CN109650415B - Method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder - Google Patents
Method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder Download PDFInfo
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- 239000000843 powder Substances 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 52
- 238000000034 method Methods 0.000 title claims abstract description 43
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000011575 calcium Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000005485 electric heating Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000002686 phosphate fertilizer Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 206010001497 Agitation Diseases 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder, which comprises eight steps of preparing positive electrode powder, circularly leaching, filtering, washing and the like. The invention aims to provide a method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder, and the method has the advantages of environment friendliness, low energy consumption, low production cost and low pollution discharge capacity, efficiently realizes comprehensive utilization of resources, and meets the requirement of industrial production.
Description
Technical Field
The invention relates to the technical field of secondary resource recycling and circular economy, in particular to a method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder.
Background
As a secondary battery with the highest energy density in an energy storage device capable of being applied in a large scale, a lithium ion battery covers most of mobile communication and digital product markets and has an important influence on technical progress of the mobile communication and digital product markets, in recent years, along with improvement of performance and manufacturing level, the lithium ion battery is applied to energy storage industry, green and environment-friendly new energy electric vehicles and other electric vehicles, becomes a very important product in the new energy industry, and the demand of international and domestic markets for the lithium ion battery is in a blowout situation.
With the application of lithium ion batteries, a large number of discarded lithium ion batteries with the expired service cycle need to be safely, environmentally and efficiently treated every year. The recovery of the waste lithium batteries has great practical significance on the sustainable development of new energy, the recovery work of the waste lithium batteries can reduce the influence of the waste lithium batteries on the environment, resources can be saved, the production cost of the batteries is reduced, and great economic benefits are generated.
Since lithium battery recycling is a new industry that has emerged in recent years, past production practices and technological accumulation are almost blank. In recent years, domestic technicians continuously apply for a plurality of patents for recycling waste lithium batteries, for example, a Chinese patent with the application number of 201410354162.5, and the scrapped positive electrode of the lithium iron phosphate battery is disassembled into a lithium iron phosphate electrode and a graphite plate electrode, the lithium iron phosphate electrode and the graphite plate electrode are placed into an electrolytic cell and added with electrolyte for electrolysis, so that lithium ions are separated from the electrolyte and enter the electrolyte, and then the electrolyte is concentrated to extract lithium salts. The method is feasible in principle and difficult to implement in practice, and in practice of disassembling the lithium battery, most of the positive plates containing lithium iron phosphate are basically damaged in the disassembling, packaging and transporting processes, so that the lithium iron phosphate electrode plates cannot be obtained from waste lithium batteries, and the method has the advantages of huge energy consumption for electrolyzing and concentrating lithium-containing solution, is not feasible economically and cannot be applied to production fundamentally. For example, in CN102280673A, CN104362468A and CN102751548A, the method of extracting lithium is to calcine old lithium iron phosphate tablets (powder) at high temperature, remove organic substances and ferrous oxides, and then ball milling, air separation, solvent leaching, impurity removal and precipitation are carried out. In the methods, high-temperature roasting is used in the step of separating lithium iron phosphate from an aluminum current collector, in the process of high-temperature roasting, due to the fact that a fluorine-containing oily binder PVDF exists in a pole piece, and substances such as a plastic diaphragm and a carbonate solvent are mixed in the pole piece, during high-temperature roasting, the substances can generate fluoride and carcinogenic dioxin gas, so that the environment is seriously polluted and the human body is seriously influenced.
Aiming at a series of problems encountered in the production practice of lithium extraction of the anode of the waste lithium iron phosphate battery, the continuous research and improvement are carried out in the production practice, the low-temperature electric heating, rubbing, separating, screening and cyclone separating of lithium iron phosphate powder and aluminum particles of the waste lithium iron phosphate anode plate are established, the lithium iron phosphate powder is directly leached by dynamic circulation of sulfuric acid, and after solid-liquid separation of leachate, iron removal, aluminum removal, phosphorus removal and filtration are carried out on the solution, calcium and magnesium are removed by adding caustic soda into the filtrate, and then the simple process flow of precipitating lithium carbonate by adding sodium carbonate after concentration is carried out.
Disclosure of Invention
The invention aims to provide a method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder, and the method has the advantages of environment friendliness, low energy consumption, low production cost and low pollution discharge capacity, efficiently realizes comprehensive utilization of resources, and meets the requirement of industrial production.
In order to realize the purpose, the invention adopts the technical scheme that: a method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder is characterized by comprising the following steps:
step 1: preparing anode powder: putting the disassembled waste lithium iron phosphate battery positive plate into a low-temperature electric heating rubbing mill, adjusting the heating time to 1-3 minutes, adjusting the temperature to be within the range of 150-300 ℃, and separating the aluminum current collector from the lithium iron phosphate powder by screening and cyclone dust collection;
step 2: and (3) circulating leaching: adding the lithium iron phosphate anode powder obtained in the step (1) into a circulating chemical combination barrel filled with water or filter residue washing liquor according to a solid-liquid ratio of 1: 3.5-5, wherein the circulating chemical combination barrel is two steel-lined anticorrosive ceramic tiles with the same volume of 25m & lt 3 & gt-50 m & lt 3 & gt, and is a barrel with a stirring cover; the difference of the installation heights is 300-1000 mm, the barrel with the high installation position is called a chemical combination barrel I, and the barrel with the low installation position is called a chemical combination barrel II; the upper parts of the chemical combination barrel I and the chemical combination barrel II are connected by a phi 350mm PP pipe; the bottom of the chemical combination barrel II is provided with a circulating pump which is pumped from the upper part of the chemical combination barrel I; adding concentrated sulfuric acid from the mixing barrel I according to 30-70% of the weight of the anode powder without heating; as the positive electrode powder contains more organic matters and about 2-3% of aluminum powder, when concentrated sulfuric acid is added for reaction, a thick layer of thick foam can be generated at the upper part of the combination barrel, the thick foam can continuously overflow from a groove, the thick foam continuously flows to the combination barrel II from the combination barrel I through a PP pipe with the diameter of 350mm, the foam and liquid are continuously pumped into the combination barrel I from the upper part through a circulating pump arranged at the lower part of the combination barrel II, the whole reaction process is circulated all the time, the reaction time is 2-6 h, and calcium carbonate powder is added to adjust the PH value to 2-5 after the qualified detection;
and step 3: filtering and washing: pumping the slurry reacted in the step 2 into an automatic chamber type filter press for filtering, feeding filtrate into the next process, putting filter residues into a filter residue stirring and washing barrel for stirring and washing, then filtering, after stirring and washing for 1-3 times, when the soluble lithium content of the detected residues is less than 0.02% -0.1%, washing the residues to be qualified, respectively putting washing liquid into a liquid storage barrel, putting the residues into a residue storage, and performing centralized treatment;
and 4, step 4: removing phosphorus, iron and aluminum: adding the leachate obtained in the step 3 into an impurity removal barrel, heating to 60-90 ℃, adding 5-30 kg of 32% hydrogen peroxide into each cubic leachate, oxidizing for 60-90 minutes, then adding Ca (OH) 2, adjusting the pH value to 6-10, filtering by using a filter press after detecting that iron, aluminum and phosphorus in the solution are qualified, putting filter residues into a slag warehouse for unified treatment, and putting the solution into the next process;
and 5: removing calcium and magnesium from the solution: putting the filtrate obtained in the step (4) into an impurity removal barrel, heating to 75-90 ℃, and adding caustic soda flakes to adjust the pH value to be more than 12; after reacting for 30-60 minutes, filtering after detecting that calcium and magnesium are qualified, putting filter residues into a slag warehouse for unified treatment, and putting the filtrate into the next procedure;
step 6: concentrating impurity-removed liquid: pumping the impurity-removed liquid obtained in the step 5 into a liquid storage tank, evaporating and concentrating in a four-effect evaporator, and when the purified liquid is concentrated to contain 40-60 g/l of lithium oxide, putting the purified liquid into a sedimentation tank for cooling and sedimentation;
and 7: precipitating a lithium carbonate product: after the step 6 is concentrated, supernatant liquid is extracted from the upper part of the solution after the solution is kept stand in a sedimentation tank for 24 hours and then added into a lithium precipitation kettle, food-grade soda ash solid powder is added into the kettle according to the molar ratio of lithium of 1.1 to 1.6 times, complexing agent EDTA disodium is added into the kettle according to the proportion of adding 0.5 to 2kg of each cubic solution, the temperature is raised to 70 to 95 ℃, the stirring is carried out for 60 to 150 minutes, and after the sampling is qualified, dehydration, washing and drying are carried out to obtain a lithium carbonate product;
and 8: treating lithium precipitation tail water: pumping the lithium precipitating tail liquid and the washing water obtained in the step 7 into an MVR evaporator for high-temperature crystallization to produce a anhydrous sodium sulphate product, and returning the condensed water to the step three to be used as washing water;
further, in the step 1, the mesh number of the lithium iron phosphate powder separated from the low-temperature electric heating rubbing mill is up to 300-400 meshes and accounts for 85%, and the aluminum content is less than or equal to 3%.
Furthermore, in the step 2, the lithium oxide in the filter residue washing liquid put into the circulating combination barrel reaches 3.5-4.5 g/l, and the lithium oxide content of the leaching liquid is 17-18 g/l.
Furthermore, in the step 3, the filter residue is washed by adopting a reverse flow type washing of the residue and washing water, the amount of the washing liquid is equal to that of the leaching solution, the water system is kept balanced, and the water system is prevented from expanding.
Further, in the step 4, ca (OH) 2 is added to prepare an emulsion.
Further, in the step 5, when caustic soda flakes are added to remove calcium and magnesium, if the pH value is above 12 and the calcium and magnesium do not reach the standard, 20% of sodium carbonate solution can be added, and the addition amount is 1.5 times of the sum of the molar amounts of calcium and magnesium.
Further, in the step 7, in order to wash soluble substances such as sodium ions, potassium ions, sulfate radicals, chloride radicals and the like to reach the standard during the lithium carbonate washing operation, an operation flow of secondary stirring washing and tertiary automatic centrifuge dewatering is adopted.
Furthermore, the leached slag can be used as a raw material for producing phosphate fertilizer and smelting ferro-phosphorus.
The invention has the beneficial effects that:
1. when the scrapped lithium battery positive plate is treated, the innovative technology of separating the lithium iron phosphate and the aluminum current collector by low-temperature electric heating rubbing is adopted, the heating temperature is controlled in the temperature range that the PVDF (polyvinylidene fluoride) containing binder just fails and fluorine is not decomposed, and the plastic diaphragm and the carbonate solvent are not decomposed within the temperature range, so that the problems that harmful fluorine-containing gas is generated and carcinogenic dioxin gas is generated to harm the environment and the physical and mental health of people during high-temperature roasting of the lithium battery positive plate are solved.
2. In order to solve the problems that the leaching operation cannot be carried out due to the overflow of a groove during the acid leaching of the lithium iron phosphate anode powder, an innovative process of circulating leaching is designed, and the normal production is ensured.
3. The whole production process design has the characteristics of short flow, energy conservation, low production cost, high lithium recovery rate and good product quality: the comprehensive recovery rate of lithium is more than 92 percent and is about 8 percent higher than the average level in China at present; the product quality reaches the standard of battery-grade lithium carbonate.
4. The production process is environment-friendly, a small amount of acid-containing waste gas generated in the whole production is sprayed by the acid mist spray tower and then is discharged after reaching the standard, the waste water is subjected to closed cycle after the anhydrous sodium sulphate is extracted, and the waste residue contains a large amount of phosphorus and iron and is a raw material for producing phosphate fertilizer and ferrophosphorus.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
FIG. 2 is a graph showing the comparison of the effects of the present invention in the embodiment.
Detailed Description
TABLE 1 chemical composition of anode powder of scrapped lithium iron phosphate battery (%)
Example one
Step 1: putting 2kg of scrapped lithium iron phosphate positive plate into an electric heating rubbing mill to separate the positive electrode powder and aluminum, wherein the electric heating time is 1.5 minutes, the heating temperature is 220 ℃, the mesh number of the lithium iron phosphate positive plate powder is-400 accounting for 87%, the ratio of the lithium iron phosphate positive plate powder to aluminum particles is = 80: 20, the weight of the lithium iron phosphate positive plate powder is 1.6kg, and the aluminum particles are 0.4kg. The compositions are shown in Table 1.
And 2, step: obtaining 1.6kg of lithium iron phosphate anode powder, adding water into a reaction tank according to the solid-liquid ratio of 1: 4.5, mixing into slurry, slowly adding concentrated sulfuric acid (the acid adding time is controlled to be more than 1 h) according to the proportion of the anode powder to acid (the weight ratio) = 1: 0.4, keeping the reaction time at 4h without heating, then adding limestone powder (CnCO 3 is more than or equal to 90%), adjusting the pH value of the solution to 4, carrying out suction filtration, washing filter residues twice by using water in a countercurrent manner, measuring the washing water amount by 4.5 times of the anode powder amount, and collecting the washing water for next leaching. The residue rate of the leaching residue dry agent is 1.5 times of that of the anode powder.
And step 3: adding 32% hydrogen peroxide into the leachate according to the proportion of adding 10kg of 1m3 of the leachate, adding the leachate to 80 ℃, stirring the leachate at a constant temperature for 70 minutes, adding lime milk to adjust the pH value to 7.5, sampling and detecting that iron ions, aluminum ions and phosphate ions are all less than 0.008g/l, and filtering.
And 4, step 4: and (4) heating the solution obtained in the step (3) to 85 ℃, adding solid sodium hydroxide, adjusting the pH value of the solution to be more than 12, after reacting for 40 minutes, sampling, detecting whether the calcium and the magnesium are less than 0.01g/l, and then adding 20% of sodium carbonate solution according to the sum of the molar ratio of the calcium to the magnesium until the calcium and the magnesium are qualified, and then filtering.
And 5: and (4) evaporating and concentrating the solution filtered in the step (4) to 1/2.5 of the original solution, and putting the solution into a precipitation barrel for cooling and precipitating for 24 hours.
And 6: and putting the supernatant of the solution precipitated for 24 hours into a lithium precipitation reaction tank, adding food-grade sodium carbonate according to the molar ratio of 1.25 times of lithium, adding 0.8kg of EDTA disodium into every 1m < 3 > of the solution, heating to 90 ℃, reacting for 120 minutes, carrying out suction filtration on the precipitated lithium carbonate, leaching twice with 500ml of deionized water, and drying to obtain a lithium carbonate product. The results are shown in FIG. 2.
Example two
Compared with the first embodiment, 1.6kg of lithium iron phosphate positive electrode powder separated from 2kg of scrapped lithium iron phosphate positive electrode plates by an electric heating rubbing mill in the step 2 is characterized in that water is added into a reaction tank for size mixing according to a solid-to-liquid ratio of 1: 3, the previous and subsequent processes are the same as the first embodiment, and the result is shown in fig. 2.
EXAMPLE III
Compared with the first embodiment, 1.6kg of lithium iron phosphate positive electrode powder separated from 2kg of scrapped lithium iron phosphate positive electrode sheets by the electric heating rubbing mill in the step 2 is characterized in that concentrated sulfuric acid is slowly added according to the ratio of the positive electrode powder to acid = 1: 0.65, the leaching residue drying agent residue rate is 2.2 times of that of the positive electrode powder, and the previous and subsequent processes are the same as the first embodiment, and the result is shown in fig. 2.
Comparative example 1
Compared with the first embodiment, in step 1, 2kg of scrapped lithium iron phosphate positive electrode sheets are subjected to an electric heating rubbing mill to separate lithium iron phosphate positive electrode powder and aluminum, the electric heating time is 3 minutes, the heating temperature is 320 ℃, the mesh number of the lithium iron phosphate positive electrode powder is-400 meshes and accounts for 92%, the ratio of the lithium iron phosphate positive electrode powder to the aluminum is = 86: 14, namely 1.72kg of the positive electrode powder, and 0.28kg of the aluminum is obtained. In the composition of table 1, the Li2O content was changed to 7.79%, the Al content was changed to 3.50%, and the other compositions were not changed so much, and the influence factors were negligible. The subsequent process is the same as that of the first embodiment, and the result is shown in FIG. 2.
Comparative example No. two
Compared with the first example, the difference is that in the step 2, the solution pH value is adjusted to 4 by adding lime powder (CaCO 3 is more than or equal to 90 percent) instead of being adjusted to 4 by NaOH, the leaching residue drying agent rate is 1.2 times of that of the positive electrode powder, and the previous and subsequent processes are the same as the first example, and the result is shown in the figure 2.
Comparative example No. three
Compared with the first embodiment, the difference is that solid sodium hydroxide is added in the step 4, the pH value of the solution is adjusted to be more than 12, solid sodium carbonate is added, the pH value of the solution is adjusted to be more than 12, the previous and subsequent processes are the same as the first embodiment, and the result is shown in figure 2.
As can be seen from fig. 2, a series of factors such as the content of aluminum in the lithium iron phosphate positive electrode powder, the solid-to-liquid ratio, the addition amount of sulfuric acid, the selection of PH regulators for removing aluminum, iron, phosphorus and calcium and magnesium have significant effects on the recovery rate of lithium in the lithium iron phosphate positive electrode powder and the purity of lithium carbonate products.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. It should be noted that there are no specific structures but rather a few limitations to the preferred embodiments of the present invention, and that many modifications, adaptations, and variations are possible and can be made by one skilled in the art without departing from the principles of the present invention; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (8)
1. A method for extracting lithium carbonate from scrapped lithium iron phosphate battery positive electrode powder is characterized by comprising the following steps:
step 1: preparing anode powder: putting the disassembled waste lithium iron phosphate battery positive plate into a low-temperature electric heating rubbing mill, adjusting the heating time to 1-3 minutes, adjusting the temperature to be within the range of 150-300 ℃, and separating the aluminum current collector from the lithium iron phosphate powder by screening and cyclone dust collection;
step 2: and (3) circulating leaching: adding the lithium iron phosphate anode powder obtained in the step (1) into a circulating chemical combination barrel filled with water or filter residue washing liquor according to a solid-liquid ratio of 1: 3.5-5, wherein the circulating chemical combination barrel is two steel-lined anticorrosive tiles with the same volume of 25m & lt 3 & gt-50 m & lt 3 & gt, and is a barrel with a stirring cover; the difference of the installation heights is 300-1000 mm, the barrel with the high installation position is called a chemical combination barrel I, and the barrel with the low installation position is called a chemical combination barrel II; the upper parts of the chemical combination barrel I and the chemical combination barrel II are connected by a PP pipe with the diameter phi of 350 mm; the bottom of the chemical combination barrel II is provided with a circulating pump which is pumped from the upper part of the chemical combination barrel I; adding concentrated sulfuric acid from the mixing barrel I according to 30-70% of the weight of the anode powder without heating; as the anode powder contains more organic matters and 2-3% of aluminum powder, when concentrated sulfuric acid is added for reaction, a thick layer of thick foam is generated at the upper part of the chemical combination barrel and can continuously overflow out of the tank, the thick foam continuously flows from the chemical combination barrel I to the chemical combination barrel II through a phi 350mm PP pipe, the foam and liquid are continuously pumped into the chemical combination barrel I from the upper part through a circulating pump arranged at the lower part of the chemical combination barrel II, the whole reaction process is circulated all the time, the reaction time is 2-6 h, and calcium carbonate powder is added to adjust the pH value to 2-5 after the qualified product is detected;
and step 3: filtering and washing: pumping the slurry reacted in the step 2 into an automatic box-type filter press for filtering, allowing filtrate to enter the next process, putting filter residues into a filter residue stirring and washing barrel for stirring and washing, and then filtering, after stirring and washing for 1-3 times, detecting that the soluble lithium content in the residues is less than 0.1%, washing the residues to be qualified, respectively putting washing liquid into a liquid storage barrel, putting the residues into a residue storage, and performing centralized treatment;
and 4, step 4: removing phosphorus, iron and aluminum: adding the leachate obtained in the step 3 into an impurity removal barrel, heating to 60-90 ℃, adding 5-30 kg of 32% hydrogen peroxide into each cubic leachate, oxidizing for 60-90 minutes, then adding Ca (OH) 2, adjusting the pH value to 6-10, filtering by using a filter press after the iron, aluminum and phosphorus in the solution are detected to be qualified, uniformly treating the filtered residues in a slag warehouse, and allowing the solution to enter the next process;
and 5: removing calcium and magnesium from the solution: putting the filtrate obtained in the step (4) into an impurity removal barrel, heating to 75-90 ℃, and adding caustic soda flakes to adjust the pH value to be more than 12; after reacting for 30-60 minutes, filtering after detecting that calcium and magnesium are qualified, putting filter residues into a slag warehouse for unified treatment, and putting the filtrate into the next procedure;
step 6: concentrating impurity-removed liquid: pumping the impurity-removed liquid obtained in the step 5 into a liquid storage tank, evaporating and concentrating in a four-effect evaporator, and when the purified liquid is concentrated to contain 40-60 g/l of lithium oxide, putting the purified liquid into a sedimentation tank for cooling and sedimentation;
and 7: precipitating a lithium carbonate product: after the step 6 is concentrated, supernatant liquid is extracted from the upper part of the solution after the solution is kept stand in a sedimentation tank for 24 hours and then is added into a lithium precipitation kettle, food-grade soda ash solid powder is added into the kettle according to the molar ratio of lithium being 1.1-1.6 times, complexing agent EDTA disodium is added into the kettle according to the proportion of adding 0.5-2 kg into each cubic solution, the temperature is raised to 70-95 ℃, the stirring is carried out for 60-150 minutes, and after the sampling is qualified, dehydration, washing and drying are carried out to obtain a lithium carbonate product;
and 8: treating lithium precipitation tail water: pumping the lithium precipitating tail liquid and the washing water obtained in the step 7 into an MVR evaporator for high-temperature crystallization to produce a anhydrous sodium sulphate product, and returning the condensed water to the step three to be used as washing water.
2. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder according to claim 1, wherein in the step 1, the lithium iron phosphate powder separated from the low-temperature electric heating and milling machine has a mesh size of 300-400 meshes accounting for 85%, and the aluminum content is less than or equal to 3%.
3. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder according to claim 1, wherein in the step 2, the filter residue washing liquid put into the circulating combination barrel contains 3.5-4.5 g/l of lithium oxide, and the lithium oxide content of the final leaching solution is 17-18 g/l.
4. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder according to claim 1, wherein in the step 3, the filter residue is washed by a countercurrent washing method using the filter residue and washing water, the amount of the washing liquid is equal to that of the leaching solution, the water system is kept in balance, and the water system is prevented from expanding.
5. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder according to claim 1, wherein in the step 4, the added Ca (OH) 2 is prepared into an emulsion.
6. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder as claimed in claim 1, wherein in the step 5, when the calcium and magnesium are removed by adding caustic soda flakes and the pH value is above 12 and the calcium and magnesium do not reach the standard, 20% sodium carbonate solution is added, and the addition amount is 1.5 times of the sum of the molar amounts of the calcium and the magnesium.
7. The method for extracting lithium carbonate from the discarded lithium iron phosphate battery positive electrode powder as claimed in claim 1, wherein in the step 7, in order to wash soluble substances such as sodium ions, potassium ions, sulfate radicals and chloride radicals to reach the standard during the lithium carbonate washing operation, an operation flow of secondary agitation washing and tertiary automatic centrifuge dewatering is adopted.
8. The method for extracting lithium carbonate from the scrapped lithium iron phosphate battery positive electrode powder as claimed in claim 1, wherein the leaching residue can be used as a raw material for producing phosphate fertilizer and smelting ferrophosphorus.
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| CN112687973B (en) * | 2019-09-02 | 2022-03-15 | 江西迈特循环科技有限公司 | Method and equipment for treating material containing lithium iron phosphate |
| CN110980776A (en) * | 2019-12-03 | 2020-04-10 | 四川致远锂业有限公司 | High-efficiency aluminum removal method for lithium salt production |
| CN111187913B (en) * | 2020-02-20 | 2021-07-02 | 广东省稀有金属研究所 | A method for selectively recovering lithium and copper in waste lithium iron phosphate batteries |
| CN115210391A (en) * | 2020-03-02 | 2022-10-18 | 锂电池循环有限公司 | Method for treating multiple waste lithium iron phosphate batteries |
| CN111484043A (en) * | 2020-03-05 | 2020-08-04 | 赣州龙凯科技有限公司 | Comprehensive recovery method of waste lithium manganate and lithium iron phosphate cathode material |
| AU2021330014B2 (en) * | 2020-08-24 | 2024-04-18 | Green Li-ion Pte Ltd. | Process for removing impurities in the recycling of lithium-ion batteries |
| CN113373321B (en) * | 2021-06-25 | 2023-03-31 | 许昌学院 | Method for recycling lithium element from scrapped lithium iron phosphate battery by wet method |
| CN113526546B (en) * | 2021-07-08 | 2023-09-08 | 安徽超威电源有限公司 | A system and method for cleaning and converting waste lead paste to prepare battery-grade lead oxide |
| CN116462232A (en) * | 2023-05-22 | 2023-07-21 | 甘肃睿思科新材料有限公司 | Method for recovering phosphorus and iron from iron phosphate waste residue generated in selective lithium extraction process of lithium iron phosphate |
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