CN117616140A - Method for producing pig iron aluminum slag in full-chain integrated recovery battery recovery - Google Patents
Method for producing pig iron aluminum slag in full-chain integrated recovery battery recovery Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 93
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000011084 recovery Methods 0.000 title claims abstract description 35
- 229910000805 Pig iron Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003518 caustics Substances 0.000 claims description 8
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 38
- 238000004064 recycling Methods 0.000 abstract description 20
- 239000011575 calcium Substances 0.000 abstract description 8
- 239000010413 mother solution Substances 0.000 abstract description 8
- 239000002910 solid waste Substances 0.000 abstract description 5
- 231100001261 hazardous Toxicity 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 210000000582 semen Anatomy 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- -1 cobalt-iron-aluminum Chemical compound 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000012045 crude solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 1
- 229910001811 natroalunite Inorganic materials 0.000 description 1
- 229910001813 natrojarosite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for producing pig iron aluminum slag in full chain integrated recovery battery recovery, the method comprising the steps of: (1) Mixing iron aluminum slag with water, performing pressurized water leaching to obtain water leaching slag and water leaching liquid, and washing the water leaching slag by using water to obtain a lithium-rich solution; (2) Evaporating and concentrating the lithium-rich solution, crystallizing at low temperature, carrying out solid-liquid separation to obtain sodium sulfate crystals and lithium precipitation mother liquor, mixing the lithium precipitation mother liquor with sodium carbonate, and carrying out solid-liquid separation to obtain lithium carbonate; (3) Mixing the water leaching slag with mother liquor, carrying out pressurized alkaline leaching, and carrying out solid-liquid separation to obtain alkaline leaching slag and alkaline leaching liquor; (4) Mixing alkaline leaching solution with impurity removing agent, carrying out solid-liquid separation to obtain calcium fluophosphate impurity precipitation and impurity removing refined solution, and carrying out crystallization treatment on the impurity removing refined solution to obtain aluminum hydroxide crystals and circulating mother solution. The recycling comprehensive utilization of the hazardous solid waste iron-aluminum slag is realized by carrying out pressure leaching treatment on the iron-aluminum slag generated in the battery recycling process.
Description
Technical Field
The disclosure belongs to the technical field of resource recovery, and relates to a method for producing pig iron and aluminum slag in full-chain integrated recovery battery recovery.
Background
With the continuous development of the automobile power battery industry, the cycle life of the lithium battery is limited, and a large number of power lithium batteries are out of service. Heavy metals and organic solvents in the waste lithium batteries can cause great adverse effects on the environment if not treated, and the content of metals such as nickel, cobalt, manganese, lithium and the like in the lithium batteries is far higher than the grade of primary ores. Therefore, the waste lithium batteries can be recycled at lower cost, so that considerable economic benefits can be realized, and the environmental pressure can be relieved.
The current industrial lithium battery recycling method mainly adopts a wet leaching process, discharges, disassembles, breaks and sieves waste lithium batteries, then carries out acid leaching, and then carries out impurity removal and extraction procedures after acid leaching to recycle nickel, cobalt, manganese, lithium and other products.
The iron-aluminum slag is used as a main product of the impurity removal procedure in the wet recovery of the battery, a large amount of iron-aluminum compounds in the iron-aluminum slag are not separated, a certain content of lithium elements remain in the slag, and the iron-aluminum slag is mainly used as dangerous solid waste for piling or outsourcing treatment at present, so that aluminum and lithium resources are wasted, and the unnecessary production cost is increased.
CN105506290a discloses a method for comprehensive utilization of iron-aluminum slag, which is characterized in that the iron-aluminum slag is selectively leached, and nickel, cobalt and aluminum in slag are dissolved; then adding sodium sulfide into the nickel, cobalt and aluminum leaching solution, precipitating and recovering nickel and cobalt in the solution, and obtaining an aluminum sulfate crude solution; adding an oxidant and sodium hydroxide into the aluminum sulfate crude solution to remove iron, then adding sodium sulfate in the aluminum sulfate crude solution, and preparing the solution into a stock solution for producing sodium aluminum sulfate; evaporating and crystallizing the stock solution to obtain an aluminum sodium sulfate product.
CN115896462a discloses a method for recycling nickel-containing cobalt-iron-aluminum slag resources, which belongs to the technical field of resource recycling, and comprises the steps of adding copper removal liquid into nickel-containing cobalt-iron-aluminum slag for reaction, and obtaining primary iron-washing aluminum slag and primary iron-washing aluminum slag liquid after filter pressing; adding hydrogen peroxide into the primary iron-aluminum slag washing liquid until the 1% potassium ferricyanide solution is colorless, adding a precipitator for reaction, and performing filter pressing to obtain iron-aluminum slag and iron-aluminum removing liquid; and finally, mixing the primary iron-aluminum slag, the primary iron-aluminum slag and water, adding concentrated sulfuric acid for reaction, and then adding sodium sulfite solution for reaction to obtain the iron-aluminum slag and the iron-aluminum slag liquid.
In the recycling process of the iron-aluminum slag, although part of aluminum and iron are recycled, on one hand, the method is complex in operation and cannot remove sulfate radical, and on the other hand, the iron-aluminum slag also contains a large amount of lithium, and if the lithium is not recycled, lithium resource waste can be caused.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The method is used for separating lithium from aluminum through a pressurized water leaching and alkaline leaching process, and then purifying to obtain refined lithium carbonate, aluminum hydroxide and iron hydroxide precipitates, so that the refined lithium carbonate, aluminum hydroxide and iron hydroxide precipitates can be respectively manufactured into products with economic benefits, and the cost of waste lithium battery recovery is reduced.
To achieve the purpose, the present disclosure adopts the following technical scheme:
in a first aspect, the present disclosure provides a method of producing pig iron aluminum slag in full chain integrated recovery battery recovery, the method comprising the steps of:
(1) Mixing aluminum slag generated in battery recovery with water, performing pressurized water leaching to obtain water leaching slag and water leaching liquid, and performing washing treatment on the water leaching slag by using water to obtain a lithium-rich solution;
(2) Evaporating and concentrating the lithium-rich solution obtained in the step (1), crystallizing at low temperature, carrying out solid-liquid separation to obtain sodium sulfate crystals and lithium precipitation mother liquor, mixing the lithium precipitation mother liquor with sodium carbonate, and carrying out solid-liquid separation to obtain lithium carbonate;
(3) Mixing the water leaching slag after the washing treatment in the step (1) with mother liquor, and carrying out pressurized alkaline leaching and solid-liquid separation to obtain alkaline leaching slag and alkaline leaching liquor;
(4) Mixing alkaline leaching solution with impurity removing agent, carrying out solid-liquid separation to obtain calcium fluophosphate impurity precipitation and impurity removing refined solution, and carrying out crystallization treatment on the impurity removing refined solution to obtain aluminum hydroxide crystals and circulating mother solution.
The present disclosure does not limit the operation sequence of the step (2) and the step (3), and the step (2) may be performed first or the step (3) may be performed first.
The iron-aluminum slag produced in the recovery of the battery contains a large amount of Na + 、SO 4 2- Leaching and recovering Li + The method comprises the steps of recycling the pressurized water immersion liquid of the iron-aluminum slag, extracting valuable metal lithium in the iron-aluminum slag to obtain a lithium-rich solution, and recovering and separating the valuable metal aluminum and iron in the iron-aluminum slag through pressurized alkaline immersion.
In one embodiment, the solid-liquid mass ratio of the ferro-aluminum slag and the water in the step (1) is 1 (1-5), for example: 1:1, 1:2, 1:3, 1:4, or 1:5, etc.
In one embodiment, the pressurized water is immersed at a temperature of 100 to 300 ℃, for example: 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃, etc.
In one embodiment, the pressurized water is at a pressure of 0.1 to 8.5MPa, for example: 0.1MPa, 0.4MPa, 1.3MPa, 3.5MPa, 5MPa or 8.5MPa, etc.
In one embodiment, the pressurized water is immersed for a period of time ranging from 0.5 to 3 hours, for example: 0.5h, 1h, 1.8h, 2h or 3h, etc.
In one embodiment, the liquid obtained by the washing treatment in the step (1) is mixed with water leaching solution to obtain mixed liquid, the mixed liquid is used for carrying out pressurized water leaching on the iron-aluminum slag again, and the steps are repeated for 3-4 times to obtain lithium-rich solution.
The equation for the reaction of the disclosed step (1) method is as follows:
2NaFe 3 (SO 4 ) 2 (OH) 6 (s)＝Na 2 SO 4 (aq)+4Fe(OH) 3 (s)+Fe 2 (SO 4 ) 3 (aq)。
in one embodiment, the low temperature crystallization of step (2) has a temperature <10 ℃.
In one embodiment, the resulting sodium sulfate crystals are washed and dried.
In one embodiment, the washed detergent comprises water at a temperature <10 ℃.
The reaction equation of mixing the lithium precipitation mother liquor with sodium carbonate is as follows:
2Li + +CO 3 2- ＝Li 2 CO 3 。
in one embodiment, the solid-liquid separation in step (2) is followed by a washing and drying treatment of lithium carbonate.
In one embodiment, the washed detergent comprises water at a temperature >60 ℃.
In one embodiment, the mass ratio of the water leaching residue and the mother liquor in the step (3) is (5-12): (20-50), for example: 5:20, 8:30, 9:15, 10:40, or 12:50, etc.
In one embodiment, the solute of the mother liquor comprises sodium hydroxide and aluminum hydroxide.
In one embodiment, the mother liquor has a caustic ratio of 2 to 3, for example: 2. 2.2, 2.5, 2.8 or 3, etc., the caustic ratio refers to the ratio of the amount of sodium oxide to alumina species contained in the solution.
The present disclosure provides for leaching in a pressurized manner, and aluminum leaching can be accomplished using a mother liquor with relatively low caustic.
In one embodiment, the pressurized alkaline leaching in step (3) is at a temperature of 150 to 300 ℃, for example: 150 ℃, 180 ℃, 200 ℃, 250 ℃ or 300 ℃ and the like.
In one embodiment, the pressure of the pressurized alkaline leaching is 0.1 to 8.0MPa, for example: 0.1MPa, 0.2MPa, 0.8MPa, 1.2MPa, 3.3MPa, 5.8MPa or 8.0MPa, etc.
In one embodiment, the pressurized alkaline leaching is for a time period of 1 to 4 hours, for example: 1h, 1.3h, 2h, 3h or 4h, etc.
In one embodiment, the pressure alkaline leaching is followed by cooling to below 100 ℃ and solid-liquid separation is performed while hot.
The equation for pressurized alkaline leaching in step (3) of the present disclosure is as follows:
NaAl 3 (SO 4 ) 2 (OH) 6 (s)+6NaOH(aq)＝2Na 2 SO 4 (aq)+3NaAlO 2 (aq)+6H 2 O
NaFe 3 (SO 4 ) 2 (OH) 6 (s)+3NaOH(aq)＝2Na 2 SO 4 (aq)+3Fe(OH) 3 (aq)。
in one embodiment, the alkaline leaching residue is washed with water after the solid-liquid separation in step (3), and the obtained washing liquid is mixed with the alkaline leaching solution.
In one embodiment, the impurity removing agent of step (4) comprises calcium hydroxide.
In one embodiment, the crystallization treatment comprises a cold water bath crystallization.
In one embodiment, the crystallization treatment is followed by a solid-liquid separation treatment after standing for 20 to 60 hours (for example, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, etc.).
Impurity elements such as F, P in alkaline leaching solution can be removed in the impurity removing process of the step (4), and the reaction equation of impurity removal is as follows:
2F - +Ca 2+ →CaF 2 ↓；
2PO 4 3- +3Ca 2+ →Ca 3 (PO 4 ) 2 ↓
3Ca 3 (PO 4 ) 2 +CaF 2 →3Ca 3 (PO 4 ) 2 ·CaF 2 ↓。
in one embodiment, the recycled mother liquor of step (4) is used for the pressurized alkaline leaching of step (3).
Compared with the prior art, the method has the following beneficial effects:
(1) According to the method, the hazardous solid waste iron-aluminum slag generated in the battery recycling process is subjected to pressure leaching treatment, so that the hazardous solid waste iron-aluminum slag is recycled, valuable metal lithium in the iron-aluminum slag is extracted through the pressure water leaching liquid recycling of the iron-aluminum slag, a lithium-rich solution is obtained, valuable metal aluminum in the iron-aluminum slag is recycled through pressure alkaline leaching, the valuable metal aluminum in the iron-aluminum slag can be respectively manufactured into products with economic benefits, and the recycling cost of waste lithium batteries is reduced.
(2) After the iron aluminum slag is recovered by the process, the Li leaching rate can reach more than 91 percent, and Na is extracted 2 SO 4 The recovery rate can reach more than 90 percent, the Al leaching rate can reach more than 84 percent, and Li, al elements, sodium sulfate and the like in the iron-aluminum slag can be efficiently recovered.
Other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description.
Drawings
The accompanying drawings are included to provide a further understanding of the present technology and are incorporated in and constitute a part of this specification, illustrate the technology and together with the examples of the application, and do not constitute a limitation to the technology.
Fig. 1 is a process flow diagram of a method according to an embodiment of the present disclosure.
Detailed Description
The technical scheme of the present disclosure is further described below by means of specific embodiments. It should be apparent to those skilled in the art that the examples are merely provided to aid in the understanding of the present disclosure and should not be construed as a specific limitation on the present disclosure.
Elemental content of pig iron aluminum slag produced in the recovery of the batteries used in examples and comparative examples of the present disclosure are shown in table 1:
TABLE 1
| Na content/% | S content/% | Al content/% | Li content/% |
| 7.44％ | 7.05％ | 5.02％ | 0.11％ |
Example 1
The embodiment provides a method for producing pig iron aluminum slag in full-chain integrated recovery battery recovery, a flow diagram of the method is shown in fig. 1, and the method comprises the following steps:
(1) Mixing pig iron aluminum slag produced in battery recovery with water, pulping, controlling the mass ratio of solid to liquid to be 1:1, placing the pulp into an autoclave, carrying out pressure leaching at 300 ℃ for 3 hours, filtering and separating to obtain water leaching slag and water leaching liquid after leaching, washing the water leaching slag by using 100mL of pure water to obtain liquid, mixing the liquid with the water leaching liquid, returning to the next pressure leaching step, mixing the liquid with the raw material of the pig iron aluminum slag, carrying out pressure leaching, and recycling for 3-4 times to obtain lithium-rich solution;
(2) Evaporating and concentrating the obtained lithium-rich solution, freezing (the temperature is lower than 10 ℃) for crystallization, filtering to obtain sodium sulfate crystals with lower impurity content and a lithium precipitation mother solution, washing the residual solution of the sodium sulfate crystals with a small amount of pure water with the temperature lower than 10 ℃, filtering and drying, adding sodium carbonate into the lithium precipitation mother solution, fully precipitating and filtering to obtain a lithium carbonate crude product, washing the lithium carbonate crude product with a small amount of pure water with the temperature higher than 60 ℃ to wash out residual impurities, filtering and drying to obtain refined lithium carbonate;
(3) Mixing 50g of water leaching slag with 250g of mother liquor with a caustic ratio of 3.0, putting the mixture into an autoclave for pressure leaching, setting the pressure leaching temperature to 300 ℃, leaching for 3 hours, filtering while the mixture is hot after the leaching is finished, separating to obtain alkaline leaching slag and alkaline leaching liquor, washing the alkaline leaching slag by using 50mL of pure water, and mixing the washing liquor with the alkaline leaching liquor;
(4) Adding impurity removing agent Ca (OH) into alkaline leaching solution 2 Stirring for 2h to obtain calcium fluorophosphate impurity precipitate, separating to obtain impurity-removed semen, performing cold water bath crystallization on the impurity-removed semen, standing for 48h, and filtering and separating to obtain circulating mother liquor and Al (OH) 3 And (3) crystals, wherein the circulating mother liquor can be returned to the pressurized alkaline leaching process for recycling.
Example 2
The embodiment provides a method for producing pig iron aluminum slag in full-chain integrated recovery battery recovery, a flow diagram of the method is shown in fig. 1, and the method comprises the following steps:
(1) Mixing pig iron aluminum slag produced in battery recovery with water, pulping, controlling the mass ratio of solid to liquid to be 2:1, placing the pulp into an autoclave, carrying out pressure leaching at the pressure leaching temperature of 250 ℃ for 2 hours, filtering and separating to obtain water leaching slag and water leaching liquid after leaching, washing the water leaching slag by using 100mL of pure water to obtain liquid, mixing the liquid with the water leaching liquid, returning to the next pressure leaching step, mixing the liquid with the raw material of the pig iron aluminum slag, carrying out pressure leaching, and recycling for 3-4 times to obtain lithium-rich solution;
(2) Evaporating and concentrating the obtained lithium-rich solution, freezing (the temperature is lower than 10 ℃) for crystallization, filtering to obtain sodium sulfate crystals with lower impurity content and a lithium precipitation mother solution, washing the residual solution of the sodium sulfate crystals with a small amount of pure water with the temperature lower than 10 ℃, filtering and drying, adding sodium carbonate into the lithium precipitation mother solution, fully precipitating and filtering to obtain a lithium carbonate crude product, washing the lithium carbonate crude product with a small amount of pure water with the temperature higher than 60 ℃ to wash out residual impurities, filtering and drying to obtain refined lithium carbonate;
(3) Mixing 50g of water leaching slag with 300g of mother liquor with caustic ratio of 2, putting the mixture into an autoclave for pressure leaching, setting the pressure leaching temperature to be 250 ℃, leaching for 3 hours, filtering while hot after leaching is finished when the temperature in the autoclave is reduced to below 100 ℃, separating to obtain alkaline leaching slag and alkaline leaching liquor, washing the alkaline leaching slag by using 50mL of pure water, and mixing the washing liquor with the alkaline leaching liquor;
(4) Adding impurity removing agent Ca (OH) into alkaline leaching solution 2 Stirring for 2h to obtain calcium fluorophosphate impurity precipitate, separating to obtain impurity-removed semen, performing cold water bath crystallization on the impurity-removed semen, standing for 48h, and filtering and separating to obtain circulating mother liquor and Al (OH) 3 And (3) crystals, wherein the circulating mother liquor can be returned to the pressurized alkaline leaching process for recycling.
Example 3
The embodiment provides a method for producing pig iron aluminum slag in full-chain integrated recovery battery recovery, a flow diagram of the method is shown in fig. 1, and the method comprises the following steps:
(1) Mixing pig iron aluminum slag produced in battery recovery with water, pulping, controlling the mass ratio of solid to liquid to be 1:5, placing the pulp into an autoclave, carrying out pressure leaching at the pressure leaching temperature of 100 ℃ for 3 hours, filtering and separating to obtain water leaching slag and water leaching liquid after leaching, washing the water leaching slag by using 50mL of pure water to obtain liquid, mixing the liquid with the water leaching liquid, returning to the next pressure leaching step, mixing the liquid with the raw material of the pig iron aluminum slag, carrying out pressure leaching, and recycling for 3-4 times to obtain lithium-rich solution;
(2) Evaporating and concentrating the obtained lithium-rich solution, freezing (the temperature is lower than 10 ℃) for crystallization, filtering to obtain sodium sulfate crystals with lower impurity content and a lithium precipitation mother solution, washing the residual solution of the sodium sulfate crystals with a small amount of pure water with the temperature lower than 10 ℃, filtering and drying, adding sodium carbonate into the lithium precipitation mother solution, fully precipitating and filtering to obtain a lithium carbonate crude product, washing the lithium carbonate crude product with a small amount of pure water with the temperature higher than 60 ℃ to wash out residual impurities, filtering and drying to obtain refined lithium carbonate;
(3) Mixing 120g of water leaching slag with 500g of mother liquor with a caustic ratio of 2.5, placing the mixture into an autoclave for pressure leaching, setting the pressure leaching temperature to be 150 ℃, leaching for 3 hours, filtering while the mixture is hot after the leaching is finished, separating to obtain alkaline leaching slag and alkaline leaching liquor, washing the alkaline leaching slag by using 50mL of pure water, and mixing the washing liquor with the alkaline leaching liquor;
(4) Adding impurity removing agent Ca (OH) into alkaline leaching solution 2 Stirring for 2h to obtain calcium fluorophosphate impurity precipitate, separating to obtain impurity-removed semen, performing cold water bath crystallization on the impurity-removed semen, standing for 48h, and filtering and separating to obtain circulating mother liquor and Al (OH) 3 And (3) crystals, wherein the circulating mother liquor can be returned to the pressurized alkaline leaching process for recycling.
Example 4
This example differs from example 1 only in that the temperature of the pressurized water immersion is 400 ℃, and other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the pressurized alkaline leaching temperature is 120℃and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the pressurized alkaline leaching temperature is 400 ℃, and other conditions and parameters are exactly the same as in example 1.
Comparative example 1
This comparative example provides a method of recovering pig iron aluminum slag produced in battery recovery, the method comprising the steps of:
(1) Mixing and pulping the solid waste iron-aluminum slag recovered from the battery with pure water, controlling the mass ratio of the solid to the liquid to be 1:1, carrying out water bath heating leaching on the slurry in a beaker, wherein the leaching temperature is 95 ℃, the leaching time is 3 hours, filtering and separating to obtain water leaching slag and water leaching liquid after leaching is finished, washing the water leaching slag by using 100ml of pure water, mixing the washing liquid with the water leaching liquid, and carrying out water leaching with the iron-aluminum slag raw material before returning to the next pressurized water leaching step, and recycling for 3-4 times to obtain a lithium-rich solution;
(2) Evaporating and concentrating the obtained lithium-rich solution, freezing (the temperature is lower than 10 ℃) for crystallization, and filtering to obtain sodium sulfate crystals with lower impurity content and lithium-precipitating mother liquor. Washing the sodium sulfate crystals with a small amount of pure water at a temperature below 10 ℃ to remove the residual solution, filtering and drying;
(3) Mixing 50g of water leaching slag with 250g of mother liquor with a caustic ratio of 3.0, putting the mixture into a beaker, heating in a water bath, setting the leaching temperature to 95 ℃, leaching for 3 hours, filtering while hot after leaching is finished, separating to obtain alkaline leaching slag and alkaline leaching liquor, washing 50mL of pure water with the alkaline leaching slag, and mixing the washing liquor with the alkaline leaching liquor;
(4) Adding impurity removing agent Ca (OH) into alkaline leaching solution 2 Stirring for 2h to obtain calcium fluorophosphate impurity precipitate, separating to obtain impurity-removed semen, performing cold water bath crystallization on the impurity-removed semen, standing for 48h, and filtering to obtain circulating mother liquor and crude Al (OH) 3 And (5) a crystal.
Performance test:
the leaching rate results of the respective elements in the processes of water leaching and alkaline leaching in the methods described in examples and comparative examples are shown in table 2:
TABLE 2
As can be seen from Table 2, examples 1 to 6 show that the Li leaching rate can reach more than 91% and Na is obtained after the iron-aluminum slag is recovered by the process of the present disclosure 2 SO 4 The recovery rate can reach more than 90 percent, and the Al leaching rate can be realizedMore than 84 percent, can efficiently recycle Li, al element, sodium sulfate and the like in the iron-aluminum slag, and can recycle Li and Na when the leaching temperature is higher 2 SO 4 The Al leaching rate is high, and the required water and mother liquor are less, so that experimental resources can be efficiently utilized.
By comparing the embodiment 1 with the embodiment 4, in the recycling process disclosed by the disclosure, the recycling effect can be influenced by the temperature of pressurized water leaching, the temperature of the pressurized water leaching is controlled to be 100-300 ℃, the recycling effect is good, if the temperature of the pressurized water leaching is too high, the element leaching rate is improved less, and the electric energy utilization rate is low.
As can be obtained by comparing example 1 with examples 5-6, in the recovery process disclosed in this disclosure, the temperature of pressurized alkaline leaching will affect the recovery effect, the temperature of pressurized alkaline leaching is controlled between 150-300 ℃, the recovery effect is better, if the temperature of pressurized alkaline leaching is too low, the reaction time is longer and the leaching rate of Al is lower, if the temperature of pressurized alkaline leaching is too high, the improvement of the leaching rate of elements is smaller, and the utilization rate of electric energy is lower.
By comparing the embodiment 1 with the comparative example 1, the method adopts a pressurizing mode, combines water leaching and alkaline leaching, realizes separation of lithium and aluminum, obtains hydroxide precipitation of refined lithium carbonate, aluminum hydroxide and iron through impurity removal, can respectively prepare the products with economic benefits, and reduces the recovery cost of waste lithium batteries.
Claims (16)
1. A method for producing pig iron aluminum slag in full chain integrated recovery battery recovery, the method comprising the steps of:
(1) Mixing aluminum slag generated in battery recovery with water, performing pressurized water leaching to obtain water leaching slag and water leaching liquid, and performing washing treatment on the water leaching slag by using water to obtain a lithium-rich solution;
(2) Evaporating and concentrating the lithium-rich solution obtained in the step (1), crystallizing at low temperature, carrying out solid-liquid separation to obtain sodium sulfate crystals and lithium precipitation mother liquor, mixing the lithium precipitation mother liquor with sodium carbonate, and carrying out solid-liquid separation to obtain lithium carbonate;
(3) Mixing the water leaching slag after the washing treatment in the step (1) with mother liquor, and carrying out pressurized alkaline leaching and solid-liquid separation to obtain alkaline leaching slag and alkaline leaching liquor;
(4) Mixing alkaline leaching solution with a impurity removing agent, carrying out solid-liquid separation to obtain calcium fluorophosphate impurity precipitation and impurity removing refined solution, and carrying out crystallization treatment on the impurity removing refined solution to obtain aluminum hydroxide crystals and circulating mother liquor;
wherein the operation sequence of the step (2) and the step (3) is not sequential.
2. The method of claim 1, wherein the solid-liquid mass ratio of the ferro-aluminum slag and the water in the step (1) is 1 (1-5).
3. The method of claim 1 or 2, wherein the pressurized water is immersed at a temperature of 100 to 300 ℃.
4. A process according to any one of claims 1 to 3, wherein the pressure of the pressurized water is in the range 0.1 to 8.5MPa.
5. The method of any one of claims 1-4, wherein the pressurized water is immersed for a period of time ranging from 0.5 to 3 hours.
6. The method according to any one of claims 1 to 5, wherein the liquid obtained by the washing treatment in the step (1) is mixed with water leaching solution to obtain a mixed liquid, and the mixed liquid is used for carrying out pressurized water leaching on the iron-aluminum slag again, and the steps are repeated for 3 to 4 times to obtain a lithium-rich solution.
7. The method of any one of claims 1-6, wherein the low temperature crystallization of step (2) is at a temperature <10 ℃;
optionally, washing and drying the obtained sodium sulfate crystals;
optionally, the washed detergent comprises water at a temperature <10 ℃.
8. The method according to any one of claims 1 to 7, wherein the solid-liquid separation in step (2) is followed by washing and drying of lithium carbonate;
optionally, the washed detergent comprises water at a temperature >60 ℃.
9. The method according to any one of claims 1 to 8, wherein the mass ratio of the water leaching residue to the mother liquor in the step (3) is (5-12): 20-50;
optionally, the solute of the mother liquor comprises sodium hydroxide and aluminum hydroxide;
optionally, the caustic ratio of the mother liquor is 2 to 3.
10. The process of any one of claims 1-9, wherein the pressurized alkaline leaching in step (3) is at a temperature of 150-300 ℃.
11. The method of any one of claims 1-10, wherein the pressure of the pressurized alkaline leaching is 0.1-8.0 MPa.
12. The method of any one of claims 1-11, wherein the pressurized alkaline leaching is for a time of 1-4 hours.
13. The method according to any one of claims 1 to 12, wherein the pressurized alkaline leaching is followed by cooling to below 100 ℃ and solid-liquid separation is performed while hot.
14. The process according to any one of claims 1 to 13, wherein the alkaline leaching residue is washed with water after the solid-liquid separation in step (3), and the resulting washing solution is mixed with the alkaline leaching solution.
15. The method of any one of claims 1-14, wherein the impurity removing agent of step (4) comprises calcium hydroxide;
optionally, the crystallization treatment mode comprises cold water bath crystallization;
optionally, standing for 20-60 h after the crystallization treatment, and then carrying out solid-liquid separation treatment.
16. The process of any one of claims 1-15, wherein the recycled mother liquor of step (4) is used for the pressurized alkaline leaching of step (3).
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