CN103088215B - Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio - Google Patents
Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio Download PDFInfo
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- CN103088215B CN103088215B CN201210392293.3A CN201210392293A CN103088215B CN 103088215 B CN103088215 B CN 103088215B CN 201210392293 A CN201210392293 A CN 201210392293A CN 103088215 B CN103088215 B CN 103088215B
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011572 manganese Substances 0.000 title claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 11
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 36
- 239000011734 sodium Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 241000220317 Rosa Species 0.000 claims description 4
- PAMMESUSQVJOMA-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] PAMMESUSQVJOMA-UHFFFAOYSA-L 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 21
- 238000002386 leaching Methods 0.000 abstract description 20
- 238000001914 filtration Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 5
- 235000010265 sodium sulphite Nutrition 0.000 abstract 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 abstract 1
- 229940044175 cobalt sulfate Drugs 0.000 abstract 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 235000013495 cobalt Nutrition 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 238000000926 separation method Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating nickel-cobalt and manganese in a nickel-cobalt-manganese material with a high manganese-cobalt ratio. The method comprises the following steps of: providing a nickel-cobalt-manganese material with the high manganese-cobalt ratio of 0.5-1.2; mixing the nickel-cobalt-manganese material with the high manganese-cobalt ratio with a mixed solution of dilute sulphuric acid and sodium sulfite; adjusting the final-point pH of the solution to 0-3.5; filtering and retaining first filtrate after the sufficient reaction; adding soluble persulfate to the first filtrate, adjusting the final-point pH of the mixed solution to 2-6; and filtering after the sufficient reaction to obtain second filtrate containing nickel sulfate and cobalt sulfate. According to the method for separating nickel-cobalt and manganese in the nickel-cobalt-manganese material with high manganese-cobalt ratio disclosed by the invention, the manganese is separated from nickel-cobalt in the solution by reducing and leaching out the nickel-cobalt-manganese from the mixed solution of the dilute sulphuric acid and the sodium sulfite, and then oxidizing and settling the manganese by adopting the soluble persulfate; compared with the conventional separating method for nickel-cobalt and manganese in the nickel-cobalt-manganese material, the process is simple and easy to apply, the production cost is low and the nickel-cobalt recovery rate is high.
Description
Technical field
The present invention relates to hydrometallurgy and chemical production technical field, particularly relate to the separation method of a kind of high cobalt manganese than nickel cobalt and manganese in nickel cobalt manganese raw material.
Background technology
Nickle cobalt lithium manganate, as a kind of novel battery positive electrode material, just progressively replaces the high lithium cobaltate cathode material of cost for the manufacture of the lithium-ion secondary cell on power tool, electric bicycle and electromobile.Manufacturing in a large amount of useless pole piece and refuse battery and waste nickel cobalt manganic acid lithium ionization cell produced in nickle cobalt lithium manganate process containing valuable metals such as a large amount of nickel cobalts, there is larger recovery value.And also exist both at home and abroad a large amount of containing manganese cobalt raw material or waste material.Effectively carrying out high manganese cobalt is the gordian technique reclaiming high manganese cobalt raw material or waste material than separation of cobalt from manganese in cobalt manganese raw material.
Traditional high manganese cobalt is than nickel cobalt and manganese separation method in nickel cobalt manganese raw material, and nickel and cobalt recovery rate is lower.
Summary of the invention
Based on this, the high manganese cobalt being necessary to provide a kind of nickel and cobalt recovery rate higher is than the separation method of nickel cobalt and manganese in nickel cobalt manganese raw material.
The method that high manganese cobalt is separated with manganese than nickel cobalt in nickel cobalt manganese raw material, comprises the steps:
Manganese cobalt ratio is provided to be that the high manganese cobalt of 0.5 ~ 1.2 is than nickel cobalt manganese raw material;
Described high manganese cobalt is mixed with the mixed solution of dilute sulphuric acid and S-WAT than nickel cobalt manganese raw material, regulates terminal pH to be 0 ~ 3.5, fully filter and retain the first filtrate after reaction;
In described first filtrate, add solubility persulphate, adjustment terminal pH is 2 ~ 6, fully filters the oxide precipitation obtaining manganese and the second filtrate containing single nickel salt and rose vitriol after reaction.
In one embodiment, described high manganese cobalt is manufacture the useless pole piece, waste nickel cobalt manganic acid lithium ionization cell, manganese cobalt ore or the manganese cobalt raw material that produce in nickle cobalt lithium manganate process than nickel cobalt manganese raw material.
In one embodiment, in the described operation mixed than the mixed solution of nickel cobalt manganese raw material and dilute sulphuric acid and S-WAT by described high manganese cobalt, the add-on of described S-WAT is 1 times ~ 1.6 times of theoretical value.
In one embodiment, in the described operation mixed than the mixed solution of nickel cobalt manganese raw material and dilute sulphuric acid and S-WAT by described high manganese cobalt, temperature is 50 DEG C ~ 95 DEG C, and liquid-solid ratio is 3kg/1kg ~ 10kg/1kg.
In one embodiment, described adjustment terminal pH is in the operation of 0 ~ 3.5, adopts Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o is as neutralizing agent.
In one embodiment, describedly add in the operation of solubility persulphate in described first filtrate, the add-on of described solubility persulphate is 1 times ~ 1.8 times of theoretical value.
In one embodiment, described solubility persulphate is Sodium Persulfate or ammonium persulphate.
In one embodiment, describedly add in the operation of solubility persulphate in described filtrate, temperature is 50 DEG C ~ 95 DEG C.
In one embodiment, described adjustment terminal pH is in the operation of 2 ~ 6, adopts Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o is as neutralizing agent.
The method that this high manganese cobalt is separated with manganese than nickel cobalt in nickel cobalt manganese raw material is by the mixed solution reducing leaching nickel cobalt manganese of dilute sulphuric acid and S-WAT, then solubility persulfate oxidation is adopted to be separated manganese, thus by Separation of nickel and cobalt out, relative to the method that nickel cobalt in traditional nickel cobalt manganese raw material is separated with manganese, nickel and cobalt recovery rate is higher.
Accompanying drawing explanation
Fig. 1 is the schema of the method that the high manganese cobalt of an embodiment is separated with manganese than nickel cobalt in nickel cobalt manganese raw material;
Fig. 2 is the schematic diagram of the method that high manganese cobalt is as shown in Figure 1 separated with manganese than nickel cobalt in nickel cobalt manganese raw material.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The high manganese cobalt of an embodiment as depicted in figs. 1 and 2, than the separation method of nickel cobalt and manganese in nickel cobalt manganese raw material, comprises the steps:
S10, provide manganese cobalt ratio to be 0.5 ~ 1.2 high manganese cobalt than nickel cobalt manganese raw material.
High manganese cobalt ratio refers to that manganese cobalt ratio is 0.5 ~ 1.2.
High manganese cobalt can be manufacturing a large amount of useless pole piece produced in nickle cobalt lithium manganate process, waste nickel cobalt manganic acid lithium ionization cell, manganese cobalt ore or manganese cobalt raw material than nickel cobalt manganese raw material.
S20, the high manganese cobalt obtained by S10 mix with the mixed solution of dilute sulphuric acid and S-WAT than nickel cobalt manganese raw material, regulate terminal pH to be 0 ~ 3.5, fully filter and retain the first filtrate after reaction.
Adopt sulfuric acid as leach liquor, S-WAT as reductive agent, the elements such as reducing leaching nickel cobalt manganese.
In reducing leaching process, corresponding reaction formula is as follows:
CoO+H
2SO
4=CoSO
4+2H
2O ；
Co
2O
3+2H
2SO
4+Na
2SO
3=2CoSO
4+Na
2SO
4+2H
2O ；
NiO+2H
2SO
4=NiSO
4+H
2O ；
MnO+2H
2SO
4=MnSO
4+H
2O ；
Mn
2O
3+2H
2SO
4+Na
2SO
3=2MnSO
4+Na
2SO
4+2H
2O ；
MnO
2+H
2SO
4+Na
2SO
3=MnSO
4+Na
2SO
4+H
2O 。
After reducing leaching, nickel cobalt manganese exists in solution with the form of vitriol, and other impurity is precipitation, retains the first filtrate after filtering.
The operation of filtering can adopt press filtration.
The add-on of S-WAT is 1.5 times ~ 1.6 times of theoretical value.
Sulfuric acid dosage is theoretical amount 1.2 times ~ 1.5 times.
During reducing leaching, temperature of reaction is 50 DEG C ~ 95 DEG C, and liquid-solid ratio is 3kg/1kg ~ 10kg/1kg.
When regulating terminal pH to be 1.5, adopt Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o is as neutralizing agent.
In S20, the leaching rate of recovery of nickel is more than 99%, and the leaching rate of recovery of cobalt is more than 98.5%, and the leaching rate of recovery of manganese is more than 98.5%.
Add solubility persulphate in S30, the first filtrate of obtaining to S20, regulate terminal pH to be 2.0 ~ 6.0, fully after reaction, filter the oxide precipitation obtaining manganese and the second filtrate containing single nickel salt and rose vitriol.
Adopt solubility persulfate oxidation to be separated manganese, corresponding reaction formula is as follows:
2MnSO
4+Na
2S
2O
8+2H
2O=Mn
2O
3↓+Na
2SO
4+2H
2SO
4 ；
3MnSO
4+Na
2S
2O
8+4H
2O=Mn
3O
4↓+Na
2SO
4+4H
2SO
4 ；
MnSO
4+2Na
2S
2O
8+3H
2O=MnO
2↓+2Na
2SO
4+3H
2SO
4 。
After oxidation is separated, manganese is present in precipitation, and nickel cobalt exists in solution with the form of vitriol, and the second filtrate obtained after filtration is the mixed solution of rose vitriol and single nickel salt.
Second filtrate can prepare nickel cobalt product further, such as, prepare metallic nickel and cobalt metal product for the preparation of high purity nickel cobalt salt product or electrodeposition
The second filter residue obtained is crude oxidation manganese, may be used for preparing manganese salt further.
The operation of filtering can adopt press filtration.
The add-on of solubility persulphate is 1 times ~ 1.6 times of theoretical value.
Solubility persulphate is Sodium Persulfate or ammonium persulphate.
When oxidation is separated, the temperature of reaction is 50 DEG C ~ 95 DEG C.
Na can be adopted
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o, as neutralizing agent, regulates terminal pH to be 2 ~ 6.
In S30, the rate of recovery of nickel is more than 99%, and the rate of recovery of cobalt is more than 98%, and the precipitation clearance of manganese is more than 99%.
The method that this high manganese cobalt is separated with manganese than nickel cobalt in nickel cobalt manganese raw material is by the mixed solution reducing leaching nickel cobalt manganese of dilute sulphuric acid and S-WAT, then solubility persulfate oxidation precipitate and separate manganese is adopted, thus from solution, precipitate and separate is out by manganese, relative to the separation method of nickel cobalt and manganese in traditional nickel cobalt manganese raw material, simple for process, production cost is low, nickel and cobalt recovery rate is higher.
It is below specific embodiment.
Embodiment 1
Cobalt nickel manganese raw material (Co 13.8%, Ni 12.9%, Cu 0.36%, Mn 10.16%, Zn 1.23%, Fe1.15%, Pb 0.21%, Si 0.13%, Ca 0.21%, Mg 0.66%), uses H
2sO
4+ Na
2sO
3(Na
2sO
3theoretical amount 1.5 ~ 1.6 times) leach, liquid-solid ratio 8kg/1kg, temperature 75 DEG C, churning time 2.5h, Na
2cO
3for neutralizing agent, terminal pH 1.5.The leaching rate of recovery of cobalt is 98.71%, and the leaching rate of recovery of nickel is 99.12%, and the leaching rate of recovery of manganese is 98.76%.
Leach liquor Na
2s
2o
8(theoretical amount 1.6 times) is oxygenant, Na
2cO
3for neutralizing agent, temperature 75 DEG C, churning time 1.5hr, terminal pH 4.5 precipitates demanganization.The precipitation clearance of manganese is 99.32%, and the leaching rate of recovery of cobalt is 99.13%.The leaching rate of recovery of nickel is 99.53%.
After separation of cobalt from manganese, single nickel salt cobalt liquor prepares metallic nickel and cobalt metal product for the preparation of high purity nickel cobalt salt product or electrodeposition, and crude oxidation manganese is for the preparation of manganese product salt.
Embodiment 2
Waste nickel cobalt-manganese ternary anode of secondary battery material (Li 6.99%, Co 4.82%, Ni 12.11%, Cu 0.01%, Mn 6.61%, Zn 0.02%, Fe 0.06%, Al 3.75%, Ca 0.001%, Mg 0.001%), uses H
2sO
4+ Na
2sO
3(Na
2sO
3theoretical amount 1.5 ~ 1.6 times) leach, liquid-solid ratio 6kg/1kg, temperature 75 DEG C, churning time 2.5h, Na
2cO
3for neutralizing agent, terminal pH 1.5.The leaching rate of recovery of cobalt is 98.68%, and the leaching rate of recovery of nickel is 99.33%, and the leaching rate of recovery of manganese is 98.71%.
Leach liquor (NH
4)
2s
2o
8(theoretical amount 1.6 times) is oxygenant, Na
2cO
3for neutralizing agent, temperature 75 DEG C, churning time 1.5hr, terminal pH 4.5 precipitates demanganization.The precipitation clearance of manganese is 99.63%, and the leaching rate of recovery of cobalt is 98.18%.The leaching rate of recovery of nickel is 98.67%.
The above embodiment only have expressed one or more embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. the method that is separated with manganese than nickel cobalt in nickel cobalt manganese raw material of high manganese cobalt, is characterized in that, comprise the steps:
There is provided manganese cobalt than being that the high manganese cobalt of 0.5 ~ 1.2 is than nickel cobalt manganese raw material;
Described high manganese cobalt is mixed with the mixed solution of dilute sulphuric acid and S-WAT than nickel cobalt manganese raw material, regulates terminal pH to be 0 ~ 3.5, fully filter and retain the first filtrate after reaction;
In described first filtrate, add solubility persulphate, adjustment terminal pH is 2 ~ 6, fully filters the oxide precipitation obtaining manganese and the second filtrate containing single nickel salt and rose vitriol after reaction;
Described high manganese cobalt is manufacture the useless pole piece, waste nickel cobalt manganic acid lithium ionization cell or the manganese cobalt ore that produce in nickle cobalt lithium manganate process than nickel cobalt manganese raw material;
Describedly add in the operation of solubility persulphate in described first filtrate, the add-on of described solubility persulphate is 1 times ~ 1.8 times of theoretical value;
Described solubility persulphate is Sodium Persulfate or ammonium persulphate;
Describedly add in the operation of solubility persulphate in described filtrate, temperature is 50 DEG C ~ 95 DEG C.
2. the method that is separated with manganese than nickel cobalt in nickel cobalt manganese raw material of high manganese cobalt as claimed in claim 1, it is characterized in that, in the described operation mixed than the mixed solution of nickel cobalt manganese raw material and dilute sulphuric acid and S-WAT by described high manganese cobalt, the add-on of described S-WAT is 1 times ~ 1.6 times of theoretical value.
3. the method that is separated with manganese than nickel cobalt in nickel cobalt manganese raw material of high manganese cobalt as claimed in claim 1, it is characterized in that, in the described operation that described high manganese cobalt is mixed than the mixed solution of nickel cobalt manganese raw material and dilute sulphuric acid and S-WAT, temperature is 50 DEG C ~ 95 DEG C, and liquid-solid ratio is 3kg/1kg ~ 10kg/1kg.
4. the method that is separated with manganese than nickel cobalt in nickel cobalt manganese raw material of high manganese cobalt as claimed in claim 1, it is characterized in that, described adjustment terminal pH is in the operation of 0 ~ 3.5, adopts Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o is as neutralizing agent.
5. the method that is separated with manganese than nickel cobalt in nickel cobalt manganese raw material of high manganese cobalt as claimed in claim 1, it is characterized in that, described adjustment terminal pH is in the operation of 2 ~ 6, adopts Na
2cO
3, (NH
4)
2cO
3, NH
4hCO
3, NaOH or NH
3h
2o is as neutralizing agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210392293.3A CN103088215B (en) | 2012-10-16 | 2012-10-16 | Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210392293.3A CN103088215B (en) | 2012-10-16 | 2012-10-16 | Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio |
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|---|---|
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| CN103088215B true CN103088215B (en) | 2015-01-07 |
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