CN106319228A - Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese - Google Patents

Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese Download PDF

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Publication number
CN106319228A
CN106319228A CN201610737450.8A CN201610737450A CN106319228A CN 106319228 A CN106319228 A CN 106319228A CN 201610737450 A CN201610737450 A CN 201610737450A CN 106319228 A CN106319228 A CN 106319228A
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manganese
nickel
cobalt
extraction
saponification
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CN106319228B (en
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许开华
盛广宏
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for recycling nickel, cobalt and manganese synchronously from a sulfuric acid leaching solution containing waste residues of nickel, cobalt and manganese. The method comprises the steps of firstly, removing iron and aluminum from the leaching solution through an oxidation and precipitation method; then, removing the element copper through extraction; then, extracting zinc; and finally, extracting nickel, cobalt and manganese synchronously with tributyl phosphate and saponified neodecanoic acid. By means of the method, nickel, cobalt and manganese in the leaching solution containing the waste residues of nickel, cobalt and manganese can be extracted and recycled synchronously; calcium and magnesium in a raw solution cannot exert an influence on the extraction process; separation cost for recycling the elements nickel, cobalt and manganese separately is lowered; and raw material cost for preparing a nickel-cobalt-manganese-salt ternary battery material is lowered.

Description

A kind of method synchronizing to reclaim nickel cobalt manganese from nickel and cobalt containing manganese waste slag
Technical field
The present invention relates to environmental conservation and resource circulation utilization field, be specifically related to a kind of synchronization from nickel and cobalt containing manganese waste slag The method reclaiming nickel cobalt manganese.
Background technology
Nickel-cobalt-manganternary ternary anode material is Olivine-type Cathode Material in Li-ion Batteries, and it has capacity height, Heat stability is good, property Valency compares advantages of higher.Nickel cobalt manganese salt is the primary raw material preparing nickel-cobalt-manganternary ternary anode material presoma, generally use cobaltous sulfate, Nickel-cobalt-manganese ternary presoma is prepared in the crystallization that is hydrolyzed the most in the basic conditions of nickel sulfate and manganese sulfate.
Cobalt majority and nickel phase association, occur at mineral, as in nickel laterite the most simultaneously.Can produce in a lot of industries and contain The waste residue of the valuable metal such as nickel, cobalt, such as electricity nickel are containing cobalt waste residue, discarded power battery material, dead catalyst, many in these waste residues Number contains higher manganese the most simultaneously, has the highest recovery value, they can be carried out recovery and be used for preparing nickel-cobalt-manganese ternary Presoma.
Process the main way of waste residue of nickel and cobalt containing manganese at present for by being extracted respectively by nickel-cobalt-manganese ternary element after acidleach Take separation or use chemical precipitation method to respectively obtain cobalt salt, nickel salt and manganese salt, carrying out deep processing the most again, but it is to nickel cobalt manganese Organic efficiency the most relatively low, and technique is cumbersome.Additionally, due to magnesium is impurity more typically in nickel cobalt waste residue, especially I The nickel raw material laterite of state is High Mg raw materials, thus the content of magnesium is the highest in its acid leaching liquor.Shadow due to magnesium addition Ring, need first nickel cobalt manganese first to be separated with magnesium, thus raw material is relatively costly.
Summary of the invention
In view of this, the invention provides a kind of method synchronizing from nickel and cobalt containing manganese waste slag and reclaiming nickel cobalt manganese, the method Can realize synchronizing extraction and recovery, the calcium in material liquid, magnesium pair by the nickel in the sulphuric leachate of nickel and cobalt containing manganese waste slag, cobalt and manganese Extraction process will not produce impact, reduces the separation costs being separately recovered nickel, cobalt, manganese element, reduces preparation nickel cobalt manganese three The cost of material of unit's positive electrode.
The invention provides a kind of method synchronizing from nickel and cobalt containing manganese waste slag and reclaiming nickel cobalt manganese, comprise the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, adds sulphuric acid and carries out acidleach, filter and separate solid-liquid, collect leachate；
(2) except ferrum, aluminum: take described leachate, add oxidant, regulate pH=5.0-5.5, make the ferrum in leachate, aluminum Element precipitates, and then filters, the filtrate after obtaining except ferrum aluminum, and wherein, described oxidant is sodium chlorate；
(3) extracting copper: take the filtrate in above-mentioned steps (2), regulates pH=2.0-2.5, add Mextral984H or The first organic extractant that CP150 is formed with diluent, through being obtained by extraction cupric organic facies and the first raffinate；
(4) extracting zinc: take described first raffinate, regulates pH=2.0-2.3, adds P507 and the kerosene mixing shape of saponification The second organic extractant become, through being obtained by extraction the second raffinate, and containing zinc, the organic facies of a small amount of manganese；
The described organic facies dilute sulfuric acid containing zinc, a small amount of manganese is washed, then uses sulphuric acid back extraction, obtain containing Zn, Mn Sulfate, then use P204 to carry out extract and separate in the described sulfate containing Zn, Mn, obtain zinc sulfate and manganese sulfate；
(5) synchronize extraction nickel cobalt manganese: take described second raffinate, regulate pH=1.7-2.3, add tributyl phosphate (TBP) and the mixed extractant that formed of neodecanoic acid and the diluent of saponification, the organic facies of nickel and cobalt containing manganese is obtained through counter-current extraction；Its In, described counter-current extraction time control organic facies is 1/1～1/2 with volume ratio O/A of aqueous phase, in described mixed extractant, and 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 facies dilute sulfuric acid of described nickel and cobalt containing manganese is washed, to remove calcium, the magnesium addition carried secretly, then uses sulphuric acid Carry out countercurrent reextraction, obtain the sulfate of nickel cobalt manganese.
In the embodiment of the present invention, described nickel and cobalt containing manganese waste slag is multiple nickel and cobalt containing manganese waste material and the mixture of Ore, as long as It is that the raw material containing compositions such as listed Ni, Co, Mn, Mg, Fe, Al, Cu, Ca, Zn all can be by the method in the present invention.Described nickeliferous Cobalt manganese waste slag may come from the mixture such as refuse battery, manganese liquid purification slag, low-grade laterite.
In step (1), in described nickel cobalt manganese waste residue add sulphuric acid carry out acidleach, can make the Ni in waste residue, Co, Mn, The cycling of elements such as Mg, Fe, Al, Cu, Ca, Zn, Fe are ionic species and enter in leachate, obtain the mixing containing ion molten Liquid, is conducive to its further separation and recovery.Containing units such as Ni, Co, Mn, Mg, Fe, Al, Cu, Ca, Zn, Fe in described leachate Element.Without Li ion in described leachate.
Preferably, described nickel cobalt manganese waste residue is (100-150): 1g/L with the solid-to-liquid ratio of the sulphuric acid of described acidleach, described The temperature of acidleach is 50～80 DEG C, and the time of acidleach is 15～35min, and pH when controlling the leaching terminal of described acidleach is 0.5 ～1.2；Mixing speed 150-200rpm during described acidleach.
It is further preferred that the mass fraction of the sulphuric acid used by described acidleach is 20-30%.
Step (2) is primarily to the Fe that removes in described leachate2+、Fe3+And Al3+Ion, obtains Al after aging (OH)3、Fe(OH)3Precipitation.In step (2), regulation pH to 5.0-5.5, both can ensure that oxidant had preferably with this understanding Oxidisability, make Fe2+Fully it is oxidized to Fe3+, ensure again Fe simultaneously3+And Al3+From with this understanding can be the most precipitated, with Exempt from the dedoping step interfered with below.In step (2), regulation pH is to use sodium hydroxide solution or ammonia to carry out.
In step (2), described in make the ferrum in leachate, aluminium element precipitate particularly as follows: at temperature is 50-60 DEG C Ageing 30-60min.
Preferably, in step (2), the addition of described oxidant is that the theory aoxidizing described leachate ferrous ions needs To be measured 1.5-2.5 times.
It is further preferred that in step (2), described oxidant is sodium chlorate, the mole of described sodium chlorate is described leaching Go out 0.3-0.42 times of mole of liquid ferrous ions.
It is further preferred that in step (2), described oxidant is sodium hypochlorite, the mole of described sodium hypochlorite is institute State 0.75-1.0 times of mole of leachate ferrous ions.
In the application, the operation in step (3) is primarily to remove described except the Cu element in ferrum aluminum filtrate, after extraction Described first raffinate in containing Ni, Co, Mn, Mg, Ca, Zn element.
Preferably, in step (3), described Mextral 984H or CP150 volume in described first organic extractant Mark is 20-30%；Described first organic extractant (organic facies) with described except the volume ratio of the filtrate (aqueous phase) after ferrum aluminum is 1/1～1/2.Mextral 984H or CP150 is copper extractant, after extraction, makes Cu2+Enter organic facies so that it is he enters by ion Aqueous phase, thus realize existing Cu2+With the separation of other ions, obtain purity higher containing Cu2+Organic facies.Wherein, cupric organic facies Possibly together with a small amount of cobalt and the first raffinate of carrying secretly, washed by dilute sulfuric acid, can be removed, in order to avoid affecting returning of copper Receive.
Preferably, in step (3), described extraction is to carry out at 30～50 DEG C.
Preferably, in step (3), described diluent is sulfonated kerosene or Mextral DT100.
It is further preferred that when using Mextral 984H, described diluent is Mextral DT100；Work as employing During CP150, described diluent is sulfonated kerosene or Mextral DT100.Certainly, it is possible to use other diluent.
Preferably, in step (3), also include: take described cupric organic facies, use dilute sulfuric acid that it is washed, then use Sulphuric acid back extraction, obtains copper-bath.
It is further preferred that in step (3), in described stripping process, control cupric organic facies and aqueous phase (sulfuric acid solution) Volume ratio be 4/1～2/1.
It is further preferred that in step (3), the temperature 20 of described back extraction～40 DEG C.
It is further preferred that in step (3), wash the pH=3.5-4.0 of the dilute sulfuric acid of described cupric organic facies；Back extraction The concentration of sulphuric acid during cupric organic facies is 0.8-1.5mol/L.It is further preferred that the dilute sulfuric acid of described washing is dense Degree is 0.1-0.32mmol/L.
Preferably, in step (3), described extraction is 1 grade of extraction, and extraction time is 3-5min；Described back extraction be 1 grade anti- Extraction.The copper-bath that in step (3), back extraction obtains can be through evaporation and concentration to prepare copper sulfate crystal；What back extraction obtained has Machine is the first organic extractant after extraction mutually, can be with recycling.
In step (4), using P507 when extracting, major part manganese remains in the second raffinate, a small amount of manganese with Organic facies is together entered with substantial amounts of zinc.Containing Ni, Co, Mn, Mg, Ca element in described second raffinate.Use sulphuric acid to having Machine carries out back extraction mutually, and the organic facies that the back extraction of step (4) produces is P507, can continue returning again to after its saponification to extraction stages Continuous use；And sulfur acid zinc and manganese sulfate in the aqueous phase after back extraction, re-use P204 and carry out extract and separate.
Preferably, in step (4), using described second organic extractant is at temperature is 20～40 DEG C when extracting Carry out.
Preferably, in step (4), in described second organic extractant, the volume fraction of the P507 of described saponification is 20%～30%, the volume ratio (O/A) at extraction time control organic facies and aqueous phase is 1/1～1/2, the i.e. second organic extractant and The volume ratio of described first raffinate is 1/1～1/2.
Preferably, in step (4), the P507 of described saponification be the NaOH solution using mass fraction to be 20% by 40～ The saponification rate of 60% carries out saponification to P507 and obtains.That is, the saponification rate of described P507 is 40～60%.
It is further preferred that in step (4), washing is described containing zinc, the pH=3.5-of the dilute sulfuric acid of the organic facies of a small amount of manganese 4.0；The concentration of sulphuric acid during back extraction is 0.8-1.5mol/L.
In the step (4) of the present invention, when using P507 extraction, under pH=2.0-2.3 during extracting zinc, may be a small amount of Calcium, cobalt also can be extracted in organic facies.The purpose washed by organic facies dilute sulfuric acid containing zinc, a small amount of manganese removes carries secretly Calcium, cobalt, and a small amount of manganese can be washed off, reduce the extraction yield of manganese.Washing organic facies after extraction, one can remove the water carried secretly Phase, that extracted in extractant but that adhesion is more weak composition can be removed by two.
Preferably, in step (4), described back extraction containing zinc, a small amount of manganese organic facies during, control organic facies (containing zinc, The organic facies of a small amount of manganese) it is 4/1～2/1 with the volume ratio (O/A) of aqueous phase (sulphuric acid).Wherein, temperature 20 during described back extraction～ 40℃。
It is further preferred that in step (4), the extraction using the second organic extractant to carry out is 1 grade of extraction；Described back extraction It it is 1 grade of back extraction.
It is further preferred that in step (4), described employing P204 carries out extract and separate, particularly as follows:
Taking the described sulfate containing Zn, Mn, regulate pH=1.5～2.0, the P204 of addition saponification and sulfonated kerosene are formed 3rd organic extractant, carries out two stage countercurrent extractions, the P204 of described saponification volume integral in described 3rd organic extractant Number for 20-30%, control to compare O/A=1/1～1/2 (the most described 3rd organic extractant and the described sulfate containing Zn, Mn Volume ratio), obtain containing zinc organic facies and manganese sulfate solution；
The described organic facies dilute sulfuric acid containing zinc is carried out washing 2-4 time, to remove cobalt, calcium and the aqueous phase carried secretly on a small quantity, then Carry out 1 grade of back extraction with sulphuric acid, when controlling back extraction, compare O/A=2/1～1/2, obtain copper-bath；Wherein phase during back extraction Than O/A=2/1～1/2.
Additionally, back extraction is 20～40 DEG C containing temperature during zinc organic facies.P204 after back extraction can after returning extraction section saponification To be continuing with.
Preferably, the P204 of described saponification be use mass fraction be that the NaOH solution of 20% is by the saponification rate of 40-60% P204 is carried out saponification obtain.
It is further preferred that the pH=3.5-4.0 of the described dilute sulfuric acid containing zinc organic facies of washing；When back extraction is containing zinc organic facies The concentration of sulphuric acid be 0.8-1.5mol/L.
In the step (4) of the application, first using P507 extraction, then use P204 to come extract and separate zinc, manganese, P507 is front master If for preferably extracting zinc, and reduce the extraction to cobalt manganese, and the extraction of calcium.
In step (5) in the application, use the neodecanoic acid of tributyl phosphate TBP and saponification as common extractant, Synchronization for nickel, cobalt, manganese extracts, and utilizes the synergism between the two extractant, and regulates and controls the ratio of neodecanoic acid and TBP And pH value, it is possible to achieve to nickel, cobalt, the efficient extraction of manganese these three metal ion, and magnesium addition is hardly to nickel cobalt manganese Extraction impacts.Relative in prior art, use such as the extractants such as P507, P204, separate in the case of adjusting higher pH Cobalt, nickel and for easily causing a large amount of magnesium also into organic facies, the extracting process in the present invention is relatively simple, and extraction efficiency is high, miscellaneous Matter impact is little.
In the embodiment of the present invention, described neodecanoic acid, have another name called ten carbonic acid, versatic acid Versatic 10, versatic acid V10, its No. CAS is 26896-20-8.
Preferably, in step (5), the neodecanoic acid of described saponification be the NaOH solution using mass fraction to be 20% by 10～ The saponification rate of 30% carries out saponification to neodecanoic acid and obtains.
Preferably, in step (5), described diluent is sulfonated kerosene or Mextral DT100.
It is further preferred that in step (5), described counter-current extraction is 5～10 grades；Described counter-current extraction time control organic facies It is 1/1 with volume ratio O/A of aqueous phase.
Preferably, in step (5), the temperature of described counter-current extraction is 20～40 DEG C.
In the step (5) of the present invention, when described second raffinate is extracted, except obtaining the organic of nickel and cobalt containing manganese Outside mutually, its aqueous phase obtained is the solution of remaining calcic, magnesium ion, and the nickel cobalt manganese not being extracted extremely on a small quantity, its Waste water workshop can be sent to carry out processing discharge.
Preferably, in step (5), wash the pH=3.5-4.0 of the dilute sulfuric acid of the organic facies of described nickel and cobalt containing manganese, wash 2- 4 times；The concentration of the sulphuric acid of described countercurrent reextraction is 0.8-1.5mol/L.
Preferably, in step (5), described countercurrent reextraction is 4～5 grades；Described countercurrent reextraction time control organic facies and aqueous phase Volume ratio O/A=2/1～1/1.The organic facies obtained after described countercurrent reextraction is described mixed extractant, can be circulated Utilize.
Preferably, in step (5), the temperature of described countercurrent reextraction is 20～40 DEG C.
In foregoing invention content, as required, the alkali liquor used during regulation pH is sodium hydroxide solution or ammonia, acid solution For sulphuric acid.It is understood that when the hydrochloric acid leachate from nickel and cobalt containing manganese waste slag synchronizes to reclaim nickel cobalt manganese, correspondingly, institute State washing, adjust pH be hydrochloric acid, back extraction the most still uses sulphuric acid.
The beneficial effect of the application:
The invention provides a kind of method synchronizing from nickel and cobalt containing manganese waste slag and reclaiming nickel cobalt manganese, the method is with nickel and cobalt containing manganese Waste residue is raw material, through sulfuric acid leaching, obtains the leachate containing elements such as Ni, Co, Mg, Mn, Cu, Ca, Zn, more heavy by oxidation Shallow lake method removes Fe, Al element, the most again extracting Cu, afterwards with P507 extraction Zn and Mn, P204 extract and separate Zn and Mn；The most again The neodecanoic acid using tributyl phosphate TBP and saponification synchronizes extraction nickel cobalt manganese, obtains the sulfate of nickel cobalt manganese, Ke Yitong after back extraction The ratio between three kinds of elements of nickel cobalt manganese of overregulating is further used as producing the raw material of nickel-cobalt-manganese ternary cell positive material presoma.
Nickel cobalt manganese in positive pole waste residue leachate can be realized synchronizing extraction and recovery by the inventive method, and in material liquid Calcium, magnesium extraction process will not be produced upper impact, follow-up can supplement in the ratio of nickel-cobalt-manganternary ternary anode material production requirement Other components.The method technique is simple, and exploitativeness is strong, reduces the separation costs being separately recovered nickel, cobalt, manganese element, and then Reduce the production cost of preparation nickel-cobalt-manganternary ternary anode material.Processing procedure environmental protection, economy, efficiently.The method is to copper The response rate up to 98%, the response rate of zinc is reached 98.5%, and synchronizes in extraction process the response rate to cobalt, nickel and manganese and divide Not can reach 98%, 97.5% and more than 60%, always reclaiming up to 98% of manganese.
Accompanying drawing explanation
In order to be illustrated more clearly that technical scheme, the accompanying drawing used required in embodiment will be made below Introduce simply, it should be apparent that, the accompanying drawing in describing below is only some embodiments of the present invention, general for this area From the point of view of logical technical staff, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the process chart of the embodiment of the present invention one.
Detailed description of the invention
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is carried out clearly Chu, it is fully described by.
Embodiment one
Refer to the process chart in Fig. 1, the present embodiment one provides one and synchronizes back from nickel and cobalt containing manganese waste slag The method receiving nickel cobalt manganese, comprises the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, described nickel and cobalt containing manganese waste slag comes from refuse battery, manganese liquid purification slag, low The mixture such as grade laterite；According to solid-to-liquid ratio be 100:1g/L add mass fraction be 30% sulfuric acid solution carry out acidleach, The temperature of acidleach is 50 DEG C, and the time of acidleach is 30min, and pH when controlling to leach terminal is 1.0, filters and separates solid-liquid, collects Leachate；
In described leachate, the concentration of main component is: 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 ferrum, aluminum: take above-mentioned leachate, by 1.5 times of the theoretical requirement aoxidizing described leachate ferrous ions Add oxidant sodium chlorate (i.e. n (NaClO3)=0.3n (Fe2+)), regulate pH=5.5 with NaOH, be aged at temperature is 50 DEG C 30-60min, then filter press, obtain except ferrum aluminum filtrate, Fe and Al ion is respectively with Al (OH)3、Fe(OH)3The form of precipitation It is removed；
(3) extracting copper: take above-mentioned filtrate, regulates pH=2.0 with sulphuric acid, selects Mextral 984H to make copper extractant, will It forms first organic extractant that volume fraction is 20% of Mextral 984H with Mextral DT100 dilution, in temperature It is at 30 DEG C, to carry out 1 grade of extraction, controls to compare O/A=1/2, stir 4min, then stand 5min split-phase, obtain cupric organic facies With the first raffinate；
The dilute sulfuric acid that described cupric organic facies uses pH=4.0 washs 1 time, removes a small amount of cobalt and the aqueous phase carried secretly, Then the sulphuric acid using concentration to be 0.8mol/L is back washing agent, carries out 1 grade of back extraction at temperature is 20 DEG C, controls in stripping process Compare O/A=2/1, stir 4min, then stand 5min, obtain copper-bath；Copper-bath can after pervaporation, concentration To prepare copper sulfate crystal, in this step, the response rate of copper reaches 98.5%.
(4) extracting zinc: the NaOH solution using mass fraction to be 20% carries out saponification by the saponification rate of 60% to P507 and obtains To the P507 of saponification, and to be diluted to volume fraction with sulfonated kerosene be 20%, obtains the second organic extractant；Take above-mentioned first extraction Remaining liquid, regulates pH=2.0, uses described second organic extractant to carry out 1 grade of extraction at temperature is 20 DEG C, controls to compare O/A =1/2, stir 4min, then stand 5min split-phase, obtain the second raffinate, and containing zinc, the organic facies of a small amount of manganese, major part Manganese and nickel, cobalt remain in the second raffinate；
Carry out washing 3 times by the described dilute sulfuric acid containing zinc, organic facies pH=3.5 of a small amount of manganese, with removal carry secretly calcium, Magnesium, cobalt, and reduce the extraction yield of manganese, then carry out 1 grade of back extraction with the sulphuric acid that concentration is 1mol/L, compare O/A=2/ during back extraction 1, temperature 20 DEG C, stirs 4min, then stands 5min, obtain the sulfate containing Zn, Mn and organic facies the second organic extractant, have Machine is continuing with after returning extraction section saponification mutually；
Use P204 to carry out extract and separate in the described sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, specifically grasp Make as follows: take the described sulfate containing Zn, Mn, regulate pH=1.5 with sulphuric acid, be added thereto to be diluted to volume with sulfonated kerosene Mark be 20% saponification P204 carry out two stage countercurrent extractions, the P204 of saponification be use mass fraction be the NaOH solution of 20% Saponification rate by 50% carries out saponification to P204 and obtains, and controls the O/A=1/2 that compares when extracting, temperature 30 DEG C, stirs 4min, Then stand 5min split-phase, obtain containing zinc organic facies and manganese sulfate solution；Zinc is extracted entrance organic facies, and manganese is predominantly retained in In aqueous phase；Carry out washing 2 times by the described dilute sulfuric acid containing zinc organic facies pH=3.5, to remove cobalt, calcium and the water carried secretly on a small quantity Phase, then carries out 1 grade of back extraction with the sulphuric acid of 1.0mol/L, compares O/A=1/1 during back extraction, and temperature 30 DEG C stirs 4min, so Rear standing 5min, obtains solution of zinc sulfate, and the P204 that wherein back extraction obtains can be continuing with after can returning extraction section saponification. This step reaches 98.7% to the response rate of zinc, and the response rate of manganese is 25.3%.
(5) synchronize extraction nickel cobalt manganese: take above-mentioned second raffinate, regulate pH=1.7, add tributyl phosphate (TBP) and Versatic acid Versatic 10 (neodecanoic acid) extracts together, selects sulfonated kerosene to make diluent, wherein before extraction Versatic10 mass fraction is the sodium hydroxide saponification of 30%, saponification rate 20%；The versatic acid Versatic 10 of saponification is dilute Release to volume fraction be 20%；It is 5% that TBP is diluted to volume fraction, carries out 10 stage countercurrent extractions at temperature is 20 DEG C, controls Compare O/A=1, stir 4min, then stand 5min split-phase, obtain the organic facies of nickel and cobalt containing manganese；
Carry out washing 2 times by the dilute sulfuric acid of organic facies pH=3.5 of described nickel and cobalt containing manganese, to remove calcium, the magnesium carried secretly Foreign ion, then carries out 4 stage countercurrent back extractions with the sulphuric acid of 1.5mol/L, compares O/A=1/1, temperature 30 DEG C during back extraction, stirs Mix 4min, then stand 5min, obtain the sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of nickel cobalt manganese, this step pair The response rate of cobalt reaches 98.7%, the response rate 97.3% of nickel, and the response rate of manganese is 73.1%, and the extractant that back extraction obtains is permissible Recycle, and the sulfate of the nickel cobalt manganese that back extraction obtains, the manganese sulfate solution obtained together with step (4), through condensing crystallizing After, can be used as producing nickel-cobalt-manganese ternary cell positive material presoma by the ratio between regulation three kinds of elements of nickel cobalt manganese Raw material.
Embodiment two
A kind of method synchronizing to reclaim nickel cobalt manganese from nickel and cobalt containing manganese waste slag sulphuric leachate, comprises the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, according to solid-to-liquid ratio be 120:1g/L add mass fraction be 25% 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 controlling to leach terminal is 0.5, Filter and separate solid-liquid, collect leachate；
In described leachate, the concentration of main component is: 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 ferrum, aluminum: take above-mentioned leachate, by 2.0 times of the theoretical requirement aoxidizing described leachate ferrous ions Add oxidant sodium chlorate (i.e. n (NaClO3)=0.42n (Fe2+)), regulate pH=5.3 with NaOH, old at temperature is 55 DEG C Changing 60min, then filter press, obtain except ferrum aluminum filtrate, Fe and Al ion is respectively with Al (OH)3、Fe(OH)3The form of precipitation It is removed；
(3) extracting copper: take above-mentioned filtrate, regulates pH=2.2 with sulphuric acid, selects CP150 to make copper extractant, is used sulfonation Kerosene cutback forms first organic extractant that volume fraction is 25% of CP150, carries out 1 grade of extraction at temperature is 35 DEG C, Control to compare O/A=1/1, stir 4min, then stand 5min split-phase, obtain cupric organic facies and the first raffinate；
The dilute sulfuric acid that described cupric organic facies uses pH=3.5 washs 1 time, and then using concentration is the sulfur of 1.5mol/L Acid is back washing agent, carries out 1 grade of back extraction at temperature is 30 DEG C, controls to compare O/A=4/1 in stripping process, stirs 4min, then Stand 5min, obtain copper-bath；Copper-bath can prepare copper sulfate crystal after pervaporation, concentration, this step In rapid, the response rate of copper reaches 98.2%.
(4) extracting zinc: the NaOH solution using mass fraction to be 20% carries out saponification by the saponification rate of 50% to P507 and obtains To the P507 of saponification, and to be diluted to volume fraction with sulfonated kerosene be 30%, obtains the second organic extractant；Take above-mentioned first extraction Remaining liquid, regulates pH=2.3, uses described second organic extractant to carry out 1 grade of extraction at temperature is 35 DEG C, controls to compare O/A =1/2, stir 4min, then stand 5min split-phase, obtain the second raffinate, and containing zinc, the organic facies of a small amount of manganese, major part Manganese and nickel, cobalt remain in the second raffinate；
Carry out washing 2 times by the described dilute sulfuric acid containing zinc, organic facies pH=4.0 of a small amount of manganese, then by concentration be The sulphuric acid of 1.5mol/L carries out 1 grade of back extraction, compares O/A=4/1 during back extraction, and temperature 20 DEG C stirs 4min, then stands 5min, obtains the sulfate containing Zn, Mn and organic facies the second organic extractant, and organic facies continues to make after returning extraction section saponification With；
Use P204 to carry out extract and separate in the described sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, specifically grasp Make as follows: take the described sulfate containing Zn, Mn, regulate pH=1.5 with sulphuric acid, be added thereto to be diluted to volume with sulfonated kerosene Mark be 20% saponification P204 carry out two stage countercurrent extractions, the P204 of saponification be use mass fraction be the NaOH solution of 20% Saponification rate by 50% carries out saponification to P204 and obtains, and controls to compare O/A=1/1, temperature 20 DEG C, stirs 4min, then stand 5min split-phase, obtains containing zinc organic facies and manganese sulfate solution；The described dilute sulfuric acid containing zinc organic facies pH=3.5 is washed 2 times, then carry out 1 grade of back extraction with the sulphuric acid of 0.8mol/L, during back extraction, compare O/A=1/1, temperature 20 DEG C, stirs 4min, so Rear standing 5min, obtains solution of zinc sulfate, and the P204 that wherein back extraction obtains can be continuing with after can returning extraction section saponification. This step reaches 98.7% to the response rate of zinc, and the response rate of manganese is 26%.
(5) synchronize extraction nickel cobalt manganese: take above-mentioned second raffinate, regulate pH=2.0, add tributyl phosphate (TBP) and Versatic acid Versatic 10 extracts together, selects Mextral DT100 to make diluent, wherein Versatic10 before extraction It is the sodium hydroxide saponification of 30% with mass fraction, saponification rate 10%；The versatic acid Versatic 10 of saponification is diluted to volume integral Number is 30%；It is 7% that TBP is diluted to volume fraction, carries out 5 stage countercurrent extractions at temperature is 20 DEG C, controls to compare O/A=1/ 1, stir 4min, then stand 5min split-phase, obtain the organic facies of nickel and cobalt containing manganese；
The dilute sulfuric acid of organic facies pH=4.0 of described nickel and cobalt containing manganese is carried out washing 3 times, then with the sulfur of 1.5mol/L Acid carries out 4 stage countercurrent back extractions, compares O/A=2/1 during back extraction, and temperature 30 DEG C stirs 4min, then stands 5min, obtain nickel The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of cobalt manganese, this step reaches 98.6% to the response rate of cobalt, returning of nickel Yield 97.0%, the response rate of manganese is 72.6% (wherein the overall recovery of manganese is 98.6%).
Embodiment three
A kind of method synchronizing to reclaim nickel cobalt manganese from nickel and cobalt containing manganese waste slag sulphuric leachate, comprises the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, according to solid-to-liquid ratio be 150:1g/L add mass fraction be the sulfur of 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 controlling to leach terminal is 1.2, mistake Filter separates solid-liquid, collects leachate；
In described leachate, the concentration of main component is: 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 ferrum, aluminum: take above-mentioned leachate, by 1.5 times of the theoretical requirement aoxidizing described leachate ferrous ions Add oxidizing agent sodium hypochlorite (i.e. n (NaClO)=0.75n (Fe2+)), regulate pH=5.0 with NaOH, old at temperature is 60 DEG C Changing 45min, then filter press, obtain except ferrum aluminum filtrate, Fe and Al ion is respectively with Al (OH)3、Fe(OH)3The form of precipitation It is removed；
(3) extracting copper: take above-mentioned filtrate, regulates pH=2.0 with sulphuric acid, selects Mextral 984H to make copper extractant, will It forms first organic extractant that volume fraction is 30% of Mextral 984H with Mextral DT100 dilution, in temperature It is at 40 DEG C, to carry out 1 grade of extraction, controls to compare O/A=1/2, stir 4min, then stand 5min split-phase, obtain cupric organic facies With the first raffinate；
The dilute sulfuric acid that described cupric organic facies uses pH=3.5 washs 1 time, and then using concentration is the sulfur of 1.2mol/L Acid is back washing agent, carries out 1 grade of back extraction at temperature is 30 DEG C, controls to compare O/A=2/1 in stripping process, stirs 4min, then Stand 5min, obtain copper-bath；Copper-bath can prepare copper sulfate crystal after pervaporation, concentration, this step In rapid, the response rate of copper reaches 98.2%.
(4) extracting zinc: the NaOH solution using mass fraction to be 20% carries out saponification by the saponification rate of 50% to P507 and obtains To the P507 of saponification, and to be diluted to volume fraction with sulfonated kerosene be 20%, obtains the second organic extractant；Take above-mentioned first extraction Remaining liquid, regulates pH=2.0, uses described second organic extractant to carry out 1 grade of extraction at temperature is 20 DEG C, controls to compare O/A =1/2, stir 4min, then stand 5min split-phase, obtain the second raffinate, and containing zinc, the organic facies of a small amount of manganese, major part Manganese and nickel, cobalt remain in the second raffinate；
Carry out washing 4 times by the described dilute sulfuric acid containing zinc, organic facies pH=4.0 of a small amount of manganese, then by concentration be The sulphuric acid of 1.2mol/L carries out 1 grade of back extraction, compares O/A=4/1 during back extraction, and temperature 40 DEG C stirs 4min, then stands 5min, obtains the sulfate containing Zn, Mn and organic facies the second organic extractant, and organic facies continues to make after returning extraction section saponification With；
Use P204 to carry out extract and separate in the described sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, specifically grasp Make as follows: take the described sulfate containing Zn, Mn, regulate pH=2.0 with sulphuric acid, be added thereto to be diluted to volume with sulfonated kerosene Mark be 30% saponification P204 carry out two stage countercurrent extractions, the P204 of saponification be use mass fraction be the NaOH solution of 20% Saponification rate by 40% carries out saponification to P204 and obtains, and compares O/A=1/2 when controlling counter-current extraction, temperature 40 DEG C, stirring 4min, then stands 5min split-phase, obtains containing zinc organic facies and manganese sulfate solution；By described containing zinc organic facies pH=3.5 Dilute sulfuric acid carries out washing 2 times, then carries out 1 grade of back extraction with the sulphuric acid of 1.5mol/L, compares O/A=2/1, temperature 30 during back extraction DEG C, stirring 4min, then stand 5min, obtain solution of zinc sulfate, the P204 that wherein back extraction obtains can return extraction section saponification After can be continuing with.This step reaches 98.9% to the response rate of zinc, and the response rate of manganese is 21.7%.
(5) synchronize extraction nickel cobalt manganese: take above-mentioned second raffinate, regulate pH=2.3, add tributyl phosphate (TBP) and Versatic acid Versatic 10 extracts together, selects Mextral DT100 to make diluent, wherein Versatic10 before extraction It is the sodium hydroxide saponification of 30% with mass fraction, saponification rate 10%；The versatic acid Versatic 10 of saponification is diluted to volume integral Number is 20%；It is 10% that TBP is diluted to volume fraction, carries out 9 stage countercurrent extractions at temperature is 40 DEG C, controls to compare O/A= 1/1, stir 4min, then stand 5min split-phase, obtain the organic facies of nickel and cobalt containing manganese；
The dilute sulfuric acid of organic facies pH=4.0 of described nickel and cobalt containing manganese is carried out washing 4 times, then with the sulfur of 0.8mol/L Acid carries out 5 stage countercurrent back extractions, compares O/A=1/1 during back extraction, and temperature 35 DEG C stirs 4min, then stands 5min, obtain nickel The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of cobalt manganese, this step reaches 98.8% to the response rate of cobalt, returning of nickel Yield 97.5%, the response rate of manganese is 75.9% (overall recovery of manganese is 97.6%).
Embodiment four
A kind of method synchronizing to reclaim nickel cobalt manganese from nickel and cobalt containing manganese waste slag sulphuric leachate, comprises the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, according to solid-to-liquid ratio be 100:1g/L add mass fraction be the sulfur of 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 controlling to leach terminal is 0.5, mistake Filter separates solid-liquid, collects leachate；
In described leachate, the concentration of main component is: 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 ferrum, aluminum: take above-mentioned leachate, by 1.7 times of the theoretical requirement aoxidizing described leachate ferrous ions Add oxidant sodium chlorate (i.e. n (NaClO3)=0.35n (Fe2+)), regulate pH=5.3 with NaOH, old at temperature is 55 DEG C Changing 60min, then filter press, obtain except ferrum aluminum filtrate, Fe and Al ion is respectively with Al (OH)3、Fe(OH)3The form of precipitation It is removed；
(3) extracting copper: take above-mentioned filtrate, regulates pH=2.0 with sulphuric acid, selects Mextral 984H to make copper extractant, will It forms first organic extractant that volume fraction is 20% of Mextral 984H with Mextral DT100 dilution, in temperature It is at 40 DEG C, to carry out 1 grade of extraction, controls to compare O/A=1/1, stir 4min, then stand 5min split-phase, obtain cupric organic facies With the first raffinate；
The dilute sulfuric acid that described cupric organic facies uses pH=4.0 washs 1 time, and then using concentration is the sulfur of 0.8mol/L Acid is back washing agent, carries out 1 grade of back extraction at temperature is 35 DEG C, controls to compare O/A=2/1 in stripping process, stirs 4min, then Stand 5min, obtain copper-bath；Copper-bath can prepare copper sulfate crystal after pervaporation, concentration, this step In rapid, the response rate of copper reaches 98.4%.
(4) extracting zinc: the NaOH solution using mass fraction to be 20% carries out saponification by the saponification rate of 40% to P507 and obtains To the P507 of saponification, and to be diluted to volume fraction with sulfonated kerosene be 30%, obtains the second organic extractant；Take above-mentioned first extraction Remaining liquid, regulates pH=2.2, uses described second organic extractant to carry out 1 grade of extraction at temperature is 30 DEG C, controls to compare O/A =1/1, stir 4min, then stand 5min split-phase, obtain the second raffinate, and containing zinc, the organic facies of a small amount of manganese, major part Manganese and nickel, cobalt remain in the second raffinate；
Carry out washing 3 times by the described dilute sulfuric acid containing zinc, organic facies pH=3.5 of a small amount of manganese, then be 1mol/ by concentration The sulphuric acid of L carries out 1 grade of back extraction, compares O/A=2/1 during back extraction, and temperature 20 DEG C stirs 4min, then stands 5min, contained The sulfate of Zn, Mn and organic facies the second organic extractant, organic facies is continuing with after returning extraction section saponification；
Use P204 to carry out extract and separate in the described sulfate containing Zn, Mn again, obtain zinc sulfate and cobaltous sulfate, specifically grasp Make as follows: take the described sulfate containing Zn, Mn, regulate pH=1.5 with sulphuric acid, be added thereto to be diluted to volume with sulfonated kerosene Mark be 20% saponification P204 carry out two stage countercurrent extractions, the P204 of saponification be use mass fraction be the NaOH solution of 20% Saponification rate by 50% carries out saponification to P204 and obtains, and compares O/A=1/2 when controlling counter-current extraction, temperature 30 DEG C, stirring 4min, then stands 5min split-phase, obtains containing zinc organic facies and manganese sulfate solution；By described containing zinc organic facies pH=3.5 Dilute sulfuric acid carries out washing 2 times, then carries out 1 grade of back extraction with the sulphuric acid of 1.0mol/L, compares O/A=1/1, temperature 30 during back extraction DEG C, stirring 4min, then stand 5min, obtain solution of zinc sulfate, the P204 that wherein back extraction obtains can return extraction section saponification After can be continuing with.This step reaches 99.0% to the response rate of zinc, and the response rate of manganese is 24.8%.
(5) synchronize extraction nickel cobalt manganese: take above-mentioned second raffinate, regulate pH=1.9, add tributyl phosphate (TBP) and Versatic acid Versatic 10 extracts together, selects sulfonated kerosene to make diluent, wherein Versatic10 mass before extraction Mark is the sodium hydroxide saponification of 30%, saponification rate 20%；The versatic acid Versatic 10 of saponification is diluted to volume fraction 20%；It is 7% that TBP is diluted to volume fraction, carries out 8 stage countercurrent extractions at temperature is 25 DEG C, controls to compare O/A=1/1, stirs Mix 4min, then stand 5min split-phase, obtain the organic facies of nickel and cobalt containing manganese；
The dilute sulfuric acid of organic facies pH=3.5 of described nickel and cobalt containing manganese is carried out washing 2 times, then with the sulfur of 1.5mol/L Acid carries out 4 stage countercurrent back extractions, compares O/A=21 during back extraction, and temperature 40 DEG C stirs 4min, then stands 5min, obtain nickel cobalt The sulfate (i.e. containing cobaltous sulfate, nickel sulfate and manganese sulfate) of manganese, this step reaches 98.5% to the response rate of cobalt, the recovery of nickel Rate 97.9%, the response rate 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, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (10)

1. the method synchronizing to reclaim nickel cobalt manganese from nickel and cobalt containing manganese waste slag, it is characterised in that comprise the following steps:
(1) sulfuric acid leaching: take nickel and cobalt containing manganese waste slag, adds sulphuric acid and carries out acidleach, filter and separate solid-liquid, collect leachate；
(2) except ferrum, aluminum: take described leachate, add oxidant, regulate pH=5.0-5.5, make the ferrum in leachate, aluminium element Precipitating, filter, the filtrate after obtaining except ferrum, aluminum, wherein, described oxidant is hypochlorite, chlorate or nitric acid；
(3) extracting copper: take the filtrate in above-mentioned steps (2), regulates pH=2.0-2.5, add Mextral984H or CP150 with The first organic extractant that diluent is formed, through being obtained by extraction cupric organic facies and the first raffinate；
(4) extracting zinc: take described first raffinate, regulates pH=2.0-2.3, and the P507 of addition saponification and kerosene are mixed to form Second organic extractant, through being obtained by extraction the second raffinate, and containing zinc, the organic facies of a small amount of manganese；
The described organic facies dilute sulfuric acid containing zinc, a small amount of manganese is washed, then uses sulphuric acid back extraction, obtain the sulphuric acid containing Zn, Mn Salt, then use P204 to carry out extract and separate in the described sulfate containing Zn, Mn, obtain zinc sulfate and manganese sulfate；
(5) synchronize extraction nickel cobalt manganese: take described second raffinate, regulate pH=1.7-2.3, addition tributyl phosphate and saponification The mixed extractant that neodecanoic acid is formed with diluent, obtains the organic facies of nickel and cobalt containing manganese through counter-current extraction；Wherein, described adverse current extraction Volume ratio O/A taking time control organic facies and aqueous phase is 1/1～1/2, in described mixed extractant, and the volume integral of tributyl phosphate Number is 5-10%, and the volume fraction of the neodecanoic acid of saponification is 20%～30%；
The organic facies dilute sulfuric acid of described nickel and cobalt containing manganese is washed, the calcium and magnesium impurity carried secretly with removing, then carry out with sulphuric acid Countercurrent reextraction, obtains the sulfate of nickel cobalt manganese.
Method the most according to claim 1, it is characterised in that in step (5), described counter-current extraction is 5～10 grades；Described Counter-current extraction time control organic facies is 1/1 with volume ratio O/A of aqueous phase.
Method the most according to claim 1, it is characterised in that in step (5), described countercurrent reextraction is 4～5 grades；Described Countercurrent reextraction time control organic facies and volume ratio O/A=2/1～1/1 of aqueous phase.
Method the most according to claim 1, it is characterised in that in step (5), the pH=of the dilute sulfuric acid of described washing 3.5-4.0；The concentration of the sulphuric acid of described back extraction is 0.8-1.5mol/L.
Method the most according to claim 1, it is characterised in that in step (5), the neodecanoic acid of described saponification is to use quality Mark be 20% NaOH solution by the saponification rate of 10～30%, neodecanoic acid is carried out saponification and obtains.
Method the most according to claim 1, it is characterised in that in step (2), described oxidant is sodium chlorate, described chlorine 0.3-0.42 times of the mole that mole is described leachate ferrous ions of acid sodium.
Method the most according to claim 1, it is characterised in that in step (3), described Mextral 984H or CP150 exists Volume fraction in described first organic extractant is 20-30%；Described first organic extractant extraction time control is used to be shaped with machine It is 1/1～1/2 with the volume ratio of aqueous phase.
Method the most according to claim 1, it is characterised in that in step (4), in described second organic extractant, institute The volume fraction of the P507 stating saponification is 20%～30%；Use described second organic extractant extraction time control organic facies and water The volume ratio of phase is 1/1～1/2.
Method the most according to claim 1, it is characterised in that in step (4), described employing P204 carries out extract and separate, Particularly as follows:
Take the described sulfate containing Zn, Mn, regulate pH=1.5～2.0, add the P204 and the 3rd of sulfonated kerosene formation the of saponification Organic extractant, controls to compare O/A=1/1～1/2, carries out two stage countercurrent extractions, and the P204 of described saponification has the described 3rd Volume fraction in machine extractant is 20-30%, obtains containing zinc organic facies and manganese sulfate solution；
The described organic facies dilute sulfuric acid containing zinc is carried out washing 2-4 time, then carries out 1 grade of back extraction with sulphuric acid, obtain solution of zinc sulfate； Wherein control during back extraction to compare O/A=2/1～1/2.
Method the most according to claim 1, it is characterised in that in step (3), also include: take described cupric organic facies, Use dilute sulfuric acid that it is washed, then use sulphuric acid back extraction, obtain copper-bath.
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