CN109055746A - A method of recycling valuable metal from nickelic lithium ion cell anode waste - Google Patents
A method of recycling valuable metal from nickelic lithium ion cell anode waste Download PDFInfo
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- CN109055746A CN109055746A CN201811136229.2A CN201811136229A CN109055746A CN 109055746 A CN109055746 A CN 109055746A CN 201811136229 A CN201811136229 A CN 201811136229A CN 109055746 A CN109055746 A CN 109055746A
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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
- 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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- 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
- C22B23/0407—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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- 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
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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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- 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
- 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
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B7/007—Wet processes by acid leaching
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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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- 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
Abstract
The method that the invention discloses a kind of to recycle valuable metal from nickelic lithium ion cell anode waste.Firstly, selective extraction has gone out manganese and cobalt from nickelic leachate using solvent extraction；Then, nickel and lithium further use Solvent Extraction Separation in raffinate；Finally, the manganese and cobalt that extraction and separation obtain are precipitated manganese ion using the selective oxidation precipitation method, the separation of cobalt and manganese is realized.With tradition from leachate successively one by one compared with the method for separating element, the present invention borrows the co-extraction characteristic and redox sex differernce of cobalt and manganese, not only a step separates it with nickel lithium, and efficiently separate cobalt and manganese, and two kinds of elements of nickel and lithium are only remained in raffinate, system is simple, and separating effect greatly improves.Medicament used in the present invention is cheap, and operating procedure step is simple, and excessive nickel group can be overcome to give separation and Extraction bring adverse effect, realize the full constituent high efficiente callback of nickel, cobalt, manganese and lithium resource in nickelic lithium ion battery waste material.
Description
Technical field
The present invention relates to old and useless battery recycling fields, return from nickelic lithium ion cell anode waste more particularly, to one kind
The method for receiving valuable metal.
Technical background
Currently, ternary lithium ion battery material has become the main product on power lithium-ion battery material market, need
The amount of asking is increasing.LiNi0.33Co0.33Mn0.33O2As one of most important ternary lithium ion battery material, occupy extremely heavy
The market share.In order to cope with ternary lithium ion battery material LiNi0.33Co0.33Mn0.33O2The arriving of date of retirement, people are directed to
Its composition characteristic develops a variety of methods that nickel, cobalt, manganese and lithium are extracted from waste material.For example, by ternary lithium ion battery waste material
After being leached with sulfuric acid and mixed solution of hydrogen peroxide, by the way that KMnO is added into leachate4, Mn in oxidation precipitation leachate2 +；Secondly, adding dimethylglyoxime (C4H8N2O2), make the Ni in solution2+With Precipitation, then by precipitating acid dissolution, then
Sodium hydroxide pellets nickel component is added；Then, it will adjust except the pH value of filtrate after nickel to 11 or so, the cobalt in solution is with Co
(OH)2Form be precipitated；Finally, Na is added into surplus solution2CO3, by lithium remaining in solution with Li2CO3Form recycling.
The technique of this method nickel recycling is relatively cumbersome, when nickel content is high in solution, can consume a large amount of precipitating reagent and soda acid, returns
Rate of producing effects is not good enough.
At the same time, the requirement with people to electric car performance is higher and higher, LiNi0.33Co0.33Mn0.33O2?
It is increasingly difficult to meet the needs of market is to high-capacity lithium ion cell material.With LiNi0.33Co0.33Mn0.33O2Ternary material phase
Than, rich nickel lithium ion battery material, such as LiNi0.5Co0.2Mn0.3O2, LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2Deng,
Capacity is high, cobalt content is low, has price advantage, has been increasingly becoming the most popular production of power lithium-ion battery Material Field
Product, application and consumption figure constantly expand.The pressure scrapped in face of rich nickel lithium ion battery, nickelic lithium ion battery waste material return
Receive the great attention for having caused people.Existing research shows that the leaching of nickelic lithium ion battery waste material uses similar ternary material
When Leaching Systems (sulfuric acid+hydrogen peroxide) of material, it is ensured that the leaching rate of nickel, cobalt, manganese and lithium.But in nickelic waste material leachate,
Cobalt and manganese content is low, nickel content is high, applies waste and old LiNi0.33Co0.33Mn0.33O2The method of positive electrode leachate metal separation
The low efficiency of its nickel and cobalt recovery, nickel loss are serious.Therefore, it needs to develop more efficient for rich nickel lithium ion cell anode waste
Valuable metal component extracting process.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind from nickelic lithium ion cell anode waste
The method for recycling valuable metal.
A kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention, by nickelic lithium-ion electric
Cobalt, manganese in the anode waste acid leaching solution of pond are separated with nickel, lithium, are obtained containing cobalt, the liquid phase of manganese and nickeliferous, lithium liquid
Then phase is separated and recovered from nickel, the lithium in nickeliferous, lithium liquid phase, divides cobalt, the manganese in the liquid phase containing cobalt, manganese
From and recycle.
Preferably, a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention,
By the method for extraction, cobalt, the manganese in nickelic lithium ion cell anode waste acid leaching solution are separated with nickel, lithium, obtained
The organic liquid phase and nickeliferous, lithium liquid phase of cobalt, manganese must be contained, extractant used in the extraction is that (ethylhexyl phosphoric acid is mono- by P507
2- ethylhexyl), control extraction equilibrium pH value is 3~5.
Inventors have found that for nickelic lithium ion cell anode waste acid leaching solution, using P507 as extractant,
In the nickelic lithium ion cell anode waste acid leaching solution of separation jointly that can be efficient, selective in above-mentioned pH value range
Cobalt manganese, and other extractant separating effects is used to be deteriorated, while pH value influences also also very big to separating effect, pH value does not exist
The extraction yield decline of cobalt, manganese is not only resulted in the scope of the invention, and will increase the loss late of nickel, lithium.
Scheme as a further preference, control extraction equilibrium pH value are 4~5.
Scheme as a further preference, diluent used in the extraction are sulfonated kerosene；The extractant has in extraction
Volume fraction in machine phase is 10~40%, and when the extraction, extraction organic phase and water phase volume ratio are 0.25~1:1.
Scheme as a further preference, the extraction time are 5~20 minutes, and extraction temperature is 20~40 DEG C, extraction
Series is 3~5.
Preferably, a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention,
Using the method for multi-stage counter current extraction, nickeliferous, lithium liquid phase is separated, nickeliferous organic liquid phase and liquid phase containing lithium are obtained,
Extractant used by the multi-stage counter current extraction is selected from P507 (the mono- 2- ethylhexyl of ethylhexyl phosphoric acid), P204 (two (2-
Ethylhexyl) phosphate), any one in Cynex272, control extraction equilibrium pH value is 3-8.
Scheme as a further preference, diluent used in the multi-stage counter current extraction are sulfonated kerosene；The extractant
Volume fraction in extraction organic phase is 30~60%, when the multi-stage counter current extraction, extracts the volume of organic phase and water phase
Than for 0.5~1:1.
Scheme as a further preference, the multi-stage counter current extraction time are 5~10 minutes, P204 multi-stage counter current extraction
Temperature is 20~40 DEG C, and the series of multi-stage counter current extraction is 3~5.
Scheme as a further preference, when extractant used by the multi-stage counter current extraction is P204, control extraction
Equilibrium ph is 3~5；When extractant used by the multi-stage counter current extraction is P507, control extraction equilibrium pH value is 6~7；
When extractant used by the multi-stage counter current extraction is Cynex272, control extraction equilibrium pH value is 7~8.
During the present invention is using multi-stage counter current extraction separation nickel, lithium, the extraction yield of nickel and lithium can be with pH value
Raising and become larger, but due to the valence state of lithium ion be+1, nickel be+divalent, lithium and extractant binding ability are weaker than nickel, nickel extract
Rate increase speed faster, so that the lithium entered in extraction phase because pH value is excessively high can be by counter-current extraction by subsequent excessive
Nickel replaces the separation for realizing nickel and lithium.
Scheme as a further preference, the nickeliferous organic liquid phase first use deionized water backwash, then using use
Sulfuric acid solution is stripped the organic phase of nickel-loaded, obtains nickel sulfate solution, and the concentration of the sulfuric acid solution is 0.5~
1.5mol/L。
As a further preferred solution, when the back extraction, the volume ratio for extracting organic phase and water phase is 0.5~1: 1,
The Stripping times are 10~20 minutes.
Preferably, a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention,
By the organic liquid phase containing cobalt, manganese carry out back extraction obtain the strip liquor containing cobalt, manganese, then use oxidation precipitation method, will contain cobalt,
Manganese carries out oxidation precipitation in the strip liquor of manganese, is separated by solid-liquid separation, and obtains containing manganese precipitating and liquid phase containing cobalt.
Scheme as a further preference, when the back extraction, stripping agent used is sulfuric acid solution, the sulfuric acid solution it is dense
Degree is 1~2mol/L；When the back extraction, the volume ratio for extracting organic phase and water phase is 0.5~1: 1, and the Stripping times are 10
~20 minutes.
Scheme as a further preference, the oxidation precipitation agent are selected from sodium persulfide, potassium permanganate, chloric acid, hypochlorous acid
At least one of sodium, sodium perchlorate.
1.2~2.2 times of additions of heavy manganese theoretical amount are pressed in scheme as a further preference, the oxidation precipitation agent.
As a further preferred solution, 1.8~2.2 times of additions of heavy manganese theoretical amount are pressed in the oxidation precipitation agent.
Addition oxidation precipitation agent can precipitate manganese completely in amounts indicated above, can also be to avoid its precipitating of cobalt manganese, at this
In invention, heavy manganese, which refers to, to be aoxidized divalent manganesetion to form precipitating.
Scheme as a further preference, the oxidation precipitation carry out under stiring, and control mixing speed is 100~300
Rev/min kind, reaction temperature are 20-60 DEG C, and the reaction time is 1~2h, pH value in reaction 1-4.
Preferred scheme, a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention, institute
State the acquisition modes of nickelic lithium ion cell anode waste acid leaching solution are as follows: waste and old nickelic lithium ion battery material is placed in and is contained
In the acid solution of reducing agent in 50~90 DEG C of 1~3h of leaching to get.
As a further preferred solution, the acid solution is sulfuric acid solution, the concentration of the sulfuric acid solution is 2~
4mol/L。
As a further preferred solution, the reducing agent is hydrogen peroxide, and the hydrogen peroxide is in an acidic solution
Concentration be 2~4mol/L.
As a further preferred solution, the chemical molecular formula of the waste and old nickelic lithium ion battery material is
LiNixCoyMn1-x-yO2(1 > x >=0.5, y > 0,1-x-y > 0), the waste and old nickelic lithium ion battery material, which is selected from, meets above-mentionedization
At least one material that credit minor requires.
A kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste of the present invention, the nickelic lithium ion
In cell anode waste acid leaching solution, nickel concentration is 1.6~8 times of cobalt concentration, and nickel concentration is 2.5~8 times of manganese concentration.
The principle of the present invention and advantage:
The characteristics of what the present invention initiated is directed to richness nickel lithium ion cell anode waste, develops nickelic lithium ion cell positive
The technique stream of " the preferential coextraction of cobalt, manganese-extract liquor manganese selective precipitation-raffinate nickel lithium extraction and separation " in material extract
Journey, first selective extraction has gone out manganese and cobalt from nickelic leachate, and then the nickel in raffinate and lithium can be further using extractions
Method separation, the manganese and cobalt for finally obtaining extraction and separation are separated using oxidation-precipitation method.The nickelic lithium ion of program step by step arithmetic
Cobalt, manganese, nickel and lithium component in battery waste, it is high-efficient, operability is good, great commercial value.
With tradition from leachate successively one by one compared with the method for separating element, the present invention borrow cobalt and manganese co-extraction characteristic and
Redox sex differernce, not only a step separates it with nickel lithium, but also efficiently separates cobalt and manganese, and in raffinate only remain nickel and
Two kinds of elements of lithium, system is simple, and separating effect greatly improves.
Medicament used in the present invention is cheap, and operating procedure step is simple, and excessive nickel group can be overcome to give separation and mentioned
It takes bring to adversely affect, realizes the full constituent high efficiente callback of nickel, cobalt, manganese and lithium resource in nickelic lithium ion battery waste material.
Specific embodiment
The present invention is specifically described below with reference to specific implementation example.
Embodiment 1
Take 10gLiNi0.8Co0.1Mn0.1O2Anode waste is placed in the solution that 100ml concentration is 4mol/L, controls solution
Concentration of hydrogen peroxide is 2mol/L, and temperature is 90 DEG C.After leaching 3 hours, nickel, cobalt, manganese and lithium concentration be respectively 48g/L,
6.04g/L, 5.60g/L and 6.93g/L, leaching rate is close to 100%.
10ml leachate is taken, when the mono- 2- ethylhexyl of extractant ethylhexyl phosphoric acid is dissolved in sulfonated kerosene, shared by extractant
Percentage by volume be 20%, the volume ratio for controlling extraction oil phase and water phase is 0.5, extraction time 10 minutes, extraction temperature 25
DEG C, extraction equilibrium pH value is 4.5, extracts 5 grades of series.The extraction yield of cobalt and manganese is 99.5%.After the completion of extraction, with volume ratio 1:
Then 1 deionized water backwash 3 times is stripped, Stripping times 15 minutes with the sulfuric acid solution of 1mol/L, compare 1:1.The back extraction of cobalt
Rate 100%, the back extraction ratio 98% of manganese, in the solution obtained after back extraction, the content of nickel is less than 2mg/L, and the content of lithium is less than 1mg/
L。
Raffinate after taking 10ml to extract, using di-(2-ethylhexyl)phosphoric acid ester as extractant, sulfonated kerosene is dilution
Agent, extractant are that 4:6 is uniformly mixed with sulfonated kerosene by volume, and the volume ratio for controlling extraction oil phase and water phase is 1, when extraction
Between 10 minutes, 25 DEG C of extraction temperature, extraction pH value is 4, and the monopole extraction yield of nickel is 50%, and the extraction yield of lithium is lower than 20%, to the greatest extent
Tube portion lithium can by co-extraction, but due to lithium be+1 valence, it is weaker than nickel with extractant binding ability, thus by 5 stage countercurrents extraction after,
The lithium that extraction enters organic phase can be replaced by subsequent excessive nickel.
After the completion of extraction, with deionized water backwash 3 times of volume ratio 1:1, then it is stripped with the sulfuric acid solution of 1mol/L, instead
The extraction time 15 minutes compares 1:1.In the solution obtained after back extraction, the overall rate of recovery 98% of nickel.
The cobalt manganese strip liquor that 100ml is isolated is taken, potassium permanganate is added into solution to 40 DEG C for heating water bath, control
The additional amount of potassium permanganate is 2.2 times of heavy manganese theoretical amount, pH value in reaction 1.8, and the reaction time 1 hour, stirring hastened 200
Rev/min, the rate of deposition of manganese is close to 100% as the result is shown, and the rate of deposition of cobalt is less than 5%.
Embodiment 2
The waste material leaching method that the present embodiment uses is same as Example 1, and difference is that waste material used is
LiNi0.6Co0.2Mn0.2O2, nickel, cobalt, the leaching rate and embodiment of manganese and lithium are essentially identical, close to 100%.
The extraction of manganese and cobalt is identical with embodiment 1 in leachate, repeats no more.Raffinate after taking 10ml to extract
Liquid, using the mono- 2- ethylhexyl of ethylhexyl phosphoric acid as extractant, sulfonated kerosene is diluent, and extractant and sulfonated kerosene press body
For product than being that 3:7 is uniformly mixed, the volume ratio for controlling extraction oil phase and water phase is 1, extraction time 10 minutes, 25 DEG C of extraction temperature,
Extracting pH value is 6, and the monopole extraction yield of nickel is more than 60%, after the extraction of 3 stage countercurrents, the deionization of extract liquor volume ratio 1:1
It water backwash 3 times, is then stripped with the sulfuric acid solution of 1mol/L, Stripping times 15 minutes, compares 1:1.The solution obtained after back extraction
In, the rate of recovery 99% of nickel.
The cobalt manganese strip liquor that 100ml is isolated is taken, control solution temperature is 50 DEG C, sodium peroxydisulfate is added into solution,
Sodium peroxydisulfate additional amount is 2 times of theoretical amount needed for aoxidizing divalent manganese atom.Low whipping speed is that 300 revs/min of reactions 1 are small
Shi Hou, the rate of deposition of manganese are 99%, and the rate of deposition of cobalt is less than 3%.
Embodiment 3
The waste material leaching method that the present embodiment uses is identical as Examples 1 and 2, and difference is that waste material used is
LiNi0.5Co0.2Mn0.3O2, nickel, cobalt, the leaching rate and embodiment of manganese and lithium are essentially identical, close to 100%.
The extraction of manganese and cobalt is identical with Examples 1 and 2 in leachate, repeats no more.Extraction after taking 10ml to extract
Extraction raffinate, using Cynex272 as extractant, sulfonated kerosene is diluent, and extractant is that 3:7 is uniformly mixed with sulfonated kerosene by volume
It closes, the volume ratio for controlling extraction oil phase and water phase is 1, and extraction time 10 minutes, 25 DEG C of extraction temperature, extraction pH value was 8, nickel
Monopole extraction yield is more than 80%, and after the extraction of 3 stage countercurrents, then the deionized water backwash of extract liquor volume ratio 1:1 3 times is used
The sulfuric acid solution of 1mol/L is stripped, and Stripping times 15 minutes, compares 1:1.In the solution obtained after back extraction, the rate of recovery of nickel reaches
99%.
The cobalt manganese strip liquor that 100ml is isolated is taken, control solution temperature is 25 DEG C, sodium hypochlorite is added into solution,
The additional amount of sodium hypochlorite is 1.8 times of theoretical amount needed for aoxidizing divalent manganese atom.Low whipping speed is 200 revs/min anti-
After answering 1.5 hours, the rate of deposition of manganese is 99%, and the rate of deposition of cobalt is less than 5%.
Comparative example 1
The method of waste material, leaching and coextraction cobalt manganese that the present embodiment uses is identical as the condition in embodiment 1.It is distinguished
It is, the equilibrium ph of coextraction cobalt manganese is 5.5, and the series of multi-stage counter current extraction is 3 grades, the extraction yield 99.5% of manganese, cobalt
Extraction yield is 94%, while the extraction yield of nickel is more than 10%, and separation is not thorough.
Comparative example 2
The method and the condition in embodiment 1 of waste material, leaching, coextraction cobalt manganese and separation nickel and lithium that the present embodiment uses
It is identical.Its difference is, when separating nickel and lithium using di-(2-ethylhexyl)phosphoric acid ester, extraction equilibrium pH value is 6, and extraction is completed
Afterwards, the extraction yield of nickel can reach 100%, but the extraction yield of lithium is more than 20%, and separation is not thorough.
Comparative example 3
The method and the condition in embodiment 2 of waste material, leaching, coextraction cobalt manganese and separation nickel and lithium that the present embodiment uses
It is identical.Its difference is that when using the mono- 2- ethylhexyl separation nickel of ethylhexyl phosphoric acid and lithium, extraction equilibrium pH value is 7, warp
After crossing the extraction of 3 stage countercurrents, the extraction yield 99% of nickel, but the extraction yield of lithium is more than 15%, and separation is not thorough
Comparative example 4
The method and the condition in embodiment 3 of waste material, leaching, coextraction cobalt manganese and separation nickel and lithium that the present embodiment uses
It is identical.Its difference is, when Cynex272 being used to separate nickel and lithium for extractant, extraction equilibrium pH value is 6, by 3 stage countercurrents
After extraction, for the extraction yield of nickel less than 60%, separation is incomplete.
The above content is combine specific preferred embodiment to the further description done of the present invention, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those skilled in the art of the present invention, do not taking off
Under the premise of from present inventive concept, several equivalent substitutes or obvious deformation are made obtaining, is regarded as belonging to protection of the invention
Range.
Claims (10)
1. it is a kind of from nickelic lithium ion cell anode waste recycle valuable metal method, it is characterised in that: by nickelic lithium from
Cobalt, manganese in sub- cell anode waste acid leaching solution are separated with nickel, lithium, are obtained containing cobalt, the liquid phase of manganese and nickeliferous, lithium
Liquid phase, then nickel, the lithium in nickeliferous, lithium liquid phase are separated and recovered from, in the liquid phase containing cobalt, manganese cobalt, manganese into
Row is separated and recovered from.
2. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 1,
The method for being characterized by extraction, by nickelic lithium ion cell anode waste acid leaching solution cobalt, manganese and nickel, lithium into
Row separation, obtains organic liquid phase and nickeliferous, lithium liquid phase containing cobalt, manganese, and extractant used in the extraction is P507；Control extraction
Taking equilibrium ph is 3~5.
3. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 2,
Be characterized in that: diluent used in the extraction is sulfonated kerosene；Volume fraction of the extractant in extraction organic phase is 10
~40%, when the extraction, extraction organic phase and water phase volume ratio are 0.25~1:1；The extraction time is 5~20 minutes,
Extraction temperature is 20~40 DEG C, and extraction series is 3~5.
4. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 1,
Be characterized in that: using the method for multi-stage counter current extraction, nickeliferous, lithium liquid phase being separated, obtain nickeliferous organic liquid phase and
Liquid phase containing lithium, extractant used by the multi-stage counter current extraction are selected from P507, any one in P207, Cynex272, control
Extraction equilibrium pH value processed is 3-8.
5. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 4,
Be characterized in that: diluent used in the multi-stage counter current extraction is sulfonated kerosene；Volume of the extractant in extraction organic phase
Score is 30~60%, when the multi-stage counter current extraction, and the volume ratio for extracting organic phase and water phase is 0.5~1:1；The multistage
The counter-current extraction time is 5~10 minutes, and multi-stage counter current extraction temperature is 20~40 DEG C, and the series of multi-stage counter current extraction is 3~5.
6. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 5,
Be characterized in that: when extractant used by the multi-stage counter current extraction is P204, control extraction equilibrium pH value is 3~5；It is described more
When extractant used by stage countercurrent extracts is P507, control extraction equilibrium pH value is 6~7；The multi-stage counter current extraction is adopted
When extractant is Cynex272, control extraction equilibrium pH value is 7~8.
7. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 1,
It is characterized in that: the organic liquid phase containing cobalt, manganese being subjected to back extraction and obtains the strip liquor containing cobalt, manganese, then uses the side of oxidation precipitation
Manganese in strip liquor containing cobalt, manganese is carried out oxidation precipitation, is separated by solid-liquid separation by method, is obtained containing manganese precipitating and liquid phase containing cobalt.
8. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 7,
Be characterized in that: the oxidation precipitation agent in sodium persulfide, potassium permanganate, chloric acid, sodium hypochlorite, sodium perchlorate at least one
Kind；1.2~2.2 times of additions of heavy manganese theoretical amount are pressed in the oxidation precipitation agent；
The oxidation precipitation carries out under stiring, and control mixing speed is 100~300 revs/min of kinds, reaction temperature 20-60
DEG C, reaction time 1h, pH value in reaction 1-4.
9. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 1,
It is characterized in that: the acquisition modes of the nickelic lithium ion cell anode waste acid leaching solution are as follows: by waste and old nickelic lithium-ion electric
Pond material be placed in the acid solution containing reducing agent in 90 DEG C of leaching 3h to get；
The acid solution is sulfuric acid solution, and the concentration of the sulfuric acid solution is 2~4mol/L；
The reducing agent is hydrogen peroxide, and the concentration of the hydrogen peroxide in an acidic solution is 2~4mol/L.
10. a kind of method that valuable metal is recycled from nickelic lithium ion cell anode waste according to claim 1,
Be characterized in that: the chemical molecular formula of the waste and old nickelic lithium ion battery material is LiNixCoyMn1-x-yO2(1 > x >=0.5, y > 0,
1-x-y > 0), the waste and old nickelic lithium ion battery material is selected from at least one material for meeting above-mentioned chemical molecular formula requirement.
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