CN117776130A - Method for producing lithium phosphate by using waste lithium iron phosphate battery - Google Patents
Method for producing lithium phosphate by using waste lithium iron phosphate battery Download PDFInfo
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- CN117776130A CN117776130A CN202311854719.7A CN202311854719A CN117776130A CN 117776130 A CN117776130 A CN 117776130A CN 202311854719 A CN202311854719 A CN 202311854719A CN 117776130 A CN117776130 A CN 117776130A
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- Prior art keywords
- lithium
- phosphate
- solution
- iron phosphate
- lithium iron
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- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 58
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 58
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 8
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- 239000006012 monoammonium phosphate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 calcium hydroxide-ammonium (hydrogen) carbonate-ammonia Chemical compound 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of secondary resource recycling of batteries, in particular to a method for producing lithium phosphate by using waste lithium iron phosphate batteries, which comprises the following steps: treating the waste lithium iron phosphate battery to obtain lithium iron phosphate battery powder; preparing lithium iron phosphate battery powder into slurry, and adding concentrated sulfuric acid to obtain leaching liquid; adding an oxidant into the leaching solution, and filtering to obtain a lithium sulfate solution; adding calcium hydroxide into the lithium sulfate solution to remove copper, aluminum and iron elements, fully reacting, and filtering to obtain primary filtrate; adjusting the pH value of the primary filtrate by adopting ammonia water, adding ammonium carbonate or ammonium bicarbonate, removing calcium, magnesium, nickel and manganese impurities in the primary filtrate, and filtering to obtain a lithium-rich solution; concentrating the lithium-rich solution to obtain a concentrated solution; and regulating the pH value of the concentrated solution by using ammonia water, adding a saturated ammonium phosphate solution or a diammonium hydrogen phosphate solution or a monoammonium hydrogen phosphate solution, washing the product, and drying to obtain the high-purity lithium phosphate. The lithium precipitation rate is high, the purity of the lithium phosphate product is high, and the impurity content is low.
Description
Technical Field
The invention relates to the technical field of secondary resource recycling of batteries, in particular to a method for producing lithium phosphate by using waste lithium iron phosphate batteries.
Background
In recent years, with the increasing demand of new energy automobiles, the yield of lithium ion batteries has also increased year by year. Because of the characteristics of high safety, non-toxic materials and low price, the lithium iron phosphate battery becomes one of the lithium ion batteries which are greatly developed by the state. Since the average service life of the lithium iron phosphate battery is 5 to 8 years, in the future, china will face the situation of large-scale retirement of the lithium iron phosphate battery, and if the lithium iron phosphate battery cannot be properly treated, serious environmental and safety problems will be caused. Meanwhile, the retired lithium iron phosphate battery is rich in strategic valuable resources such as lithium, phosphorus, iron, graphite and the like, and the lithium resources are rich, so that the content of the retired lithium iron phosphate battery is higher than that of common lithium ores, and the retired lithium iron phosphate battery has great recovery value. The waste lithium iron phosphate battery is a high-quality urban mineral resource, and the recycling of the waste lithium iron phosphate battery can relieve the environmental pressure caused by battery waste, can also relieve the supply pressure of lithium resources, and is beneficial to the green sustainable development of the whole industry.
Lithium phosphate is a multifunctional phosphate with unique optical, catalytic and electrochemical properties, and thus has a wide range of applications. The lithium phosphate is used as a fluxing agent to produce color fluorescent powder because of short illumination time and long light effect time; the heat resistance is strong, and the material is not easy to decompose, and is a high-temperature resistant material; the catalyst can also be used as a catalyst, has the characteristics of high conversion rate and good selectivity, and is an ideal catalyst for the isomerization reaction of the alkylene oxide; can also be used for preparing the lithium ion battery anode material LiFePO 4 Or as an electrolyte additive of a lithium battery, the ion transmission of the high-voltage electrode material in the charge and discharge processes is promoted, and the electrochemical cycling stability of the high-voltage electrode material is improved; in addition, the method is also used for producing materials such as special glass, ceramics, gas sensors, lasers, organic light-emitting diodes, atomic energy and the like.
At present, regarding the preparation of lithium phosphate by using waste lithium iron phosphate batteries, the industrial lithium product lithium hydroxide or lithium carbonate prepared by using waste lithium iron phosphate batteries is reacted with phosphoric acid to prepare lithium phosphate, the process flow is complex, and the recovery rate of lithium is low due to the high solubility of lithium carbonate.
Disclosure of Invention
The invention aims to provide a method for producing lithium phosphate by using waste lithium iron phosphate batteries, which comprises the steps of carrying out pretreatment such as discharging, disassembling, separating and crushing on the waste lithium iron phosphate batteries to obtain lithium iron phosphate black powder, carrying out selective leaching of lithium by using concentrated sulfuric acid and an oxidant to obtain leaching liquid, removing a large amount of impurity elements such as copper, aluminum and iron in the leaching liquid by using calcium hydroxide, removing calcium and magnesium elements in the leaching liquid by using ammonia water and ammonium carbonate or ammonium bicarbonate, and simultaneously deeply removing metal ion impurities such as nickel and manganese to obtain a purer lithium sulfate solution; the solution is concentrated and then added with saturated ammonium phosphate, diammonium hydrogen phosphate or monoammonium phosphate solution to react to obtain lithium phosphate precipitate, and the lithium phosphate is washed with water to obtain the high-purity lithium phosphate product.
The scheme adopted by the invention for achieving one of the purposes is as follows: a method for producing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps:
step 1: discharging, disassembling, separating and crushing the waste lithium iron phosphate battery to obtain lithium iron phosphate battery powder;
step 2: preparing the lithium iron phosphate battery powder obtained in the step 1 into slurry, adding concentrated sulfuric acid for leaching reaction to obtain a lithium ion battery containing Li + 、Fe 2+ 、PO 4 3- Is added to the leaching solution;
step 3: adding an oxidant into the leaching solution to enable Fe in the solution to be 2+ Oxidation to Fe 3+ With PO in solution 4 3- Generating ferric phosphate precipitate, and filtering to obtain lithium sulfate solution;
step 4: adding calcium hydroxide into the lithium sulfate solution to adjust the pH value of the lithium sulfate solution to 6-8, primarily removing copper, aluminum and iron elements, fully reacting, and filtering to obtain primary filtrate;
step 5: ammonia water is adopted to adjust the pH value of primary filtrate to 9-11, then ammonium carbonate or ammonium bicarbonate is added, calcium, magnesium, nickel and manganese impurities in the primary filtrate are removed through full reaction, and lithium-rich solution is obtained through filtration;
step 6: concentrating the lithium-rich solution obtained in the step 5 to obtain a concentrated solution;
step 7: adjusting the pH of the concentrated solution to 11-12 by using ammonia water, adding saturated ammonium phosphate solution or diammonium hydrogen phosphate solution or monoammonium hydrogen phosphate solution, and fully reacting to obtain lithium phosphate;
step 8: and (3) washing the lithium phosphate obtained in the step (7), and drying to obtain the high-purity lithium phosphate.
Preferably, in the step 2, the mass ratio of the lithium iron phosphate battery powder to the pure water in the slurry is 1:3-7, wherein the mass percentage of the concentrated sulfuric acid is 98%, the adding amount of the concentrated sulfuric acid is that the pH value of the solution reaches 2-3, and the reaction time is 3-6h.
Preferably, in the step 3, the oxidant is hydrogen peroxide, and the addition amount of the hydrogen peroxide is Fe in the leaching solution 2+ 1-2 times of stoichiometric ratio, the percentage of hydrogen peroxide is 10 percent, the percentage of hydrogen peroxide is-30 percent, and the reaction time is 3-6 hours.
Preferably, in the step 4, the reaction temperature is 50-60 ℃, the time is 1-2h, and the stirring speed is 200-300r/min.
Preferably, in the step 5, the addition amount of ammonium carbonate or ammonium bicarbonate is 2-5 times of the theoretical amount of the total content of calcium and magnesium ions in the primary filtrate obtained in the step 4, the reaction temperature is 50-60 ℃, the time is 1-2h, and the stirring speed is 200-300r/min.
Preferably, in the step 6, the concentration of Li in the concentrated solution is 10-20g/L.
Preferably, in the step 7, the addition amount of the saturated ammonium phosphate solution or the diammonium hydrogen phosphate solution or the monoammonium hydrogen phosphate solution is 1.0-1.5 times of theoretical amount according to the lithium content of the concentrated solution, the reaction temperature is 60-90 ℃, and the reaction time is 1-2 hours.
Preferably, in the step 8, the lithium phosphate is washed with hot pure water, the temperature of the hot pure water is 90-95 ℃, and the mass of the hot pure water and the lithium phosphate solution is (10-30): 1, the washing time is 0.5-2.0h.
In the method, main impurity elements such as copper, iron, aluminum and the like are removed in the first step by utilizing calcium hydroxide, so that the re-dissolution of aluminum hydroxide precipitation caused by subsequent pH rise is avoided, and NH is avoided 4+ And Cu 2+ Is complex; and in the second step, ammonia water is used for raising the pH value, ammonium (hydrogen) carbonate is added to efficiently remove magnesium ions and calcium ions introduced by earlier stage calcium hydroxide, and impurities of other metal ions such as nickel, manganese and the like are further removed. The impurity removing process does not introduce sodium ions and other impurities which are difficult to remove in the whole process, and ensuresThe purity of the lithium phosphate product, and the price of the auxiliary materials is low, so that the pollution to the environment is small; the lithium-rich solution after impurity removal is reacted by using saturated ammonium phosphate, diammonium phosphate or monoammonium phosphate solution to obtain lithium phosphate precipitate, the lithium precipitation rate is high, the recovery rate of the whole process lithium is more than 90%, the purity of the lithium phosphate product can be more than 99.5%, and the process flow is simple and has the advancement of green and environment protection.
And in the step 4, the calcium hydroxide has the following advantages: ca (Ca) 2+ Will be CaF 2 Form (F) of the removal solution - The generation of excessive lithium fluoride in the subsequent lithium phosphate precipitation reaction is avoided, so that the purity of the lithium phosphate is influenced; and OH is - The pH is increased, and the aim of removing main impurity elements such as copper, iron, aluminum and the like in the first step of impurity removal is fulfilled.
The invention has the following advantages and beneficial effects:
the method for preparing the lithium phosphate product by using the waste lithium iron phosphate battery adopts the calcium hydroxide-ammonium (hydrogen) carbonate-ammonia water process to remove impurities, has good effect of removing impurities such as copper, aluminum, iron and the like in the lithium-rich leaching solution, has high impurity removal rate, reduces the introduction of impurities which are difficult to remove such as sodium ions and the like, adopts ammonium phosphate salt to precipitate lithium, and has high lithium precipitation rate, high purity of the lithium phosphate product and low impurity content. The process has the advantages of simple whole flow, high feasibility and environmental friendliness.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
In this embodiment, the preparation method of the lithium iron phosphate battery powder includes: and discharging, disassembling, separating and crushing the waste lithium iron phosphate battery to obtain lithium iron phosphate battery powder.
Example 1
As shown in fig. 1, a method for preparing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps:
1000g of lithium iron phosphate battery powder is takenAdding 6000mL of pure water into the mixture, stirring and slurrying the mixture for 30min, adding 98% of concentrated sulfuric acid to adjust the pH=2.5 of the slurry, reacting for 3.0H, and adding 600g of 30% H by mass fraction 2 O 2 After 6h of reaction, filtering, heating the filtrate to 60 ℃ and stirring at a rate of 300r/min, adding calcium hydroxide to adjust the pH of the solution to be 7.0, reacting for 1.0h, filtering, adding ammonia water to the filtrate to adjust the pH to be 10.5, adding 23g of ammonium bicarbonate, reacting at a constant temperature of 60 ℃ for 1.0h, and filtering. Evaporating and concentrating the solution after impurity removal until the Li content is 12g/L, adding ammonia water to adjust the pH value of the solution to be 12, adding 183g of monoammonium phosphate (prepared into saturated monoammonium phosphate solution), reacting for 1.0h at 85 ℃, and filtering the residue according to a liquid-solid ratio of 20:1 is added with pure water at 80 ℃ for washing for 1.0h, after washing for 3 times, filtration and drying are carried out, 164g of lithium phosphate product is obtained, the purity of the detected lithium phosphate is 99.54%, and the calculated lithium recovery rate is 90.23%.
Example 2
As shown in fig. 1, a method for preparing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps:
1000g of lithium iron phosphate battery powder is taken, 6000mL of pure water is added into the powder to be stirred and pulped for 30min, 98% of concentrated sulfuric acid is added into the powder to adjust the pH value of the slurry to be=2.8, and 658g of 30% of H by mass fraction is added after the reaction for 5.0H 2 O 2 After 6h of reaction, filtration is carried out, the filtrate is heated to 60 ℃ and stirred at a rate of 300r/min, calcium hydroxide is added to adjust the pH of the solution to be 7.0, the reaction is carried out for 1.0h, filtration is carried out, ammonia water is added to the filtrate to adjust the pH to be 10.5, 29g of ammonium carbonate is added, and the reaction is carried out for 1.0h at a constant temperature of 60 ℃ and then filtration is carried out. Evaporating and concentrating the solution after impurity removal until the Li content is 15g/L, adding ammonia water to adjust the pH value of the solution to be 12, adding 193g monoammonium phosphate (prepared into saturated monoammonium phosphate solution), reacting for 1.5h at 90 ℃, and filtering the residue according to a liquid-solid ratio of 20:1 adding pure water at 90 ℃ for washing for 0.5h, filtering after washing for 3 times, drying to obtain 180g of lithium phosphate product, detecting the purity of the lithium phosphate to be 99.73%, and calculating the recovery rate of the lithium to be 90.47%.
Example 3
As shown in fig. 1, a method for preparing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps:
1000g of lithium iron phosphate battery powder was taken and added thereto3000mL of pure water is stirred and pulped for 30min, 98% of concentrated sulfuric acid is added to adjust the pH=2 of the slurry, after 3.0H of reaction, 880g of H with the mass fraction of 10% is added 2 O 2 Filtering after reacting for 6 hours, heating the filtrate to 50 ℃ and stirring at a speed of 200r/min, adding calcium hydroxide to adjust the pH value of the solution to be 6.0, reacting for 1.0 hour, filtering, adding ammonia water to adjust the pH value of the filtrate to be 9, adding 20g of ammonium bicarbonate, reacting at a constant temperature of 50 ℃ for 1.0 hour, and filtering. Evaporating and concentrating the solution after impurity removal until the Li content is 12g/L, adding ammonia water to adjust the pH value of the solution to be 11, adding 237g of ammonium phosphate (prepared into a saturated ammonium phosphate solution), reacting for 1.0h at 60 ℃, and filtering to obtain filter residues according to a liquid-solid ratio of 10:1 adding pure water at 80 ℃ for washing for 1.0h, filtering after washing for 3 times, drying to obtain 173g of lithium phosphate product, detecting the purity of the lithium phosphate to be 99.60%, and calculating the recovery rate of the lithium to be 89.93%.
Example 4
As shown in fig. 1, a method for preparing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps:
1000g of lithium iron phosphate battery powder is taken, 7000mL of pure water is added into the lithium iron phosphate battery powder, the slurry is stirred and pulped for 30min, 98% of concentrated sulfuric acid is added into the lithium iron phosphate battery powder to adjust the pH=3 of the slurry, after 3.0H of reaction, 590g of H with the mass fraction of 30% is added 2 O 2 After 6h of reaction, filtration is carried out, the filtrate is heated to 55 ℃ and stirred at a speed of 280r/min, calcium hydroxide is added to adjust the pH of the solution to be 8.0, the reaction is carried out for 1.0h, filtration is carried out, ammonia water is added to the filtrate to adjust the pH to be 11, 46g of ammonium carbonate is added, and the reaction is carried out at a constant temperature of 60 ℃ for 1.0h and then filtration is carried out. Evaporating and concentrating the solution after impurity removal until the Li content is 12g/L, adding ammonia water to adjust the pH value of the solution to be 12, adding 190g of monoammonium phosphate (prepared into saturated monoammonium phosphate solution), reacting for 1.0h at 90 ℃, and filtering the residue according to a liquid-solid ratio of 30:1 adding pure water at 80 ℃ for washing for 1.0h, filtering after washing for 3 times, drying to obtain 179g of lithium phosphate product, detecting to obtain 99.69% of lithium phosphate purity, and calculating to obtain 90.11% of lithium recovery rate.
Comparative example 1
A method for preparing lithium phosphate by using waste lithium iron phosphate batteries comprises the following steps,
taking 1000g of lithium iron phosphate battery powder, adding sodium hydroxide solution, removing residual aluminum and aluminum oxide in the powder, filtering, retaining filter mud, adding water into the filter mud, controlling the pH value of the solution to be 0.4 by adding sulfuric acid, controlling the reaction temperature to be 60 ℃, removing filter residues after the reaction result to obtain a lithium solution, adjusting the pH value of the solution to be 1.5 by sodium hydroxide, adding a small amount of iron in p204 extraction solution, standing, separating out an aqueous phase, adjusting the pH value of the aqueous phase to be 8 by sodium hydroxide, adding 1.3 times of sodium phosphate solid, and filtering to obtain lithium phosphate precipitate. 161g of lithium phosphate product is obtained after drying, the purity of the lithium phosphate is 89.35% after detection, and the recovery rate of the lithium is 75.60% after calculation.
The data in Table 1 are the main components of lithium phosphate prepared in examples 1-3 and comparative example 1.
TABLE 1 Main Components of lithium phosphate prepared in examples 1-3 and comparative example 1
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (8)
1. The method for producing the lithium phosphate by using the waste lithium iron phosphate battery is characterized by comprising the following steps of:
step 1: discharging, disassembling, separating and crushing the waste lithium iron phosphate battery to obtain lithium iron phosphate battery powder;
step 2: preparing the lithium iron phosphate battery powder obtained in the step 1 into slurry, adding concentrated sulfuric acid for leaching reaction to obtain a lithium ion battery containing Li + 、Fe 2+ 、PO 4 3- Is added to the leaching solution;
step 3: adding an oxidant into the leaching solution to enable Fe in the solution to be 2+ Oxidation to Fe 3+ With PO in solution 4 3- Generating ferric phosphate precipitate, filtering to obtain sulfuric acidA lithium solution;
step 4: adding calcium hydroxide into the lithium sulfate solution to adjust the pH value of the lithium sulfate solution to 6-8, primarily removing copper, aluminum and iron elements, fully reacting, and filtering to obtain primary filtrate;
step 5: ammonia water is adopted to adjust the pH value of primary filtrate to 9-11, then ammonium carbonate or ammonium bicarbonate is added, calcium, magnesium, nickel and manganese impurities in the primary filtrate are removed through full reaction, and lithium-rich solution is obtained through filtration;
step 6: concentrating the lithium-rich solution obtained in the step 5 to obtain a concentrated solution;
step 7: adjusting the pH of the concentrated solution to 11-12 by using ammonia water, adding saturated ammonium phosphate solution or diammonium hydrogen phosphate solution or monoammonium hydrogen phosphate solution, and fully reacting to obtain lithium phosphate;
step 8: and (3) washing the lithium phosphate obtained in the step (7), and drying to obtain the high-purity lithium phosphate.
2. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 2, the mass ratio of the lithium iron phosphate battery powder to the pure water in the slurry is 1:3-7, wherein the mass percentage of the concentrated sulfuric acid is 98%, and the adding amount of the concentrated sulfuric acid is that the pH value of the solution reaches 2-3.
3. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 3, the oxidant is hydrogen peroxide, and the addition amount of the hydrogen peroxide is Fe in the leaching solution 2+ 1-2 times of the stoichiometric ratio of the catalyst, and the percentage of hydrogen peroxide is 10% -30%.
4. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 4, the reaction temperature is 50-60 ℃, and the stirring speed is 200-300r/min.
5. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 5, the addition amount of ammonium carbonate or ammonium bicarbonate is 2-5 times of theoretical amount of total content of calcium and magnesium ions in the primary filtrate obtained in the step 4, the reaction temperature is 50-60 ℃, and the stirring speed is 200-300r/min.
6. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 6, the concentration of Li in the concentrated solution is 10-20g/L.
7. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 7, the addition amount of the saturated ammonium phosphate solution or the diammonium hydrogen phosphate solution or the monoammonium hydrogen phosphate solution is 1.0-1.5 times of theoretical amount according to the lithium content of the concentrated solution, and the reaction temperature is 60-90 ℃.
8. The method for producing lithium phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 8, the lithium phosphate is washed by hot pure water, the temperature of the hot pure water is 90-95 ℃, and the mass of the hot pure water and the lithium phosphate liquid is (10-30): 1, the washing time is 0.5-2.0h.
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