium iron phosphate batteries | |
| CN114394582B (en) | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag | |
| CN108075202B (en) | Comprehensive recovery method of lithium iron phosphate anode material | |
| KR102008582B1 (en) | A Method for Preparing Nickel-Cobalt-Manganese Complex Sulfate Solution by Recycling A Waste Cathode Material of Lithium Secondary Battery Using Solvent Extraction Process to Control Impurities | |
| CN107739830A (en) | A kind of recovery method of positive material of waste lithium iron phosphate | |
| CN107017444A (en) | A kind of method of metal recovery in waste lithium iron phosphate battery | |
| CN108642304B (en) | Comprehensive recovery method of lithium iron phosphate waste | |
| CN110835683B (en) | Method for selectively extracting lithium from waste lithium ion battery material | |
| CN101899576A (en) | Method for recycling lead from lead-acid battery paste | |
| CN112310499B (en) | Recovery method of waste lithium iron phosphate material and obtained recovery liquid | |
| CN109576498A (en) | A kind of recovery method of lithium battery graphite cathode material | |
| CN113104897A (en) | Method for preparing battery-grade manganese sulfate by separating nickel, cobalt, lithium and manganese from battery black powder | |
| CN114506834A (en) | Treatment method of waste lithium iron phosphate powder and carbon-coated lithium iron phosphate | |
| WO2023029573A1 (en) | Method for extracting lithium from waste lithium battery | |
| CN112267023A (en) | Two-stage defluorination method for fluorine-containing material | |
| CN112777580B (en) | Industrial method for treating substance containing lithium iron phosphate | |
| KR102228192B1 (en) | Preparing method of nickel-cobalt-manganese complex sulphate solution by recycling wasted electrode material | |
| CN116995327A (en) | Method for recycling lithium from ternary positive electrode 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 | |
| CN114614136B (en) | Method for preparing dihydrate ferric phosphate and ternary positive electrode material from laterite nickel ore | |
| CN210560650U (en) | Reaction device | |
| CN112687973B (en) | Method and equipment for treating material containing lithium iron phosphate | |
| WO2021134516A1 (en) | Comprehensive treatment method for applying sodium-containing ammonium waste liquid to laterite nickel ore | |
| CN114525408B (en) | Method for combined treatment of waste lithium cobalt oxide anode material and tungsten-containing solid waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |