CN109449523A - A kind of comprehensive recovering process of waste and old lithium ion battery - Google Patents
A kind of comprehensive recovering process of waste and old lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- C22B47/00—Obtaining manganese
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- 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
- C22B7/007—Wet processes by acid 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
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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
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Abstract
The present invention provides a kind of waste and old lithium ion battery comprehensive recovering process, comprising: leaches ternary waste lithium cell battery core powder for the first time with sulfuric acid and potassium permanganate, obtains the first leachate and the first leached mud；With sodium carbonate to the first leachate sinker, lithium carbonate is obtained；The first leached mud is leached with hydrogen peroxide and sulfuric acid selective reduction, obtains the second leachate and the second leached mud；The pH to 4.2-4.5 for adjusting the second leachate extracts the second leachate with P204, obtains P204 raffinate and P204 load organic phases；P204 load organic phases are stripped with sulfuric acid, manganese sulfate is made in evaporative crystallization；The pH value of P204 raffinate is adjusted to 4.5-5, P204 raffinate is extracted with C272, obtains C272 extract liquor and C272 load organic phases；Cobalt sulfate solution is obtained to C727 load organic oppositing back-extraction with sulfuric acid, battery grade cobalt sulfate is made in evaporative crystallization；The pH value for adjusting C272 raffinate is 5-5.5, extracts to obtain P507 load organic phases with P507 to C272 extract liquor, P507 load organic phases are stripped to obtain nickel sulfate solution through sulfuric acid, and evaporative crystallization obtains nickel sulfate.
Description
Technical field
The invention belongs to waste and old lithium ion battery comprehensive recovering process, and it is comprehensive to be more particularly to a kind of waste and old lithium ion battery
Recovery method.
Background technique
Cobaltous sulfate is mainly used for lithium battery, is in addition also used to plating, ceramic glaze and paint drier, production face containing cobalt
Material, catalyst, analytical reagent, feed addictive, tire adhesive and other cobalt products；Nickel sulfate is mainly used for lithium battery, electricity
Plating and catalyst industry；Lithium carbonate is mainly used for lithium battery, is also used to prepare catalyst, semiconductor, ceramics, the electricity of chemical reaction
Depending on, medicine and atomic energy industry.
In recent years, under the support of national policy, new energy industry is developed rapidly, but the following waste and old lithium
Ion battery is scrapped also will be more and more, containing there are many toxic organic solvents and rare metal in waste and old lithium ion battery, if
It is not disposed, environment will be caused great harm, so waste and old lithium ion battery comprehensive reutilization is extremely urgent.
According to the difference of extraction process in removal process, the recycling of waste and old lithium ion battery mainly includes dry method and wet
Method and bioanalysis.Dry recovery mainly includes mechanical sorting method and high temperature pyrolytic cracking (HTP).It is primarily referred to as not passing through the media such as solution,
It is directly realized by the recycling of material or valuable metal.Dry recovery has many advantages, such as that process flow is short, easy to operate；But recycling is directed to
Property is not strong.Hydrometallurgic recovery is relayed in solution mainly using acid-base solution as medium, by metal ion from electrode material, is then passed through
Chemical precipitation, ion exchange perhaps the means such as extraction by metal ion in the form of metal salt or metal oxide from solution
In extract.Wet recycling process Technical comparing is complicated, but recovery rate of valuable metals is high, is that current old and useless battery recycles
Prevailing technology.Bioanalysis mainly utilizes the leaching of microorganism, converts soluble compounds for useful constituent in system, obtains valuable
The solution of metal, realization target components and impurity composition efficiently separate.Bioanalysis is low with cost recovery, pollution is small, can weigh
The advantages that utilizing again, but Period Process is longer, metal recovery rate is low.Although the existing documents such as patent and periodical are open or report
Waste and old lithium ion battery method of comprehensive utilization, but process flow is longer, and especially lithium recovery process is longer, and concentration is low, cannot
Direct sinker prepares lithium carbonate product.
Patent CN1301337C discloses a kind of method that nickel sulfate is recycled from ni-mh, nickel-cadmium cell.This method is first
After ni-mh, nickel-cadmium cell are leached, pH to 4.5-5.0 is adjusted, by P204 abstraction impurity removal, raffinate is nickel sulfate solution.But
Research is not made to the extraction and separation of high concentration nickel cobalt manganese.
Based on the technology of existing patent disclosure, it can not achieve and efficiently preferentially mention lithium by raw material of waste and old lithium ion battery, together
When prepare nickel cobalt manganese sulfate product technique.
Summary of the invention
The object of the present invention is to provide a kind of simple process, the waste and old lithium ion batteries being easy to realize industrial production to integrate back
Receiving method.
According to an aspect of the invention, there is provided a kind of waste and old lithium ion battery comprehensive recovering process, comprising:
Ternary waste lithium cell battery core powder is leached for the first time with sulfuric acid and potassium permanganate, obtains the first leachate and the first leaching
It slags tap；
With sodium carbonate to the first leachate sinker, lithium carbonate is obtained；
First leached mud is leached with hydrogen peroxide and sulfuric acid selective reduction, obtains the second leachate and the second leached mud；
The pH to 4.2-4.5 for adjusting second leachate extracts second leachate through 10-15 grades with P204,
Obtain P204 raffinate and P204 load organic phases；
The P204 load organic phases are stripped with sulfuric acid, manganese sulfate is made in evaporative crystallization；
The pH value of the P204 raffinate is adjusted to 4.5-5, the P204 raffinate is extracted through 14-18 grades with C272,
Obtain C272 extract liquor and C272 load organic phases；
Cobalt sulfate solution is obtained to the C727 load organic oppositing back-extraction with sulfuric acid, battery grade cobalt sulfate is made in evaporative crystallization；
Adjust C272 raffinate pH value be 5-5.5, to the C272 extract liquor with P507 extract P507 load it is organic
Phase, the P507 load organic phases are stripped to obtain nickel sulfate solution through sulfuric acid, and evaporative crystallization obtains nickel sulfate.
In some embodiments, the temperature of first leaching step is 50 DEG C -100 DEG C.
In some embodiments, the mass ratio of the potassium permanganate and ternary waste lithium cell battery core powder is 0.2-
1.2:1.
In some embodiments, the extraction time of the ternary waste lithium cell battery core powder is 2h-12h.
In some embodiments, the temperature that the selective reduction is leached is 30 DEG C -100 DEG C.
In some embodiments, used sulphuric acid is reason when carrying out reducing leaching to first leached mud
0.9-1.1 times of stoichiometric, used hydrogen peroxide additional amount is theoretical amount when carrying out reducing leaching to first leached mud
1.1-1.4 again.
In some embodiments, the concentration of the P204 is 20%-35%.
In some embodiments, the P204 load organic phases are selectively stripped with sulfuric acid, the outlet of control manganese sulfate
Acidity is 10g/L sulfuric acid.
In some embodiments, the concentration of the C272 is 20%-35%.
In some embodiments, cobalt sulfate solution is stripped to obtain with sulfuric acid to the C727 load organic phases, controls sulfuric acid
Cobalt exports pH=3.5.
It has the advantage that: the present invention is by after waste and old lithium ion battery Selectively leaching, leachate passes through sinker, obtains electricity
Pond level lithium carbonate；Leached mud is leached by selective reduction, leaches terminal pH control in 4.2-4.5, leachate uses two sections points
The technique for evaporating extraction is used as the impurity such as extractant extracting copper, iron, manganese using di-(2-ethylhexyl)phosphoric acid ester (P204) first,
When being just stripped, using selective back extraction, pure manganese sulfate solution is obtained, by evaporative crystallization, obtains the production of LITHIUM BATTERY manganese sulfate
Product；P204 raffinate extracts cobalt using C272, is stripped, obtains pure cobalt sulfate solution, by evaporative crystallization, obtains electricity
Pond grade cobaltous sulfate product；C272 raffinate is pure nickel sulfate solution, by evaporative crystallization, obtains LITHIUM BATTERY nickel sulfate and produces
Product.
The present invention is raw material using waste and old lithium ion battery, and selectivity preferentially mentions lithium first, and leached mud uses selectivity also
Original leaches, and then uses extracting process, obtains the sulfate of LITHIUM BATTERY nickel cobalt manganese.The engineering process is simple, easily realizes industrialization
Production, not only solves the problem of lithium high concentration enriching and recovering, and realize waste and old lithium ion battery harmlessness disposing, valuable
Metal obtains effective recycling.Using process conditions provided by the invention and technological parameter, it can be achieved that efficiently preferentially mention lithium and
Prepare LITHIUM BATTERY nickel cobalt manganese sulfate product.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of waste and old lithium ion battery comprehensive recovering process of an embodiment of the present invention；
Fig. 2 is a kind of waste and old lithium ion battery comprehensive recovering process old and useless battery at different temperatures of an embodiment of the present invention
Leaching effect schematic diagram；
Fig. 3 is that a kind of waste and old lithium ion battery comprehensive recovering process of an embodiment of the present invention is waste and old with ternary in potassium permanganate
The leaching effect schematic diagram of lithium battery electric core powder different quality ratio；
Fig. 4 be an embodiment of the present invention a kind of waste and old lithium ion battery comprehensive recovering process under different time old and useless battery
Leaching effect schematic diagram.
Specific embodiment
As shown in Figure 1, a kind of waste and old lithium ion battery comprehensive recovering process, comprising: leach three with sulfuric acid and potassium permanganate
The first of first waste lithium cell battery core powder is leached, and the first leachate and the first leached mud are obtained.The temperature of first leaching step is
50℃-100℃.The mass ratio of potassium permanganate and ternary waste lithium cell battery core powder is 0.2-1.2:1.Ternary waste lithium cell
The extraction time of battery core powder is 2h-12h.With sodium carbonate to the first leachate sinker, lithium carbonate is obtained.It is selected with hydrogen peroxide and sulfuric acid
The second of the first leached mud of selecting property reducing leaching is leached, and the second leachate and the second leached mud are obtained.Second temperature leached is 30
℃-100℃.Used sulphuric acid is 0.9-1.1 times of theoretical amount when carrying out reducing leaching to leached mud, to leaching
Slag carries out 1.1-1.4 times that used hydrogen peroxide additional amount when reducing leaching is theoretical amount.Adjust the pH of the second leachate extremely
4.2-4.5 extracts the second leachate through 10-15 grades with P204, obtains P204 raffinate and P204 load organic phases.P204's
Concentration is 20%-35%.P204 load organic phases are selectively stripped with sulfuric acid, it is 10g/L sulphur that control manganese sulfate, which goes out mouth acidity,
Acid.P204 load organic phases are stripped with sulfuric acid, manganese sulfate is made in evaporative crystallization.The pH value of P204 raffinate is adjusted to 4.5-5,
P204 raffinate is extracted through 14-18 grades with C272, obtains C272 extract liquor and C272 load organic phases.The concentration of C272 is
20%-35%.Cobalt sulfate solution is stripped to obtain with sulfuric acid to C727 load organic phases, control cobaltous sulfate exports pH=3.5.Use sulfuric acid
Cobalt sulfate solution is obtained to C727 load organic oppositing back-extraction, battery grade cobalt sulfate is made in evaporative crystallization.Adjust the pH of C272 raffinate
Value is 5-5.5, extracts to obtain P507 load organic phases with P507 to C272 extract liquor, P507 load organic phases are stripped to obtain sulphur through sulfuric acid
Sour nickel solution, evaporative crystallization obtain nickel sulfate.Theoretical amount in the present invention is obtained for the molar ratio according to chemical equation
Amount.
In the following, based on following embodiments and the present invention will be described in detail.Following embodiments is of the invention for illustrating
Example, the scope of protection of present invention proper right claim is limited, and is not limited to lifted embodiment.
Embodiment one
Ternary waste lithium cell powder 50g is taken, 4mol/L sulfuric acid is added, 10g additive potassium permanganate (KMnO is added4),
At 20 °C, after being stirred to react 2h, filtering obtains the mixing of filtrate sulfur acid nickel, cobaltous sulfate, manganese sulfate and lithium sulfate
Solution and leached mud, leaching effect are as shown in Figure 1,2 and 3.Filtrate pH ≈ 5.5 is adjusted, is cleaned, it is molten containing lithium to obtain high concentration
Liquid carries out sinker technique using sodium carbonate to lithium-containing solution, obtains pure lithium carbonate product.
Leached mud uses sulfuric acid and hydrogen peroxide reducing leaching, and sulfuric acid is 1.1 times of theoretical amount, and hydrogen peroxide is theoretical amount 1.4
Times, under the conditions of 60 DEG C, obtain the sulfur acid nickel of high concentration, the mixed solution of cobaltous sulfate and manganese sulfate, wherein nickel: 65g/L,
Cobalt: 25g/L, manganese: 37g/L.Adjust nickel and cobalt containing manganese solution pH ≈ 4.5, use concentration for 30% di-(2-ethylhexyl)phosphoric acid
Ester (P204) abstraction impurity removal, extraction series are 14 grades, after nickel soap, are extracted, remove the impurity such as copper, zinc, calcium, magnesium, iron, manganese.
P204 raffinate is the sulfuric acid nickel and cobalt solution that 10mg/L is respectively less than containing copper, zinc, calcium, magnesium, iron, iron, manganese, and P204 load is organic
Mutually in stripping section, selective back extraction is carried out using 2mol/L sulfuric acid, control manganese sulfate goes out mouth acidity 10g/L sulfuric acid, can get pure
Net manganese sulfate solution can get manganese sulfate product by evaporative crystallization.
For P204 extract liquor, pH value ≈ 5 is extracted using 25% double-(2,4,4- trimethyl) amyl phosphonic acids (C272)
Cobalt, extraction series are 18 grades, obtain containing copper, zinc, calcium, magnesium, iron, manganese, the equal < 10mg/L of cobalt nickel sulfate solution, C272 is negative
Organic phase is carried in stripping section, is stripped using 2mol/l sulfuric acid, control cobaltous sulfate exports pH=3.5, after selectively back extraction, obtains
To the solution for containing only cobaltous sulfate, cobalt sulfate solution passes through evaporative crystallization, battery grade cobalt sulfate can be made.
For C272 raffinate, pH ≈ 5.5, extract liquor passes through 2- ethylhexyl phosphoric acid single 2-ethyl hexyl ester (P507)
Extraction of nickel, load organic phases obtain the solution for containing only nickel sulfate after back extraction, and by evaporative crystallization, nickel sulfate product is made.
Embodiment two
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, 30g additive KMnO is added4, at 50 DEG C
Under the conditions of, after being stirred to react 4h, filtering obtains the solution and leached mud containing nickel cobalt lithium, and leaching effect is shown in Fig. 1,2 and 3, adjustment
Filtrate pH ≈ 5-5.5, cleans, and obtains high concentration lithium-containing solution, then carries out sinker work to lithium-containing solution using sodium carbonate
Skill obtains lithium carbonate product.
Leached mud uses sulfuric acid and hydrogen peroxide reducing leaching, and sulfuric acid is 1.05 times of theoretical amount, and hydrogen peroxide is theoretical amount
Under the conditions of 1.3 times, 60 DEG C, the lithium-containing solution of high concentration is obtained, wherein nickel: 61.75g/L, cobalt: 23.75g/L, manganese: 35.15g/
L.The pH ≈ 4.5 for adjusting lithium-containing solution, using 30% P204 abstraction impurity removal, extracting series is 12 grades, after nickel soap, is extracted
It takes, removes the impurity such as copper, zinc, calcium, magnesium, iron, manganese.P204 raffinate is to be respectively less than 10mg/L containing copper, zinc, calcium, magnesium, iron, manganese
Sulfuric acid nickel and cobalt solution.P204 load organic phases carry out selective back extraction in stripping section, using 2mol/L sulfuric acid, control manganese sulfate
Mouth acidity 10g/L sulfuric acid out can get pure manganese sulfate solution, by evaporative crystallization, can get manganese sulfate product.
For P204 raffinate, pH ≈ 5 extracts cobalt using 35% C272, and extraction series is 16 grades, obtain containing copper,
The nickel sulfate solution of the equal < 10mg/L of zinc, calcium, magnesium, iron, manganese, cobalt, C272 load organic phases are in stripping section, using 2mol/L sulphur
Acid back extraction, control cobaltous sulfate export pH=3.5, after selectively back extraction, obtain the solution for containing only cobaltous sulfate, cobalt sulfate solution
By evaporative crystallization, battery grade cobalt sulfate can be made.
For C272 raffinate, pH ≈ 5.5, extract liquor passes through P507 extraction of nickel, and load organic phases obtain after back extraction
Nickel sulfate product is made by evaporative crystallization in the solution for containing only nickel sulfate.
Embodiment three
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, additive KMnO is added440g, at 80 DEG C
Under the conditions of, after being stirred to react 12h, filtering obtains the solution (leaching effect is shown in Fig. 1,2,3) containing nickel lithium manganese, adjusts filtrate pH
≈ 5-5.5, cleans, and obtains high concentration lithium-containing solution, then carries out sinker technique, obtains lithium carbonate product
Leached mud uses sulfuric acid and hydrogen peroxide reducing leaching, and sulfuric acid is 0.95 times of theoretical amount, and hydrogen peroxide is theoretical amount
Under the conditions of 1.1 times, 60 DEG C, the solution of the nickel and cobalt containing manganese of high concentration is obtained, nickel: 55.25g/L, cobalt: 21.25g/L, manganese:
31.45g/L adjusts pH value of solution ≈ 4.5, and after nickel soap, using 25%P204 abstraction impurity removal, extracting series is 12 grades, remove copper,
The impurity such as zinc, calcium, magnesium, iron, manganese, P204 raffinate are the sulfuric acid nickel cobalt that 10mg/L is respectively less than containing copper, zinc, calcium, magnesium, iron, manganese
Solution, P204 load organic phases carry out selective back extraction in stripping section, using 2mol/L sulfuric acid, and control manganese sulfate goes out mouth acidity
10g/L sulfuric acid can get pure manganese sulfate solution, by evaporative crystallization, can get manganese sulfate product.
For P204 raffinate, pH ≈ 5 extracts cobalt using 25%C272, and extraction series is 14 grades, obtain containing copper, zinc,
The nickel sulfate solution of the equal < 10mg/L of calcium, magnesium, iron, manganese, cobalt, C272 load organic phases are anti-using 2mol/L sulfuric acid in stripping section
Extraction, control cobaltous sulfate exports pH=3.5, after selectively back extraction, obtains the solution for containing only cobaltous sulfate, cobalt sulfate solution passes through
Battery grade cobalt sulfate can be made in evaporative crystallization.
For C272 raffinate, pH ≈ 5.5, extract liquor passes through P507 extraction of nickel, and load organic phases obtain after back extraction
Nickel sulfate product is made by evaporative crystallization in the solution for containing only nickel sulfate.
Case study on implementation four
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, additive KMnO is added460g, at 90 DEG C
Under the conditions of, after being stirred to react 8h, filtering obtains the solution (leaching effect is shown in Fig. 1,2,3) containing lithium, adjusts filtrate pH ≈ 5-
5.5, it cleans, obtains high concentration lithium-containing solution, then carry out sinker technique, obtain lithium carbonate product.
Leached mud uses sulfuric acid and hydrogen peroxide reducing leaching, and sulfuric acid is 1.05 times of theoretical amount, and hydrogen peroxide is theoretical amount
Under the conditions of 1.3 times, 60 DEG C, the solution of the nickel and cobalt containing manganese of high concentration is obtained, nickel: 55.25g/L, cobalt: 20g/L, manganese: 31.45g/
L adjusts pH value of solution ≈ 4.5, and after nickel soap, using 20%P204 abstraction impurity removal, extracting series is 10 grades, remove copper, zinc, calcium, magnesium,
The impurity such as iron, manganese, P204 raffinate are the sulfuric acid nickel and cobalt solution that 10mg/L is respectively less than containing copper, zinc, calcium, magnesium, iron, manganese, P204
Load organic phases carry out selective back extraction in stripping section, using 2mol/L sulfuric acid, and control manganese sulfate goes out mouth acidity 10g/l sulfuric acid,
It can get pure manganese sulfate solution, by evaporative crystallization, can get manganese sulfate product.
For P204 raffinate, pH ≈ 5 extracts cobalt using 20%C272, and extraction series is 16 grades, obtain containing copper, zinc,
The nickel sulfate solution of the equal < 10mg/L of calcium, magnesium, iron, manganese, cobalt, C272 load organic phases are anti-using 2mol/L sulfuric acid in stripping section
Extraction, control cobaltous sulfate exports pH=3.5, after selectively back extraction, obtains the solution for containing only cobaltous sulfate, cobalt sulfate solution passes through
Battery grade cobalt sulfate can be made in evaporative crystallization.
For C272 raffinate, pH ≈ 5.5, extract liquor passes through P507 extraction of nickel, and load organic phases obtain after back extraction
Nickel sulfate product is made by evaporative crystallization in the solution for containing only nickel sulfate.
Case study on implementation five
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, additive KMnO is added450g, 100
Under the conditions of DEG C, after being stirred to react 8h, filtering obtains the solution (leaching effect is shown in Fig. 1,2,3) containing lithium, adjusts filtrate pH ≈
5-5.5 cleans, and obtains high concentration lithium-containing solution, then carries out sinker technique, obtains lithium carbonate product.
Leached mud uses sulfuric acid and hydrogen peroxide reducing leaching, and sulfuric acid is 0.9 times of theoretical amount, and hydrogen peroxide is theoretical amount
Under the conditions of 1.1 times, 60 DEG C, the solution of the nickel and cobalt containing manganese of high concentration is obtained, nickel: 48.75g/L, cobalt: 18.75g/L, manganese:
27.75g/L adjusts pH value of solution ≈ 4.5, and after nickel soap, using 20%P204 abstraction impurity removal, extracting series is 10 grades, remove copper,
The impurity such as zinc, calcium, magnesium, iron, manganese, P204 raffinate are the sulfuric acid nickel cobalt that 10mg/L is respectively less than containing copper, zinc, calcium, magnesium, iron, manganese
Solution, P204 load organic phases carry out selective back extraction in stripping section, using 2mol/L sulfuric acid, and control manganese sulfate goes out mouth acidity
10g/L sulfuric acid can get pure manganese sulfate solution, by evaporative crystallization, can get manganese sulfate product.
For P204 raffinate, pH ≈ 5 extracts cobalt using 20%C272, and extraction series is 14 grades, obtain containing copper, zinc,
The nickel sulfate solution of the equal < 10mg/L of calcium, magnesium, iron, manganese, cobalt, C272 load organic phases are anti-using 2mol/L sulfuric acid in stripping section
Extraction, control cobaltous sulfate exports pH=3.5, after selectively back extraction, obtains the solution for containing only cobaltous sulfate, cobalt sulfate solution passes through
Battery grade cobalt sulfate can be made in evaporative crystallization.
For C272 raffinate, pH ≈ 5.5, extract liquor passes through P507 extraction of nickel, and load organic phases obtain after back extraction
Nickel sulfate product is made by evaporative crystallization in the solution for containing only nickel sulfate.
Embodiment six
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, 20g additive potassium permanganate is added
(KMnO4), respectively under conditions of 20 DEG C, 50 DEG C, 80 DEG C, 90 DEG C and 100 DEG C, after being stirred to react 12h, filtering is leached
Slag and leachate.Leaching effect is as shown in Fig. 2, as shown in Figure 2, under conditions of 20-100 DEG C, nickel cobalt manganese lithium all has preferably
Leaching rate, better effect under conditions of 80-100 DEG C.
Embodiment seven
Take ternary waste lithium cell battery core powder 50g, 4mol/L sulfuric acid be added, be separately added into 10g, 20g, 30g, 40g and
Additive potassium permanganate (the KMnO of 50g4), under conditions of 100 DEG C, it is stirred to react 12h, filters, obtains leached mud and leaching
Liquid.Leaching effect is as shown in figure 3, from the figure 3, it may be seen that the mass ratio in potassium permanganate and ternary waste lithium cell battery core powder is
Under conditions of 0.2-1.2:1, nickel cobalt manganese lithium all has preferable leaching rate.
Embodiment eight
Ternary waste lithium cell battery core powder 50g is taken, 4mol/L sulfuric acid is added, 20g additive potassium permanganate is added
(KMnO4), under conditions of 100 DEG C, the time being stirred to react is respectively 2h, 6h, 8h, 10h, 12h, filtering, obtains leached mud
And leachate.Leaching effect is as shown in figure 4, as shown in Figure 4, under conditions of mixing time is 2-12h, nickel cobalt manganese lithium all have compared with
Good leaching rate, better effect under conditions of 6-12h.
Above-described is only some embodiments of the present invention.For those of ordinary skill in the art, it is not taking off
Under the premise of from concept of the invention, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (10)
1. a kind of waste and old lithium ion battery comprehensive recovering process characterized by comprising
Ternary waste lithium cell battery core powder is leached for the first time with sulfuric acid and potassium permanganate, is obtained the first leachate and first and is leached
Slag；
With sodium carbonate to the first leachate sinker, lithium carbonate is obtained；
First leached mud is leached with hydrogen peroxide and sulfuric acid selective reduction, obtains the second leachate and the second leached mud；
The pH to 4.2-4.5 for adjusting second leachate extracts second leachate through 10-15 grades with P204, obtains
P204 raffinate and P204 load organic phases；
The P204 load organic phases are stripped with sulfuric acid, manganese sulfate is made in evaporative crystallization；
The pH value of the P204 raffinate is adjusted to 4.5-5, the P204 raffinate is extracted through 14-18 grades with C272, is obtained
C272 extract liquor and C272 load organic phases；
Cobalt sulfate solution is obtained to the C727 load organic oppositing back-extraction with sulfuric acid, battery grade cobalt sulfate is made in evaporative crystallization；
The pH value for adjusting C272 raffinate is 5-5.5, extracts to obtain P507 load organic phases, institute with P507 to the C272 extract liquor
It states P507 load organic phases and is stripped to obtain nickel sulfate solution through sulfuric acid, evaporative crystallization obtains nickel sulfate.
2. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that described first leaches step
Rapid temperature is 50 DEG C -100 DEG C.
3. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that the potassium permanganate with
The mass ratio of ternary waste lithium cell battery core powder is 0.2-1.2:1.
4. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that the waste and old lithium of ternary
The extraction time of battery battery core powder is 2h-12h.
5. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that the selective reduction leaching
Temperature out is 30 DEG C -100 DEG C.
6. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that leached to described first
Slag carries out 0.9-1.1 times that used sulphuric acid when reducing leaching is theoretical amount, goes back to first leached mud
Used hydrogen peroxide additional amount is 1.1-1.4 times of theoretical amount when original leaching.
7. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that the concentration of the P204
For 20%-35%.
8. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that loaded to the P204
Organic phase is selectively stripped with sulfuric acid, and it is 10g/L sulfuric acid that control manganese sulfate, which goes out mouth acidity,.
9. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that the concentration of the C272
For 20%-35%.
10. waste and old lithium ion battery comprehensive recovering process according to claim 1, which is characterized in that negative to the C727
It carries organic phase and is stripped to obtain cobalt sulfate solution with sulfuric acid, control cobaltous sulfate exports pH=3.5.
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