CN106684489A - Method for recycling valuable metal from waste polybasic lithium ion batteries - Google Patents
Method for recycling valuable metal from waste polybasic lithium ion batteries Download PDFInfo
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- CN106684489A CN106684489A CN201710182628.1A CN201710182628A CN106684489A CN 106684489 A CN106684489 A CN 106684489A CN 201710182628 A CN201710182628 A CN 201710182628A CN 106684489 A CN106684489 A CN 106684489A
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- extraction
- raffinate
- roasting
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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
-
- 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
-
- 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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- 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 invention provides a method for recycling valuable metal from waste polybasic lithium ion batteries. The method comprises the following steps of: performing segmented roasting and acid leaching of a waste polybasic lithium ion battery cathode material, removing Al<3+> and Fe<3+> at first, then, performing first extraction after removing PO<4><3->, so that first raffinate including manganese, cobalt, nickel and lithium metal elements is obtained, performing extraction and impurity removing of the first raffinate, performing third extraction of second raffinate to recycle manganese, performing fourth extraction of third raffinate to recycle cobalt and nickel, and then, performing lithium sedimentation of Li-containing solution to obtain Li<2>CO<3>. By means of the recycling method provided by the invention, for different kinds of waste polybasic lithium ion batteries, valuable metal can be recycled; furthermore, on the premise that the high recycling rate of valuable metal including lithium, nickel, cobalt, manganese and copper is ensured, impurity elements, such as aluminium and iron, can be effectively removed; the product quality can be ensured; the added value of the product is high; extraction raw materials can be recycled and utilized; the economical efficiency is high; furthermore, equipment is simple; the process is environment friendly; and the method is simple and easy to control.
Description
Technical field
The present invention relates to waste and old lithium ion battery technical field of resource recovery, more particularly to one kind is from waste and old polynary lithium ion
The method that valuable metal is reclaimed in battery.
Background technology
Lithium ion battery is made up of the part such as positive electrode, negative material, binding agent, Copper Foil, aluminium foil, electrolyte, has
Security is good, energy density is high, have extended cycle life, memory-less effect the advantages of, have been widely used 3C numbers, energy storage, communication,
The fields such as electric automobile.With the fast development of the industries such as mobile phone, new-energy automobile, the recovery of waste and old lithium ion battery is urgently solved
Certainly.
At present, the common positive electrode of in the market includes LiCoO2、LiMnO4、LiNiMnO4、LiNiCoMnO2、
LiNiCoAlO2、LiFePO4、LiMnFePO4Deng containing valuable metals such as abundant Co, Ni, Mn, Li, content is far above primary
Mineral grade.In addition, primary cobalt ore, nickel minerals, manganese ore, lithium ore deposit mineral existence are complicated, extraction process is complicated and the rate of recovery is low
Problem.Therefore, to the recycling of valuable metal in old and useless battery positive electrode and Copper Foil, solution is not only facilitated valuable
Metals resources shortage problem, additionally aids and realizes recycling for material element in lithium ion battery.
Because positive electrode is varied, such as CN102676827A, CN102910607B, CN102881960B,
Battery valuable metal recovery method disclosed in CN105591171A and CN105441682A is just for LiNiCoMnO2、
LiFePO4Etc. single positive electrode, the waste and old lithium ion battery source of actual recovered is complicated, it is difficult to accomplish precise classification, implements
Process feasible is low, it is impossible to carry out the recovery of valuable metal to the positive electrode of different compositions using same recovery method.
The content of the invention
In view of this, valuable metal is reclaimed from waste and old polynary lithium ion battery it is an object of the invention to provide a kind of
Method, the recovery of valuable metal can be realized to different types of waste and old polynary lithium ion battery, and ensureing valuable metal
On the premise of lithium, nickel, cobalt, manganese, copper high-recovery, the impurity elements such as aluminium, iron are effectively removed, it is ensured that product quality, product is added
Value is high, and extraction feed is recyclable to be recycled, and economy is high.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The present invention has put forward a kind of method that valuable metal is reclaimed from waste and old polynary lithium ion battery, comprises the following steps：
(1) by waste and old polynary anode material for lithium-ion batteries baking inphases, product of roasting is obtained；
(2) mixing the product of roasting that the step (1) is obtained with hydrogen peroxide and inorganic acid carries out acidleach, obtains acidleach
Solution；
(3) pH value of the acid dip solution that the step (2) obtains is adjusted using inorganic base substance and removes Al to 3~53+With
Fe3+, then Al is removed using inorganic base substance regulation3+And Fe3+Acid dip solution pH value to 7~9 remove PO4 3-, removed
Mixture solution；
(4) step (3) is adjusted using inorganic acid and obtains the pH value except mixture solution to 2~4, then carry out the first extraction,
The first raffinate and organic phase containing Cu are obtained, first raffinate includes Mn2+、Co2+、Ni2+、Li+And trace impurity, it is described
Trace impurity includes Cu2+、Fe3+And Al3+；
(5) adjusted using inorganic acid and inorganic base substance the pH value of the first raffinate that the step (4) obtains to 2~
2.5, then the second extraction is carried out, the second raffinate and impure organic phase are obtained, second raffinate includes Mn2+、Co2+、
Ni2+And Li+；
(6) pH value of the second raffinate that the step (5) obtains is adjusted to 2.6~4 using inorganic base substance, then is entered
Row the 3rd is extracted, and obtains the 3rd raffinate and organic phase containing Mn, and the 3rd raffinate includes Co2+、Ni2+And Li+；
(7) pH value of the 3rd raffinate that the step (6) obtains to 4.5 is adjusted using inorganic acid and inorganic base substance
~5, then the 4th extraction is carried out, the 4th raffinate and organic phase containing Co are obtained, the 4th raffinate includes Ni2+And Li+；
The pH value of the 4th raffinate is adjusted to 5.1~5.5 using inorganic base substance, then carries out the 5th extraction,
Obtain solution containing Ni and solution containing Li；
(8) use the pH value containing Li solution that the inorganic base substance regulation step (7) obtains to 12~14, will obtain
Alkalescence solution containing Li with heat saturated sodium carbonate solution reaction, obtain Li2CO3；
The solution containing Ni is concentrated, NiSO is obtained4·6H2O。
Preferably, baking inphases include two-stage roasting in the step (1), and first paragraph roasting is carried out in a nitrogen atmosphere,
Second segment roasting is carried out under oxygen atmosphere.
Preferably, the two-stage roasting is：
Waste and old polynary anode material for lithium-ion batteries is carried out into first paragraph roasting, the temperature of the first paragraph roasting is 300
~500 DEG C, the time of the first paragraph roasting is 2~4h；
The product that the first paragraph is calcined is carried out into second segment roasting, product of roasting, the temperature of the second segment roasting is obtained
It is 600~700 DEG C to spend, and the time of the second segment roasting is 3~6h.
Preferably, hydrogen peroxide is added in the form of hydrogen peroxide in the step (2), and the mass concentration of the hydrogen peroxide is
10~30%, the hydrogen peroxide and the gross mass of inorganic acid and the mass ratio of product of roasting are 3~8:1.
Preferably, the first extraction includes di-(2-ethylhexyl)phosphoric acid, isooctyl phosphoric acid with extractant in the step (4)
The mixture of one or more in single different monooctyl ester and efficient copper extractant；
The second extraction extractant is di-(2-ethylhexyl)phosphoric acid in the step (5)；
The 4th extraction extractant is independently selected in the 3rd extraction extractant and the step (7) in the step (6)
From including di-(2-ethylhexyl)phosphoric acid, the different monooctyl ester of isooctyl phosphoric acid list, two (2,4,4- tri-methyl-amyls) hypophosphorous acid and three alkane
The mixture of one or more in base amine.
Preferably, the pH value in the step (4) except mixture solution is adjusted to 2.5~3.5.
Preferably, the pH value of the second raffinate is adjusted to 3~3.5 in the step (6).
Preferably, also include after the first extraction in the step (4)：By the organic phase containing Cu through pickling and electrolysis, obtain
To Ni metal.
Preferably, also include after the 3rd extraction in the step (6)：By the organic phase containing Mn through pickling and concentration, obtain
To MnSO4·H2O。
Preferably, also include after the 4th extraction in the step (7)：By the organic phase containing Co through pickling and concentration, obtain
To CoSO4·7H2O。
The invention provides a kind of method that valuable metal is reclaimed from waste and old polynary lithium ion battery, by waste and old polynary lithium
With hydrogen peroxide and inorganic acid mixing acidleach after ion battery positive electrode baking inphases, the pH value of acid dip solution is adjusted to 3
~5 remove Al3+And Fe3+, then the pH value of solution is adjusted to 7~9 removing PO4 3-Obtain except mixture solution, by except the pH of mixture solution
Value regulation carries out the first extraction to 2~4, obtain including manganese, cobalt, nickel, the first raffinate of lithium metal element and trace impurity copper,
Iron and aluminium element, the pH value of the first raffinate is adjusted to 2~2.5 carries out the second extraction, obtains including manganese, cobalt, nickel, lithium metal
Second raffinate of element, the pH value of the second raffinate is adjusted to 2.6~4 carries out the 3rd extraction, obtains including cobalt, nickel, lithium
3rd raffinate of metallic element, the pH value of the 3rd raffinate is adjusted to 4.5~5 carries out the 4th extraction, obtains including nickel, lithium
4th raffinate of metallic element, the pH value of the 4th raffinate is adjusted to 5.1~5.5, then carries out the 5th extraction, is contained
Ni solution and solution containing Li, the solution containing Ni is concentrated, and obtains NiSO4·6H2O, the pH value containing Li solution is adjusted to 12~
Saturated sodium carbonate solution after 14 with heat mixes, and obtains Li2CO3.The recovery method that the present invention is provided is to different types of waste and old more
First lithium ion battery can realize the recovery of valuable metal, and ensure valuable metal lithium, nickel, cobalt, manganese, copper high-recovery
Under the premise of, effectively remove the impurity elements such as aluminium, iron, it is ensured that product quality, added value of product is high, wherein the recovery of Cu, Mn and Li
Rate be both greater than the rate of recovery of 95%, Co and Ni more than 96%, the Cu rate of recovery be up to 96.23%, the Mn rate of recovery be up to 96.43%,
The rate of recovery that the Co rate of recovery is up to 96.73%, Ni is up to 97.56%, the Li rate of recovery and is up to 95.94%, and extraction feed can be followed
Ring is recycled, and economy is high, and the raw material, the equipment that use are simply, environmental friendly, simple easily controllable.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the flow chart that the present invention reclaims valuable metal from waste and old polynary lithium ion battery.
Specific embodiment
The invention provides a kind of method that valuable metal is reclaimed from waste and old polynary lithium ion battery, including following step
Suddenly：
(1) by waste and old polynary anode material for lithium-ion batteries baking inphases, product of roasting is obtained；
(2) mixing the product of roasting that the step (1) is obtained with hydrogen peroxide and inorganic acid carries out acidleach, obtains acidleach
Solution；
(3) pH value of the acid dip solution that the step (2) obtains is adjusted using inorganic base substance and removes Al to 3~53+With
Fe3+, then Al is removed using inorganic base substance regulation3+And Fe3+Acid dip solution pH value to 7~9 remove PO4 3-, removed
Mixture solution；
(4) step (3) is adjusted using inorganic acid and obtains the pH value except mixture solution to 2~4, then carry out the first extraction,
The first raffinate and organic phase containing Cu are obtained, first raffinate includes Mn2+、Co2+、Ni2+、Li+And trace impurity, it is described
Trace impurity includes Cu2+、Fe3+And Al3+；
(5) adjusted using inorganic acid and inorganic base substance the pH value of the first raffinate that the step (4) obtains to 2~
2.5, then the second extraction is carried out, the second raffinate and impure organic phase are obtained, second raffinate includes Mn2+、Co2+、
Ni2+And Li+；
(6) pH value of the second raffinate that the step (5) obtains is adjusted to 2.6~4 using inorganic base substance, then is entered
Row the 3rd is extracted, and obtains the 3rd raffinate and organic phase containing Mn, and the 3rd raffinate includes Co2+、Ni2+And Li+；
(7) pH value of the 3rd raffinate that the step (6) obtains to 4.5 is adjusted using inorganic acid and inorganic base substance
~5, then the 4th extraction is carried out, the 4th raffinate and organic phase containing Co are obtained, the 4th raffinate includes Ni2+And Li+；
The pH value of the 4th raffinate is adjusted to 5.1~5.5 using inorganic base substance, then carries out the 5th extraction,
Obtain solution containing Ni and solution containing Li；
(8) use the pH value containing Li solution that the inorganic base substance regulation step (7) obtains to 12~14, will obtain
Alkalescence solution containing Li with heat saturated sodium carbonate solution reaction, obtain Li2CO3；
The solution containing Ni is concentrated, NiSO is obtained4·6H2O。
In the present invention, the waste and old polynary anode material for lithium-ion batteries includes LiCoO2、LiMnO4、LiNiMnO4、
LiNiCoMnO2、LiNiCoAlO2、LiFePO4、LiMnFePO4In it is any two or more.
Waste and old polynary anode material for lithium-ion batteries baking inphases are obtained product of roasting by the present invention.
In the present invention, the baking inphases preferably include two-stage roasting, specifically include first paragraph roasting and second segment roasting
Burn；In the present invention, the first paragraph roasting is preferably carried out in a nitrogen atmosphere, obtains first paragraph product of roasting, the nitrogen
The pressure of atmosphere is preferably 0.2~0.5Mpa, more preferably 0.3~0.4Mpa；The temperature of the first paragraph roasting is preferably 300
~500 DEG C, more preferably 400~450 DEG C；The time of the first paragraph roasting is preferably 2~4h, more preferably 3~3.5h.
In the present invention, the first paragraph roasting can crack the binding agent in waste and old polynary anode material for lithium-ion batteries, by afflux
Body aluminium foil, Copper Foil are separated with positive electrode, carbon material, obtain aluminium foil, Copper Foil, positive electrode, carbon material and remaining binders
Mixture.
After obtaining first paragraph product of roasting, first paragraph product of roasting is preferably carried out second segment roasting by the present invention, is roasted
Burn product.In the present invention, the second segment roasting is preferably carried out under oxygen atmosphere, and the pressure of the oxygen atmosphere is preferably
0.5~1Mpa, more preferably 0.8~0.9Mpa；The temperature of the second segment roasting is preferably 600~700 DEG C, more preferably
650~680 DEG C；The time of the second segment roasting is preferably 3~6h, more preferably 4~5h.In the present invention, described second
Section roasting can crack part carbon material and be oxidized to CO2, simultaneous oxidation aluminium foil and Copper Foil help subsequently to carry out acidleach molten
Solution.
In the present invention, the mode to the roasting does not have any special restriction, is known using those skilled in the art
Calcining manners.
After obtaining product of roasting, the present invention mixes product of roasting with hydrogen peroxide and inorganic acid carries out acidleach, obtains acid
Leaching solution.
In the present invention, the hydrogen peroxide is added in the form of hydrogen peroxide, and the mass concentration of the hydrogen peroxide is preferably
10~30%, more preferably 12~25%.
In the present invention, the inorganic acid includes the mixture of one or more in sulfuric acid, hydrochloric acid and nitric acid.The present invention
There is no any special restriction to the consumption of each inorganic acid in the mixture, those skilled in the art can select according to actual needs
Select the mixture of the inorganic acid of any mass ratio.
In the present invention, the gross mass of the hydrogen peroxide and inorganic acid is preferably 3~8 with the mass ratio of product of roasting:1,
More preferably 5~6:1.
In the present invention, the temperature of the acidleach is preferably 60~95 DEG C, more preferably 70~90 DEG C, most preferably 80~
85℃；The time of the acidleach is preferably 6~12h, more preferably 8~10h.
After obtaining acid dip solution, the pH value using the inorganic base substance regulation acid dip solution of the invention to 3~5 is removed
Al3+And Fe3+, then using inorganic base substance continue adjust solution pH value to 7~9 remove PO4 3-, obtain except mixture solution.
In the present invention, the inorganic base substance preferably includes CaO, NaOH, Ca (OH)2、Na2CO3With in KOH
Plant or several mixtures；As removing Al3+And Fe3+When, the inorganic base substance is more preferably NaOH or Na2CO3, most preferably
It is Na2CO3, the removing Al3+And Fe3+When solution temperature be preferably 70~90 DEG C, more preferably 75~85 DEG C, the removing
Al3+And Fe3+'sReaction time is preferably 1~6h, more preferably 2~4h；As removing PO4 3-When, the inorganic base substance is more excellent
Elect CaO or Ca (OH) as2, most preferably Ca (OH)2, the removing PO4 3-When solution temperature be preferably 80~100 DEG C, more preferably
It is 85~95 DEG C, the removing PO4 3-The reaction time is preferably 2~8h, more preferably 4~6h.
Obtain except after mixture solution, the present invention is described except the pH value of mixture solution is to 2~4 using inorganic acid regulation, then carry out the
One extraction, obtains the first raffinate and organic phase containing Cu, and first raffinate includes Mn2+、Co2+、Ni2+、Li+It is miscellaneous with micro
Matter, the trace impurity includes Cu2+、Fe3+And Al3+.The present invention preferably adjusts the pH value except mixture solution with inorganic acid
2.5~3.5.
In the present invention, the first extraction extractant preferably includes di-(2-ethylhexyl)phosphoric acid, isooctyl phosphoric acid
The mixture of one or more in single different monooctyl ester and efficient copper extractant AD100.In the present invention, the first extraction extraction
Take agent to use as a solution, the solvent of the first extraction extraction agent solution preferably includes sulfonated kerosene, chloroform, tetrachloro
Change the mixture of one or more in carbon；The first extraction extractant is preferably 1 with the mass ratio of solvent:4~3:2.
In the present invention, the first extraction extraction agent solution is preferably used after inorganic base substance saponification, first extraction
1 is preferably with the mass ratio of extractant and inorganic base substance:4~3:2, the inorganic base substance includes Ca (OH)2、NaOH
And NH3·H2The mixture of one or more in O, the present invention is to each inorganic alkaline thing in the inorganic base substance mixture
The consumption of matter does not have any special restriction, and those skilled in the art can according to actual needs select the inorganic base of any mass ratio
The mixture of property material.
In the present invention, except the volume ratio of mixture solution and the first extraction extractant is preferably 1 during first extraction：
0.2~0.4.
After first extraction, the first raffinate that will obtain of the present invention carries out follow-up extraction processing, will preferably obtain
The electrolytic recovery Cu after pickling of organic phase containing Cu.In the present invention, the detergent that the pickling is used includes inorganic acid, more preferably
It is hydrochloric acid and nitric acid.
In the present invention, the time of the electrolysis be preferably 1~20h, more preferably 6~12h；The electrolysis temperature is preferred
It is 20~50 DEG C, more preferably 30~40 DEG C；The current density of the electrolysis is preferably 100~300A/m2, more preferably 150
~250A/m2, electrolytic pole board spacing is preferably 0.5~10cm, preferably 3~6cm, the tank voltage during electrolysis during electrolysis
Preferably 1~3V, more preferably 1.5~2.5V.
After obtaining the first raffinate, the present invention adjusts the pH of first raffinate using inorganic acid and inorganic base substance
Value is to 2~2.5, then carries out the second extraction, obtains the second raffinate and impure organic phase, and second raffinate includes
Mn2+、Co2+、Ni2+And Li+。
In the present invention, the second extraction extractant is preferably di-(2-ethylhexyl)phosphoric acid；Second extraction
Preferably used as a solution with extractant, it is described second extraction with extraction agent solution solvent include sulfonated kerosene, chloroform,
The mixture of one or more in carbon tetrachloride, the second extraction extractant is 1 with the mass ratio of solvent:4~1:1.
In the present invention, the second extraction extraction agent solution is preferably used after inorganic base substance saponification, second extraction
1 is preferably with the mass ratio of extractant and inorganic base substance:4~3:2, the inorganic base substance includes Ca (OH)2、NaOH
And NH3·H2The mixture of one or more in O, the present invention is to each inorganic alkaline thing in the inorganic base substance mixture
The consumption of matter does not have any special restriction, and those skilled in the art can according to actual needs select the inorganic base of any mass ratio
The mixture of property material.
In the present invention, the volume ratio of the first raffinate and the second extraction extractant is preferably 1 during second extraction：
0.2~0.5, more preferably 1：0.3~0.4.
After obtaining the second raffinate, the pH value using inorganic base substance regulation second raffinate of the invention to 2.6
~4, then the 3rd extraction is carried out, the 3rd raffinate and organic phase containing Mn are obtained, the 3rd raffinate includes Co2+、Ni2+And Li+。
The pH value that the present invention preferably adjusts second raffinate with inorganic base substance is 3~3.5.
In the present invention, the 3rd extraction extractant preferably includes di-(2-ethylhexyl)phosphoric acid, isooctyl phosphoric acid
The mixture of one or more in single different monooctyl ester, two (2,4,4- tri-methyl-amyls) hypophosphorous acid and trialkylamine.The present invention is right
The consumption of extractant does not have any special restriction in the extractant mixture, and those skilled in the art can be according to actual needs
Select the mixture of the extractant of any mass ratio.
In the present invention, the 3rd extraction extractant is preferably used as a solution, the second extraction extraction
The mixture of one or more that the solvent of agent solution is included in sulfonated kerosene, chloroform, carbon tetrachloride is taken, the 3rd extraction is used
Extractant is 1 with the mass ratio of solvent:4~13:7.In the present invention, the 3rd extraction extraction agent solution is preferably through inorganic
Used after alkaline matter saponification, the 3rd extraction extractant is preferably 1 with the mass ratio of inorganic base substance:4~3:2,
The inorganic base substance includes Ca (OH)2, NaOH and NH3·H2The mixture of one or more in O, the present invention is to described
The consumption of each inorganic base substance does not have any special restriction in inorganic base substance mixture, and those skilled in the art can root
According to the mixture for being actually needed the inorganic base substance for selecting any mass ratio.
In the present invention, the volume ratio of the second raffinate and the 3rd extraction extractant is preferably 1 during the 3rd extraction：
0.2~0.5, more preferably 1：0.3~0.4.
After 3rd extraction, the 3rd raffinate and organic phase containing Mn are obtained, the present invention preferably will the organic phase containing Mn
Through pickling and concentration, MnSO is obtained4·H2O.In the present invention, the washing lotion of the pickling is sulfuric acid；The temperature of the concentration is preferred
It is 80~90 DEG C；The time of the concentration is preferably 1~10h, more preferably 3~6h.
After obtaining the 3rd raffinate, the present invention coordinates regulation the 3rd raffinate using inorganic acid and inorganic base substance
PH value to 4.5~5, then carry out the 4th extraction, obtain the 4th raffinate and organic phase containing Co, the 4th raffinate includes
Ni2+And Li+。
In the present invention, the 4th extraction extractant preferably includes di-(2-ethylhexyl)phosphoric acid, isooctyl phosphoric acid
The mixture of one or more in single different monooctyl ester, two (2,4,4- tri-methyl-amyls) hypophosphorous acid and trialkylamine.The present invention is right
The consumption of each extractant does not have any special restriction in the extractant mixture, and those skilled in the art can be according to actual need
Select the mixture of the extractant of any mass ratio.
In the present invention, the 4th extraction extractant is preferably used as a solution, the 4th extraction extraction
The mixture of one or more that the solvent of agent solution is included in sulfonated kerosene, chloroform, carbon tetrachloride is taken, the 4th extraction is used
Extractant is 1 with the mass ratio of solvent:4~1:1.In the present invention, the 4th extraction extraction agent solution is preferably through inorganic
Used after alkaline matter saponification, the 4th extraction extractant is that saponification rate is 3 with the mass ratio of inorganic base substance:7~
7:3, the inorganic base substance includes Ca (OH)2, NaOH and NH3·H2The mixture of one or more in O, the present invention is right
The consumption of each inorganic base substance does not have any special restriction, those skilled in the art in the inorganic base substance mixture
The mixture of the inorganic base substance of any mass ratio can according to actual needs be selected.
In the present invention, the volume ratio of the 3rd raffinate and the 4th extraction extractant is preferably 1 during the 4th extraction：
0.5~1.2, more preferably 1：0.7~0.9.
After 4th extraction, the 4th raffinate and organic phase containing Co are obtained, the present invention preferably will the organic phase containing Co
Through pickling and concentration, CoSO is obtained4·7H2O.In the present invention, the pickling uses sulfuric acid；The temperature of the concentration is preferably
80~100 DEG C, more preferably 85~95 DEG C；The time of the concentration is preferably 1~10h, more preferably 2~5h.
After obtaining the 4th raffinate, the pH value using inorganic base substance regulation the 4th raffinate of the invention to 5.1
~5.5, then the 5th extraction is carried out, solution containing Ni and solution containing Li are obtained, the inorganic base substance is NaOH.
In the present invention, the 5th extraction extractant is preferably used as a solution, the 5th extraction extraction
The mixture of one or more that the solvent of agent solution is included in sulfonated kerosene, chloroform, carbon tetrachloride is taken, the 5th extraction is used
Extractant is 1 with the mass ratio of solvent:4~1:1.In the present invention, the 5th extraction extraction agent solution is preferably through inorganic
Used after alkaline matter saponification, the 5th extraction extractant is that saponification rate is 3 with the mass ratio of inorganic base substance:7~
7:3, the inorganic base substance includes Ca (OH)2, NaOH and NH3·H2The mixture of one or more in O, the present invention is right
The consumption of each inorganic base substance does not have any special restriction, those skilled in the art in the inorganic base substance mixture
The mixture of the inorganic base substance of any mass ratio can according to actual needs be selected.
In the present invention, the 4th raffinate and the 5th extractant are preferably 1 by volume during the 5th extraction：0.5~
1.2。
In the present invention, the solution containing Ni condensing crystallizing after pickling, obtains NiSO4·6H2O.In the present invention, institute
The temperature for stating concentration is preferably 90~100 DEG C, more preferably 90~95 DEG C；The time of the concentration is preferably 2~8h, more preferably
It is 4~5h.
In the present invention, the solution containing Ni is water phase, and the solution containing Li is organic phase, using those skilled in the art
Well known layered mode；Preferably use in embodiments of the present invention carries out multi_layer extraction in separatory funnel.
After obtaining solution containing Li, the present invention contains the pH value of Li solution to 12~14 using described in inorganic base substance regulation,
Li is obtained after the alkalescence solution containing Li that will be obtained and the 1~5h of saturated sodium carbonate solution hybrid reaction of heat2CO3, the inorganic alkaline
Material includes the mixture of one or more in NaOH, potassium hydroxide and calcium hydroxide, more preferably NaOH.
In the present invention, the temperature of the saturated sodium carbonate solution of the heat is preferably 70~90 DEG C, more preferably 80~85
℃；The concentration of the saturated sodium carbonate solution of the heat is preferably 2~4mol/L.
The invention provides a kind of method that valuable metal is reclaimed from waste and old polynary lithium ion battery, by waste and old polynary lithium
With hydrogen peroxide and inorganic acid mixing acidleach after ion battery positive electrode baking inphases, the pH value of acid dip solution is adjusted to 3
~5 remove Al3+And Fe3+, then the pH value of solution is adjusted to 7~9 removing PO4 3-Obtain except mixture solution, by except the pH of mixture solution
Value regulation carries out the first extraction to 2~4, obtain including manganese, cobalt, nickel, the first raffinate of lithium metal element and trace impurity copper,
Iron and aluminium element, the pH value of the first raffinate is adjusted to 2~2.5 carries out the second extraction, obtains including manganese, cobalt, nickel, lithium metal
Second raffinate of element, the pH value of the second raffinate is adjusted to 2.6~4 carries out the 3rd extraction, obtains including cobalt, nickel, lithium
3rd raffinate of metallic element, the pH value of the 3rd raffinate is adjusted to 4.5~5 carries out the 4th extraction, obtains including nickel, lithium
4th raffinate of metallic element, the pH value of the 4th raffinate is adjusted to 5.1~5.5, then carries out the 5th extraction, is contained
Ni solution and solution containing Li, the solution containing Ni is concentrated, and obtains NiSO4·6H2O, the pH value containing Li solution is adjusted to 12~
Saturated sodium carbonate solution after 14 with heat mixes, and obtains Li2CO3.The recovery method that the present invention is provided is to different types of waste and old more
First lithium ion battery can realize the recovery of valuable metal, and ensure valuable metal lithium, nickel, cobalt, manganese, copper high-recovery
Under the premise of, effectively remove the impurity elements such as aluminium, iron, it is ensured that product quality, added value of product is high, wherein the recovery of Cu, Mn and Li
Rate be both greater than the rate of recovery of 95%, Co and Ni more than 96%, the Cu rate of recovery be up to 96.23%, the Mn rate of recovery be up to 96.43%,
The rate of recovery that the Co rate of recovery is up to 96.73%, Ni is up to 97.56%, the Li rate of recovery and is up to 95.94%, and extraction feed is recycled
Recycle, economy is high, and the raw material, the equipment that use are simply, it is environmental friendly, it is simple easily controllable.
The method that valuable metal is reclaimed from waste and old polynary lithium ion battery provided the present invention with reference to embodiment
It is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Weigh waste and old polynary pole piece 1000.0g baking inphases.It is heat-treated for the first time in the 500 DEG C of roastings of 0.2Mpa nitrogen atmospheres
2h.It is heat-treated for the second time in 700 DEG C of roasting 3h of 0.5Mpa oxygen atmospheres, heating rate is controlled to 10 DEG C/min.
By solid-to-liquid ratio 1:Product of roasting is put into mol ratio 1 by 3:3rd, the H of total concentration 5mol/L2O2With H2SO4Mixed acid is molten
Liquid, extraction temperature is 95 DEG C, and stirring reaction 6h is filtrated to get 5L filtrates, is detected through ICP-AES, Cu, Ni, Co, Mn, Li, Al3+、
Fe3+Content be respectively 40.24g/L, 1.64g/L, 40.17g/L, 0.81g/L, 1.12g/L, 12.03g/L, 50.37g/L.
Solid Na is slowly added to toward filtrate2CO3Regulation pH value is 3.0, and solution temperature is 70 DEG C, and reaction 6h removes Al3+、
Fe3+, filter to get filtrate.Again toward being slowly added to solid Ca (OH) in filtrate2Regulation pH value is 9.0, and solution temperature is 80 DEG C, reaction
8h removes PO4 3-。
By the different monooctyl ester of isooctyl phosphoric acid list and sulfonated kerosene in mass ratio 1：After 4 dilutions, then by the extraction solution after dilution
With solid NaOH in mass ratio 3：2 saponification obtain the first extractant, will remove solution and the first extractant after ferro-aluminum by volume
1：0.2 extraction, 3mol/L H2SO4Regulation extraction system pH is 4.0.Organic phase is through 0.5mol/L H after extraction2SO4Pickling is once
The first raffinate is obtained, pickle is 96.08% through reclaiming metals blister copper 193.31g, the Cu rate of recovery.Electrolytic process parameter
It is electrolysis time 1h, 50 DEG C of electrolysis temperature, it is 300A/m that current density is excellent2, electrolytic pole board spacing 0.5cm, tank voltage 3V.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 1：1 dilution after, then with solid NaOH in mass ratio 1：4
Saponification obtains the second extractant, 3mol/L H2SO4Regulation extraction system pH is 2.5, and the first raffinate is pressed with the second extractant
Volume ratio 1：0.5, the impurity such as micro Cu, Fe, Ca, Al in solution removed through extraction separates liquid phase and obtains the second raffinate.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 1：4 dilution after, then with solid NaOH in mass ratio 3：2
Saponification obtains the 3rd extractant, by the second raffinate and the 3rd extractant by volume 1：0.5 is extracted, and 4mol/LNaOH is adjusted
Section extraction system pH is 2.6.Organic phase is through 0.5mol/L H2SO4The 3rd raffinate containing Mn that pickling is once obtained afterwards is through 80 DEG C
Chemical pure MnSO is obtained after evaporating, concentrating and crystallizing 10h4.H2O 11.91g, the Mn rate of recovery are 95.61%.
The different monooctyl ester of isooctyl phosphoric acid list and two (2,4,4- tri-methyl-amyls) hypophosphorous acid extractant mol ratios 5：2 and sulfonated coal
Oil dilution in mass ratio 1：1 dilution after, then with solid NaOH in mass ratio 3：7 saponification obtain the 4th extractant, by the 4th extraction
Agent with except the raffinates of Mn the 3rd by volume 1：1.2 are extracted, and 4mol/LNaOH regulation extraction systems pH is 5.0.After separation
The 4th raffinate and organic phase are obtained, organic phase is through 0.5mol/L H2SO4After pickling, then after 100 DEG C of evaporating, concentrating and crystallizing 1h
Obtain chemical CoSO4·7H2O 921.86g, the Co rate of recovery are 96.20%.4th raffinate and the 5th extractant by volume 1：
After 1.2 extractions, the 5th extractant is identical with the 4th extractant, and the organic phase of separation is through 0.5mol/L H2SO4After pickling, then pass through
100 DEG C of concentration and evaporation crystallization 2h obtain chemical pure NiSO4·6H2The rate of recovery of O 35.82g, Ni is 97.56%.
Filtrate is adjusted pH to 12 by 4mol/L NaOH, and sinker temperature 70 C adds 70 DEG C of 4mol/L
Na2CO396.4ml, reacts 1h, and filtering, 90 DEG C of hot washes obtain Li 5 times2CO328.49g, the rate of recovery is 95.53%.
Embodiment 2
Weigh waste and old polynary pole piece 1500.0g baking inphases.It is heat-treated for the first time in the 300 DEG C of roastings of 0.5Mpa nitrogen atmospheres
4h.It is heat-treated for the second time in 600 DEG C of roasting 6h of 1Mpa oxygen atmospheres, heating rate is controlled to 10 DEG C/min.
By solid-to-liquid ratio 1:Product of roasting is put into mol ratio 1 by 7:8th, the H of total concentration 5mol/L2O2With H2SO4Mixed acid is molten
Liquid, extraction temperature be 60 DEG C, stirring reaction 12h is filtrated to get 8.0L filtrates, through ICP-AES detect, Cu, Ni, Co, Mn, Li,
Al3+、Fe3+Content be respectively 36.43g/L, 8.36g/L, 27.17g/L, 7.91g/L, 1.32g/L, 12.03g/L,
30.87g/L。
Solid Na is slowly added to toward filtrate2CO3Regulation pH value is 5.0, and solution temperature is 90 DEG C, and reaction 1h removes Al3+、
Fe3+, filter to get filtrate.Again toward being slowly added to solid Ca (OH) in filtrate2Regulation pH value is 7, and solution temperature is 100 DEG C, reaction
2h removes PO4 3-。
By the different monooctyl ester of isooctyl phosphoric acid list and sulfonated kerosene in mass ratio 3：After 2 dilutions, then by the extraction solution after dilution
With solid NaOH in mass ratio 1：4 saponification obtain the first extractant, will remove solution and the first extractant after ferro-aluminum by volume
1：0.4 extraction, 3mol/L H2SO4Regulation extraction system pH is 2.Organic phase is through 0.5mol/L H after extraction2SO4Pickling is once obtained
To the first raffinate, pickle is 95.46% through reclaiming metals blister copper 278.21g, the Cu rate of recovery.Electrolytic process parameter is
Electrolysis time 20h, 20 DEG C of electrolysis temperature, it is 100A/m that current density is excellent2, electrolytic pole board spacing 10cm, tank voltage 1V.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 1：4 dilution after, then with solid NaOH in mass ratio 3:2
Saponification obtains the second extractant, 3mol/L H2SO4Regulation extraction system pH is 2, and the first raffinate and the second extractant are pressed into body
Product compares 1：0.2, the impurity such as micro Cu, Fe, Ca, Al in solution removed through extraction separates liquid phase and obtains the second raffinate.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 13:7 dilution after, then with solid NaOH in mass ratio 1：
4 saponification obtain the 3rd extractant, by the second raffinate and the 3rd extractant by volume 1：0.2 is extracted, 4mol/LNaOH
Regulation extraction system pH is 4.Organic phase is through 0.5mol/L H2SO4The 3rd raffinate containing Mn that pickling is once obtained afterwards is through 90 DEG C
Chemical pure MnSO is obtained after evaporating, concentrating and crystallizing 1h4.H2O 187.53g, the Mn rate of recovery are 96.43%.
The different monooctyl ester of isooctyl phosphoric acid list and two (2,4,4- tri-methyl-amyls) hypophosphorous acid extractant mol ratios 2：3 and sulfonated coal
Oil dilution in mass ratio 1：4 dilution after, then with solid NaOH in mass ratio 7:3 saponification obtain the 4th extractant, by the 4th extraction
Agent with except the raffinates of Mn the 3rd by volume 1：0.5 is extracted, and 4mol/LNaOH regulation extraction systems pH is 5.After separation
To the 4th raffinate and organic phase, organic phase is through 0.5mol/L H2SO4After pickling, then after 80 DEG C of evaporating, concentrating and crystallizing 10h
To chemical pure CoSO4·7H2O 1007.20g, the Co rate of recovery are 96.73%.4th raffinate and the 5th extractant are by volume
1：After 0.5 extraction, the 5th extractant is identical with the 4th extractant, and the organic phase of separation is through 0.5mol/L H2SO4After pickling, then pass through
90 DEG C of concentration and evaporation crystallization 8h obtain chemical pure NiSO4·6H2The rate of recovery of O 290.31g, Ni is 97.32%.4mol/L
Filtrate is adjusted pH to 14 by NaOH, and 90 DEG C of sinker temperature adds 90 DEG C of 2mol/L Na2CO3182.6ml, reacts 5h, filter,
90 DEG C of hot washes obtain Li 5 times2CO328.49g, the rate of recovery is 95.94%.
Embodiment 3
Weigh waste and old polynary pole piece 1000.0g baking inphases.It is heat-treated for the first time in the 400 DEG C of roastings of 0.4Mpa nitrogen atmospheres
4h.It is heat-treated for the second time in 680 DEG C of roasting 5h of 0.9Mpa oxygen atmospheres, heating rate is controlled to 10 DEG C/min.
By solid-to-liquid ratio 1:Product of roasting is put into mol ratio 1 by 5:3rd, the H of total concentration 5mol/L2O2With H2SO4Mixed acid is molten
Liquid, extraction temperature is 85 DEG C, and stirring reaction 8h is filtrated to get 5L filtrates, is detected through ICP-AES, Cu, Ni, Co, Mn, Li, Al3+、
Fe3+Content be respectively 40.76g/L, 1.73g/L, 39.85g/L, 0.78g/L, 1.04g/L, 11.73g/L, 42.83g/L.
Solid Na is slowly added to toward filtrate2CO3Regulation pH value is 4.5, and solution temperature is 80 DEG C, and reaction 4h removes Al3+、
Fe3+, filter to get filtrate.Again toward being slowly added to solid Ca (OH) in filtrate2Regulation pH value is 8.5, and solution temperature is 85 DEG C, reaction
4h removes PO4 3-。
By the different monooctyl ester of isooctyl phosphoric acid list and sulfonated kerosene in mass ratio 1：After 3 dilutions, then by the extraction solution after dilution
With solid NaOH in mass ratio 1：2 saponification obtain the first extractant, will remove solution and the first extractant after ferro-aluminum by volume
1：0.4 extraction, 3mol/L H2SO4Regulation extraction system pH is 4.0.Organic phase is through 0.5mol/L H after extraction2SO4Pickling is once
The first raffinate is obtained, pickle is 96.23% through reclaiming metals blister copper 196.12g, the Cu rate of recovery.Electrolytic process parameter
It is electrolysis time 1h, 50 DEG C of electrolysis temperature, it is 250A/m that current density is excellent2, electrolytic pole board spacing 2.5cm, tank voltage 1.9V.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 1：2 dilution after, then with solid NaOH in mass ratio 1：4
Saponification obtains the second extractant, 3mol/L H2SO4Regulation extraction system pH is 2.2, and the first raffinate is pressed with the second extractant
Volume ratio 1：0.3, the impurity such as micro Cu, Fe, Ca, Al in solution removed through extraction separates liquid phase and obtains the second raffinate.
Di-(2-ethylhexyl)phosphoric acid and sulfonated kerosene in mass ratio 1：5 dilution after, then with solid NaOH in mass ratio 1：2
Saponification obtains the 3rd extractant, by the second raffinate and the 3rd extractant by volume 1：0.4 is extracted, and 4mol/LNaOH is adjusted
Section extraction system pH is 3.2.Organic phase is through 0.5mol/L H2SO4The 3rd raffinate containing Mn that pickling is once obtained afterwards is through 80 DEG C
Chemical pure MnSO is obtained after evaporating, concentrating and crystallizing 5h4.H2O 11.55g, the Mn rate of recovery are 96.37%.
The different monooctyl ester of isooctyl phosphoric acid list and two (2,4,4- tri-methyl-amyls) hypophosphorous acid extractant mol ratios 3：2 and sulfonated coal
Oil dilution in mass ratio 1：1 dilution after, then with solid NaOH in mass ratio 1：2 saponification obtain the 4th extractant, by the 4th extraction
Agent with except the raffinates of Mn the 3rd by volume 1：0.7 is extracted, and 4mol/LNaOH regulation extraction systems pH is 5.0.After separation
The 4th raffinate and organic phase are obtained, organic phase is through 0.5mol/L H2SO4After pickling, then after 90 DEG C of evaporating, concentrating and crystallizing 5h
To chemical pure CoSO4·7H2O 919.56g, the Co rate of recovery are 96.34%.4th raffinate and the 5th extractant by volume 1：
After 0.9 extraction, the 5th extractant is identical with the 4th extractant, and the organic phase of separation is through 0.5mol/L H2SO4After pickling, then through 90
DEG C concentration and evaporation crystallization 4h obtains chemical pure NiSO4·6H2The rate of recovery of O 36.92g, Ni is 96.26%.4mol/L NaOH will
Filtrate adjusts pH to 12, and sinker temperature 70 C adds 70 DEG C of 4mol/L Na2CO389.6ml, reacts 2h, filtering, 90 DEG C of hot water
Washing obtains Li 5 times2CO326.49g, the rate of recovery is 95.71%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method that valuable metal is reclaimed from waste and old polynary lithium ion battery, comprises the following steps：
(1) by waste and old polynary anode material for lithium-ion batteries baking inphases, product of roasting is obtained；
(2) mixing the product of roasting that the step (1) is obtained with hydrogen peroxide and inorganic acid carries out acidleach, obtains acidleach molten
Liquid；
(3) pH value of the acid dip solution that the step (2) obtains is adjusted using inorganic base substance and removes Al to 3~53+And Fe3+,
Be further continued for using inorganic base substance regulation solution pH value to 7~9 remove PO4 3-, obtain except mixture solution；
(4) step (3) is adjusted using inorganic acid and obtains the pH value except mixture solution to 2~4, then carry out the first extraction, obtained
First raffinate and organic phase containing Cu, first raffinate include Mn2+、Co2+、Ni2+、Li+And trace impurity, it is described micro
Impurity includes Cu2+、Fe3+And Al3+；
(5) pH value of the first raffinate that the step (4) obtains is adjusted to 2~2.5 using inorganic acid and inorganic base substance,
The second extraction is carried out again, the second raffinate and impure organic phase is obtained, and second raffinate includes Mn2+、Co2+、Ni2+
And Li+；
(6) pH value of the second raffinate that the step (5) obtains is adjusted to 2.6~4 using inorganic base substance, then carries out the
Three extractions, obtain the 3rd raffinate and organic phase containing Mn, and the 3rd raffinate includes Co2+、Ni2+And Li+；
(7) pH value of the 3rd raffinate that the step (6) obtains is adjusted to 4.5~5 using inorganic acid and inorganic base substance,
The 4th extraction is carried out again, the 4th raffinate and organic phase containing Co is obtained, and the 4th raffinate includes Ni2+And Li+；
The pH value of the 4th raffinate is adjusted to 5.1~5.5 using inorganic base substance, then carries out the 5th extraction, obtained
Solution containing Ni and solution containing Li；
(8) pH value containing Li solution that the inorganic base substance regulation step (7) obtains to 12~14, the alkali that will be obtained is used
Property solution containing Li with heat saturated sodium carbonate solution reaction, obtain Li2CO3；
The solution containing Ni is concentrated, NiSO is obtained4·6H2O。
2. method according to claim 1, it is characterised in that baking inphases include two-stage roasting in the step (1), the
One section of roasting is carried out in a nitrogen atmosphere, and second segment roasting is carried out under oxygen atmosphere.
3. method according to claim 2, it is characterised in that the two-stage roasting is：
Waste and old polynary anode material for lithium-ion batteries is carried out into first paragraph roasting, the temperature of the first paragraph roasting is 300~500
DEG C, the time of the first paragraph roasting is 2~4h；
The product that the first paragraph is calcined is carried out into second segment roasting, product of roasting is obtained, the temperature of the second segment roasting is
600~700 DEG C, the time of the second segment roasting is 3~6h.
4. method according to claim 1, it is characterised in that hydrogen peroxide is in the form of hydrogen peroxide in the step (2)
Add, the mass concentration of the hydrogen peroxide is 10~30%, the matter of the gross mass and product of roasting of the hydrogen peroxide and inorganic acid
Amount is than being 3~8:1.
5. method according to claim 1, it is characterised in that the first extraction includes two with extractant in the step (4)
The mixture of one or more in (2- ethylhexyls) phosphoric acid, the different monooctyl ester of isooctyl phosphoric acid list and efficient copper extractant；
The second extraction extractant is di-(2-ethylhexyl)phosphoric acid in the step (5)；
In the step (6) in the 3rd extraction extractant and the step (7) the 4th extraction extractant independently selected from two
In (2- ethylhexyls) phosphoric acid, the different monooctyl ester of isooctyl phosphoric acid list, two (2,4,4- tri-methyl-amyls) hypophosphorous acid and trialkylamine
The mixture of one or more.
6. method according to claim 1, it is characterised in that the pH value in the step (4) except mixture solution is adjusted to 2.5
~3.5.
7. method according to claim 1, it is characterised in that the pH value of the second raffinate is adjusted to 3 in the step (6)
~3.5.
8. method according to claim 1, it is characterised in that also include after the first extraction in the step (4)：Will be described
Organic phase containing Cu obtains metallic copper through pickling, electrolysis.
9. method according to claim 1, it is characterised in that also include after the 3rd extraction in the step (6)：Will be described
Organic phase containing Mn obtains MnSO through pickling and concentration4·H2O。
10. method according to claim 1, it is characterised in that also include after the 4th extraction in the step (7)：By institute
Organic phase containing Co is stated through pickling and concentration, CoSO is obtained4·7H2O。
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