CN115896461A - Method for recovering waste lithium battery by ammonia leaching of lithium - Google Patents
Method for recovering waste lithium battery by ammonia leaching of lithium Download PDFInfo
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- CN115896461A CN115896461A CN202211655110.2A CN202211655110A CN115896461A CN 115896461 A CN115896461 A CN 115896461A CN 202211655110 A CN202211655110 A CN 202211655110A CN 115896461 A CN115896461 A CN 115896461A
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- sodium nitrite
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002386 leaching Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 12
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000011888 foil Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000007654 immersion Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 238000000197 pyrolysis Methods 0.000 abstract description 7
- 238000003795 desorption Methods 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
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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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- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering waste lithium batteries by ammonia leaching lithium, which comprises the steps of crushing the waste lithium batteries, drying the crushed waste lithium batteries to remove electrolyte, mixing and heating the crushed waste lithium batteries with sodium nitrite, dropping anode powder, adding ammonia water to quickly dissolve sodium salt, screening to obtain copper-aluminum foil and slurry, soaking the slurry, adding calcium nitrate to obtain graphite slag and ammonia leaching solution, performing ammonia evaporation treatment to obtain nickel-cobalt hydroxide and lithium-containing solution, introducing carbon dioxide to precipitate lithium, and performing evaporation concentration on the sodium salt solution to obtain sodium nitrite. The invention adopts the combined treatment of molten salt pyrolysis desorption, ammonia extraction of lithium and ammonia evaporation precipitation to recover and obtain high-value copper-aluminum foil, lithium carbonate and crude nickel cobalt hydroxide, and the regenerated sodium nitrite is continuously used as the molten salt.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for recovering waste lithium batteries by ammonia leaching of lithium.
Background
With the rapid update of electronic products and the rapid development of power automobiles, more and more waste lithium ion batteries are generated. In addition, the waste lithium ion batteries contain abundant valuable metals and can be used as important secondary resources, so that the recycling of the waste lithium ion batteries becomes a global focus.
The leaching of the battery powder refers to that the obtained positive electrode active material powder is converted into a water-soluble ion state from an oxide state by a hydrometallurgical method to obtain enriched metal ions (Li) + ，Ni 2+ ，Co 2+ And Mn 2+ Etc.) of the leaching solution. Wherein, the leaching process is a key step for recovering valuable metal elements in the waste lithium ion battery through the whole hydrometallurgy. In combination with the related literature reports, the leaching of the anode powder can be divided into inorganic acid leaching, organic acid leaching, ammonia leaching and biological leaching according to different leaching agents and leaching methods. In addition, the leaching process of the valuable metal elements can be obviously strengthened by adopting auxiliary measures such as mechanochemical methods, ultrasound and electric fields.
The principles of mineral acids, organic acids and bioleaching are based on the reaction between hydrogen ions and the active powder of the positive electrode in an acidic medium. The concentration of the residual acid in the leachate obtained after the acid leaching treatment is often high, and for the recovery of the precursor, the pH of the complete precipitation of nickel, cobalt and manganese hydroxides is above 10, so that a large amount of alkali is required to neutralize the residual acid in the leachate, which causes additional cost. Unlike the leaching methods described above, ammonia leaching is based on the complexation of the metal ions with ammonia ions in a strongly alkaline environment. The ammonia leaching process avoids the problem of high concentration of residual acid in the leachate obtained in the acid leaching process, and the high-efficiency leaching of Co and Ni can be realized by adjusting the composition of a leaching agent, while Mn and Al are basically not leached. However, there have been few studies on the treatment of the subsequent leachate of the ammonia leaching process.
In addition, in the recovery process of battery powder, a pyrolysis pretreatment process is usually adopted to remove the binder, so that black powder falls off, the decomposition of the binder needs higher temperature, otherwise, the binder can be stripped incompletely to cause black powder loss, but higher pyrolysis temperature has greater safety risk, if local combustion reaction is severe, thermit reaction causes instantaneous temperature to rise rapidly, and high-temperature pyrolysis can oxidize copper and aluminum, partially oxidized copper and aluminum can enter the battery powder, the cost of subsequent purification is increased, oxygen-free pyrolysis is carried out by introducing inert gas to improve the oxidation condition of copper and aluminum, but the complete sealing of the current equipment is difficult to realize, and the copper and aluminum are still partially oxidized.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a method for recovering waste lithium batteries by ammonia leaching of lithium, which comprises the steps of enabling positive and negative electrode powder to fall off by low-temperature molten salt co-heating to obtain complete copper-aluminum foil, further performing ammonia leaching, and recovering transition metal elements.
According to one aspect of the invention, the method for recovering the waste lithium battery by ammonia leaching lithium is provided, and comprises the following steps:
s1: discharging, disassembling and crushing the waste lithium ion battery, and heating and drying the obtained crushed material to obtain a dried material;
s2: mixing the dried material with sodium nitrite, heating to 280-320 ℃ for reaction, adding ammonia water after the reaction is finished, and screening the obtained mixed material to obtain copper-aluminum foil and slurry;
s3: adding calcium nitrate into the slurry, heating for reaction, and performing solid-liquid separation after the reaction is finished to obtain graphite slag and ammonia immersion liquid;
s4: heating the ammonia immersion liquid to evaporate ammonia, and performing solid-liquid separation to obtain rough nickel cobalt hydroxide and a lithium-containing solution;
s5: and introducing carbon dioxide into the lithium-containing solution for lithium precipitation reaction, performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution, adding nitrous acid into the sodium salt solution to adjust the pH value, and performing evaporation concentration to obtain sodium nitrite crystals.
In some embodiments of the invention, in step S1, the size of the crushed material is 5cm or less.
In some embodiments of the present invention, in step S1, the waste lithium ion battery is at least one of a ternary lithium ion battery, a lithium cobalt acid battery or a lithium nickel acid battery.
In some embodiments of the present invention, in step S1, the temperature for heating and drying is 180-200 ℃. Further, the heating and drying time is 1-2h. The purpose of the heat drying is to remove the electrolyte.
In some embodiments of the present invention, in step S2, the mass ratio of the drying material to the sodium nitrite is 1: (1.5-2.0).
In some embodiments of the invention, in step S2, the reaction time is 1-2h.
In some embodiments of the invention, in step S2, the sieve has a mesh size of 2 to 3mm.
In some embodiments of the present invention, in step S2, the solid-to-liquid ratio of the reacted material to the ammonia water is 1g: (5-10) mL, and the concentration of the ammonia water is 4-10mol/L.
In some embodiments of the invention, in step S3, the amount of the calcium nitrate added is 2% to 5% of the mass of the oven dry material.
In some embodiments of the present invention, in step S3, the temperature of the heating reaction is 40 to 60 ℃, and the time of the heating reaction is 8 to 12 hours.
In some embodiments of the invention, in step S4, the temperature of the heated ammonia still ranges from 70 to 90 ℃.
In some embodiments of the invention, in step S4, the ammonia is distilled by heating until the ammonia concentration in the ammonia leach solution is less than 10mg/L.
In some embodiments of the invention, in step S5, the pH is 8 to 9.
According to a preferred embodiment of the invention, at least the following advantages are achieved:
1. in the invention, aiming at the problems that the waste lithium ion battery is easy to have potential safety hazards at a higher pyrolysis temperature, the copper and aluminum are oxidized in a large area and the residual acid amount in the acid leaching process is large, the combined treatment of fused salt pyrolysis desorption, ammonia leaching lithium and ammonia evaporation precipitation is adopted, the high-value copper-aluminum foil, lithium carbonate and crude nickel cobalt hydroxide (MHP) are recovered, and sodium nitrite is regenerated to be continuously used as the fused salt.
2. Firstly, crushing waste lithium batteries, drying the crushed waste lithium batteries to remove electrolyte, mixing the crushed waste lithium batteries with sodium nitrite, and then heating the mixture, wherein the sodium nitrite has oxidability and reducibility and can have stronger reducibility and oxidability in a molten state, and when the sodium nitrite is molten, a binder on a positive plate is also molten and is oxidized and decomposed by the sodium nitrite to enable positive powder to fall off, and the sodium nitrite also has certain reducibility and can further react with the positive powder, so that the subsequent leaching process is facilitated, the ammonia leaching efficiency is improved, and the main reaction formula is as follows;
NaNO 2 +2LiCoO 2 →NaNO 3 +2CoO+Li 2 O
the sodium salt can be quickly dissolved by ammonia water, and the mixture is sieved to obtain complete copper-aluminum foil;
further soaking to dissolve nickel and cobalt, adding calcium nitrate to precipitate fluorine ions and phosphate ions, avoiding the combination of the fluorine ions and the phosphate ions with lithium ions to generate precipitates, and reducing the yield of lithium, wherein the main reaction formula is as follows;
6NH 3 ·H 2 O+CoO→[Co(NH 3 ) 6 ] 2+ +2OH - +5H 2 O
finally, ammonia evaporation treatment is carried out, and along with the reduction of the ammonia concentration, the nickel cobalt gradually forms precipitates to obtain rough nickel cobalt hydroxide; meanwhile, the sodium nitrate has stronger oxidizability and is reduced by ammonia water, so that only Li, na and NO exist in the solution 2 - Ammonia water, carbon dioxide is introduced, lithium carbonate is precipitated, nitrous acid is added to adjust the pH value,evaporating and concentrating to obtain the recovered sodium nitrite which can be reused as molten salt for desorption.
3. Compared with other molten salt desorption modes, the sodium nitrite is beneficial to further reduction of the anode material, so that the leaching efficiency is improved, and meanwhile, as the sodium nitrate has oxidability and is difficult to act with the anode material, the generated sodium nitrate is consumed under the action of ammonia water, the ammonia water is used as a leaching agent and a reducing agent, so that the problem that a large amount of sodium nitrate is remained in the recovered sodium nitrite is solved, and the recovered sodium nitrite can be directly used for molten salt desorption.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
A method for recovering waste lithium batteries by ammonia leaching of lithium refers to FIG. 1, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 180 ℃, drying for 2h, and removing the electrolyte to obtain a dried material;
step 3, mixing the drying material with sodium nitrite according to the mass ratio of 1.5, heating to 310 ℃, and keeping the temperature for 1h;
step 4, adding the mixture into 10mol/L ammonia water according to the solid-to-liquid ratio of 1g to 5mL, and screening the mixture through a screen with the aperture of 0.25mm to obtain a copper-aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 2% of the mass of the dried material into the slurry, heating the slurry to 40 ℃, and continuing for 12 hours;
step 6, carrying out filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 70 ℃, condensing generated gas through a condenser to obtain ammonia water, and discharging generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, carrying out solid-liquid separation to obtain crude nickel cobalt hydroxide and a lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitate is generated, and performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH value to 8-9, and recovering to obtain sodium nitrite crystals after evaporation concentration.
Example 2
A method for recovering waste lithium batteries by ammonia leaching of lithium comprises the following specific processes:
step 1, discharging and disassembling a waste lithium cobaltate battery, and crushing the waste lithium cobaltate battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 190 ℃, drying for 1.5h, and removing the electrolyte to obtain a dried material;
step 3, mixing the drying material with sodium nitrite according to the mass ratio of 1.8, heating to 300 ℃, and keeping the temperature for 1.5 hours;
step 4, adding the mixture into 7mol/L ammonia water according to the solid-liquid ratio of 1g to 8mL, and screening the mixture through a screen with the aperture of 0.25mm to obtain copper-aluminum foil and slurry;
step 5, adding calcium nitrate with the mass of 4% of that of the dried material into the slurry, heating the slurry to 50 ℃, and continuing for 10 hours;
step 6, carrying out filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 80 ℃, condensing generated gas through a condenser to obtain ammonia water, and discharging generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, carrying out solid-liquid separation to obtain rough nickel cobalt hydroxide and a lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitate is generated, and performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH value to 8-9, and recovering to obtain sodium nitrite crystals after evaporation and concentration.
Example 3
A method for recovering waste lithium batteries by ammonia leaching of lithium comprises the following specific processes:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 200 ℃, drying for 1h, and removing the electrolyte to obtain a dried material;
step 3, mixing the dried material with sodium nitrite according to the mass ratio of 1;
step 4, adding the mixture into 4mol/L ammonia water according to the solid-liquid ratio of 1g to 10mL, and screening the mixture through a screen with the aperture of 0.25mm to obtain copper-aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 5 percent of the mass of the dried material into the slurry, heating the slurry to 60 ℃, and continuing for 8 hours;
step 6, carrying out filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 90 ℃, condensing generated gas through a condenser to obtain ammonia water, and discharging generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, carrying out solid-liquid separation to obtain crude nickel cobalt hydroxide and a lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitate is generated, and performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH value to 8-9, and recovering to obtain sodium nitrite crystals after evaporation concentration.
Comparative example 1
The method for recycling the waste lithium batteries by ammonia leaching of lithium is different from the method in the embodiment 1 in that the molten salt in the step 3 is sodium nitrate, and the molten salt is separated by centrifugation while the molten salt is hot, and the specific process comprises the following steps:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 180 ℃, drying for 2h, and removing the electrolyte to obtain a dried material;
step 3, mixing the dried material and sodium nitrate according to a mass ratio of 1.5, heating to 310 ℃, preserving heat for 1h, and centrifuging to separate out molten salt at the temperature to obtain a solid material (preventing the sodium nitrate from consuming a large amount of ammonia water);
step 4, adding the solid material into 10mol/L ammonia water according to the solid-liquid ratio of 1g;
step 5, adding calcium nitrate with the mass being 2% of that of the dried material into the slurry, heating the slurry to 40 ℃, and keeping for 12 hours;
step 6, carrying out filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 70 ℃, condensing generated gas through a condenser to obtain ammonia water, and discharging generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, carrying out solid-liquid separation to obtain crude nickel cobalt hydroxide and a lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitate is generated, and performing solid-liquid separation to obtain lithium carbonate and wastewater;
and step 10, adding nitrous acid into the wastewater to adjust the pH value to 8-9, and evaporating and concentrating to obtain sodium salt crystals.
Comparative example 2
The method for recovering the waste lithium batteries by ammonia leaching lithium is different from the method in the embodiment 3 in that the ammonia water is replaced by hydrochloric acid in the step 4, and the specific process comprises the following steps:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed materials to 200 ℃, drying for 1h, and removing the electrolyte to obtain dried materials;
step 3, mixing the dried material with sodium nitrite according to the mass ratio of 1;
step 4, adding the mixture into 4mol/L hydrochloric acid according to the solid-to-liquid ratio of 1g to 10mL, and screening the mixture through a screen with the aperture of 0.25mm to obtain copper-aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 5 percent of the mass of the dried material into the slurry, heating the slurry to 60 ℃, and continuing for 8 hours;
step 6, carrying out filter pressing on the slurry to obtain graphite slag and pickle liquor;
step 7, adding sodium hydroxide into the pickle liquor to adjust the pH value to 10.5-11.0;
step 8, carrying out solid-liquid separation to obtain crude nickel cobalt hydroxide and a lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitate is generated, and performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution;
and step 10, evaporating and concentrating the sodium salt solution, and recovering to obtain sodium salt crystals.
The graphite slag, copper-aluminum foil and sodium salt crystals of the examples and comparative examples were examined, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the graphite slag of comparative example 1 has a high nickel-cobalt content, which indicates that the ammonia leaching rate is low, a large amount of nickel-cobalt remains, and sodium nitrate does not play a role in promoting leaching; comparative example 2 adopts acid leaching, a large amount of sodium salt is introduced, and nitrite ions are easily decomposed under strong acid, so the content of sodium nitrite in the recovered sodium salt crystal is low.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for recovering waste lithium batteries by ammonia leaching of lithium is characterized by comprising the following steps:
s1: discharging, disassembling and crushing the waste lithium ion battery, and heating and drying the obtained crushed material to obtain a dried material;
s2: mixing the dried material with sodium nitrite, heating to 280-320 ℃ for reaction, adding ammonia water after the reaction is finished, and screening the obtained mixed material to obtain copper-aluminum foil and slurry;
s3: adding calcium nitrate into the slurry, heating for reaction, and carrying out solid-liquid separation after the reaction is finished to obtain graphite slag and ammonia immersion liquid;
s4: heating the ammonia immersion liquid to evaporate ammonia, and performing solid-liquid separation to obtain rough nickel cobalt hydroxide and a lithium-containing solution;
s5: and introducing carbon dioxide into the lithium-containing solution for lithium precipitation reaction, performing solid-liquid separation to obtain lithium carbonate and a sodium salt solution, adding nitrous acid into the sodium salt solution to adjust the pH value, and performing evaporation concentration to obtain sodium nitrite crystals.
2. The method according to claim 1, wherein in step S1, the particle size of the crushed material is less than or equal to 5cm.
3. The method according to claim 1, wherein in step S1, the waste lithium ion battery is at least one of a ternary lithium ion battery, a lithium cobalt acid battery or a lithium nickel acid battery.
4. The method according to claim 1, wherein the temperature of the heat drying in step S1 is 180-200 ℃.
5. The method according to claim 1, wherein in step S2, the mass ratio of the drying material to the sodium nitrite is 1: (1.5-2.0).
6. The method according to claim 1, wherein in step S2, the solid-to-liquid ratio of the reacted material to the ammonia water is 1g: (5-10) mL, wherein the concentration of the ammonia water is 4-10mol/L.
7. The method according to claim 1, characterized in that in the step S3, the calcium nitrate is added in an amount of 2-5% by mass of the drying material.
8. The method according to claim 1, wherein in step S3, the temperature of the heating reaction is 40-60 ℃, and the time of the heating reaction is 8-12h.
9. The method according to claim 1, wherein the temperature of the heated ammonia distillation in step S4 is 70-90 ℃.
10. The method according to claim 1, wherein the pH is 8 to 9 in step S5.
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| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| JP2018040035A (en) * | 2016-09-07 | 2018-03-15 | Ｊｘ金属株式会社 | Process for treating lithium-ion battery scrap |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN111690812A (en) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | Recovery method of waste ternary lithium battery |
| CN115058605A (en) * | 2022-06-29 | 2022-09-16 | 广东邦普循环科技有限公司 | Method for recovering waste lithium battery material |
| CN115161483A (en) * | 2022-07-05 | 2022-10-11 | 广西师范大学 | Method for fully recycling waste lithium ion batteries and realizing metal separation |
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| JP2018040035A (en) * | 2016-09-07 | 2018-03-15 | Ｊｘ金属株式会社 | Process for treating lithium-ion battery scrap |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN111690812A (en) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | Recovery method of waste ternary lithium battery |
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