CN112553477A - Method for recovering aluminum lithium element by sintering method - Google Patents
Method for recovering aluminum lithium element by sintering method Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 78
- 229910001148 Al-Li alloy Inorganic materials 0.000 title claims abstract description 17
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 148
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 148
- 238000001556 precipitation Methods 0.000 claims abstract description 83
- 238000002386 leaching Methods 0.000 claims abstract description 70
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000002699 waste material Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000004090 dissolution Methods 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000001939 inductive effect Effects 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 8
- 230000002411 adverse Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- -1 lithium-iron-lithium-aluminum-lithium-aluminum-lithium Chemical compound 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- 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
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- 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
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- 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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Abstract
The invention provides a method for recovering aluminum lithium elements by a sintering method. The method comprises the following steps: crushing and slurrying: crushing the positive electrode of the waste lithium battery to obtain crushed materials; preparing a slurry comprising crushed material, ammonium salt and carbonate; sintering: sintering the slurry at the temperature of 500-800 ℃ to obtain a sintering material and sintering tail gas; leaching: leaching the sintered material by using a dilute alkali solution to obtain a leaching solution; and (3) lithium precipitation: adding a lithium precipitation agent into the dissolution liquid for lithium precipitation reaction to obtain lithium precipitation and a liquid after lithium precipitation; the method comprises the following steps: and introducing the sintering tail gas into the solution after lithium precipitation, evaporating and concentrating, adding seed crystals into the concentrated solution, and stirring to induce and separate out aluminum precipitate. The method effectively solves the problems that the aluminum and the electrode powder of the waste lithium battery can not be effectively separated and the subsequent acid leaching or alkali dissolving process is adversely affected in the prior art.
Description
Technical Field
The invention relates to the technical field of waste battery resource recovery, in particular to a method for recovering aluminum lithium by a sintering method.
Background
With the large-scale popularization and application of new energy automobiles, the output and sale quantity of new energy automobiles in China are stabilized in the first place around the world, and future power batteries face the problem of large-scale retirement. In 2020, a batch of power batteries popularized at the earliest will be retired, the scrapped power batteries are precious urban mines, and the efficient recovery and recycling of valuable metals can improve the resource utilization efficiency. The problem of how to comprehensively utilize the resources is particularly urgent, and the method has important significance for reducing the external dependence of China, realizing the strategic safety of national resources and developing the circular economy.
At the present stage, the recovery concept of the waste lithium batteries generally takes dry method and traditional hydrometallurgy linkage recovery as main materials, namely, the waste lithium batteries are crushed and screened to obtain anode and cathode powder, aluminum particles, copper particles, a crushed diaphragm and the like, and then the anode and cathode powder is subjected to acid leaching, impurity removal, extraction, chemical precipitation and the like to recover various element salts. However, the aluminum particles obtained by crushing carry polar powder, so that the purity is low, and a small amount of fine aluminum particles can be carried in the polar powder. The conventional method for treating the crushed aluminum particles comprises the steps of burning off the binder by a roasting method, dissolving aluminum by using liquid alkali, and achieving a separation effect by using a flotation table mechanochemistry and the like; the electrode powder enters a wet system and valuable metals such as nickel, cobalt, manganese and the like are recovered through processes such as acid leaching and the like.
However, the aluminum powder mixed in the electrode powder enters a wet system, which increases the acid consumption in the leaching process, and the alkali consumption in the impurity removal process also increases correspondingly. Therefore, how to effectively separate aluminum from the extreme powder in an efficient, rapid and environment-friendly manner and improve the recovery rate of valuable elements in the waste lithium battery is a difficult point to be solved urgently in the field of resource recovery.
Disclosure of Invention
The invention mainly aims to provide a method for recovering aluminum and lithium elements by a sintering method, and aims to solve the problems that in the prior art, aluminum and electrode powder of waste lithium batteries cannot be effectively separated, and adverse effects are generated on subsequent acid leaching or alkali dissolution processes.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for recovering aluminum lithium element by a sintering method, comprising the steps of: crushing and slurrying: crushing the positive electrode of the waste lithium battery to obtain crushed materials; preparing a slurry comprising crushed material, ammonium salt and carbonate; sintering: sintering the slurry at the temperature of 500-800 ℃ to obtain a sintering material and sintering tail gas; leaching: leaching the sintered material by using a dilute alkali solution to obtain a leaching solution; and (3) lithium precipitation: adding a lithium precipitation agent into the dissolution liquid for lithium precipitation reaction to obtain lithium precipitation and a liquid after lithium precipitation; the method comprises the following steps: and introducing the sintering tail gas into the solution after lithium precipitation, evaporating and concentrating, adding seed crystals into the concentrated solution, and stirring to induce and separate out aluminum precipitate.
Further, in the step of crushing and pulping, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate; preferably, the carbonate is one or more selected from sodium carbonate, sodium bicarbonate, potassium carbonate and calcium carbonate.
Furthermore, in the step of crushing and slurrying, the weight ratio of the crushed material to the ammonium salt to the carbonate is 1 (0.1-0.5) to 0.1-0.2; preferably, the liquid-solid ratio in the slurry is 1 (2-5).
Further, the particle size of the pulverized material is 50 to 150 mesh.
Further, the sintering step comprises: putting the slurry into a converter, sintering for 2-6 h at the temperature of 500-800 ℃, and collecting sintering tail gas; and after sintering, cooling to obtain a sintered material.
Further, in the leaching step, the dilute alkali solution is selected from one or more aqueous solutions of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate; preferably, the weight concentration of the dilute alkali solution is 5-10 g/L.
Further, in the leaching step, the liquid-solid ratio of the dilute alkali solution to the sintering material is (3-6): 1; preferably, the leaching temperature in the leaching step is 80-95 ℃, and the leaching time is 1-5 h.
Further, in the step of precipitating lithium, the lithium precipitating agent is selected from one or more of sodium carbonate, sodium phosphate and sodium fluoride; preferably, the addition amount of the lithium precipitating agent is 1.2-1.5 times of the theoretical required amount of Li in the dissolution liquid; preferably, the temperature of the lithium precipitation reaction is 85-95 ℃ and the time is 1-4 h.
Further, the seed separation step comprises: introducing sintering tail gas into the solution after lithium precipitation for 0.5-2 h; evaporating and concentrating the reacted solution after lithium precipitation at 90-100 ℃ to obtain a concentrated solution; adding aluminum hydroxide with a seed crystal ratio of 0.05-0.2 into the concentrated solution as a seed crystal, and inducing and separating out aluminum precipitate under the stirring state at 50-70 ℃.
Further, in the seed precipitation step, after aluminum precipitation is induced to be separated out, the method also comprises the step of returning the residual seed precipitation mother liquor as part of dilute alkali solution for leaching the sintering material.
The method for recovering the aluminum lithium element by the sintering method comprises the following steps: crushing and slurrying: crushing the positive electrode of the waste lithium battery to obtain crushed materials; preparing a slurry comprising crushed material, ammonium salt and carbonate; sintering: sintering the slurry at the temperature of 500-800 ℃ to obtain a sintering material and sintering tail gas; leaching: leaching the sintered material by using a dilute alkali solution to obtain a leaching solution; and (3) lithium precipitation: adding a lithium precipitation agent into the dissolution liquid for lithium precipitation reaction to obtain lithium precipitation and a liquid after lithium precipitation; the method comprises the following steps: and introducing the sintering tail gas into the solution after lithium precipitation for reaction, evaporating and concentrating, adding seed crystals into the concentrated solution, and stirring to induce and separate out aluminum precipitate.
In the method provided by the invention, the anode of the waste lithium battery is crushed, mixed with ammonium salt and carbonate for size mixing, and then sintered. By using the slurry mixing and sintering, aluminum in the crushed materials can be converted into metaaluminate, lithium can be converted into soluble lithium salt, and the polar powder material in the sintering process cannot be changed due to the inherent oxide alloy composition. Then, metaaluminate and soluble lithium salt in the sintering material can be fully dissolved in the dilute alkali solution, and further, the metaaluminate and the soluble lithium salt are fully separated from the polar powder. After the leaching, lithium precipitation and aluminum precipitation can be respectively recovered through a lithium precipitation step and a seed precipitation step. Different from the traditional aluminum recovery method of the waste lithium battery, the invention combines the pyrometallurgical process and the hydrometallurgical process to recycle the anode of the waste lithium battery. Lithium and aluminum in the anode of the waste lithium battery can be directly separated and extracted through sintering-leaching, acid-base consumption in the conventional leaching-aluminum removing process is avoided, and loss of aluminum and lithium elements is effectively reduced. The crude lithium precipitate and aluminum precipitate obtained by sintering, leaching, lithium precipitation and seed separation have low impurity content and can be directly used for respective next process.
In a word, the method effectively solves the problems that the aluminum and the electrode powder of the waste lithium battery can not be effectively separated and the subsequent acid leaching or alkali dissolving process is adversely affected in the prior art.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic flow chart of a method for recovering aluminum lithium element by a sintering method according to an embodiment of the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to more effectively separate aluminum, lithium and pole powder in waste lithium batteries, the invention provides a method for recovering aluminum lithium elements by a sintering method, as shown in figure 1, and the method comprises the following steps: crushing and slurrying: crushing the positive electrode of the waste lithium battery to obtain crushed materials; preparing a slurry comprising crushed material, ammonium salt and carbonate; sintering: sintering the slurry at the temperature of 500-800 ℃ to obtain a sintering material and sintering tail gas; leaching: leaching the sintered material by using a dilute alkali solution to obtain a leaching solution; and (3) lithium precipitation: adding a lithium precipitation agent into the dissolution liquid for lithium precipitation reaction to obtain lithium precipitation and a liquid after lithium precipitation; seed separation step (seed crystal separation step): and introducing the sintering tail gas into the solution after lithium precipitation, evaporating and concentrating, adding seed crystals into the concentrated solution, and stirring to induce and separate out aluminum precipitate.
In the method provided by the invention, the anode of the waste lithium battery is crushed, mixed with ammonium salt and carbonate for size mixing, and then sintered. By using the slurry mixing and sintering, aluminum in the crushed materials can be converted into metaaluminate, lithium can be converted into soluble lithium salt, and the polar powder material in the sintering process cannot be changed due to the inherent oxide alloy composition. Then, metaaluminate and soluble lithium salt in the sintering material can be fully dissolved in the dilute alkali solution, and further, the metaaluminate and the soluble lithium salt are fully separated from the polar powder. After the leaching, lithium precipitation and aluminum precipitation can be respectively recovered through a lithium precipitation step and a seed precipitation step. Different from the traditional aluminum recovery method of the waste lithium battery, the invention combines the pyrometallurgical process and the hydrometallurgical process to recycle the anode of the waste lithium battery. Lithium and aluminum in the anode of the waste lithium battery can be directly separated and extracted through sintering-leaching, acid-base consumption in the conventional leaching-aluminum removing process is avoided, and loss of aluminum and lithium elements is effectively reduced. The crude lithium precipitate and aluminum precipitate obtained by sintering, leaching, lithium precipitation and seed separation have low impurity content and can be directly used for respective next process.
In a word, the method effectively solves the problems that the aluminum and the electrode powder of the waste lithium battery can not be effectively separated and the subsequent acid leaching or alkali dissolving process is adversely affected in the prior art.
In order to further improve the sintering effect and enable lithium and aluminum to be more fully sintered and reacted to be converted into soluble salts, in a preferred embodiment, in the crushing and slurrying step, ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate; preferably, the carbonate is one or more selected from sodium carbonate, sodium bicarbonate, potassium carbonate and calcium carbonate. By adopting the ammonium salt and the carbonate, the temperature of lithium and aluminum is more adaptive in the sintering process, the lithium and aluminum can react more fully at the temperature of 500-800 ℃, and the lithium-iron-lithium-aluminum-lithium-aluminum-lithium. More preferably, the ammonium salt is selected from ammonium chloride and/or ammonium sulfate, and the carbonate is selected from sodium carbonate and/or sodium bicarbonate.
For the purpose of promoting the reaction to be more fully carried out and simultaneously reducing the waste of resources, in a preferred embodiment, in the step of crushing and slurrying, the weight ratio of the crushed material, the ammonium salt and the carbonate is 1 (0.1-0.5) to 0.1-0.2; more preferably, the liquid-solid ratio in the slurry is 1 (2-5). In order to improve the reaction efficiency, it is preferable that the particle size of the pulverized material is 50 to 150 mesh. In the actual operation process, a crusher is adopted to crush the positive electrode of the waste lithium battery.
In a preferred embodiment, the sintering step includes: putting the slurry into a converter, sintering for 2-6 h at the temperature of 500-800 ℃, and collecting sintering tail gas; and after sintering, cooling to obtain a sintered material. Controlling the reaction conditions within the above range allows more sufficient sintering reaction, more sufficient reaction of lithium and aluminum, and more effective separation from the electrode powder. And the sintering step is accompanied by tail gas generation, and the main components of the sintering step are carbon dioxide and ammonia gas. The alkalinity of the solution after lithium precipitation can be adjusted within a more appropriate range by introducing the solution into the solution after lithium precipitation, and the temperature of the solution after lithium precipitation can be adjusted, so that aluminum can be promoted to be fully precipitated after concentration and seed crystal addition, and meanwhile, the full utilization of resources and less pollution are realized.
In order to leach out the soluble lithium salt and the aluminum salt more sufficiently, in a preferred embodiment, in the leaching step, the dilute alkali solution is selected from one or more aqueous solutions of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate; preferably, the weight concentration of the dilute alkali solution is 5-10 g/L. More preferably, in the leaching step, the liquid-solid ratio of the dilute alkali solution to the sintering material is 3-6: 1; preferably, the leaching temperature in the leaching step is 80-95 ℃, and the leaching time is 1-5 h. In actual operation, leaching, filtering to obtain a leaching solution and leaching slag, and delivering the leaching slag to an acid leaching and purifying system for recovering valuable elements.
In the step of depositing lithium, adding a lithium depositing agent to promote lithium ions to deposit and separate from aluminum, in a preferred embodiment, in the step of depositing lithium, the lithium depositing agent is selected from one or more of sodium carbonate, sodium phosphate and sodium fluoride; preferably, the addition amount of the lithium precipitating agent is 1.2-1.5 times of the theoretical required amount of Li in the dissolution liquid; preferably, the temperature of the lithium precipitation reaction is 85-95 ℃ and the time is 1-4 h. Under the above reagents and conditions, lithium ions can be more sufficiently precipitated, and the formed lithium carbonate or lithium fluoride has higher purity and less impurities, and can be directly used in the subsequent process.
In a preferred embodiment, the seed separation step includes: introducing sintering tail gas into the solution after lithium precipitation for 0.5-2 h; evaporating and concentrating the reacted solution after lithium precipitation at 90-100 ℃ to obtain a concentrated solution; adding aluminum hydroxide with a seed crystal ratio of 0.05-0.2 into the concentrated solution as a seed crystal, and inducing and separating out aluminum precipitate under the stirring state at 50-70 ℃. Under the conditions, aluminum ions can be promoted to be precipitated in the form of aluminum hydroxide precipitate, and the aluminum hydroxide has high purity and less impurities. The above seed ratio means a weight ratio between the seed aluminum hydroxide added and the precipitated aluminum precipitate.
In summary, the present invention is directed to solving the problems of the prior art. Therefore, the invention provides a method for recovering aluminum and lithium elements by a sintering method, namely crushing and sintering the anode of a waste lithium battery, and then dissolving and separating aluminum and lithium, which specifically comprises the following steps: crushing the positive electrode of the waste lithium battery to a certain granularity by using a crusher, and adding a mixed solution of carbonate and ammonium salt for slurrying; then placing the slurried material into a converter for sintering, and placing the sintered slurry material into an alkenyl alkali solution for dissolution; introducing sintering tail gas into the dissolution liquid, reacting at a certain temperature, then adding a lithium precipitation agent, reacting and filtering to obtain a lithium precipitation liquid and a crude lithium salt; evaporating and concentrating the lithium precipitation solution, and then adding seed crystals to obtain aluminum hydroxide; according to the method for recovering the aluminum and lithium elements by the sintering method, the aluminum and lithium elements can be extracted by one step through sintering, so that the influence of aluminum on the subsequent wet purification and other processes is removed. In addition, CO2 generated by roasting can be introduced into the dissolution liquid, the temperature and the pH value of the dissolution liquid are adjusted, the full utilization of resources is realized, and the pollution is reduced.
The method is suitable for the positive electrode of the waste lithium battery, and the positive electrode of the waste lithium battery comprises but is not limited to a ternary lithium battery positive electrode, a lithium carbonate battery positive electrode, a lithium iron phosphate battery positive electrode, a lithium cobaltate battery positive electrode and the like. These positive electrode current collectors are aluminum foils.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
In this embodiment, the anode of the waste ternary lithium battery is treated as follows:
(1) crushing and slurrying: crushing the positive electrode of the waste lithium battery to 100 +/-50 meshes, uniformly mixing 100g of crushed material, 30g of ammonium chloride and 15g of sodium carbonate, and adding water according to a liquid-solid ratio of 1:3 for mixing and pulping to obtain slurry;
(2) sintering: putting the slurry uniformly mixed in the step (1) into a converter, sintering at 650 ℃ for 4h, and cooling to room temperature to obtain a sintered material;
(3) leaching: taking the sintered material obtained in the step (2), adding 5g/L of sodium hydroxide aqueous solution according to the liquid-solid ratio of 3:1, leaching at 85 +/-5 ℃, filtering after leaching for 3 hours to obtain a leaching solution and leaching residues;
(4) and (3) lithium precipitation: adding a lithium precipitation agent sodium phosphate into the dissolution liquid obtained in the step (3) according to a theoretical coefficient which is 1.3 times of the content of Li, fully reacting for 2 hours at 90 +/-5 ℃, and filtering to obtain crude lithium precipitation and a liquid after lithium precipitation;
(5) the method comprises the following steps: and (3) introducing the gas generated in the step (2) into the lithium precipitation solution obtained in the step (4) for 1h, then evaporating and concentrating at 95 +/-5 ℃ until Na is less than or equal to 80g/L and Li is greater than or equal to 6g/L, then slowly adding aluminum hydroxide seed crystals with the seed crystal ratio of 0.2 at 65 +/-5 ℃, fully stirring and inducing for 5h, and filtering after reaction to obtain aluminum hydroxide and circulating mother liquor.
ICP detection shows that the lithium content in the lithium precipitate is 15.83%, the aluminum content in the aluminum hydroxide is 21.14%, the aluminum content in the slag dissolved out in the step 3 is 0.27%, the lithium content is 0.56%, the recovery rate of lithium is 91.67%, and the recovery rate of aluminum is 99.37%.
Example 2
In this embodiment, the anode of the waste ternary lithium ion battery is treated as follows:
(1) crushing and slurrying: crushing the positive electrode of the waste lithium battery to 100 +/-50 meshes, uniformly mixing 100g of crushed material, 10g of ammonium chloride and 10g of sodium carbonate, and adding water according to a liquid-solid ratio of 1:2 for mixing and pulping to obtain slurry;
(2) sintering: putting the slurry uniformly mixed in the step (1) into a converter, sintering at 500 ℃ for 6h, and cooling to room temperature to obtain a sintered material;
(3) leaching: taking the sintered material obtained in the step (2), adding 10g/L of sodium hydroxide aqueous solution according to the liquid-solid ratio of 6:1, leaching at 85 +/-5 ℃, filtering after leaching for 3 hours to obtain a leaching solution and leaching residues;
(4) and (3) lithium precipitation: adding a lithium precipitation agent sodium phosphate into the dissolution liquid obtained in the step (3) according to a theoretical coefficient which is 1.2 times of the content of Li, fully reacting for 4 hours at 90 +/-5 ℃, and filtering to obtain crude lithium precipitation and a liquid after lithium precipitation;
(5) the method comprises the following steps: and (3) introducing the gas generated in the step (2) into the lithium precipitation solution obtained in the step (4) for 2 hours, evaporating and concentrating at 95 +/-5 ℃ until Na is less than or equal to 80g/L and Li is greater than or equal to 6g/L, slowly adding aluminum hydroxide seed crystals with the seed crystal ratio of 0.05 at 65 +/-5 ℃, fully stirring and inducing for 5 hours, and filtering after reaction to obtain aluminum hydroxide and circulating mother liquor.
ICP detection shows that the lithium content in the lithium precipitate is 15.28%, the aluminum content in the aluminum hydroxide is 20.79%, the aluminum content in the slag dissolved out in the step 3 is 0.44%, the lithium content is 0.71%, the recovery rate of lithium is 90.50%, and the recovery rate of aluminum is 98.73%.
Example 3
In this embodiment, the anode of the waste ternary lithium ion battery is treated as follows:
(1) crushing and slurrying: crushing the positive electrode of the waste lithium battery to 100 +/-50 meshes, uniformly mixing 100g of crushed material, 50g of ammonium chloride and 20g of sodium carbonate, and adding water according to a liquid-solid ratio of 1:5 for mixing and pulping to obtain slurry;
(2) sintering: putting the slurry uniformly mixed in the step (1) into a converter, sintering at 800 ℃ for 2h, and cooling to room temperature to obtain a sintered material;
(3) leaching: adding 8g/L sodium hydroxide aqueous solution into the sintered material obtained in the step (2) according to the liquid-solid ratio of 3:1, leaching at 85 +/-5 ℃, filtering after leaching for 3 hours to obtain a leaching solution and leaching residues;
(4) and (3) lithium precipitation: adding a lithium precipitation agent sodium phosphate into the dissolution liquid obtained in the step (3) according to a theoretical coefficient which is 1.5 times of the content of Li, fully reacting for 1h at 90 +/-5 ℃, and filtering to obtain crude lithium precipitation and a liquid after lithium precipitation;
(5) the method comprises the following steps: and (3) introducing the gas generated in the step (2) into the lithium precipitation solution obtained in the step (4) for 0.5h, then evaporating and concentrating at 95 +/-5 ℃ until Na is less than or equal to 80g/L and Li is greater than or equal to 6g/L, then slowly adding aluminum hydroxide seed crystals with the seed crystal ratio of 0.1 at 65 +/-5 ℃, fully stirring and inducing for 5h, and filtering after reaction to obtain aluminum hydroxide and circulating mother liquor.
ICP detection shows that the lithium content in the lithium precipitate is 16.07%, the aluminum content in the aluminum hydroxide is 22.24%, the aluminum content in the slag dissolved out in the step 3 is 0.21%, the lithium content is 0.45%, the recovery rate of lithium is 93.06%, and the recovery rate of aluminum is 99.81%.
Example 4
In this embodiment, the anode of the waste ternary lithium ion battery is treated as follows:
(1) crushing and slurrying: crushing the positive electrode of the waste lithium battery to 100 +/-50 meshes, uniformly mixing 100g of crushed material, 30g of ammonium sulfate and 15g of sodium bicarbonate, and adding water according to a liquid-solid ratio of 1:3 for mixing and pulping to obtain slurry;
(2) sintering: putting the slurry uniformly mixed in the step (1) into a converter, sintering at 650 ℃ for 4h, and cooling to room temperature to obtain a sintered material;
(3) leaching: adding 5g/L sodium carbonate aqueous solution into the sintering material obtained in the step (2) according to the liquid-solid ratio of 3:1, leaching at 85 +/-5 ℃, filtering after leaching for 3 hours to obtain a leaching solution and leaching residues;
(4) and (3) lithium precipitation: adding a lithium precipitation agent sodium carbonate into the dissolution liquid obtained in the step (3) according to a theoretical coefficient which is 1.3 times of the content of Li, fully reacting for 2 hours at 90 +/-5 ℃, and filtering to obtain crude lithium carbonate precipitation and a liquid after lithium precipitation;
(5) the method comprises the following steps: and (3) introducing the gas generated in the step (2) into the lithium precipitation solution obtained in the step (4) for 1h, then evaporating and concentrating at 95 +/-5 ℃ until Na is less than or equal to 80g/L and Li is greater than or equal to 6g/L, then slowly adding aluminum hydroxide seed crystals with the seed crystal ratio of 0.2 at 65 +/-5 ℃, fully stirring and inducing for 5h, and filtering after reaction to obtain aluminum hydroxide and circulating mother liquor.
ICP detection shows that the lithium content in the lithium precipitate is 14.68%, the aluminum content in the aluminum hydroxide is 21.38%, the aluminum content in the slag dissolved out in the step 3 is 0.33%, the lithium content is 0.52%, the recovery rate of lithium is 90.12%, and the recovery rate of aluminum is 98.81%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recovering aluminum lithium elements by a sintering method is characterized by comprising the following steps:
crushing and slurrying: crushing the positive electrode of the waste lithium battery to obtain crushed materials; preparing a slurry comprising the crushed material, an ammonium salt and a carbonate;
sintering: sintering the slurry at the temperature of 500-800 ℃ to obtain a sintering material and sintering tail gas;
leaching: leaching the sintering material by using a dilute alkali solution to obtain a leaching solution;
and (3) lithium precipitation: adding a lithium precipitation agent into the dissolution liquid for lithium precipitation reaction to obtain lithium precipitation and a liquid after lithium precipitation;
the method comprises the following steps: and introducing the sintering tail gas into the lithium precipitation solution, evaporating and concentrating, adding seed crystals into the concentrated solution, and stirring to induce and separate out aluminum precipitates.
2. The method for recovering the aluminum lithium element by the sintering method according to claim 1, wherein in the step of crushing and slurrying, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate; preferably, the carbonate is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and calcium carbonate.
3. The method for recovering the aluminum lithium element by the sintering method according to claim 1 or 2, wherein in the step of crushing and slurrying, the weight ratio of the crushed material to the ammonium salt to the carbonate is 1 (0.1-0.5) to (0.1-0.2);
preferably, the liquid-solid ratio in the slurry is 1 (2-5).
4. The sintering method for recovering the aluminum lithium element according to claim 3, wherein the particle size of the crushed material is 50 to 150 meshes.
5. The method for recovering the elemental aluminum and lithium by sintering according to claim 1 or 2, wherein the sintering step comprises:
putting the slurry into a converter, sintering for 2-6 h at the temperature of 500-800 ℃, and collecting sintering tail gas;
and after sintering is finished, cooling to obtain the sintered material.
6. The sintering method for recovering the aluminum lithium element according to claim 1 or 2, wherein in the leaching step, the dilute alkali solution is selected from one or more of aqueous solution of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide and potassium carbonate; preferably, the weight concentration of the dilute alkali solution is 5-10 g/L.
7. The method for recovering the aluminum lithium element by the sintering method according to claim 6, wherein in the leaching step, the liquid-solid ratio of the dilute alkali solution to the sintering material is (3-6): 1; preferably, the leaching temperature in the leaching step is 80-95 ℃, and the leaching time is 1-5 h.
8. The sintering method for recovering the aluminum lithium element according to claim 1 or 2, wherein in the lithium precipitation step, the lithium precipitation agent is selected from one or more of sodium carbonate, sodium phosphate and sodium fluoride; preferably, the addition amount of the lithium precipitating agent is 1.2-1.5 times of the theoretical required amount of Li element in the dissolution liquid; preferably, the temperature of the lithium precipitation reaction is 85-95 ℃ and the time is 1-4 h.
9. The method for recovering the aluminum lithium element by the sintering method according to claim 1 or 2, wherein the seed precipitation step comprises:
introducing the sintering tail gas into the lithium-precipitated liquid and keeping for 0.5-2 h;
evaporating and concentrating the reacted solution after lithium precipitation at 90-100 ℃ to obtain a concentrated solution;
adding aluminum hydroxide with a seed crystal ratio of 0.05-0.2 into the concentrated solution as the seed crystal, and inducing and separating out the aluminum precipitate under the stirring state at 50-70 ℃.
10. The method for recovering the aluminum lithium element by the sintering method according to claim 9, wherein in the seed precipitation step, after the aluminum precipitation is induced to be separated out, the method further comprises the step of returning the residual seed precipitation mother liquor as part of the dilute alkali solution for leaching the sintering material.
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