CN106319228B - A kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing - Google Patents
A kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing Download PDFInfo
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- CN106319228B CN106319228B CN201610737450.8A CN201610737450A CN106319228B CN 106319228 B CN106319228 B CN 106319228B CN 201610737450 A CN201610737450 A CN 201610737450A CN 106319228 B CN106319228 B CN 106319228B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of methods of recycling nickel cobalt manganese synchronous from the sulphuric leachate of nickel and cobalt containing manganese waste slag, this method first passes through oxidation-precipitation method by the iron in leachate, aluminium removes, copper is extracted again, extracting zinc again, finally again using tributyl phosphate extraction nickel cobalt manganese synchronous with the neodecanoic acid of saponification, nickel cobalt manganese in nickel cobalt manganese waste slag leachate can be realized synchronous extraction and recovery by this method, calcium in material liquid, magnesium will not have an impact extraction process, it reduces and nickel is separately recovered, cobalt, the separation costs of manganese element, reduce the cost of material for preparing nickel cobalt manganese salt ternary battery material.
Description
Technical field
The present invention relates to environmental protections and resource circulation utilization field, and in particular to one kind is synchronous from nickel and cobalt containing manganese waste slag
The method for recycling nickel cobalt manganese.
Background technology
Nickel-cobalt-manganternary ternary anode material is Olivine-type Cathode Material in Li-ion Batteries, with capacity is high, thermal stability is good, property
Valency than it is high the advantages that.Nickel cobalt manganese salt is to prepare the primary raw material of nickel-cobalt-manganternary ternary anode material presoma, generally use cobaltous sulfate,
Nickel sulfate and manganese sulfate are hydrolyzed crystallization and prepare nickel-cobalt-manganese ternary presoma under alkaline condition by a certain percentage.
Cobalt majority and nickel phase association, occur in mineral, simultaneously mostly such as in nickel laterite.It can generate and contain in many industries
The waste residue of the valuable metals such as nickel, cobalt, such as electric nickel waste residue containing cobalt, discard power battery material, dead catalyst, it is more in these waste residues
Number also simultaneously containing higher manganese, has very high recovery value, they can be carried out to recycling and be used to prepare nickel-cobalt-manganese ternary
Presoma.
The main way of the waste residue of processing nickel and cobalt containing manganese is by extracting nickel-cobalt-manganese ternary element respectively after acidleach at present
It takes separation or cobalt salt, nickel salt and manganese salt is respectively obtained using chemical precipitation method, then carry out deep processing again, but it is to nickel cobalt manganese
Organic efficiency it is usually relatively low, and technique is cumbersome.Further, since magnesium is impurity more typical in nickel cobalt waste residue, especially I
Nickel raw material-laterite of state is High Mg raw materials, thus the content of magnesium is very high in its acid leaching liquor.Due to the shadow of magnesium addition
It rings, needs first first to detach nickel cobalt manganese with magnesium, thus the cost of raw material is higher.
Invention content
In view of this, the present invention provides a kind of method of recycling nickel cobalt manganese synchronous in manganese waste slag from nickel and cobalt containing, this method
Can be by nickel, cobalt and the synchronous extraction and recovery of manganese realization in the sulphuric leachate of nickel and cobalt containing manganese waste slag, calcium, magnesium pair in material liquid
Extraction process will not produce influence, reduce the separation costs that nickel, cobalt, manganese element is separately recovered, and reduce and prepare nickel cobalt manganese three
The cost of material of first positive electrode.
The present invention provides a kind of methods of recycling nickel cobalt manganese synchronous in manganese waste slag from nickel and cobalt containing, include the following steps：
(1) sulfuric acid leaching：Nickel and cobalt containing manganese waste slag is taken, sulfuric acid is added in and carries out acidleach, be separated by filtration solid-liquid, collect leachate；
(2) except iron, aluminium：The leachate is taken, adds in oxidant, pH=5.0-5.5 is adjusted, makes iron, the aluminium in leachate
Element precipitates, and then filters, and obtains except the filtrate after iron aluminium, wherein, the oxidant is sodium chlorate；
(3) extracting copper：Take the filtrate in above-mentioned steps (2), adjust pH=2.0-2.5, add in Mextral984H or
The first organic extractant that CP150 is formed with diluent, through cupric organic phase and the first raffinate is obtained by extraction；
(4) extracting zinc：First raffinate is taken, adjusts pH=2.0-2.3, adds in the P507 of saponification and kerosene mixing shape
Into the second organic extractant, the organic phase through the second raffinate is obtained by extraction and containing zinc, a small amount of manganese；
The organic phase containing zinc, a small amount of manganese with dilute sulfuric acid is washed, then be stripped with sulfuric acid, is obtained containing Zn, Mn
Sulfate, then extraction and separation are carried out using P204 to the sulfate containing Zn, Mn, obtain zinc sulfate and manganese sulfate；
(5) synchronous extraction nickel cobalt manganese：Second raffinate is taken, adjusts pH=1.7-2.3, adds in tributyl phosphate
(TBP) and the mixed extractant that is formed of the neodecanoic acid of saponification and diluent, the organic phase of nickel and cobalt containing manganese is obtained through counter-current extraction；Its
In, the volume ratio O/A of the counter-current extraction time control organic phase and water phase is 1/1~1/2, in the mixed extractant, phosphoric acid
The volume fraction of tributyl is 5-10%, and the volume fraction of the neodecanoic acid of saponification is 20%~30%；
The organic phase of the nickel and cobalt containing manganese is washed with dilute sulfuric acid, to remove the calcium of deentrainment, magnesium addition, then use sulfuric acid
Countercurrent reextraction is carried out, obtains the sulfate of nickel cobalt manganese.
In the embodiment of the present invention, the nickel and cobalt containing manganese waste slag is the mixture of a variety of nickel and cobalt containing manganese waste materials and ore, as long as
It is that the raw material containing ingredients such as listed Ni, Co, Mn, Mg, Fe, Al, Cu, Ca, Zn can use the method in the present invention.It is described nickeliferous
Cobalt manganese waste slag may come from the mixtures such as refuse battery, manganese liquid purification slag, low-grade laterite.
In step (1), into the nickel cobalt manganese waste slag adding in sulfuric acid carries out acidleach, can make Ni, Co in waste residue, Mn,
The cycling of elements such as Mg, Fe, Al, Cu, Ca, Zn, Fe is ionic species and enter in leachate, and it is molten to obtain the mixing containing ion
Liquid is conducive to further separate and recover it.Containing members such as Ni, Co, Mn, Mg, Fe, Al, Cu, Ca, Zn, Fe in the leachate
Element.Li ions are free of in the leachate.
Preferably, the solid-to-liquid ratio of the nickel cobalt manganese waste slag and the sulfuric acid of the acidleach is (100-150)：1g/L, it is described
The temperature of acidleach is 50~80 DEG C, and the time of acidleach is 15~35min, and pH when leaching terminal for controlling the acidleach is 0.5
~1.2；Mixing speed 150-200rpm during the acidleach.
It is further preferred that the mass fraction of the sulfuric acid used in the acidleach is 20-30%.
Step (2) is primarily to remove the Fe in the leachate2+、Fe3+And Al3+Ion obtains Al after aging
(OH)3、Fe(OH)3Precipitation.PH to 5.0-5.5 is adjusted in step (2), it is preferable can both to have ensured that oxidant had on this condition
Oxidisability, make Fe2+Fully it is oxidized to Fe3+, while ensure Fe again3+And Al3+From can fully be deposited on this condition, with
Exempt to interfere with dedoping step below.PH is adjusted in step (2) to be carried out using sodium hydroxide solution or ammonium hydroxide.
In step (2), the iron made in leachate, aluminium element precipitate specially：In the case where temperature is 50-60 DEG C
It is aged 30-60min.
Preferably, in step (2), the addition of the oxidant is that the theoretical of the oxidation leachate ferrous ions needs
To be measured 1.5-2.5 times.
It is further preferred that in step (2), the oxidant is sodium chlorate, and the mole of the sodium chlorate is the leaching
Go out 0.3-0.42 times of the mole of liquid ferrous ions.
It is further preferred that in step (2), the oxidant is sodium hypochlorite, and the mole of the sodium hypochlorite is institute
State the mole of leachate ferrous ions 0.75-1.0 times.
In the application, the operation in step (3) is primarily to remove the Cu elements except in iron aluminium filtrate, after extraction
First raffinate in contain Ni, Co, Mn, Mg, Ca, Zn element.
Preferably, in step (3), volumes of the Mextral 984H or CP150 in first organic extractant
Score is 20-30%；The volume ratio of first organic extractant (organic phase) and the filtrate (water phase) except after iron aluminium is
1/1~1/2.Mextral 984H or CP150 are copper extractant, after extraction, make Cu2+Into organic phase, enter other ions
Water phase, so as to fulfill existing Cu2+With the separation of other ions, obtain purity it is higher containing Cu2+Organic phase.Wherein, cupric organic phase
The first raffinate also containing a small amount of cobalt and entrainment, is washed by dilute sulfuric acid, can be removed, in order to avoid influence returning for copper
It receives.
Preferably, in step (3), the extraction is carried out at 30~50 DEG C.
Preferably, in step (3), the diluent is sulfonated kerosene or Mextral DT100.
It is further preferred that when using Mextral 984H, the diluent is Mextral DT100；Work as use
During CP150, the diluent is sulfonated kerosene or Mextral DT100.Certainly, other diluents can also be used.
Preferably, it in step (3), further includes：The cupric organic phase is taken, it is washed, then uses using dilute sulfuric acid
Sulfuric acid is stripped, and obtains copper-bath.
It is further preferred that in step (3), in the stripping process, control cupric organic phase and water phase (sulfuric acid solution)
Volume ratio be 4/1~2/1.
It is further preferred that in step (3), 20~40 DEG C of the temperature of the back extraction.
It is further preferred that in step (3), the pH=3.5-4.0 of the dilute sulfuric acid of the cupric organic phase is washed；Back extraction
A concentration of 0.8-1.5mol/L of sulfuric acid during cupric organic phase.It is further preferred that the dilute sulfuric acid of the washing is dense
It spends for 0.1-0.32mmol/L.
Preferably, in step (3), the extraction is extracted for 1 grade, extraction time 3-5min；The back extraction is anti-for 1 grade
Extraction.The copper-bath that back extraction obtains in step (3) can prepare copper sulfate crystal by evaporation and concentration；What back extraction obtained has
Machine is mutually the first organic extractant after extraction, can be with recycling.
In step (4), when being extracted using P507, most of manganese is remained in the second raffinate, a small amount of manganese with
Enter organic phase together with a large amount of zinc.Contain Ni, Co, Mn, Mg, Ca element in second raffinate.Using sulfuric acid to having
Machine is mutually stripped, the organic phase that the back extraction of step (4) generates for P507, can will be returned again to after its saponification to extraction stages after
It is continuous to use；And sulfur acid zinc and manganese sulfate in the water phase after being stripped, it reuses P204 and carries out extraction and separation.
Preferably, it is at 20~40 DEG C in temperature in step (4), when second organic extractant being used to be extracted
It carries out.
Preferably, in step (4), in second organic extractant, the volume fraction of the P507 of the saponification is
20%~30%, in the volume ratio (O/A) of extraction time control organic phase and water phase for 1/1~1/2, i.e. the second organic extractant with
The volume ratio of first raffinate is 1/1~1/2.
Preferably, in step (4), the P507 of the saponification be use mass fraction for 20% NaOH solution by 40~
60% saponification rate carries out saponification to P507 and obtains.That is, the saponification rate of the P507 is 40~60%.
It is further preferred that in step (4), the pH=3.5- containing zinc, the dilute sulfuric acid of the organic phase of a small amount of manganese is washed
4.0；A concentration of 0.8-1.5mol/L of sulfuric acid during back extraction.
In the step (4) of the present invention, when being extracted using P507, under pH=2.0-2.3 during extracting zinc, may be a small amount of
Calcium, cobalt can be also extracted into organic phase.Organic phase containing zinc, a small amount of manganese is removed into deentrainment with the purpose that dilute sulfuric acid washs
Calcium, cobalt, and a small amount of manganese can be washed off, reduce the extraction yield of manganese.Organic phase is washed after extraction, one can remove the water of deentrainment
Phase, two can remove ingredient extracted in extractant but weaker binding force.
Preferably, in step (4), it is described back extraction containing zinc, a small amount of manganese organic phase during, control organic phase (containing zinc,
The organic phase of a small amount of manganese) with the volume ratio (O/A) of water phase (sulfuric acid) it is 4/1~2/1.Wherein, the temperature 20 during the back extraction~
40℃。
It is further preferred that in step (4), the extraction that the second organic extractant carries out is used as 1 grade of extraction；The back extraction
For 1 grade of back extraction.
It is further preferred that in step (4), it is described that extraction and separation are carried out using P204, specially：
The sulfate containing Zn, Mn is taken, adjusts pH=1.5~2.0, the P204 of saponification is added in and sulfonated kerosene is formed
Third organic extractant carries out two level counter-current extraction, the P204 of the saponification volume in the third organic extractant point
Number for 20-30%, control compared to O/A=1/1~1/2 (i.e. described third organic extractant and the sulfate containing Zn, Mn
Volume ratio), obtain organic phase containing zinc and manganese sulfate solution；
The organic phase containing zinc is subjected to washing 2-4 times with dilute sulfuric acid, to remove cobalt, calcium and the water phase carried secretly on a small quantity, then
1 grade of back extraction is carried out with sulfuric acid, O/A=2/1~1/2 is compared when control is stripped, obtains copper-bath；Phase when being wherein stripped
Than O/A=2/1~1/2.
In addition, temperature during back extraction organic phase containing zinc is 20~40 DEG C.P204 after back extraction can after returning to extraction section saponification
To be continuing with.
Preferably, the P204 of the saponification be use mass fraction for 20% NaOH solution by 40-60% saponification rate
Saponification is carried out to P204 to obtain.
It is further preferred that the pH=3.5-4.0 of the dilute sulfuric acid of the washing organic phase containing zinc；When being stripped organic phase containing zinc
A concentration of 0.8-1.5mol/L of sulfuric acid.
It in the step of the application (4), is first extracted using P507, then using P204 come extraction and separation zinc, manganese, P507 is in preceding master
If it for preferably extracting zinc, and reduces to the extraction of cobalt manganese and the extraction of calcium.
In step (5) in the application, using tributyl phosphate TBP and the neodecanoic acid of saponification as common extractant,
For the synchronous extraction of nickel, cobalt, manganese, using the synergistic effect between the two extractants, and regulate and control neodecanoic acid and the ratio of TBP
And pH value, it can realize the efficient extraction to nickel, cobalt, manganese these three metal ions, and magnesium addition is hardly to nickel cobalt manganese
Extraction impacts.Relative in the prior art, using extractants such as such as P507, P204, detached in the case where adjusting higher pH
Cobalt, nickel and a large amount of magnesium is easily caused also to enter for organic phase, the extracting process in the present invention is simpler, and extraction efficiency is high, miscellaneous
Matter influences small.
In the embodiment of the present invention, the neodecanoic acid also known as ten carbonic acid, versatic acid Versatic 10, versatic acid V10,
No. CAS is 26896-20-8.
Preferably, in step (5), the neodecanoic acid of the saponification be use mass fraction for 20% NaOH solution by 10~
30% saponification rate carries out saponification to neodecanoic acid and obtains.
Preferably, in step (5), the diluent is sulfonated kerosene or Mextral DT100.
It is further preferred that in step (5), the counter-current extraction is 5~10 grades；The counter-current extraction time control organic phase
Volume ratio O/A with water phase is 1/1.
Preferably, in step (5), the temperature of the counter-current extraction is 20~40 DEG C.
In the step (5) of the present invention, when being extracted to second raffinate, in addition to obtaining the organic of nickel and cobalt containing manganese
Outside phase, obtained water phase is the remaining solution containing calcium and magnesium ion and extremely a small amount of nickel cobalt manganese not being extracted,
Waste water workshop can be sent to and carry out processing discharge.
Preferably, in step (5), the pH=3.5-4.0 of the dilute sulfuric acid of the organic phase of the nickel and cobalt containing manganese is washed, washs 2-
4 times；A concentration of 0.8-1.5mol/L of the sulfuric acid of the countercurrent reextraction.
Preferably, in step (5), the countercurrent reextraction is 4~5 grades；The countercurrent reextraction time control organic phase and water phase
Volume ratio O/A=2/1~1/1.The organic phase obtained after the countercurrent reextraction is the mixed extractant, can be recycled
It utilizes.
Preferably, in step (5), the temperature of the countercurrent reextraction is 20~40 DEG C.
In foregoing invention content, as needed, adjust pH when used lye be sodium hydroxide solution or ammonium hydroxide, acid solution
For sulfuric acid.It is understood that when synchronous recycling nickel cobalt manganese in the hydrochloric acid leachate from nickel and cobalt containing manganese waste slag, correspondingly, institute
It is hydrochloric acid to state washing, adjust pH's, and back extraction preferably still uses sulfuric acid.
The advantageous effect of the application：
The present invention provides a kind of methods of recycling nickel cobalt manganese synchronous in manganese waste slag from nickel and cobalt containing, and this method is with nickel and cobalt containing manganese
Waste residue is raw material, by sulfuric acid leaching, obtains the leachate containing elements such as Ni, Co, Mg, Mn, Cu, Ca, Zn, then heavy by aoxidizing
Shallow lake method removes Fe, Al element, then extracting Cu again, extracts Zn and Mn, P204 extraction and separation Zn and Mn with P507 later；Finally again
Using tributyl phosphate TBP extraction nickel cobalt manganeses synchronous with the neodecanoic acid of saponification, the sulfate of nickel cobalt manganese, Ke Yitong are obtained after back extraction
Overregulate the raw material that the ratio between three kinds of elements of nickel cobalt manganese is further used as production nickel-cobalt-manganese ternary cell positive material presoma.
Nickel cobalt manganese in anode waste residue leachate can be realized synchronous extraction and recovery by the method for the present invention, and in material liquid
Calcium, magnesium upper influence will not be produced on extraction process, can subsequently be supplemented in the ratio of nickel-cobalt-manganternary ternary anode material production requirement
Other components.This method is simple for process, and exploitativeness is strong, reduces the separation costs that nickel, cobalt, manganese element is separately recovered, and then
Reduce the production cost for preparing nickel-cobalt-manganternary ternary anode material.Processing procedure is environmentally friendly, economical, efficient.This method is to copper
The rate of recovery up to 98%, 98.5% is reached to the rate of recovery of zinc, and synchronize in extraction process to the rate of recovery point of cobalt, nickel and manganese
It not can reach 98%, 97.5% and more than 60%, total recycling of manganese is up to 98%.
Description of the drawings
In order to illustrate more clearly of technical scheme of the present invention, attached drawing needed in embodiment will be made below
Simply introduce, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, general for this field
For logical technical staff, without creative efforts, other attached drawings are can also be obtained according to these attached drawings.
Fig. 1 is the process flow chart of the embodiment of the present invention one.
Specific embodiment
Below in conjunction with the attached drawing in embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clear
Chu is fully described by.
Embodiment one
The process flow chart in Fig. 1 is referred to, one kind is provided in the present embodiment one and is synchronized back from nickel and cobalt containing manganese waste slag
The method for receiving nickel cobalt manganese, includes the following steps：
(1) sulfuric acid leaching：Take nickel and cobalt containing manganese waste slag, the nickel and cobalt containing manganese waste slag comes from refuse battery, manganese liquid purification slag, low
The mixtures such as grade laterite；It is 100 according to solid-to-liquid ratio：1g/L adds in the sulfuric acid solution that mass fraction is 30% and carries out acidleach,
The temperature of acidleach is 50 DEG C, and the time of acidleach is 30min, and it is 1.0 to control pH when leaching terminal, is separated by filtration solid-liquid, is collected
Leachate；
Main component is a concentration of in the leachate：Ni 2.84g/L、Co 40.8g/L、Mg 12.7g/L、Mn
7.2g/L、Fe 1.53g/L、Al 93mg/L、Cu 770mg/L、Ca 547mg/L、Zn 631mg/L；
(2) except iron, aluminium：Above-mentioned leachate is taken, by 1.5 times of the theoretical requirement for aoxidizing the leachate ferrous ions
Add in oxidant sodium chlorate (i.e. n (NaClO3)=0.3n (Fe2+)), pH=5.5 is adjusted with NaOH, is aged at being 50 DEG C in temperature
30-60min, then plate compression, obtains except iron aluminium filtrate, Fe and Al ions are respectively with Al (OH)3、Fe(OH)3The form of precipitation
It is removed；
(3) extracting copper：Above-mentioned filtrate is taken, pH=2.0 is adjusted with sulfuric acid, Mextral 984H is selected to make copper extractant, it will
Its diluted with Mextral DT100 to be formed Mextral 984H volume fraction be 20% the first organic extractant, in temperature
It is that 1 grade of extraction is carried out at 30 DEG C, control stirs 4min, then stand 5min split-phases, obtain cupric organic phase compared to O/A=1/2
With the first raffinate；
The cupric organic phase using the dilute sulfuric acid of pH=4.0 is washed 1 time, removes the water phase of a small amount of cobalt and entrainment,
Then the sulfuric acid of a concentration of 0.8mol/L is used as back washing agent, and 1 grade of back extraction is carried out at being 20 DEG C in temperature, is controlled in stripping process
Compared to O/A=2/1,4min is stirred, 5min is then stood, obtains copper-bath；Copper-bath can after pervaporation, concentration
Copper sulfate crystal is prepared, the rate of recovery of copper reaches 98.5% in the step.
(4) extracting zinc：Mass fraction is used to carry out saponification to P507 by 60% saponification rate for 20% NaOH solution to obtain
To the P507 of saponification, and it is 20% to be diluted to volume fraction with sulfonated kerosene, obtains the second organic extractant；Take above-mentioned first extraction
Extraction raffinate adjusts pH=2.0, second organic extractant is used to carry out 1 grade of extraction in the case where temperature is 20 DEG C, control is compared to O/A
=1/2,4min is stirred, 5min split-phases is then stood, obtains the second raffinate and the organic phase containing zinc, a small amount of manganese, it is most of
Manganese and nickel, cobalt are remained in the second raffinate；
By it is described containing zinc, a small amount of manganese organic phase with the dilute sulfuric acid of pH=3.5 carry out washing 3 times, with removal entrainment calcium,
Magnesium, cobalt, and reduce the extraction yield of manganese, then carry out 1 grade of back extraction with the sulfuric acid of a concentration of 1mol/L compare O/A=2/ during back extraction
1,20 DEG C of temperature stirs 4min, then stands 5min, obtain the second organic extractant of sulfate and organic phase containing Zn, Mn, have
Machine is continuing with after mutually returning to extraction section saponification；
Extraction and separation are carried out using P204 to the sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, it is specific to grasp
Make as follows：The sulfate containing Zn, Mn is taken, adjusts pH=1.5 with sulfuric acid, addition thereto is diluted to volume with sulfonated kerosene
Score be 20% saponification P204 carry out two level counter-current extraction, the P204 of saponification be use mass fraction for 20% NaOH solution
Saponification is carried out to P204 to obtain, O/A=1/2 is compared when control extracts by 50% saponification rate, 30 DEG C of temperature stirs 4min,
Then 5min split-phases are stood, obtain organic phase containing zinc and manganese sulfate solution；Zinc is extracted into organic phase, and manganese is predominantly retained in
In water phase；The organic phase containing zinc is subjected to washing 2 times with the dilute sulfuric acid of pH=3.5, to remove cobalt, calcium and the water carried secretly on a small quantity
Then phase carries out 1 grade of back extraction with the sulfuric acid of 1.0mol/L, during back extraction compared to O/A=1/1,30 DEG C of temperature stirs 4min, so
After stand 5min, solution of zinc sulfate is obtained, wherein the P204 being stripped can be continuing with after can returning to extraction section saponification.
The step reaches the rate of recovery of zinc 98.7%, and the rate of recovery of manganese is 25.3%.
(5) synchronous extraction nickel cobalt manganese：Take above-mentioned second raffinate, adjust pH=1.7, add in tributyl phosphate (TBP) and
Versatic acid Versatic 10 (neodecanoic acid) is extracted together, and sulfonated kerosene is selected to make diluent, wherein before extraction
Versatic10 mass fractions be 30% sodium hydroxide saponification, saponification rate 20%；The versatic acid Versatic 10 of saponification is dilute
It is 20% to release to volume fraction；It is 5% that TBP, which is diluted to volume fraction, carries out 10 stage countercurrent extractions at being 20 DEG C in temperature, controls
Compared to O/A=1,4min is stirred, 5min split-phases is then stood, obtains the organic phase of nickel and cobalt containing manganese；
The organic phase of the nickel and cobalt containing manganese is subjected to washing 2 times with the dilute sulfuric acid of pH=3.5, to remove the calcium of deentrainment, magnesium
Then foreign ion carries out 4 stage countercurrent back extraction with the sulfuric acid of 1.5mol/L, during back extraction compared to O/A=1/1,30 DEG C of temperature is stirred
4min is mixed, then stands 5min, obtains the sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of nickel cobalt manganese, this step pair
The rate of recovery of cobalt reaches 98.7%, the rate of recovery 97.3% of nickel, and the rate of recovery of manganese is 73.1%, and the extractant being stripped can be with
It recycles, and is stripped the obtained sulfate of nickel cobalt manganese, together with the manganese sulfate solution that step (4) obtains, by condensing crystallizing
Afterwards, production nickel-cobalt-manganese ternary cell positive material presoma can be used as by adjusting the ratio between three kinds of elements of nickel cobalt manganese
Raw material.
Embodiment two
The method of synchronous recycling nickel cobalt manganese, includes the following steps in a kind of manganese waste slag sulphuric leachate from nickel and cobalt containing：
(1) sulfuric acid leaching：Nickel and cobalt containing manganese waste slag is taken, is 120 according to solid-to-liquid ratio：It is 25% that 1g/L, which adds in mass fraction,
Sulfuric acid solution carries out acidleach, and the temperature of acidleach is 60 DEG C, and the time of acidleach is 35min, and pH when terminal is leached in control is 0.5,
Solid-liquid is separated by filtration, collects leachate；
Main component is a concentration of in the leachate：Ni 5.23g/L、Co 18.5g/L、Mg 6.5g/L、Mn8.2g/
L、Fe 2.19g/L、Al 147mg/L、Cu 1370mg/L、Ca 416mg/L、Zn 330mg/L；
(2) except iron, aluminium：Above-mentioned leachate is taken, by 2.0 times of the theoretical requirement for aoxidizing the leachate ferrous ions
Add in oxidant sodium chlorate (i.e. n (NaClO3)=0.42n (Fe2+)), pH=5.3 is adjusted with NaOH, is old at 55 DEG C in temperature
Change 60min, then plate compression, obtain except iron aluminium filtrate, Fe and Al ions are respectively with Al (OH)3、Fe(OH)3The form of precipitation
It is removed；
(3) extracting copper：Above-mentioned filtrate is taken, pH=2.2 is adjusted with sulfuric acid, CP150 is selected to make copper extractant, is used sulfonation
The first organic extractant that the volume fraction that kerosene cutback forms CP150 is 25% carries out 1 grade of extraction at being 35 DEG C in temperature,
Control stirs 4min, then stands 5min split-phases, obtain cupric organic phase and the first raffinate compared to O/A=1/1；
The cupric organic phase is washed 1 time using the dilute sulfuric acid of pH=3.5, then using the sulphur of a concentration of 1.5mol/L
Sour is back washing agent, and 1 grade of back extraction is carried out at being 30 DEG C in temperature, is controlled in stripping process and compares O/A=4/1, stir 4min, then
5min is stood, obtains copper-bath；Copper sulfate crystal can be prepared after pervaporation, concentration in copper-bath, the step
The rate of recovery of copper reaches 98.2% in rapid.
(4) extracting zinc：Mass fraction is used to carry out saponification to P507 by 50% saponification rate for 20% NaOH solution to obtain
To the P507 of saponification, and it is 30% to be diluted to volume fraction with sulfonated kerosene, obtains the second organic extractant；Take above-mentioned first extraction
Extraction raffinate adjusts pH=2.3, second organic extractant is used to carry out 1 grade of extraction in the case where temperature is 35 DEG C, control is compared to O/A
=1/2,4min is stirred, 5min split-phases is then stood, obtains the second raffinate and the organic phase containing zinc, a small amount of manganese, it is most of
Manganese and nickel, cobalt are remained in the second raffinate；
The organic phase containing zinc, a small amount of manganese is subjected to washing 2 times, then with a concentration of with the dilute sulfuric acid of pH=4.0
The sulfuric acid of 1.5mol/L carries out 1 grade of back extraction, during back extraction compared to O/A=4/1,20 DEG C of temperature stirs 4min, then stands
5min, obtains the second organic extractant of sulfate and organic phase containing Zn, Mn, and organic phase continues to make after returning to extraction section saponification
With；
Extraction and separation are carried out using P204 to the sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, it is specific to grasp
Make as follows：The sulfate containing Zn, Mn is taken, adjusts pH=1.5 with sulfuric acid, addition thereto is diluted to volume with sulfonated kerosene
Score be 20% saponification P204 carry out two level counter-current extraction, the P204 of saponification be use mass fraction for 20% NaOH solution
Saponification is carried out by 50% saponification rate to P204 to obtain, control is stirred 4min, then stood compared to O/A=1/1,20 DEG C of temperature
5min split-phases, obtain organic phase containing zinc and manganese sulfate solution；The organic phase containing zinc is washed with the dilute sulfuric acid of pH=3.5
2 times, then carry out 1 grade of back extraction with the sulfuric acid of 0.8mol/L, during back extraction compared to O/A=1/1,20 DEG C of temperature stirs 4min, so
After stand 5min, solution of zinc sulfate is obtained, wherein the P204 being stripped can be continuing with after can returning to extraction section saponification.
The step reaches the rate of recovery of zinc 98.7%, and the rate of recovery of manganese is 26%.
(5) synchronous extraction nickel cobalt manganese：Take above-mentioned second raffinate, adjust pH=2.0, add in tributyl phosphate (TBP) and
Versatic acid Versatic 10 is extracted together, and Mextral DT100 is selected to make diluent, wherein Versatic10 before extraction
With the sodium hydroxide saponification that mass fraction is 30%, saponification rate 10%；The versatic acid Versatic 10 of saponification is diluted to volume point
Number is 30%；It is 7% that TBP, which is diluted to volume fraction, carries out 5 stage countercurrent extractions at being 20 DEG C in temperature, control is compared to O/A=1/
1,4min is stirred, 5min split-phases is then stood, obtains the organic phase of nickel and cobalt containing manganese；
The organic phase of the nickel and cobalt containing manganese is subjected to washing 3 times with the dilute sulfuric acid of pH=4.0, then with the sulphur of 1.5mol/L
Acid carries out 4 stage countercurrent back extraction, during back extraction compared to O/A=2/1,30 DEG C of temperature stirs 4min, then stands 5min, obtain nickel
The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of cobalt manganese, this step reach the rate of recovery of cobalt 98.6%, and nickel returns
Yield 97.0%, the rate of recovery of manganese is 72.6% (wherein the overall recovery of manganese is 98.6%).
Embodiment three
The method of synchronous recycling nickel cobalt manganese, includes the following steps in a kind of manganese waste slag sulphuric leachate from nickel and cobalt containing：
(1) sulfuric acid leaching：Nickel and cobalt containing manganese waste slag is taken, is 150 according to solid-to-liquid ratio：1g/L adds in the sulphur that mass fraction is 20%
Acid solution carries out acidleach, and the temperature of acidleach is 80 DEG C, and the time of acidleach is 15min, and pH when terminal is leached in control is 1.2, mistake
Filter separation solid-liquid, collects leachate；
Main component is a concentration of in the leachate：Ni 5.12g/L、Co 27.3g/L、Mg 9.9g/L、Mn
10.4g/L、Fe 1.87g/L、Al 165mg/L、Cu 965mg/L、Ca 732mg/L、Zn 1030mg/L；
(2) except iron, aluminium：Above-mentioned leachate is taken, by 1.5 times of the theoretical requirement for aoxidizing the leachate ferrous ions
Add in oxidizing agent sodium hypochlorite (i.e. n (NaClO)=0.75n (Fe2+)), pH=5.0 is adjusted with NaOH, is old at 60 DEG C in temperature
Change 45min, then plate compression, obtain except iron aluminium filtrate, Fe and Al ions are respectively with Al (OH)3、Fe(OH)3The form of precipitation
It is removed；
(3) extracting copper：Above-mentioned filtrate is taken, pH=2.0 is adjusted with sulfuric acid, Mextral 984H is selected to make copper extractant, it will
Its diluted with Mextral DT100 to be formed Mextral 984H volume fraction be 30% the first organic extractant, in temperature
It is that 1 grade of extraction is carried out at 40 DEG C, control stirs 4min, then stand 5min split-phases, obtain cupric organic phase compared to O/A=1/2
With the first raffinate；
The cupric organic phase is washed 1 time using the dilute sulfuric acid of pH=3.5, then using the sulphur of a concentration of 1.2mol/L
Sour is back washing agent, and 1 grade of back extraction is carried out at being 30 DEG C in temperature, is controlled in stripping process and compares O/A=2/1, stir 4min, then
5min is stood, obtains copper-bath；Copper sulfate crystal can be prepared after pervaporation, concentration in copper-bath, the step
The rate of recovery of copper reaches 98.2% in rapid.
(4) extracting zinc：Mass fraction is used to carry out saponification to P507 by 50% saponification rate for 20% NaOH solution to obtain
To the P507 of saponification, and it is 20% to be diluted to volume fraction with sulfonated kerosene, obtains the second organic extractant；Take above-mentioned first extraction
Extraction raffinate adjusts pH=2.0, second organic extractant is used to carry out 1 grade of extraction in the case where temperature is 20 DEG C, control is compared to O/A
=1/2,4min is stirred, 5min split-phases is then stood, obtains the second raffinate and the organic phase containing zinc, a small amount of manganese, it is most of
Manganese and nickel, cobalt are remained in the second raffinate；
The organic phase containing zinc, a small amount of manganese is subjected to washing 4 times, then with a concentration of with the dilute sulfuric acid of pH=4.0
The sulfuric acid of 1.2mol/L carries out 1 grade of back extraction, during back extraction compared to O/A=4/1,40 DEG C of temperature stirs 4min, then stands
5min, obtains the second organic extractant of sulfate and organic phase containing Zn, Mn, and organic phase continues to make after returning to extraction section saponification
With；
Extraction and separation are carried out using P204 to the sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, it is specific to grasp
Make as follows：The sulfate containing Zn, Mn is taken, adjusts pH=2.0 with sulfuric acid, addition thereto is diluted to volume with sulfonated kerosene
Score be 30% saponification P204 carry out two level counter-current extraction, the P204 of saponification be use mass fraction for 20% NaOH solution
Saponification is carried out to P204 to obtain, control the O/A=1/2 that compares during counter-current extraction, 40 DEG C of temperature, stirring by 40% saponification rate
Then 4min stands 5min split-phases, obtains organic phase containing zinc and manganese sulfate solution；By the organic phase containing zinc with pH=3.5's
Dilute sulfuric acid carries out washing 2 times, then carries out 1 grade of back extraction with the sulfuric acid of 1.5mol/L, compares O/A=2/1, temperature 30 during back extraction
DEG C, 4min is stirred, 5min is then stood, obtains solution of zinc sulfate, wherein the P204 being stripped can return to extraction section saponification
After can be continuing with.The step reaches the rate of recovery of zinc 98.9%, and the rate of recovery of manganese is 21.7%.
(5) synchronous extraction nickel cobalt manganese：Take above-mentioned second raffinate, adjust pH=2.3, add in tributyl phosphate (TBP) and
Versatic acid Versatic 10 is extracted together, and Mextral DT100 is selected to make diluent, wherein Versatic10 before extraction
With the sodium hydroxide saponification that mass fraction is 30%, saponification rate 10%；The versatic acid Versatic 10 of saponification is diluted to volume point
Number is 20%；It is 10% that TBP, which is diluted to volume fraction, carries out 9 stage countercurrent extractions at being 40 DEG C in temperature, control is compared to O/A=
1/1,4min is stirred, 5min split-phases is then stood, obtains the organic phase of nickel and cobalt containing manganese；
The organic phase of the nickel and cobalt containing manganese is subjected to washing 4 times with the dilute sulfuric acid of pH=4.0, then with the sulphur of 0.8mol/L
Acid carries out 5 stage countercurrent back extraction, during back extraction compared to O/A=1/1,35 DEG C of temperature stirs 4min, then stands 5min, obtain nickel
The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of cobalt manganese, this step reach the rate of recovery of cobalt 98.8%, and nickel returns
Yield 97.5%, the rate of recovery of manganese is 75.9% (overall recovery of manganese is 97.6%).
Example IV
The method of synchronous recycling nickel cobalt manganese, includes the following steps in a kind of manganese waste slag sulphuric leachate from nickel and cobalt containing：
(1) sulfuric acid leaching：Nickel and cobalt containing manganese waste slag is taken, is 100 according to solid-to-liquid ratio：1g/L adds in the sulphur that mass fraction is 25%
Acid solution carries out acidleach, and the temperature of acidleach is 70 DEG C, and the time of acidleach is 25min, and pH when terminal is leached in control is 0.5, mistake
Filter separation solid-liquid, collects leachate；
Main component is a concentration of in the leachate：Ni 3.46g/L、Co 32.7g/L、Mg 8.5g/L、Mn11.3g/
L、Fe 1.77g/L、Al 105mg/L、Cu 1014mg/L、Ca 751mg/L、Zn 548mg/L；
(2) except iron, aluminium：Above-mentioned leachate is taken, by 1.7 times of the theoretical requirement for aoxidizing the leachate ferrous ions
Add in oxidant sodium chlorate (i.e. n (NaClO3)=0.35n (Fe2+)), pH=5.3 is adjusted with NaOH, is old at 55 DEG C in temperature
Change 60min, then plate compression, obtain except iron aluminium filtrate, Fe and Al ions are respectively with Al (OH)3、Fe(OH)3The form of precipitation
It is removed；
(3) extracting copper：Above-mentioned filtrate is taken, pH=2.0 is adjusted with sulfuric acid, Mextral 984H is selected to make copper extractant, it will
Its diluted with Mextral DT100 to be formed Mextral 984H volume fraction be 20% the first organic extractant, in temperature
It is that 1 grade of extraction is carried out at 40 DEG C, control stirs 4min, then stand 5min split-phases, obtain cupric organic phase compared to O/A=1/1
With the first raffinate；
The cupric organic phase is washed 1 time using the dilute sulfuric acid of pH=4.0, then using the sulphur of a concentration of 0.8mol/L
Sour is back washing agent, and 1 grade of back extraction is carried out at being 35 DEG C in temperature, is controlled in stripping process and compares O/A=2/1, stir 4min, then
5min is stood, obtains copper-bath；Copper sulfate crystal can be prepared after pervaporation, concentration in copper-bath, the step
The rate of recovery of copper reaches 98.4% in rapid.
(4) extracting zinc：Mass fraction is used to carry out saponification to P507 by 40% saponification rate for 20% NaOH solution to obtain
To the P507 of saponification, and it is 30% to be diluted to volume fraction with sulfonated kerosene, obtains the second organic extractant；Take above-mentioned first extraction
Extraction raffinate adjusts pH=2.2, second organic extractant is used to carry out 1 grade of extraction in the case where temperature is 30 DEG C, control is compared to O/A
=1/1,4min is stirred, 5min split-phases is then stood, obtains the second raffinate and the organic phase containing zinc, a small amount of manganese, it is most of
Manganese and nickel, cobalt are remained in the second raffinate；
The organic phase containing zinc, a small amount of manganese is subjected to washing 3 times, then with a concentration of 1mol/ with the dilute sulfuric acid of pH=3.5
The sulfuric acid of L carries out 1 grade of back extraction, during back extraction compared to O/A=2/1,20 DEG C of temperature stirs 4min, then stands 5min, contained
The second organic extractant of sulfate and organic phase of Zn, Mn, organic phase are continuing with after returning to extraction section saponification；
Extraction and separation are carried out using P204 to the sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, it is specific to grasp
Make as follows：The sulfate containing Zn, Mn is taken, adjusts pH=1.5 with sulfuric acid, addition thereto is diluted to volume with sulfonated kerosene
Score be 20% saponification P204 carry out two level counter-current extraction, the P204 of saponification be use mass fraction for 20% NaOH solution
Saponification is carried out to P204 to obtain, control the O/A=1/2 that compares during counter-current extraction, 30 DEG C of temperature, stirring by 50% saponification rate
Then 4min stands 5min split-phases, obtains organic phase containing zinc and manganese sulfate solution；By the organic phase containing zinc with pH=3.5's
Dilute sulfuric acid carries out washing 2 times, then carries out 1 grade of back extraction with the sulfuric acid of 1.0mol/L, compares O/A=1/1, temperature 30 during back extraction
DEG C, 4min is stirred, 5min is then stood, obtains solution of zinc sulfate, wherein the P204 being stripped can return to extraction section saponification
After can be continuing with.The step reaches the rate of recovery of zinc 99.0%, and the rate of recovery of manganese is 24.8%.
(5) synchronous extraction nickel cobalt manganese：Take above-mentioned second raffinate, adjust pH=1.9, add in tributyl phosphate (TBP) and
Versatic acid Versatic 10 is extracted together, and sulfonated kerosene is selected to make diluent, wherein Versatic10 mass before extraction
Score be 30% sodium hydroxide saponification, saponification rate 20%；The versatic acid Versatic 10 of saponification is diluted to volume fraction and is
20%；It is 7% that TBP, which is diluted to volume fraction, carries out 8 stage countercurrent extractions at being 25 DEG C in temperature, control is stirred compared to O/A=1/1
4min is mixed, 5min split-phases is then stood, obtains the organic phase of nickel and cobalt containing manganese；
The organic phase of the nickel and cobalt containing manganese is subjected to washing 2 times with the dilute sulfuric acid of pH=3.5, then with the sulphur of 1.5mol/L
Acid carries out 4 stage countercurrent back extraction, during back extraction compared to O/A=21,40 DEG C of temperature stirs 4min, then stands 5min, obtain nickel cobalt
The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of manganese, this step reach the rate of recovery of cobalt 98.5%, the recycling of nickel
Rate 97.9%, the rate of recovery of manganese is 73.1% (wherein the overall recovery of manganese is 98.6%).
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. a kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing, which is characterized in that include the following steps：
(1) sulfuric acid leaching：Nickel and cobalt containing manganese waste slag is taken, sulfuric acid is added in and carries out acidleach, be separated by filtration solid-liquid, collect leachate；
(2) except iron, aluminium：The leachate is taken, adds in oxidant, pH=5.0-5.5 is adjusted, makes iron, the aluminium element in leachate
It precipitates, filters, obtain except the filtrate after iron, aluminium, wherein, the oxidant is hypochlorite, chlorate or nitric acid；
(3) extracting copper：Take the filtrate in above-mentioned steps (2), adjust pH=2.0-2.5, add in Mextral984H or CP150 with
The first organic extractant that diluent is formed, through cupric organic phase and the first raffinate is obtained by extraction；
(4) extracting zinc：It takes first raffinate, adjusts pH=2.0-2.3, add in the P507 of saponification and kerosene is mixed to form
Second organic extractant, the organic phase through the second raffinate is obtained by extraction and containing zinc, a small amount of manganese；
The organic phase containing zinc, a small amount of manganese with dilute sulfuric acid is washed, then be stripped with sulfuric acid, obtains the sulfuric acid containing Zn, Mn
Salt, then extraction and separation are carried out using P204 to the sulfate containing Zn, Mn, obtain zinc sulfate and manganese sulfate；
(5) synchronous extraction nickel cobalt manganese：It takes second raffinate, adjusts pH=1.7-2.3, add in tributyl phosphate and saponification
The mixed extractant that neodecanoic acid is formed with diluent, the organic phase of nickel and cobalt containing manganese is obtained through counter-current extraction；Wherein, the adverse current extraction
It is 1/1~1/2 to take the volume ratio O/A of time control organic phase and water phase, in the mixed extractant, the volume point of tributyl phosphate
Number is 5-10%, and the volume fraction of the neodecanoic acid of saponification is 20%~30%；
The organic phase of the nickel and cobalt containing manganese with dilute sulfuric acid is washed, to remove the calcium and magnesium impurity of deentrainment, then is carried out with sulfuric acid
Countercurrent reextraction obtains the sulfate of nickel cobalt manganese.
2. according to the method described in claim 1, it is characterized in that, in step (5), the counter-current extraction is 5~10 grades；It is described
The volume ratio O/A of counter-current extraction time control organic phase and water phase is 1/1.
3. according to the method described in claim 1, it is characterized in that, in step (5), the countercurrent reextraction is 4~5 grades；It is described
Volume ratio O/A=2/1~1/1 of countercurrent reextraction time control organic phase and water phase.
4. according to the method described in claim 1, it is characterized in that, in step (5), the pH=of the dilute sulfuric acid of the washing
3.5-4.0；A concentration of 0.8-1.5mol/L of the sulfuric acid of the back extraction.
5. according to the method described in claim 1, it is characterized in that, in step (5), the neodecanoic acid of the saponification is using quality
The NaOH solution that score is 20% carries out saponification to neodecanoic acid by 10~30% saponification rate and obtains.
6. according to the method described in claim 1, it is characterized in that, in step (2), the oxidant is sodium chlorate, the chlorine
The mole of sour sodium is 0.3-0.42 times of the mole of the leachate ferrous ions.
7. according to the method described in claim 1, it is characterized in that, in step (3), the Mextral 984H or CP150 exist
Volume fraction in first organic extractant is 20-30%；Machine is formed with using first organic extractant extraction time control
It is mutually 1/1~1/2 with the volume ratio of water phase.
8. according to the method described in claim 1, it is characterized in that, in step (4), in second organic extractant, institute
The volume fraction for stating the P507 of saponification is 20%~30%；Time control organic phase and water are extracted using second organic extractant
The volume ratio of phase is 1/1~1/2.
9. according to the method described in claim 1, it is characterized in that, in step (4), the use P204 carries out extraction and separation,
Specially：
The sulfate containing Zn, Mn is taken, adjusts pH=1.5~2.0, adds in the third that the P204 of saponification and sulfonated kerosene are formed
Organic extractant, control carry out two level counter-current extraction, the P204 of the saponification has in the third compared to O/A=1/1~1/2
Volume fraction in machine extractant is 20-30%, obtains organic phase containing zinc and manganese sulfate solution；
The organic phase containing zinc is subjected to washing 2-4 times with dilute sulfuric acid, then carry out 1 grade of back extraction with sulfuric acid, obtains solution of zinc sulfate；
Control is compared to O/A=2/1~1/2 when being wherein stripped.
10. according to the method described in claim 1, it is characterized in that, in step (3), further include：The cupric organic phase is taken,
It is washed, then is stripped with sulfuric acid using dilute sulfuric acid, obtains copper-bath.
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