CN109536728A - A method of recycling nickel cobalt from battery electrode material leachate - Google Patents
A method of recycling nickel cobalt from battery electrode material leachate Download PDFInfo
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- CN109536728A CN109536728A CN201910075654.3A CN201910075654A CN109536728A CN 109536728 A CN109536728 A CN 109536728A CN 201910075654 A CN201910075654 A CN 201910075654A CN 109536728 A CN109536728 A CN 109536728A
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- cobalt
- nickel
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- lithium
- raffinate
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
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Abstract
A method of recycling nickel cobalt from battery electrode material leachate, steps are as follows: 1) leachate sodium hydroxide or sodium carbonate are adjusted pH value is 2~2.5, filters to obtain sediment and filtrate；2) the resulting filtrate of step 1) and extractant extraction and separation are obtained the raffinate of nickeliferous, cobalt and lithium, the organic phase of iron content, aluminium, manganese and copper by 1:5~1 by volume；3) 1:5~1 by volume, by the resulting raffinate of step 2) with extractant extraction and separation, obtain the raffinate containing lithium, the organic phase of nickel and cobalt containing；4) sulfuric acid solution that concentration is 0.2~3mol/L will be added in the resulting organic phase of step 3) to be stripped, obtains nickel and cobalt solution.The present invention recycles nickel cobalt from battery electrode material leachate using a kind of cheap extractant, reduces cost recovery, improves the economic benefit of lithium battery recycling.
Description
Technical field
The invention belongs to recycle the method for nickel cobalt from waste lithium ion battery electrode material leachate, more particularly, to lithium
The method of nickel cobalt is recycled in ion battery ternary material leachate.
Background technique
With the rapid development of lithium ion battery, lithium ion battery has 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.
Currently, common anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4 and nickel cobalt manganese in the market
Tertiary cathode material and LiFePO4 etc..When being recycled these old and useless batterys, it is sour to generally use sulfuric acid, nitric acid and hydrochloric acid etc.
Valuable metal in electrode material is leached, the metals such as nickel, cobalt, lithium, copper, manganese, aluminium and iron are contained in leachate.In leachate
Mixed metal ion still needs to just be able to achieve recycling using suitable purification process, purifying can be divided into isolate and purify and synthesize it is pure
Change, isolating and purifying is to be separated each metal one by one using selective precipitation or extraction etc.；Synthesizing and purifying is then that will mix
Regenerated metal synthesizes a kind of substance, to realize various metals while recycle, avoids metal separation.Currently, from solution
The extractant of extraction and recovery nickel cobalt is mainly P507, Cyanex272 etc., and P507 and Cyanex272 etc., these extractants are to nickel cobalt
Extraction and separation coefficient is big, but price is more expensive.Meanwhile abstraction impurity removal is mainly used before extraction and separation nickel cobalt, cause entirely to separate
There are a variety of extractants in the process, mutually pollution is easy between extractant.Therefore, it develops a kind of low in cost, environmental-friendly, suitable
The great meaning of technology of nickel cobalt is recycled in the slave waste lithium ion battery electrode material leachate of Ying Xingqiang.
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 nickel cobalt is recycled in the electrode material leachate of pond.
The battery electrode material leachate is the leachate that waste and old lithium ion battery is obtained by broken, sorting, leaching,
Wherein nickeliferous 5~40g/L, 3~20g/L of cobalt, 0.01~2g/L of aluminium, 0.01~20g/L of manganese, 2~10g/L of lithium, 0.1~2g/ of copper
0.1~3g/L of L, 0.1~3g/L of iron and phosphorus.
The method that nickel cobalt is recycled in slave battery electrode material leachate of the invention is as follows:
1) leachate sodium hydroxide or sodium carbonate are adjusted pH value is 2~2.5, filters to obtain sediment and filtrate；
2) the resulting filtrate of step 1) and extractant extraction and separation are obtained nickeliferous, cobalt and lithium by 1:1~5 by volume
Raffinate, the organic phase of iron content, aluminium, manganese and copper；
3) the resulting raffinate of step 2) and extractant extraction and separation are obtained the raffinate containing lithium by 1:1~5 by volume
Liquid, the organic phase of nickel and cobalt containing；
4) sulfuric acid solution that concentration is 0.2~3mol/L will be added in the resulting organic phase of step 3) to be stripped, obtains
To nickel and cobalt solution.
The extractant is the P204 kerosin for the 0.5~2mol/L of concentration being saponified with sodium hydroxide or sodium carbonate.
The saponification rate of the extractant is 10~30% or 50~90%.
The present invention is to reduce the cost recovery for recycling nickel cobalt in waste lithium ion battery electrode material leachate and improve
The economic benefit of lithium battery recycling, is not separated nickel cobalt metal using extraction one by one, recycles nickel cobalt mixing gold simultaneously
Belong to, avoids the cost consumption of metal separation.Meanwhile in order to further decrease production cost, using cheap P204 extractant
Separation of nickel and cobalt extractant P507, the Cyanex272 etc. being widely used at present are substituted, and is removed with being extracted before extraction and separation nickel cobalt
The extractant to collect widely is consistent, makes that the mutual pollution between extractant can be prevented only with a kind of extractant in entire separation process；
Separation process tune pH and saponification are all made of the alkaline matter that cation is sodium, are convenient for subsequent Sewage treatment.
Specific implementation method
Embodiment 1
Certain waste lithium ion battery electrode material leachate, wherein nickeliferous 5g/L, cobalt 20g/L, aluminium 1.9g/L, manganese 0.10g/
L, lithium 10g/L, copper 2g/L, iron 0.1g/L and phosphorus 0.2g/L；It is 2 that leachate sodium hydroxide, which is adjusted pH value, filters to obtain precipitating
Object and filtrate；By filtrate and sodium hydroxide saponification rate 12%, the extractant 1:5 extraction by volume that P204 concentration is 0.5mol/L
Separation, obtains the raffinate of nickel and cobalt containing lithium, nickel 4.95g/L in raffinate, cobalt 19.8g/L, aluminium 0.001g/L, manganese 0.001g/L,
Lithium 9.9g/L, copper 0.001g/L and iron 0.001g/L, the organic phase of iron content, aluminium, manganese and copper；By raffinate and sodium hydroxide saponification
Rate 50%, the P204 extractant 1:1 extraction and separation by volume that P204 concentration is 2mol/L, obtain the raffinate containing lithium, nickeliferous
The organic phase of cobalt；It is that the sulfuric acid solution of 1mol/L is stripped that concentration will be added in organic phase liquid, obtains nickel and cobalt solution, nickel cobalt is molten
Nickel 20g/L in liquid, cobalt 80g/L, aluminium 0.001g/L, manganese 0.001g/L, lithium 0.001g/L, copper 0.001g/L and iron 0.001g/L.
It is computed, nickel and cobalt recovery rate is all larger than 99%.
Embodiment 2
Certain waste lithium ion battery electrode material leachate, wherein nickeliferous 5g/L, cobalt 20g/L, aluminium 1.9g/L, manganese 0.10g/
L, lithium 10g/L, copper 2g/L, iron 0.1g/L and phosphorus 0.2g/L；It is 2.5 that leachate sodium hydroxide, which is adjusted pH value, filters heavy
Starch and filtrate；By filtrate and sodium carbonate saponification rate 30%, the extractant 1:1 extraction point by volume that P204 concentration is 1mol/L
From, the raffinate of nickel and cobalt containing lithium is obtained, nickel 4.92g/L in raffinate, cobalt 19.6g/L, aluminium 0.0005g/L, manganese 0.0004g/L,
Lithium 9.8g/L, copper 0.0001g/L and iron 0.0001g/L, the organic phase of iron content, aluminium, manganese and copper；By raffinate and hydroxide soda soap
Rate 85%, the P204 extractant 1:5 extraction and separation by volume that P204 concentration is 0.5mol/L, obtain the raffinate containing lithium,
The organic phase of nickel and cobalt containing；It is that the sulfuric acid solution of 2mol/L is stripped that concentration will be added in organic phase liquid, obtains nickel and cobalt solution, nickel
Nickel 26g/L in cobalt liquor, cobalt 96g/L, aluminium 0.0006g/L, manganese 0.0003g/L, lithium 0.0008g/L, copper 0.0001g/L and iron
0.0001g/L.It is computed, nickel and cobalt recovery rate is all larger than 96%.
Embodiment 3
Certain waste lithium ion battery electrode material leachate, wherein nickeliferous 38g/L, cobalt 8g/L, aluminium 0.9g/L, manganese 17.0g/
L, lithium 3g/L, copper 0.2g/L, iron 2.7g/L and phosphorus 2.8g/L；It is 2.2 that leachate sodium carbonate, which is adjusted pH value, filters to obtain precipitating
Object and filtrate；By filtrate and sodium hydroxide saponification rate 20%, the extractant 1:1 extraction point by volume that P204 concentration is 2mol/L
From, the raffinate of nickel and cobalt containing lithium is obtained, nickel 37.92g/L in raffinate, cobalt 7.6g/L, aluminium 0.002g/L, manganese 0.003g/L, lithium
2.8g/L, copper 0.001g/L and iron 0.0003g/L, the organic phase of iron content, aluminium, manganese and copper；By raffinate and sodium carbonate saponification rate
75%, P204 concentration is the P204 extractant 1:2 extraction and separation by volume of 1mol/L, obtains the raffinate containing lithium, nickel and cobalt containing
Organic phase；It is that the sulfuric acid solution of 1mol/L is stripped that concentration will be added in organic phase liquid, obtains nickel and cobalt solution, nickel and cobalt solution
Middle nickel 18g/L, cobalt 4.4g/L, aluminium 0.002g/L, manganese 0.0009g/L, lithium 0.0008g/L, copper 0.0001g/L and iron 0.0001g/
L.It is computed nickel and cobalt recovery rate and is all larger than 98%.
Claims (1)
1. a kind of method that nickel cobalt is recycled from battery electrode material leachate, it is characterized in that steps are as follows:
1) leachate sodium hydroxide or sodium carbonate are adjusted pH value is 2~2.5, filters to obtain sediment and filtrate；
2) the resulting filtrate of step 1) and extractant extraction and separation are obtained the raffinate of nickeliferous, cobalt and lithium by 1:5~1 by volume
Liquid, the organic phase of iron content, aluminium, manganese and copper；
3) 1:5~1 by volume, by the resulting raffinate of step 2) with extractant extraction and separation, obtain the raffinate containing lithium,
The organic phase of nickel and cobalt containing；
4) sulfuric acid solution that concentration is 0.2~3mol/L will be added in the resulting organic phase of step 3) to be stripped, obtains nickel
Cobalt liquor；
The extractant is the P204 kerosin for the 0.5~2mol/L of concentration being saponified with sodium hydroxide or sodium carbonate；
The saponification rate of the extractant of the step 1) is 10~30%；
The saponification rate of the extractant of the step 2) is 50~90%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862110A (en) * | 2019-11-26 | 2020-03-06 | 宁夏百川新材料有限公司 | Method for preparing ternary positive electrode material precursor by using waste lithium ion battery |
| CN111041218A (en) * | 2019-12-30 | 2020-04-21 | 荆门市格林美新材料有限公司 | Comprehensive extraction method for metals in waste lithium ion batteries |
| CN112251617A (en) * | 2020-09-30 | 2021-01-22 | 湖南金凯循环科技有限公司 | Method for recovering lithium from waste metal lithium battery |
| CN112941338A (en) * | 2019-12-11 | 2021-06-11 | 格林美（江苏）钴业股份有限公司 | Method for co-extracting and enriching nickel and cobalt in mixed solution |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108408745A (en) * | 2018-04-02 | 2018-08-17 | 方嘉城 | A kind of method that waste lithium cell prepares battery-level lithium carbonate |
| CN108517409A (en) * | 2018-04-04 | 2018-09-11 | 长沙矿冶研究院有限责任公司 | A method of recycling valuable metal from waste and old power battery anode waste material |
-
2019
- 2019-01-25 CN CN201910075654.3A patent/CN109536728A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108408745A (en) * | 2018-04-02 | 2018-08-17 | 方嘉城 | A kind of method that waste lithium cell prepares battery-level lithium carbonate |
| CN108517409A (en) * | 2018-04-04 | 2018-09-11 | 长沙矿冶研究院有限责任公司 | A method of recycling valuable metal from waste and old power battery anode waste material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862110A (en) * | 2019-11-26 | 2020-03-06 | 宁夏百川新材料有限公司 | Method for preparing ternary positive electrode material precursor by using waste lithium ion battery |
| CN112941338A (en) * | 2019-12-11 | 2021-06-11 | 格林美（江苏）钴业股份有限公司 | Method for co-extracting and enriching nickel and cobalt in mixed solution |
| CN111041218A (en) * | 2019-12-30 | 2020-04-21 | 荆门市格林美新材料有限公司 | Comprehensive extraction method for metals in waste lithium ion batteries |
| CN112251617A (en) * | 2020-09-30 | 2021-01-22 | 湖南金凯循环科技有限公司 | Method for recovering lithium from waste metal 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 |
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Application publication date: 20190329 |