CN109811133A - The method for preparing aluminium copper using waste lithium cell recycling - Google Patents
The method for preparing aluminium copper using waste lithium cell recycling Download PDFInfo
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- CN109811133A CN109811133A CN201910130974.4A CN201910130974A CN109811133A CN 109811133 A CN109811133 A CN 109811133A CN 201910130974 A CN201910130974 A CN 201910130974A CN 109811133 A CN109811133 A CN 109811133A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention provides a kind of methods for preparing aluminium copper using waste lithium cell recycling, waste lithium cell is crushed to first and is sub-elected the mixed-powder of active material powder and cupric aluminium, the mixed-powder of cupric aluminium is placed in Gravity Separation on shaking table later and goes out rich aluminium powder, copper-rich powder and active material powder, then the pellumina on rich aluminium powder surface is removed using the sulfuric acid solution that concentration is 0.1~0.3mol/L, extra acid solution is cleaned later and is dried, drying product and release agent are added into roaster according to a certain mass ratio, being warming up to 680~850 DEG C makes drying product and release agent be completely melt simultaneously held for some time t1, stirring melting product simultaneously removes surface scum, calciner temperature is adjusted to 720~760 DEG C again, and carbon tetrachloride is added in melting product, it stirs and protects Warm certain time t2, removes surface scum in whipping process, and molten aluminum is made, finally molten aluminum is cast to form aluminium copper.The method of the present invention, simple process is novel, pollutes small, product purity height.
Description
Technical field
The present invention relates to a kind of methods for preparing aluminium copper using waste lithium cell recycling.
Background technique
Environmental pollution and petroleum-based energy crises problem have pushed the development of electric car and power battery jointly.With the country
The fast development of electric car, the usage amount of power battery will be also gradually increased.But power battery has certain service life,
It needs replacing after a period of use and generates more old and useless battery, and contain metallic nickel, cobalt, manganese, aluminium etc. in old and useless battery, this
A little elements, which are not processed, then can generate larger threat to natural environment and human health, and can generate the biggish wasting of resources.It passes
The waste lithium cell of system can sort copper aluminium mixture, active material powder, diaphragm etc. after pretreatment, current way compared with
More is directly directly to sell copper aluminium mixture, such way, and recovery value is low；There are also handle to recycle by equipment
The technique of copper aluminium mixture, but it is existing recycling copper aluminium technology, copper aluminium separation costs are higher, and separate after be mingled with more nickel,
The elements such as cobalt, manganese, graphite, percentage of admixture are higher.
Summary of the invention
The present invention is intended to provide a kind of simple process, novelty, product purity are high, the utilization waste lithium cell of less pollution returns
The method that receipts prepare aluminium copper.
The present invention is realized by the following scheme:
A method of aluminium copper being prepared using waste lithium cell recycling, is carried out according to the following steps,
(a) waste lithium cell is crushed to and is sub-elected the mixed-powder of active material powder and cupric aluminium；It is usually broken
Generally comprise rough and torn, two steps of thin broken, the general nickeliferous, cobalt of active material powder, manganese, lithium, graphite powder and a small amount of copper, aluminium member
Element, the mixed-powder of cupric aluminium include copper, aluminium and a small amount of active material powder；
(b) mixed-powder for the cupric aluminium that step (a) sub-elects is placed in Gravity Separation on shaking table and goes out rich aluminium powder, copper-rich
Powder and active material powder；When specifically used, by adjusting shaking table underlying parameter, copper-rich material is sub-elected from shaking table lower left side,
Shaking table lower right side sub-elects rich aluminum material, and shaking table directly to the right sub-elects active material powder；Shaking table underlying parameter adjust comprising stroke,
Jig frequency, streamflow, feedstock concentrations etc.；
(c) the rich aluminium powder surface for using sulfuric acid solution removal step (b) that concentration is 0.1~0.3mol/L to isolate
Pellumina cleans extra acid solution later and dries, and drying product and release agent are added according to a certain mass ratio to roasting
In furnace, and by roasting furnace temperature elevation to 680~850 DEG C, the held for some time t1 after drying product and release agent are completely melt, it
Melting product is stirred afterwards and removes surface scum, then calciner temperature is adjusted to 720~760 DEG C, and is added in melting product
Enter carbon tetrachloride, stirs simultaneously held for some time t2, while removing surface scum in whipping process, molten aluminum is made, finally will
Molten aluminum casts to form aluminium copper.Roaster is typically chosen in intermediate frequency furnace.The surface scum of removal generally comprises on a small quantity for the first time
The surface scum of nickel cobalt compound and graphite etc., second of removal generally comprises solid oxide field trash and a small amount of gas inclusions.
Further, in the step (c), the additional amount of release agent is dry product quality 4~10%, carbon tetrachloride
Additional amount be melting product gross mass 4~12 ‰.
Further, the release agent is potassium chloride powder, sodium chloride powder, hexafluoro conjunction sodium aluminate powder and aluminium fluoride powder
The mixture at end, it is 43 that the potassium chloride powder, sodium chloride powder, hexafluoro, which close sodium aluminate powder and the mass ratio of aluminum fluoride powder,
~46:43~46:3~10:2~5.
Further, in the step (c), soaking time t1 is 10~20min, and soaking time t2 is 25~45min.
Further, 10~20min is first stood before molten aluminum casting.
The method for preparing aluminium copper using waste lithium cell recycling of the invention, simple process, novelty, production efficiency
Fastly, recycling alloy product purity is high, up to 99% or more, low energy consumption, highly-safe, and pollution is small, useless suitable for large scale processing
Old lithium pond.
Specific embodiment
The invention will be further described with reference to embodiments, but the invention is not limited to the statements of embodiment.
Embodiment 1
A method of aluminium copper being prepared using waste lithium cell recycling, is carried out according to the following steps,
(a) waste lithium cell is crushed to and is sub-elected the mixed-powder of active material powder and cupric aluminium；It is broken to include
Rough and torn, two steps of thin broken, the general nickeliferous, cobalt of active material powder, manganese, lithium, graphite powder and a small amount of copper, aluminium element, cupric
The mixed-powder of aluminium includes copper, aluminium and a small amount of active material powder；
(b) mixed-powder for the cupric aluminium that step (a) sub-elects is placed on shaking table and carries out Gravity Separation, shaken by adjusting
Bed underlying parameter sub-elects copper-rich material from shaking table lower left side, and shaking table lower right side sub-elects rich aluminum material, the sorting of shaking table directly to the right
Active material powder out；
(c) oxidation on the rich aluminium powder surface that step (b) is isolated is removed using the sulfuric acid solution that concentration is 0.1mol/L
Aluminium film is cleaned extra hydrochloric acid solution and is dried using clear water later, and drying product is placed in crucible, drying is added into crucible
The release agent of product quality 4%, release agent are potassium chloride powder, sodium chloride powder, hexafluoro conjunction sodium aluminate powder and aluminium fluoride powder
The mixture at end, it is 45:45 that potassium chloride powder, sodium chloride powder, hexafluoro, which close sodium aluminate powder and the mass ratio of aluminum fluoride powder:
Crucible equipped with drying product and release agent is placed in intermediate frequency furnace, and intermediate frequency furnace is warming up to 680 DEG C by 7:3, in drying product
10min is kept the temperature after being completely melt with release agent, stirring melting product later and removing surface includes a small amount of nickel cobalt compound and stone
The dross of ink etc., then intermediate frequency furnace temperature is adjusted to 720 DEG C, and the four of melting product gross mass 12 ‰ is added in melting product
Chlorination carbon stirs and keeps the temperature 25min, while removal includes solid oxide field trash and a small amount of gas inclusions in whipping process
Molten aluminum is made in surface scum, finally casts molten aluminum to form aluminium copper after molten aluminum stands 10min.
Product aluminium copper is detected, each component element mass content is as shown in table 1.
Each component element mass content of 1 aluminium copper of table
| Element term | Al | Cu |
| Mass content (%) | 97.01 | 2.98 |
Embodiment 2
A method of aluminium copper being prepared using waste lithium cell recycling, is carried out according to the following steps,
(a) waste lithium cell is crushed to and is sub-elected the mixed-powder of active material powder and cupric aluminium；It is broken to include
Rough and torn, two steps of thin broken, the general nickeliferous, cobalt of active material powder, manganese, lithium, graphite powder and a small amount of copper, aluminium element, cupric
The mixed-powder of aluminium includes copper, aluminium and a small amount of active material powder；
(b) mixed-powder for the cupric aluminium that step (a) sub-elects is placed on shaking table and carries out Gravity Separation, shaken by adjusting
Bed underlying parameter sub-elects copper-rich material from shaking table lower left side, and shaking table lower right side sub-elects rich aluminum material, the sorting of shaking table directly to the right
Active material powder out；
(c) oxidation on the rich aluminium powder surface that step (b) is isolated is removed using the sulfuric acid solution that concentration is 0.2mol/L
Aluminium film is cleaned extra sulfuric acid solution and is dried using clear water later, and drying product is placed in crucible, drying is added into crucible
The release agent of product quality 8%, release agent are potassium chloride powder, sodium chloride powder, hexafluoro conjunction sodium aluminate powder and aluminium fluoride powder
The mixture at end, it is 43:43 that potassium chloride powder, sodium chloride powder, hexafluoro, which close sodium aluminate powder and the mass ratio of aluminum fluoride powder:
Crucible equipped with drying product and release agent is placed in intermediate frequency furnace, and intermediate frequency furnace is warming up to 750 DEG C by 9:5, in drying product
15min is kept the temperature after being completely melt with release agent, stirring melting product later and removing surface includes a small amount of nickel cobalt compound and stone
The dross of ink etc., then intermediate frequency furnace temperature is adjusted to 740 DEG C, and the four of melting product gross mass 8 ‰ is added in melting product
Chlorination carbon stirs and keeps the temperature 35min, while removal includes solid oxide field trash and a small amount of gas inclusions in whipping process
Molten aluminum is made in surface scum, finally casts molten aluminum to form aluminium copper after molten aluminum stands 15min.
Product aluminium copper is detected, each component element mass content is as shown in table 2.
Each component element mass content of 2 aluminium copper of table
| Element term | Al | Cu |
| Mass content (%) | 96.84 | 3.14 |
Embodiment 3
A method of aluminium copper being prepared using waste lithium cell recycling, is carried out according to the following steps,
(a) waste lithium cell is crushed to and is sub-elected the mixed-powder of active material powder and cupric aluminium；It is broken to include
Rough and torn, two steps of thin broken, the general nickeliferous, cobalt of active material powder, manganese, lithium, graphite powder and a small amount of copper, aluminium element, cupric
The mixed-powder of aluminium includes copper, aluminium and a small amount of active material powder；
(b) mixed-powder for the cupric aluminium that step (a) sub-elects is placed on shaking table and carries out Gravity Separation, shaken by adjusting
Bed underlying parameter sub-elects copper-rich material from shaking table lower left side, and shaking table lower right side sub-elects rich aluminum material, the sorting of shaking table directly to the right
Active material powder out；
(c) oxidation on the rich aluminium powder surface that step (b) is isolated is removed using the sulfuric acid solution that concentration is 0.3mol/L
Aluminium film is cleaned extra hydrochloric acid solution and is dried using clear water later, and drying product is placed in crucible, drying is added into crucible
The release agent of product quality 12%, release agent are potassium chloride powder, sodium chloride powder, hexafluoro conjunction sodium aluminate powder and aluminium fluoride powder
The mixture at end, it is 46:46 that potassium chloride powder, sodium chloride powder, hexafluoro, which close sodium aluminate powder and the mass ratio of aluminum fluoride powder:
Crucible equipped with drying product and release agent is placed in intermediate frequency furnace, and intermediate frequency furnace is warming up to 850 DEG C by 4:4, in drying product
20min is kept the temperature after being completely melt with release agent, stirring melting product later and removing includes a small amount of nickel cobalt compound and graphite etc.
Surface scum, then intermediate frequency furnace temperature is adjusted to 760 DEG C, and the four of melting product gross mass 4 ‰ is added in melting product
Chlorination carbon stirs and keeps the temperature 45min, while removal includes solid oxide field trash and a small amount of gas inclusions in whipping process
Molten aluminum is made in surface scum, finally casts molten aluminum to form aluminium copper after molten aluminum stands 20min.
Product aluminium copper is detected, each component element mass content is as shown in table 3.
Each component element mass content of 3 aluminium copper of table
| Element term | Al | Cu |
| Mass content (%) | 96.34 | 3.65 |
Claims (5)
1. a kind of method for preparing aluminium copper using waste lithium cell recycling, it is characterised in that: it carries out according to the following steps,
(a) waste lithium cell is crushed to and is sub-elected the mixed-powder of active material powder and cupric aluminium；
(b) mixed-powder for the cupric aluminium that step (a) sub-elects is placed in Gravity Separation on shaking table and goes out rich aluminium powder, copper-rich powder
With active material powder；
(c) oxidation on the rich aluminium powder surface that step (b) is isolated is removed using the sulfuric acid solution that concentration is 0.1~0.3mol/L
Aluminium film is cleaned extra acid solution later and is dried, and drying product and release agent are added into roaster according to a certain mass ratio,
And by roasting furnace temperature elevation to 680~850 DEG C, the held for some time t1 after drying product and release agent are completely melt is stirred later
It mixes melting product and removes surface scum, then calciner temperature is adjusted to 720~760 DEG C, and four are added in melting product
Chlorination carbon stirs simultaneously held for some time t2, while removing surface scum in whipping process, molten aluminum is made, finally by molten aluminum
Casting forms aluminium copper.
2. the method for preparing aluminium copper using waste lithium cell recycling as described in claim 1, it is characterised in that: the step
Suddenly in (c), the additional amount of release agent is dry product quality 4~10%, and the additional amount of carbon tetrachloride is the total matter of melting product
4~the 12 ‰ of amount.
3. the method for preparing aluminium copper using waste lithium cell recycling as described in claim 1, it is characterised in that: described point
From the mixture that agent is potassium chloride powder, sodium chloride powder, hexafluoro conjunction sodium aluminate powder and aluminum fluoride powder, the potassium chloride powder
End, sodium chloride powder, hexafluoro close the mass ratio of sodium aluminate powder and aluminum fluoride powder as 43~46:43~46:3~10:2~5.
4. the method for preparing aluminium copper using waste lithium cell recycling as described in claims 1 to 3 is any, feature exist
In: in the step (c), soaking time t1 is 10~20min, and soaking time t2 is 25~45min.
5. the method for preparing aluminium copper using waste lithium cell recycling as described in claims 1 to 3 is any, feature exist
In: in the preceding first 10~20min of standing of molten aluminum casting.
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| CN201910130974.4A CN109811133B (en) | 2019-02-20 | 2019-02-20 | Method for preparing aluminum-copper alloy by recycling waste lithium batteries |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020194A (en) * | 2019-11-16 | 2020-04-17 | 银隆新能源股份有限公司 | Method for synthesizing titanium-aluminum alloy from waste lithium titanate anode and cathode powder |
| CN112458323A (en) * | 2020-10-27 | 2021-03-09 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-based alloy by recycling waste nickel-hydrogen battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101871052A (en) * | 2010-06-28 | 2010-10-27 | 江阴新仁科技有限公司 | Method for purifying aluminum and aluminum alloy melt |
| CN104577247A (en) * | 2015-01-06 | 2015-04-29 | 陈静 | Process for recovering cobalt chloride from waste lithium ion battery |
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2019
- 2019-02-20 CN CN201910130974.4A patent/CN109811133B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101871052A (en) * | 2010-06-28 | 2010-10-27 | 江阴新仁科技有限公司 | Method for purifying aluminum and aluminum alloy melt |
| CN104577247A (en) * | 2015-01-06 | 2015-04-29 | 陈静 | Process for recovering cobalt chloride from waste lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020194A (en) * | 2019-11-16 | 2020-04-17 | 银隆新能源股份有限公司 | Method for synthesizing titanium-aluminum alloy from waste lithium titanate anode and cathode powder |
| CN111020194B (en) * | 2019-11-16 | 2023-10-13 | 银隆新能源股份有限公司 | Method for synthesizing titanium-aluminum alloy from waste lithium titanate anode and cathode powder |
| CN112458323A (en) * | 2020-10-27 | 2021-03-09 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-based alloy by recycling waste nickel-hydrogen battery |
| CN112458323B (en) * | 2020-10-27 | 2021-11-16 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-based alloy by recycling waste nickel-hydrogen battery |
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