CN108517403A - A kind of method of metallic cobalt battery grade cobalt sulfate - Google Patents
A kind of method of metallic cobalt battery grade cobalt sulfate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- 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
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0484—Separation of nickel from cobalt in acidic type solutions
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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Abstract
The invention discloses a kind of methods of metallic cobalt battery grade cobalt sulfate, specifically include following steps：Step 1: excellent molten removal of impurities；Step 2: reducing leaching；Step 3: oxidation-precipitation method is except iron, arsenic, manganese；Step 4: fluoride process deliming, magnesium；Step 5: P204 extracts removing impurities；Step 6, P507 detaches nickel cobalt and step 7, cobaltous sulfate crystallizes, the method of the metallic cobalt battery grade cobalt sulfate, the leaching rate of cobalt is up to 98% or more, pass through the excellent molten crude cobalt hydroxide of hot diluted acid, effectively reduce the content of foreign metal in leachate, shorten and simplify the technological process for preparing high-purity sulphuric acid cobalt, the loss of cobalt in chemical precipitation method dedoping step is reduced simultaneously, the various impurity in crude cobalt hydroxide leachate can be effectively removed, the rate of recovery of cobalt is more than 95%, it is simple for process, it is at low cost, product quality is stablized, the quality standard for preparing lithium cobalt oxide electron level cobaltous sulfate is reached.
Description
Technical field
The present invention relates to battery grade cobalt sulfate preparing technical field, specially a kind of metallic cobalt battery grade cobalt sulfate
Method.
Background technology
Cobaltous sulfate, rose crystallization.Take on a red color powder after dehydration, is dissolved in water and methanol, is slightly soluble in ethyl alcohol.For making pottery
Glaze and paint drier are also used for plating, alkaline battery, production containing cobalt pigment and other cobalt products, are additionally operable to be catalyzed
Agent, analytical reagent, feed addictive, tire adhesive, lithopone additive etc..
Industrial production prepares lithium cobalt oxide, at present generally use high-temperature synthesis.Solid phase in the technique preparation process
Diffusion velocity is slow, and batch mixing is difficult to uniformly, and there are larger differences in structure, composition, size distribution etc. for products therefrom, thus
Cause its chemical property not easy to control, actual capacity is relatively low.It is ground for this purpose, many scholars have carried out a large amount of of novel synthesis
To study carefully, " wet chemical method for preparing lithium cobalt oxide " is invented by Changsha Mining ＆ Metallurgy Inst, using cobalt salt and lithium compound as raw material,
Lithium salts is set organically to be incorporated in one with the oxidation reaction of low price cobalt with cobalt salt uniformly mixing on molecule and atom level level
It rises, effectively controls the chemical composition and phase constituent of lithium cobalt oxide, its uniformity is made to improve, chemical property improves.This
Method is applied in the industrial production, but because current technical grade cobalt salt is difficult to meet the requirement of synthesis lithium cobalt oxide,
Therefore the production technology of high pure electronic grade cobaltous sulfate need to be studied.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, it the present invention provides a kind of method of metallic cobalt battery grade cobalt sulfate, solves
The problem of being difficult to meet synthesis lithium cobalt oxide requirement because of current technical grade cobalt salt.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs：A kind of metallic cobalt LITHIUM BATTERY sulfuric acid
The method of cobalt, includes the following steps：
Step 1: excellent molten removal of impurities：Removal of impurities processing is carried out to crude metal cobalt, makes the control of its temperature at 60--70 DEG C, dilute sulfuric acid
Solution pH value 2.0, mixing time 1.0--1.5h slowly add the slightly larger sulfuric acid of concentration in the process stirring to wash, make excellent solution PH
Value maintains between 2.0--3.0；
Step 2: reducing leaching：To after the removal of impurities completed in step 1, using in sulfuric acid medium with Na2SO3It restores
Cobalt hydroxide is leached in agent, and its experimental condition is 60--70 DEG C of temperature, Na2SO31.5--1.6 times of theoretical amount of addition, eventually
Point pH value 1.5, reaction time 2.0--3.0h form filtrate eventually by press filtration；
Step 3: oxidation-precipitation method is except iron, arsenic, manganese：Finally formed filtrate is being aoxidized in step 2, oxidation
Condition be 65 DEG C of demanganization temperature, KMnO4Addition is 1.6 times of theoretical amounts, ph value of reaction 3.5, reaction time 1.5h；Except iron arsenic
80 DEG C of temperature ＞, NaCLO3Then 3--4 times of theoretical amount of addition, terminal pH value ＞ 3.0, reaction time 1h pass through press filtration shape again
The filtrate of Cheng Xin；
Step 4: fluoride process deliming, magnesium：Finally formed filtrate is being fluorinated in step 3, and fluorinated condition is
90 DEG C of temperature ＞, NaF additions be 3--4 times of theoretical amount, terminal pH value ＞ 5.0, reaction time 1.5--2.0h, again by
Press filtration is press-filtered out filtrate；
Step 5: P204 extracts removing impurities：P204 is two-(2- ethylhexyls) phosphoric acid, and the mechanism of extracting metals can consider
It is cationic liquid exchange process：P204 is from H2SO4Various gold are extracted in medium
The sequence of category is Fe3+＞ Zn2+＞ Cd2+＞ Cu2+≈Mn2+＞ Co2+＞ Mg2+＞ Ni2+, therefore the impurity such as iron, zinc, manganese, copper can
It is extracted removing prior to cobalt, and nickel, cobalt then retain in raffinate；
Step 6: P507 detaches nickel cobalt：P507 is 2- ethylhexyl phosphoric acids list (2- ethylhexyls) ester, P507 molecules
In have ＞ POOH bases, H in the middle can be replaced by metal, extraction equation can be abbreviated as：P507 is to metal extraction capacity of water order Fe3+＞ Zn2+＞ Cu2+≈Mn2+
≈Ca2+＞ Co2+＞ Mg2+＞ Ni2+, from metal ion extraction rate and pH value relation curve it is found that by controlling extraction equilibrium PH
Value can be such that cobalt, nickel is efficiently separated；
Step 7: cobaltous sulfate crystallizes：The qualified cobalt sulfate solution that P507 is stripped to cobalt section output is put into crystallization reactor
In, it is evaporated concentration, cobalt sulfate solution is continuously replenished halfway.It is when 50--52, to stop heating, lead to when being concentrated to Baume degrees
Enter cold water, when temperature drops to 40--45 DEG C, releasing cobaltous sulfate concentrate, the further crystallisation by cooling in crystallizing pan, finally again
Centrifugal filtration, obtains cobaltous sulfate product, and sampling carries out chemical analysis.
Preferably, in step 1, the excellent molten method of diluted acid can remove about 80% cadmium in raw material, 50% or more nickel zinc,
The copper that part is brought by suction-operated can also be taken away, and cobalt loss is less than 0.5%.
Preferably, in step 4, the deliming of fluorination precipitation method, magnesium are used under test conditions, rate of deposition is respectively
89.0%, 83.0%, the concentration ratio of Co/Ca, Co/Mg are respectively 2490,3540 in solution.
Preferably, in step 5, in experimental condition, organic phase composition：15%P204+85% sulfonated kerosenes, saponification rate
75%；Feed liquid：Cobalt sulfate solution pH value 4.0.
Preferably, in step 7, being concentrated to of cobalt sulfate solution is equivalent to density when Baume degrees is 50--52 and is
1.54g/cm3。
(3) advantageous effect
The present invention provides a kind of methods of metallic cobalt battery grade cobalt sulfate.Has following advantageous effect：The metallic cobalt
The method of battery grade cobalt sulfate processed, by Step 1: excellent molten removal of impurities；Step 2: reducing leaching；Step 3: oxidation-precipitation method removes
Iron, arsenic, manganese；Step 4: fluoride process deliming, magnesium；Step 5: P204 extracts removing impurities；Step 6: P507 separation nickel cobalts and step
Seven, the series of steps of cobaltous sulfate crystallization, the leaching rate of cobalt is up to 98% or more, by the excellent molten crude cobalt hydroxide of hot diluted acid, effectively
The content for reducing foreign metal in leachate shortens and simplifies the technological process for preparing high-purity sulphuric acid cobalt, reduces simultaneously
The loss of cobalt in chemical precipitation method dedoping step, using oxidation-precipitation method except iron, arsenic, manganese, fluoride precipitates deliming, magnesium,
P204 extracts deeply purifying and removing iron, zinc, manganese, copper, P507 extraction and separation nickel, cobalt purification and impurity removal technique, thick hydrogen can be effectively removed
Various impurity in cobalt oxide leachate, the rate of recovery of cobalt are more than 95%, simple for process, at low cost, product quality is steady
It is fixed, reach the quality standard for preparing lithium cobalt oxide electron level cobaltous sulfate.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described reality
It is only a part of the embodiment of the present invention to apply example, instead of all the embodiments.Based on the embodiments of the present invention, this field
The every other embodiment that those of ordinary skill is obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
Technical problems based on background technology, the present invention provide a kind of technical solution：A kind of metallic cobalt LITHIUM BATTERY
The method of cobaltous sulfate, includes the following steps：
Step 1: excellent molten removal of impurities：Removal of impurities processing is carried out to crude metal cobalt, makes the control of its temperature at 60--70 DEG C, dilute sulfuric acid
Solution pH value 2.0, mixing time 1.0--1.5h slowly add the slightly larger sulfuric acid of concentration in the process stirring to wash, make excellent solution PH
Between value maintains 2.0--3.0, crude cobalt hydroxide raw material system drift ice is analysed cobalt and is obtained, and has been adsorbed in cobalt precipitation process a large amount of
The impurity such as zinc, cadmium, manganese, it is excellent molten using hot diluted acid, a large amount of metal impurities can be removed, shortens and simplification prepares high-purity sulphuric acid cobalt
Technological process, reduce in chemical precipitation method dedoping step chemical raw material and consume, to reduce production cost, reduction removes
The loss of cobalt during miscellaneous；
Step 2: reducing leaching：To after the removal of impurities completed in step 1, using in sulfuric acid medium with Na2SO3It restores
Cobalt hydroxide is leached in agent, and its experimental condition is 60--70 DEG C of temperature, Na2SO31.5--1.6 times of theoretical amount of addition, eventually
Point pH value 1.5, reaction time 2.0--3.0h form filtrate eventually by press filtration, and the cobalt in cobalt hydroxide is in the form of trivalent
In the presence of obtaining divalent cobalt liquor, reduction of dissolved must be carried out, adoptable reducing agent has NaCl, HCl and Na2SO3Deng, due to
First two reducing agent will release chlorine during the reaction, seriously affect operating condition, and environmental pollution, this technique is caused to use
Sodium sulfite is reducing agent, is leached under test conditions, and the leaching rate of cobalt is up to 98% or more, because excellent molten by hot diluted acid, is had
Reduce to effect the content of foreign metal in leachate；
Step 3: oxidation-precipitation method is except iron, arsenic, manganese：Finally formed filtrate is being aoxidized in step 2, oxidation
Condition be 65 DEG C of demanganization temperature, KMnO4Addition is 1.6 times of theoretical amounts, ph value of reaction 3.5, reaction time 1.5h；Except iron arsenic
80 DEG C of temperature ＞, NaCLO3Then 3--4 times of theoretical amount of addition, terminal pH value ＞ 3.0, reaction time 1h pass through press filtration shape again
The filtrate of Cheng Xin, the solution after reducing leaching, iron content, arsenic, manganese are high, in subsequent extracting system, ferrous iron and the equal nothing of arsenic
Method is efficiently removed, this not only increases the load of follow-up extraction section, will also influence product quality, therefore, enters extraction in solution
Iron and arsenic must be effectively removed before system, it is contemplated that the stability of solution, therefore a step permanganic acid is increased in our current research
Potassium demanganization；
Step 4: fluoride process deliming, magnesium：Finally formed filtrate is being fluorinated in step 3, and fluorinated condition is
90 DEG C of temperature ＞, NaF additions be 3--4 times of theoretical amount, terminal pH value ＞ 5.0, reaction time 1.5--2.0h, again by
Press filtration is press-filtered out filtrate；
Step 5: P204 extracts removing impurities：P204 is two-(2- ethylhexyls) phosphoric acid, and the mechanism of extracting metals can consider
It is cationic liquid exchange process：P204 is from H2SO4Various gold are extracted in medium
The sequence of category is Fe3+＞ Zn2+＞ Cd2+＞ Cu2+≈Mn2+＞ Co2+＞ Mg2+＞ Ni2+, therefore the impurity such as iron, zinc, manganese, copper can
It is extracted removing prior to cobalt, and nickel, cobalt then retain in raffinate；
Step 6: P507 detaches nickel cobalt：P507 is 2- ethylhexyl phosphoric acids list (2- ethylhexyls) ester, P507 molecules
In have ＞ POOH bases, H in the middle can be replaced by metal, extraction equation can be abbreviated as：P507 is to metal extraction capacity of water order Fe3+＞ Zn2+＞ Cu2+≈Mn2+
≈Ca2+＞ Co2+＞ Mg2+＞ Ni2+, from metal ion extraction rate and pH value relation curve it is found that by controlling extraction equilibrium PH
Value can be such that cobalt, nickel is efficiently separated；
Step 7: cobaltous sulfate crystallizes：The qualified cobalt sulfate solution that P507 is stripped to cobalt section output is put into crystallization reactor
In, it is evaporated concentration, cobalt sulfate solution is continuously replenished halfway.It is when 50--52, to stop heating, lead to when being concentrated to Baume degrees
Enter cold water, when temperature drops to 40--45 DEG C, releasing cobaltous sulfate concentrate, the further crystallisation by cooling in crystallizing pan, finally again
Centrifugal filtration, obtains cobaltous sulfate product, and sampling carries out chemical analysis.
The present invention, in step 1, the excellent molten method of diluted acid can remove about 80% cadmium in raw material, 50% or more nickel zinc,
The copper that part is brought by suction-operated can also be taken away, and cobalt loss is less than 0.5%.
The present invention uses the deliming of fluorination precipitation method, magnesium, rate of deposition is respectively under test conditions in step 4
89.0%, 83.0%, the concentration ratio of Co/Ca, Co/Mg are respectively 2490,3540 in solution.
The present invention, in step 5, in experimental condition, organic phase composition：15%P204+85% sulfonated kerosenes, saponification rate
75%；Feed liquid：Cobalt sulfate solution pH value 4.0.
The present invention, in step 7, being concentrated to of cobalt sulfate solution is equivalent to density when Baume degrees is 50--52 and is
1.54g/cm3。
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, without necessarily requiring or implying between these entities or operation
There are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to
Cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only that
A little elements, but also include other elements that are not explicitly listed, or further include for this process, method, article or
The intrinsic element of equipment.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited to
This, any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention
And its inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of method of metallic cobalt battery grade cobalt sulfate, which is characterized in that include the following steps：
Step 1: excellent molten removal of impurities：Removal of impurities processing is carried out to crude metal cobalt, makes the control of its temperature at 60--70 DEG C, dilution heat of sulfuric acid
PH value 2.0, mixing time 1.0--1.5h slowly add the slightly larger sulfuric acid of concentration in the process stirring to wash, excellent solution pH value are made to maintain
Between 2.0--3.0；
Step 2: reducing leaching：To after the removal of impurities completed in step 1, using in sulfuric acid medium with Na2SO3Make reducing agent leaching
Go out cobalt hydroxide, and its experimental condition is 60--70 DEG C of temperature, Na2SO31.5--1.6 times of theoretical amount of addition, terminal PH
Value 1.5, reaction time 2.0--3.0h form filtrate eventually by press filtration；
Step 3: oxidation-precipitation method is except iron, arsenic, manganese：Finally formed filtrate is being aoxidized in step 2, the condition of oxidation
For 65 DEG C of demanganization temperature, KMnO4Addition is 1.6 times of theoretical amounts, ph value of reaction 3.5, reaction time 1.5h；Except iron arsenic temperature ＞
80 DEG C, NaCLO3Then 3--4 times of theoretical amount of addition, terminal pH value ＞ 3.0, reaction time 1h are formed by press filtration new again
Filtrate；
Step 4: fluoride process deliming, magnesium：Finally formed filtrate is being fluorinated in step 3, and fluorinated condition is temperature
90 DEG C of ＞, NaF additions are 3--4 times of theoretical amount, terminal pH value ＞ 5.0, reaction time 1.5--2.0h, again by press filtration pressure
Filter out filtrate；
Step 5: P204 extracts removing impurities：P204 is two-(2- ethylhexyls) phosphoric acid, and the mechanism of extracting metals may be considered liquid
State base exchange process：P204 is from H2SO4Various metals are extracted in medium
Sequence is Fe3+＞ Zn2+＞ Cd2+＞ Cu2+≈Mn2+＞ Co2+＞ Mg2+＞ Ni2+, therefore the impurity such as iron, zinc, manganese, copper can be prior to cobalt
It is extracted removing, and nickel, cobalt then retain in raffinate；
Step 6: P507 detaches nickel cobalt：P507 is 2- ethylhexyl phosphoric acids list (2- ethylhexyls) ester, has ＞ in P507 molecules
POOH bases, H in the middle can be replaced by metal, and extraction equation can be abbreviated as：
P507 is to metal extraction capacity of water order Fe3+＞ Zn2+＞ Cu2+≈Mn2+≈Ca2+＞ Co2+＞ Mg2+＞ Ni2+, from metal from
Sub- extraction yield is with pH value relation curve it is found that cobalt, nickel can be made to be efficiently separated by controlling extraction equilibrium pH value；
Step 7: cobaltous sulfate crystallizes：The qualified cobalt sulfate solution that P507 is stripped to cobalt section output is put into crystallization reactor, is carried out
It is concentrated by evaporation, cobalt sulfate solution is continuously replenished halfway.It is when 50--52, to stop heating, be passed through cold water when being concentrated to Baume degrees,
When temperature drops to 40--45 DEG C, cobaltous sulfate concentrate is released, further crystallisation by cooling, finally centrifuged again in crystallizing pan
Filter, obtains cobaltous sulfate product, and sampling carries out chemical analysis.
2. a kind of method of metallic cobalt battery grade cobalt sulfate according to claim 1, it is characterised in that：In step 1
In, the excellent molten method of diluted acid can remove about 80% cadmium in raw material, 50% or more nickel zinc, part can also be taken away because of suction-operated
The copper brought into, and cobalt loss is less than 0.5%.
3. a kind of method of metallic cobalt battery grade cobalt sulfate according to claim 1, it is characterised in that：In step 4
In, the deliming of fluorination precipitation method, magnesium are used under test conditions, rate of deposition is respectively 89.0%, 83.0%, Co/Ca in solution,
The concentration ratio of Co/Mg is respectively 2490,3540.
4. a kind of method of metallic cobalt battery grade cobalt sulfate according to claim 1, it is characterised in that：In step 5
In, in experimental condition, organic phase composition：15%P204+85% sulfonated kerosenes, saponification rate 75%；Feed liquid：Cobalt sulfate solution pH value
4.0。
5. a kind of method of metallic cobalt battery grade cobalt sulfate according to claim 1, it is characterised in that：In step 7
In, it is 1.54g/cm3 that being concentrated to when Baume degrees is 50--52 of cobalt sulfate solution, which is equivalent to density,.
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| CN109468472A (en) * | 2018-12-18 | 2019-03-15 | 江苏理工学院 | A method of separating cobalt from the material containing cobalt and nickel |
| CN109518005A (en) * | 2018-10-29 | 2019-03-26 | 安徽寒锐新材料有限公司 | A kind of production method of battery grade cobalt sulfate crystal |
| CN109536724A (en) * | 2018-12-29 | 2019-03-29 | 启东市北新无机化工有限公司 | A method of the cobalt nickel purification based on old and useless battery metals recovery processes |
| CN110669931A (en) * | 2019-09-25 | 2020-01-10 | 宁波弗镁瑞环保科技有限公司 | Method for removing cobalt by oxidizing nickel sulfate solution |
| CN111180819A (en) * | 2019-12-30 | 2020-05-19 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution |
| CN111455175A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for removing calcium and magnesium from nickel-cobalt-manganese solution |
| CN111575480A (en) * | 2020-05-12 | 2020-08-25 | 浙江中金格派锂电产业股份有限公司 | Method for processing cobalt intermediate product |
| CN112795953A (en) * | 2020-12-28 | 2021-05-14 | 格林美（江苏）钴业股份有限公司 | Electric cobalt production method capable of recycling byproducts |
| CN113174485A (en) * | 2021-04-29 | 2021-07-27 | 金川集团镍盐有限公司 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
| CN113860392A (en) * | 2021-09-18 | 2021-12-31 | 江西江钨钴业有限公司 | Method for preparing battery-grade cobalt sulfate and cobalt chloride by acid dissolution of cobalt beans and cobalt plates |
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| CN111180819B (en) * | 2019-12-30 | 2021-07-27 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution |
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| CN113174485A (en) * | 2021-04-29 | 2021-07-27 | 金川集团镍盐有限公司 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
| CN113860392A (en) * | 2021-09-18 | 2021-12-31 | 江西江钨钴业有限公司 | Method for preparing battery-grade cobalt sulfate and cobalt chloride by acid dissolution of cobalt beans and cobalt plates |
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