CN116854062A - Efficient recycling method for waste residues after lithium extraction - Google Patents
Efficient recycling method for waste residues after lithium extraction Download PDFInfo
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- CN116854062A CN116854062A CN202310842133.2A CN202310842133A CN116854062A CN 116854062 A CN116854062 A CN 116854062A CN 202310842133 A CN202310842133 A CN 202310842133A CN 116854062 A CN116854062 A CN 116854062A
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- iron
- lithium
- phosphorus
- lithium extraction
- waste residues
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000000605 extraction Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 11
- 235000021110 pickles Nutrition 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 abstract description 16
- 229940032958 ferric phosphate Drugs 0.000 abstract description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 phosphorus ions Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a high-efficiency recycling method of waste residues after lithium extraction, which comprises the following steps: introducing chlorine into the water mixed solution for extracting lithium iron phosphate slag, and carrying out solid-liquid separation to obtain pickle liquor; then adding a phosphorus source and an iron source to adjust the iron-phosphorus ratio, adding a precipitator and adjusting the pH value to precipitate the iron and phosphorus elements to obtain an intermediate; calcining the intermediate to iron phosphate. The invention has the advantages of short recovery period, low cost, lower corrosiveness to equipment and simple operation, and is suitable for industrialized use; the recovery rate and purity of the obtained ferric phosphate are high.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a high-efficiency recovery and utilization method of waste residues after lithium extraction.
Background
Lithium ion batteries are widely used in the fields of new energy electric automobiles, portable electronic equipment and the like as a device for mutually converting chemical energy and electric energy. The lithium iron phosphate battery has become the mainstream gradually because of low price, good safety and high cycle times, and the global lithium iron phosphate battery output of 2021 reaches 172.1 GWh. The huge productivity brings with it the scrapping problem after the life-span of lithium iron phosphate battery, the valuable elements of the recovered lithium iron phosphate battery powder are leached out mainly through acid leaching at present, but the phosphorus iron slag is treated as dangerous waste more after extracting lithium, the iron phosphate graphite slag contains about 50% of iron elements and phosphorus elements, if the iron elements and the phosphorus elements are directly abandoned or improperly treated, the environment is polluted, and the waste of resources is also caused. How to effectively treat the iron phosphate graphite slag after extracting lithium so as to effectively utilize iron and phosphorus elements is a problem to be solved.
CN115448279a discloses a method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag, which comprises the steps of pulping the ferrophosphorus slag after lithium extraction, adding concentrated sulfuric acid, adding iron powder for reduction, adding oxalic acid for complexing, adjusting pH for removing impurities to obtain ferrous sulfate solution, filtering, adding hydrogen peroxide into the ferrous sulfate solution, adding water for dilution, precipitating ferric phosphate dihydrate at high temperature, adding phosphoric acid solution to convert entrained ferric hydroxide into ferric phosphate dihydrate, filtering, roasting the ferric phosphate dihydrate precipitate at high temperature, and removing the entrained complexing agent. CN111646447a provides a method for recovering iron phosphate from lithium iron phosphate slag of lithium iron phosphate batteries. Mixing lithium-iron phosphate slag extracted from a lithium iron phosphate battery with water, pulping, reacting with acid, performing solid-liquid separation to obtain leaching solution containing iron and phosphorus ions, adding iron to replace copper and removing aluminum by resin to obtain purifying solution, adding heptahydrate ferric phosphate or phosphoric acid to prepare a phosphorus-iron ratio, obtaining a synthetic stock solution with a certain ratio of P to Fe, adding hydrogen peroxide and ammonia water, regulating pH to obtain ferric phosphate precursor precipitate, and performing aftertreatment to obtain a battery-grade ferric phosphate precursor product.
The method described in CN115448279A, CN111646447a uses excessive oxidant and strong acid in the acid leaching process, and uses a large amount of alkali in the impurity removal and precipitation process, so that the production cost is high, the economic benefit is low, the waste salt production amount is large, and the strong acid and strong alkali have great corrosiveness to equipment. Meanwhile, in CN115448279A, after acid leaching, iron powder reduction is performed, and oxidation is performed, so that the process is complicated, the yield of iron and phosphorus elements leached by strong acid is low, and the waste of iron and phosphorus resources is large; the leachate of CN111646447A is subjected to a series of impurity removal, so that impurity elements can be introduced, and the impurity removal process is complicated. Improvements are needed.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-efficiency recycling method of waste residues after lithium extraction, which has the advantages of short recycling period, low cost, lower corrosiveness to equipment, simple operation and suitability for industrial use; the recovery rate and purity of the obtained ferric phosphate are high.
The invention provides a high-efficiency recycling method of waste residues after lithium extraction, which comprises the following steps: introducing chlorine into the water mixed solution for extracting lithium iron phosphate slag, and carrying out solid-liquid separation to obtain pickle liquor; then adding a phosphorus source and an iron source to adjust the iron-phosphorus ratio, adding a precipitator and adjusting the pH value to precipitate the iron and phosphorus elements to obtain an intermediate; calcining the intermediate to iron phosphate.
According to the invention, chlorine is introduced into the water mixed solution for extracting lithium-phosphorus-iron slag, so that hypochlorous acid with oxidizing property can be generated while dilute hydrochloric acid is generated, and P, fe leaching and Fe oxidation are realized in one step 2+ The method comprises the steps of carrying out a first treatment on the surface of the The recovery time can be greatly shortened, the steps are simplified, fe and P can be fully leached, and the yield is improved; the corrosiveness of the chlorine to the equipment is lower than that of concentrated sulfuric acid and strong alkali, so that the damage to the equipment can be reduced; the method has fewer impurity removal steps, and can avoid the problem that Fe and P are easy to lose in multiple impurity removal processes. The whole recovery method is simple to operate, and can realize industrial production. The iron phosphate recovered by the invention has high purity and can be directly used in batteries.
The chlorine can be industrial chlorine and recycled chlorine, so that the cost can be reduced.
Preferably, the flow rate of chlorine is 2.5-3.5mL/min.
Preferably, the time for introducing chlorine is 0.4-0.6h.
Preferably, the temperature is 70-90 ℃ when the chlorine is introduced, and the temperature is kept for 0.8-1.2h after the chlorine is introduced.
Preferably, the pH of the pickling solution is less than or equal to 1.2.
By adjusting the proper chlorine flow, time and acid leachingThe pH value of the liquid can fully leach Fe and P in the lithium-extracting iron-phosphorus slag, so that the yield is improved; and Cu can be avoided by adjusting the pH of the pickle liquor 2+ And other impurities are less dissolved in the leaching solution.
Preferably, the iron to phosphorus ratio is 0.96-0.98:1.
The iron-phosphorus ratio refers to the molar ratio of Fe to P.
Preferably, the precipitant is at least one of polyacrylamide and oxalic acid.
Preferably, after the iron-phosphorus ratio is adjusted, the molar weight ratio of the iron element to the precipitant is 0.01-0.1mol:0.1-0.3g.
Preferably, the precipitant is added and the pH is adjusted = 1.8-2.5.
Preferably, the temperature at precipitation is 70-90 ℃.
The method has the advantages that a proper iron-phosphorus ratio and a proper amount of precipitants are selected and combined with a proper pH value, so that the precipitation of iron and phosphorus can be accelerated, the recovery time is shortened, and the precipitation generated by impurity elements can be prevented from being doped in ferric sulfate by the proper pH value; can fully precipitate and separate iron and phosphorus, improve the yield and further remove impurities.
Preferably, the calcination temperature is 200-600 ℃; the calcination can also remove crystal water and organic precipitant in the ferric phosphate dihydrate, avoid the introduction of impurities, and prepare the battery grade ferric phosphate.
Preferably, the phosphorus source is at least one of ammonium phosphate and phosphoric acid.
Preferably, the iron source is at least one of iron powder and ferric chloride.
The pH can be adjusted with 32% by mass aqueous sodium hydroxide solution, 20% by mass aqueous ammonia, aqueous hydrochloric acid solution, etc.
The beneficial effects are that:
after chlorine is introduced into the ferrophosphorus slag, the method can oxidize Fe while leaching P, fe 2+ The problems of high cost and strong corrosiveness caused by using strong acid and oxidant are reduced; the recovery time can be shortened, and the recovery efficiency can be improved; the proper chlorine flow, time and pH of the pickle liquor are selected, so that Fe and P in the lithium-extracting phosphorus-iron slag can be fully leached out for extractionHigh yield; the precipitation agent with proper iron-phosphorus ratio and proper dosage is selected and combined with proper pH value, so that the iron and phosphorus precipitation is accelerated, and the recovery time is shortened; and the iron and the phosphorus are fully precipitated and separated, so that the yield is improved; the invention can well remove impurities by adjusting the pH value of each step, so that the ferric phosphate has higher purity and can be directly used in batteries.
Drawings
FIG. 1 is a process flow diagram of the method for efficiently recycling the waste residues after lithium extraction.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A method for efficiently recycling waste residues after lithium extraction comprises the following steps:
taking 20g of lithium-phosphorus-iron slag, adding 60g of water, uniformly mixing, starting a stirring and heating device, heating to 80 ℃, introducing industrial chlorine at a flow rate of 3mL/min for 0.5h, then carrying out heat preservation and stirring for 1h, and filtering to remove graphite slag to obtain a pickling solution with pH=1.0; adding phosphoric acid and iron powder into the pickle liquor to adjust the iron-phosphorus ratio to be 0.97:1 (the mole number of iron elements in the solution is 0.03mol at the moment), adding 0.2g polyacrylamide, adjusting the pH value to be 2.0 by dilute hydrochloric acid, adjusting the temperature to be 80 ℃, stirring and uniformly mixing for 0.5h, standing for 10min to enable the iron and phosphorus elements to be rapidly precipitated, and filtering to obtain a filter cake to obtain an intermediate; and calcining the intermediate at 600 ℃ for 1h to remove impurities such as crystal water, polyacrylamide and the like, thereby obtaining the ferric phosphate.
Example 2
A method for efficiently recycling waste residues after lithium extraction comprises the following steps:
taking 20g of lithium-phosphorus-iron slag, adding 60g of water, uniformly mixing, starting a stirring and heating device, heating to 70 ℃, introducing industrial chlorine at a flow rate of 2.5mL/min for 0.5h, then carrying out heat preservation and stirring for 1h, and filtering to remove graphite slag to obtain a pickling solution with pH=1.2; adding ammonium phosphate and ferric chloride into the pickle liquor to adjust the iron-phosphorus ratio to be 0.96:1 (the mole number of the iron element in the solution is 0.02mol at the moment), adding 0.1g polyacrylamide, adjusting the pH value to be 1.80 by dilute hydrochloric acid, adjusting the temperature to be 70 ℃, stirring and uniformly mixing for 0.5h, standing for 10min to enable the iron element and the phosphorus element to be rapidly precipitated, and filtering to obtain a filter cake to obtain an intermediate; and calcining the intermediate at 200 ℃ for 1h to remove impurities such as crystal water, polyacrylamide and the like, thereby obtaining the ferric phosphate.
Example 3
A method for efficiently recycling waste residues after lithium extraction comprises the following steps:
taking 20g of lithium-phosphorus-iron slag, adding 60g of water, uniformly mixing, starting a stirring and heating device, heating to 70 ℃, introducing industrial chlorine at a flow rate of 3.5mL/min for 0.5h, then carrying out heat preservation and stirring for 1h, and filtering to remove graphite slag to obtain a pickling solution with pH=0.8; then, adjusting the pH=4 of the pickle liquor by using ammonia water with the mass fraction of 20%, filtering and removing impurities to obtain filtrate; adding phosphoric acid and iron powder into the pickle liquor to adjust the iron-phosphorus ratio to be 0.98:1 (the mole number of the iron element in the solution is 0.015mol at the moment), adding 0.3g polyacrylamide, adjusting the pH value to be 2.2 by dilute hydrochloric acid, adjusting the temperature to be 70 ℃, stirring and uniformly mixing for 0.5h, standing for 10min to enable the iron element and the phosphorus element to be rapidly precipitated, and filtering to obtain a filter cake to obtain an intermediate; calcining the intermediate at 400 ℃ for 1h to remove impurities such as crystal water, polyacrylamide and the like, thereby obtaining the ferric phosphate.
Comparative example 1
The ph=1.5 of the pickle liquor, and the same weight of the lithium-extracted phosphorus iron slag as in example 1 was the same batch as that of the lithium-extracted phosphorus iron slag of example 1.
Comparative example 2
Polyacrylamide was added and ph=3 was adjusted with dilute hydrochloric acid, and the same weight of the lithium-extracted phosphorus iron slag as in example 1 was the same batch as that of the lithium-extracted phosphorus iron slag of example 1.
The iron phosphate obtained in examples 1-3 and comparative examples 1-2 was examined and the yield was counted, and the results are shown in Table 1.
TABLE 1 detection results
| Detecting items | HG/T4701-2021 | Yield% | Recovery takes time h |
| Example 1 | Meets the I-type requirement | 95.45 | 4 |
| Example 2 | Meets the I-type requirement | 94.67 | 4 |
| Example 3 | Meets the I-type requirement | 95.21 | 4 |
| Comparative example 1 | Meets the II type requirement | 90.75 | 4 |
| Comparative example 2 | Is not in compliance with the requirements | 84.48 | 4 |
Remarks: HG/T4701-2021 is the quality standard of iron phosphate for battery.
As can be seen from table 1: the quality of the recovered ferric phosphate is better, and the yield is high.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The efficient recycling method of the waste residues after lithium extraction is characterized by comprising the following steps of: introducing chlorine into the water mixed solution for extracting lithium iron phosphate slag, and carrying out solid-liquid separation to obtain pickle liquor; then adding a phosphorus source and an iron source to adjust the iron-phosphorus ratio, adding a precipitator and adjusting the pH value to precipitate the iron and phosphorus elements to obtain an intermediate; calcining the intermediate to iron phosphate.
2. The efficient recycling method of the lithium extracted waste residues according to claim 1, wherein the flow rate of chlorine is 2.5-3.5mL/min.
3. The method for efficiently recycling the waste residue after lithium extraction according to claim 1 or 2, wherein the pH value of the pickle liquor is less than or equal to 1.2.
4. The efficient recycling method of the waste residues after lithium extraction according to claim 1 or 2, wherein the iron-phosphorus ratio is 0.96-0.98:1.
5. The efficient recycling method of the waste residues after lithium extraction according to claim 1 or 2, wherein the precipitating agent is at least one of polyacrylamide and oxalic acid.
6. The efficient recycling method of waste residues after lithium extraction according to claim 1 or 2, wherein a precipitant is added and ph=1.8-2.5 is adjusted.
7. The efficient recycling method of the lithium extracted waste residue according to claim 1 or 2, wherein the calcination temperature is 200-600 ℃.
8. The method for efficiently recycling the waste residue after lithium extraction according to claim 1 or 2, wherein the phosphorus source is at least one of ammonium phosphate and phosphoric acid.
9. The method for efficiently recycling the waste residue after lithium extraction according to claim 1 or 2, wherein the iron source is at least one of iron powder and ferric chloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310842133.2A CN116854062A (en) | 2023-07-11 | 2023-07-11 | Efficient recycling method for waste residues after lithium extraction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310842133.2A CN116854062A (en) | 2023-07-11 | 2023-07-11 | Efficient recycling method for waste residues after lithium extraction |
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| CN116854062A true CN116854062A (en) | 2023-10-10 |
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| Country | Link |
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