CN109576499A - A method of recycling lithium from battery electrode material leachate - Google Patents
A method of recycling lithium from battery electrode material leachate Download PDFInfo
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- CN109576499A CN109576499A CN201910093369.4A CN201910093369A CN109576499A CN 109576499 A CN109576499 A CN 109576499A CN 201910093369 A CN201910093369 A CN 201910093369A CN 109576499 A CN109576499 A CN 109576499A
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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
- 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
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
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- 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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Abstract
A method of recycling lithium from battery electrode material leachate, leachate of the present invention is isolated nickeliferous, cobalt and lithium the solution of waste lithium ion battery electrode material leachate.Recovery method is as follows: by leachate and the acidic phosphorus-containing extractant extraction and separation of 1:1~5 by volume, obtaining the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.4~0.6, it is to stir 0.5~3 hour in 90 DEG C or more sodium carbonate liquors, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium that the raffinate containing lithium, which is added to temperature,；Mother liquor of precipitation of ammonium is mixed with acidity containing extractant, is stirred 0.5~3 hour, it is acid containing extractant and saponification mother liquor to obtain saponification；Evaporation saponification mother liquor, cooled and filtered obtain sulfate crystal and crystalline mother solution, and crystalline mother solution is added to the recycling of the raffinate containing lithium.The method of the present invention improves the rate of recovery of lithium, and has recycled sodium sulphate, reduces cost recovery, improves the economic benefit of lithium battery recycling.
Description
Technical field
The invention belongs to from waste lithium ion battery electrode material leachate recycle lithium method, more particularly, to lithium from
The method of lithium is recycled in sub- battery ternary material leachate.
Background technique
With the rapid development of lithium ion battery, lithium ion battery captured portable consumer electronics market and
Constantly expanded to fields such as New-energy electric vehicles.China has become maximum lithium battery production, consumption in the world today and goes out
Mouth state, it is contemplated that the demand to the year two thousand twenty power lithium-ion battery is up to 125Gwh, and learies are up to 2.2Gwh, about 500,000
Ton.By 2023, learies were up to 101Gwh, and about 1,160,000 tons.In short, power battery recycling is concerning safety, pollution, resource
Problem also affects the sustainable development of new-energy automobile.The exploitation of recovery technology of spent lithium ion batteries, not only contributes to ring
Border protection, there are also biggish economic benefits.
Common anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt manganese three currently on the market
First positive electrode and LiFePO4 etc..When being recycled these old and useless batterys, generalling use the acid such as sulfuric acid, nitric acid, hydrochloric acid will
Valuable metal in electrode material leaches, and the metals such as nickel, cobalt, lithium, copper, manganese, aluminium, iron are contained in leachate.In order to which lithium is recycled,
Most of research at present is all after separating nickel, cobalt, copper, manganese, aluminium, the iron in leachate, using carbonate or calcium phosphate precipitation
Lithium.Since lithium carbonate solubility product constant is 8.15 × 10-4, in order to improve the rate of deposition of lithium, universal excessive addition sodium carbonate, but sink
Lithium in lithium mother liquor is still up to 1.5g/L or so, major impurity CO3 2-、SO4 2-、Na+Plasma is a kind of water of multielement complexity
Salt system.Sinker mother liquor system is complicated, and lithium content is relatively low in mother liquor, dry by different kinds of ions in directly use or enrichment process
It disturbs, easily introduce impurity or lithium is precipitated, the direct utility value of mother liquor is poor.How low cost carries out improving the lithium rate of recovery,
And utilize disposing mother liquor, become the target that everybody constantly pursues.Therefore, a kind of low in cost, environmental-friendly, adaptability is developed
The great meaning of technology of lithium is recycled in strong slave waste lithium ion battery electrode material leachate.
Summary of the invention
The purpose of the present invention is to provide a kind of reduction cost recovery, improve the slave applying waste lithium ionic electricity of recycling economic benefit
The method of lithium is recycled in the electrode material leachate of pond.
Leachate of the present invention is the isolated nickeliferous, cobalt of waste lithium ion battery electrode material leachate and lithium
Solution, wherein nickeliferous 2~20g/L, 2~20g/L of lithium, 2~20g/L of cobalt, aluminium < 0.01g/L, manganese < 0.01g/L, 0.01 < g/L of copper
With 0.01 < g/L of iron.
The recovery method of lithium is as follows in waste lithium ion battery electrode material of the invention:
1) by leachate and the saponification acidic phosphorus-containing extractant extraction and separation nickel cobalt of 1:1~5 by volume, the extraction containing lithium is obtained
Extraction raffinate；
2) by lithium and carbonate molar ratio 1:0.4~0.6, it is 90 DEG C or more carbonic acid that the raffinate containing lithium, which is added to temperature,
In sodium solution, stirs 0.5~3 hour, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；
3) the resulting mother liquor of precipitation of ammonium of step 2) is mixed into saponification with acidic phosphorus-containing extractant, stirs 0.5~3 hour, obtains
It is saponified acidic phosphorus-containing extractant and saponification mother liquor, is saponified acidic phosphorus-containing extractant return step 1) separation nickel cobalt；
4) evaporation step 3) resulting saponification mother liquor, cooled and filtered obtains sulfate crystal and crystalline mother solution, and crystallization is female
Liquid is added to raffinate of the step 2) containing lithium and recycles.
Step 1) the saponification acidic phosphorus-containing extractant is phosphorous for the acidity of sodium hydroxide or sodium carbonate saponification 50~90%
Extractant.
The acidic phosphorus-containing extractant is one of P204, P507 or Cyanex272 of 0.5~2mol/L of concentration or several
The kerosin of kind.
In order to reduce the rate of recovery of lithium and the warp of raising lithium battery recycling in waste lithium ion battery electrode material leachate
Ji benefit.It is to try to reduce the element composition of salt-water system according to the purification key problem in technology point of compound；The circulation of mother liquor
Using ionic species should be reduced to the greatest extent, make solution based on sulfate.The present invention is to reduce cation type, is contained in saponification acidity
When phosphorus extractant, using sodium carbonate or sodium hydroxide, anions in solution is made there was only lithium and sodium.Due to being added in precipitation process
Sodium carbonate, causes to contain CO in mother liquor of precipitation of ammonium3 2-, mother liquor of precipitation of ammonium is in evaporation and crystal process, CO3 2-Meeting and Li+Generate precipitating
It is precipitated with one piece of sodium sulphate.In order to remove the CO in mother liquor of precipitation of ammonium3 2-, mother liquor of precipitation of ammonium is used for the saponification of acidic phosphorus-containing extractant,
Chemical formula is such as: 2HL+Na2CO3→2NaL+H2O+CO2(HL is acidic phosphorus-containing extractant, and NaL is saponification acidic phosphorus-containing extractant),
It both can be except the CO in mother liquor of precipitation of ammonium3 2-, while acidic phosphorus-containing extractant saponification required sodium carbonate or hydroxide can also be saved
Sodium.
Specific implementation method
Embodiment 1
Certain leachate, wherein nickeliferous 18g/L, lithium 2g/L, cobalt 19g/L, aluminium 0.008g/L, manganese 0.006g/L, copper 0.007g/
L and iron 0.008g/L；With the 0.5mol/L P204 kerosin of 50% concentration of sodium hydroxide saponification, by volume 1:5 extraction point
From obtaining the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.4, it is 92 DEG C that the raffinate containing lithium, which is added to temperature,
In saturated sodium carbonate solution, stirs 0.5 hour, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；By mother liquor of precipitation of ammonium and concentration
0.5mol/L P204 kerosin stirs 3 hours, obtains saponification P204 kerosin and is saponified mother liquor, saponification P204 kerosene is molten
Liquid returns to separation nickel cobalt；Saponification mother liquid evaporation to lithium concentration is greater than 10g/L, cooled and filtered obtains sulfate crystal and knot
Brilliant mother liquor, crystalline mother solution are added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 95%.
Embodiment 2
Certain leachate, wherein nickeliferous 3g/L, lithium 19g/L, cobalt 3g/L, aluminium 0.003g/L, manganese 0.003g/L, copper 0.003g/L
With iron 0.003g/L；With the concentration 2mol/L P507 kerosin 1:1 extraction and separation by volume of sodium hydroxide saponification 90%,
Obtain the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.6, it is 98 DEG C, concentration that the raffinate containing lithium, which is added to temperature,
To stir 3 hours, filtering while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium in the sodium carbonate liquor of 200g/L；By mother liquor of precipitation of ammonium with it is dense
It spends 2mol/L P507 kerosin to stir 0.5 hour, obtain saponification P507 kerosin and is saponified mother liquor, be saponified P507 kerosene
Solution returns to separation nickel cobalt；Will saponification mother liquid evaporation to lithium concentration be greater than 8g/L, cooled and filtered, obtain sulfate crystal object and
Crystalline mother solution, crystalline mother solution are added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 98%.
Embodiment 3
Certain leachate, wherein nickeliferous 18g/L, lithium 2g/L, cobalt 19g/L, aluminium 0.008g/L, manganese 0.006g/L, copper 0.007g/
L and iron 0.008g/L；Body is pressed with concentration 0.5mol/L P204 and the 0.5mol/LP507 kerosin of sodium hydroxide saponification 70%
Product obtains the raffinate containing lithium than 1:2 extraction and separation；By lithium and carbonate molar ratio 1:0.5, by the raffinate containing lithium be added to
Temperature is to stir 1.5 hours in 95 DEG C of saturated sodium carbonate strength solutions, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；It will sink
Shallow lake mother liquor and concentration 0.5mol/L P204 and 0.5mol/LCyanex272 kerosin stir 2 hours, obtain saponification P204 and
It is saponified Cyanex272 kerosin and saponification mother liquor, saponification P204 and saponification Cyanex272 kerosin return to separation nickel cobalt；
Saponification mother liquid evaporation to lithium concentration is greater than 12g/L, cooled and filtered obtains sulfate crystal object and crystalline mother solution, and crystallization is female
Liquid is added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 97%.
Embodiment 4
Certain leachate, wherein nickeliferous 3g/L, lithium 19g/L, cobalt 3g/L, aluminium 0.003g/L, manganese 0.003g/L, copper 0.003g/L
With iron 0.003g/L；It is pressed with concentration 0.5mol/L P507 and the 0.5mol/LCyanex272 kerosin of sodium carbonate saponification 60%
Volume ratio 1:3 extraction and separation, obtain the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.5, the raffinate containing lithium is added
It is to stir 2 hours in 94 DEG C of saturated sodium carbonate strength solutions, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium to temperature；It will sink
Shallow lake mother liquor and concentration 0.5mol/L P507 and 0.5mol/LCyanex272 kerosin stir 1 hour, obtain saponification P507 and
It is saponified Cyanex272 kerosin and saponification mother liquor, saponification P507 and saponification Cyanex272 kerosin return to separation nickel cobalt；
Saponification mother liquid evaporation to lithium concentration is greater than 11g/L, cooled and filtered obtains sulfate crystal object and crystalline mother solution, and crystallization is female
Liquid is added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 96%.
Claims (3)
1. a kind of method for recycling lithium from battery electrode material leachate, the leachate is waste and old lithium ion battery electrode material
Expect isolated nickeliferous, cobalt and lithium the solution of leachate, it is characterized in that steps are as follows:
1) by leachate and the saponification acidic phosphorus-containing extractant extraction and separation nickel cobalt of 1:1~5 by volume, the raffinate containing lithium is obtained
Liquid；
2) by lithium and carbonate molar ratio 1:0.4~0.6, it is that 90 DEG C or more sodium carbonate are molten that the raffinate containing lithium, which is added to temperature,
In liquid, stirs 0.5~3 hour, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；
3) the resulting mother liquor of precipitation of ammonium of step 2) is mixed into saponification with acidic phosphorus-containing extractant, stirs 0.5~3 hour, is saponified
Acidic phosphorus-containing extractant and saponification mother liquor, are saponified acidic phosphorus-containing extractant return step 1) separation nickel cobalt；
4) evaporation step 3) resulting saponification mother liquor, cooled and filtered obtains sulfate crystal and crystalline mother solution, and crystalline mother solution adds
Enter the raffinate to step 2) containing lithium to recycle.
2. the method according to claim 1 for recycling lithium from battery electrode material leachate, it is characterized in that the saponification
Acidic phosphorus-containing extractant is the acidic phosphorus-containing extractant of sodium hydroxide or sodium carbonate saponification 50~90%.
3. the method according to claim 1 for recycling lithium from battery electrode material leachate, it is characterized in that the acidity
Phosphorus-contained extractant is the kerosin of one or more of P204, P507 or Cyanex272 of 0.5~2mol/L of concentration.
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| CN201910093369.4A CN109576499A (en) | 2019-01-30 | 2019-01-30 | A method of recycling lithium from battery electrode material leachate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468281A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | Valuable metal separation and recovery method in a kind of waste and old cobalt acid lithium battery |
| CN113073208A (en) * | 2021-03-29 | 2021-07-06 | 华中科技大学 | Pretreatment method of extracting agent for cobalt-nickel separation and corresponding extraction method |
| WO2022228233A1 (en) * | 2021-04-25 | 2022-11-03 | 湖南金源新材料股份有限公司 | Method for extracting and preparing battery-grade lithium carbonate from p507 raffinate, and extraction device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468281A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | Valuable metal separation and recovery method in a kind of waste and old cobalt acid lithium battery |
| CN113073208A (en) * | 2021-03-29 | 2021-07-06 | 华中科技大学 | Pretreatment method of extracting agent for cobalt-nickel separation and corresponding extraction method |
| WO2022228233A1 (en) * | 2021-04-25 | 2022-11-03 | 湖南金源新材料股份有限公司 | Method for extracting and preparing battery-grade lithium carbonate from p507 raffinate, and extraction device |
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