CN106564957A - A method of preparing battery-grade high-purity manganese sulfate by utilizing low-grade manganese ore - Google Patents
A method of preparing battery-grade high-purity manganese sulfate by utilizing low-grade manganese ore Download PDFInfo
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- CN106564957A CN106564957A CN201610893839.1A CN201610893839A CN106564957A CN 106564957 A CN106564957 A CN 106564957A CN 201610893839 A CN201610893839 A CN 201610893839A CN 106564957 A CN106564957 A CN 106564957A
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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Abstract
The invention relates to a method of preparing battery-grade high-purity manganese sulfate by utilizing low-grade manganese ore. The method includes adding the low-grade manganese ore, pyrite and industrial sulfuric acid into a leaching tank, performing chemical leaching, performing solid liquid separation to obtain a primary manganese sulfate solution, then adding manganese dioxide into the primary manganese sulfate solution, adjusting the pH value of the solution, then performing solid liquid separation to obtain a secondary manganese sulfate solution, adding ethyl thiocarbamate, manganese fluoride, polyacrylamide and polyaluminum chloride into the secondary manganese sulfate solution, stirring the mixture for a certain period of time, performing solid liquid separation to obtain a purified manganese sulfate solution, adding the purified manganese sulfate solution into a crystallization kettle, performing concentration and crystallization, then performing solid liquid separation to obtain a wet manganese sulfate semi-finished product, and drying the wet manganese sulfate semi-finished product to obtain the battery-grade high-purity manganese sulfate. The method is simple in process and easy to operate. Addition of a large amount of agents is not needed in a preparing process. Secondary pollution to the environment is avoided and the production cost is low.
Description
Technical field
The present invention relates to the preparation field of LITHIUM BATTERY manganese sulfate, specially a kind of to prepare LITHIUM BATTERY height using low-grade manganese
The method of pure manganese sulfate.
Background technology
Manganese sulfate is a kind of important basic chemical industry raw material, extensive in fields such as chemical fertilizer, coating, catalyst, ceramics, ore dressings
Use.The manganese sulfate product or solution of general industry level purity can meet the demand in above-mentioned field, but can not reach lithium ion
The use requirement in battery material field, the purity requirement of lithium manganate material and nickel-cobalt-manganese multi cellulosic material to manganese sulfate are very high.Manganese
Sour lithium and nickel-cobalt-manganese multi cellulosic material are the core directions of lithium-ion-power cell materials demand, as lithium-ion-power cell exists
The gradually promotion and application of new-energy automobile, the demand meeting explosive growth to LITHIUM BATTERY high purity manganese sulfate, therefore LITHIUM BATTERY is high
The preparation of pure manganese sulfate and production technology have become the study hotspot of manganese field of metallurgy.
LITHIUM BATTERY high purity manganese sulfate compares common manganese sulfate, is that a kind of technology content is higher, production process control is very tight
A kind of high added value manganese deep processed product of lattice, its purposes mainly have three fields：Industrial circle, food pharmaceuticals industry and the energy
Field.Except having part using in addition in general industry field, food pharmaceuticals industry, which is mainly used as nickel to high purity manganese sulfate in a large number
The raw material of cobalt manganic acid lithium and LiMn2O4, is widely used as the nickle cobalt lithium manganate and LiMn2O4 of the positive electrode of electrokinetic cell
In the production of the electrokinetic cell of automobile, at present, almost each domestic automobile manufacturing enterprise manufacturing experimently, have such as BYD
The electric automobile of oneself is proposed, electric automobile is the main development direction of coming few decades international and domestic automobile industry.
At present, in order to obtain LITHIUM BATTERY high purity manganese sulfate, usually first obtain common manganese sulfate, then carry out remove impurity,
The techniques such as purification obtain high purity manganese sulfate.Now with many automobile production enterprises specially from the substantial amounts of common sulphuric acid of foreign procurement
Manganese, then obtains high purity manganese sulfate, cumbersome to its fine purification, and cost is very high.Obtain rough common manganese sulfate solution
Belong to the mature technology of wet method manganese field of metallurgy, it is representational to have sulfur dioxide solvent extraction method, two ore deposits reduction acid leaching process, roasting also
Ortho acid solvent extraction method etc., in leaching process of manganese ore, the potassium that contains in manganese ore, sodium, calcium, magnesium, ferrum, cobalt, nickel, copper, lead, zinc, every, molybdenum
Deng impurity by leaching simultaneously in solution, it is necessary to these impurity depth are removed and can just obtain highly purified manganese sulfate solution.Pass
The manganese sulfate solution impurity-removing method of system mainly has：(1) iron-based medicament is added, and sulphur removal is gone by generating autunezite, yellow sodium ferrum sail
Potassium, sodium impurity in sour manganese solution.(2) oxidant is adopted to go ferrous oxidising for ferric iron regeneration ferric hydroxide precipitate
Except ferrum.(3) corresponding sulfide precipitation is generated using all kinds of sulfide of addition remove removing heavy metals, or using addition manganese powder
Removing heavy metals are removed in displacement.(4) calcium fluoride, fluorination magnesium precipitate are generated using all kinds of fluorides of addition and removes calcium and magnesium.These methods are not
But strict temperature control, pH values are needed, a large amount of high-purity remove impurity medicaments is consumed, can also be introduced certain other impurities, and go
Except effect it is not notable.
Existing these methods typically need to sample higher manganese ore as raw material, but with high-grade manganese ore it is exhausted totally,
The effect that these methods for preparing manganese sulfate just show in the face of low-grade manganese is less good, and shortcoming is more, also considerably increases into
This.
The content of the invention
For the shortcoming of above-mentioned prior art, the present invention provides a kind of efficient, utilization low-grade manganese system of low cost
The method of standby LITHIUM BATTERY high purity manganese sulfate.
The present invention solves above-mentioned technical problem and employs the following technical solutions：It is a kind of to prepare LITHIUM BATTERY height using low-grade manganese
The method of pure manganese sulfate, comprises the following steps：
（1）Low-grade manganese, troilite, industrial sulphuric acid are put in batch extractor carries out Chemical Leaching, then after solid-liquid separation, obtains
Obtain primary manganese sulfate solution；
（2）Add manganese dioxide in the primary manganese sulfate solution, and adjust the pH value of solution, then carry out solid-liquid point again
From the secondary manganese sulfate solution of acquisition；Add manganese dioxide as iron removal by oxidation agent, regenerate hydrogen for ferric iron by ferrous oxidising
Ferrum oxide precipitation removes ferrum, good iron removal effect；
（3）Diethyldithiocarbamate is added in the secondary manganese sulfate solution；
（4）To step（3）Manganous fluoride is added in the solidliquid mixture for obtaining；
（5）To step（4）Polyacrylamide and aluminium polychlorid, stirring a period of time are added in the solidliquid mixture for obtaining；Plus
Enter the fluorion that polyacrylamide and aluminium polychlorid can also be remained in effectively removing solution, it is ensured that in product Oil repellent is not
It is exceeded；
（6）By step（5）The solidliquid mixture for obtaining carries out solid-liquid separation, obtains pure manganese sulfate solution；
（7）The pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing；
（8）By step（7）The solidliquid mixture of gained carries out solid-liquid separation again, obtains wet manganese sulfate semi-finished product；
（9）The wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY high purity manganese sulfate is obtained.
Preferably, step（1）Described in low-grade manganese manganese content be 18%～25%.
Further, step（1）Middle-low grade manganese ore, troilite, industrial sulphuric acid are 1 in mass ratio：（0.26～0.3）：
（0.30～0.35）Ratio carry out dispensing.
Preferably, the primary manganese sulfate solution concentration is 250～280g/L.
Preferably, step（2）The middle pH value for adjusting solution is to 4.2～4.5.
As further preferred, step（3）The adding proportion of middle diethyldithiocarbamate is that every liter of solution adds 0.5～1.5g second sulfur
Nitrogen.There are many metal sulfides due to leaching in the manganese sulfate that low-grade manganese is obtained, content of beary metal is higher, so adopting
Collecting agent of the diethyldithiocarbamate as metal sulfide, diethyldithiocarbamate have the features such as collecting ability is strong, flotation speed is fast, selectivity is high,
Remove heavy metal effect good.
As further preferred, step（4）The adding proportion of middle manganous fluoride is that every liter of solution adds 6～12g manganous fluorides.Adopt
With manganous fluoride, its removing calcium and magnesium effect is good.
Preferably, step（5）Described in the concentration of polyacrylamide be 3g/L, the concentration of the aluminium polychlorid is
50g/L。
As further preferred, step（5）Described in polyacrylamide and the aluminium polychlorid adding proportion be per liter
Solution adds polyacrylamide 1.5mL, aluminium polychlorid 1mL.Remove impurity, remove impurity are carried out from polyacrylamide and aluminium polychlorid
Effect is significant, to realize purifying manganese sulfate.
Further, step（5）Described in mixing time be 30～40 minutes.
The present invention is had the advantage that compared with prior art：Step is simple, it is easy to operate, it is not necessary to strict control temperature
Degree, it is not required that consume a large amount of high-purity remove impurity medicaments；Manganese dioxide is added as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Exist due to leaching in the manganese sulfate that low-grade manganese is obtained
Many metal sulfides, content of beary metal are higher, thus using diethyldithiocarbamate as metal sulfide collecting agent, diethyldithiocarbamate has
The features such as collecting ability is strong, flotation speed is fast, selectivity is high, removes heavy metal effect good；Obtain due to leaching low-grade manganese
Manganese sulfate in there is also the calcium and magnesium of high level, the present invention adopts manganous fluoride, and its removing calcium and magnesium effect is good；The present invention is also from poly-
Acrylamide and aluminium polychlorid carry out remove impurity, and impurity-eliminating effect is notable, to realize purifying manganese sulfate, meanwhile, effectively can remove
The fluorion remained in falling solution, it is ensured that Oil repellent is not exceeded in product；Condensing crystallizing is carried out by crystallization kettle again, using each miscellaneous
Residual impurity is removed by matter different dissolubility again by filtering, and impurity-eliminating effect is also more significantly, and realization is further carried
Pure manganese sulfate, finally obtains LITHIUM BATTERY high purity manganese sulfate.This technique will not bring secondary pollution to environment, low production cost, easily
In realizing industrial-scale production.
Description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Conjunction is specifically illustrating and embodiment, and the present invention is expanded on further.It should be appreciated that specific embodiment described herein is only to solve
The present invention is released, is not intended to limit the present invention.
With reference to a kind of method that Fig. 1, utilization low-grade manganese prepare LITHIUM BATTERY high purity manganese sulfate, comprise the following steps：
（1）Low-grade manganese, troilite, industrial sulphuric acid are put in batch extractor carries out Chemical Leaching, then after solid-liquid separation, obtains
Obtain primary manganese sulfate solution；
（2）Add manganese dioxide in the primary manganese sulfate solution, and adjust the pH value of solution, then carry out solid-liquid point again
From the secondary manganese sulfate solution of acquisition；Add manganese dioxide as iron removal by oxidation agent, regenerate hydrogen for ferric iron by ferrous oxidising
Ferrum oxide precipitation removes ferrum, good iron removal effect；
（3）Diethyldithiocarbamate is added in the secondary manganese sulfate solution；
（4）To step（3）Manganous fluoride is added in the solidliquid mixture for obtaining；
（5）To step（4）Polyacrylamide and aluminium polychlorid, stirring a period of time are added in the solidliquid mixture for obtaining；
（6）By step（5）The solidliquid mixture for obtaining carries out solid-liquid separation, obtains pure manganese sulfate solution；
（7）The pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing；
（8）By step（7）The solidliquid mixture of gained carries out solid-liquid separation again, obtains wet manganese sulfate semi-finished product；
（9）The wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY high purity manganese sulfate is obtained.
Embodiment 1：
It is manganese ore raw material from the low-grade manganese that manganese content is 18%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.26：0.30 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.2, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 1.5g diethyldithiocarbamates.Add in solidliquid mixture again
Enter manganous fluoride, in solution calcium content be 700mg/L, content of magnesium be 1000 mg/L, add 10g manganous fluorides, using manganous fluoride, its
Removing calcium and magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polypropylene
Amide is pre-configured to the solution of 3g/L, and aluminium polychlorid is configured to the solution of 50g/L, and its adding proportion is that every liter of solid-liquid is mixed
Compound adds polyacrylamide 1.5mL, aluminium polychlorid 1mL, then stirs 30 minutes, from polyacrylamide and polyaluminium
Aluminum carries out remove impurity, and impurity-eliminating effect is notable, to realize purifying manganese sulfate, at the same time it can also effectively remove the fluorine remained in solution
Ion, it is ensured that Oil repellent is not exceeded in product.Then the solidliquid mixture after stirring is carried out into solid-liquid separation, obtains pure sulphuric acid
Manganese solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing, solid-liquid separation is then carried out again, is obtained
Wet manganese sulfate semi-finished product, the wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY high purity manganese sulfate is obtained.Obtain after testing
Light metal impurity ＜ 25ppm, the iron content ＜ 2ppm such as manganese content ＞ 99.2% in LITHIUM BATTERY high-purity sulphuric acid manganese product, calcium and magnesium, other
Beavy metal impurity is respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as the excellent battery for preparing LiMn2O4 and Li-Ni-Mn-Co-O
The high-purity manganio raw material of level.
Embodiment 2：
It is manganese ore raw material from the low-grade manganese that manganese content is 20%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.28：0.32 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.3, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 1g diethyldithiocarbamates.Add in solidliquid mixture again
Manganous fluoride, in solution calcium content be 600mg/L, content of magnesium be 800 mg/L, add 8g manganous fluorides, using manganous fluoride, its deliming
Magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polyacrylamide
The solution of 3g/L is pre-configured to, aluminium polychlorid is configured to into the solution of 50g/L, its adding proportion is every liter of solidliquid mixture
Polyacrylamide 1.5mL, aluminium polychlorid 1mL are added, is then stirred 35 minutes.Then the solidliquid mixture after stirring is carried out
Solid-liquid separation, obtains pure manganese sulfate solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing, so
Carry out solid-liquid separation afterwards again, obtain wet manganese sulfate semi-finished product, the wet manganese sulfate semi-finished product are dried, obtain LITHIUM BATTERY high
Pure manganese sulfate.The light metal impurity ＜ such as manganese content ＞ 99.2% in the LITHIUM BATTERY high-purity sulphuric acid manganese product for obtaining after testing, calcium and magnesium
25ppm, iron content ＜ 2ppm, other beavy metal impurities are respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as preparing mangaic acid
The high-purity manganio raw material of excellent LITHIUM BATTERY of lithium and Li-Ni-Mn-Co-O.
Embodiment 3：
It is manganese ore raw material from the low-grade manganese that manganese content is 25%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.3：0.35 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.5, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 0.5g diethyldithiocarbamates.Add in solidliquid mixture again
Enter manganous fluoride, in solution calcium content be 500mg/L, content of magnesium be 700 mg/L, add 6g manganous fluorides, using manganous fluoride, which removes
Calcium and magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polyacrylamide
Amine is pre-configured to the solution of 3g/L, and aluminium polychlorid is configured to the solution of 50g/L, and its adding proportion is every liter of solid-liquid mixing
Thing adds polyacrylamide 1.5mL, aluminium polychlorid 1mL, then stirs 40 minutes.Then the solidliquid mixture after stirring is entered
Row solid-liquid separation, obtains pure manganese sulfate solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing,
Then solid-liquid separation is carried out again, wet manganese sulfate semi-finished product are obtained, and the wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY is obtained
High purity manganese sulfate.The light metal impurity ＜ such as manganese content ＞ 99.2% in the LITHIUM BATTERY high-purity sulphuric acid manganese product for obtaining after testing, calcium and magnesium
25ppm, iron content ＜ 2ppm, other beavy metal impurities are respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as preparing mangaic acid
The high-purity manganio raw material of excellent LITHIUM BATTERY of lithium and Li-Ni-Mn-Co-O.
Embodiment 4：
It is manganese ore raw material from the low-grade manganese that manganese content is 19%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.26：0.30 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.4, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 1.2g diethyldithiocarbamates.Add in solidliquid mixture again
Enter manganous fluoride, in solution calcium content be 750mg/L, content of magnesium be 950 mg/L, add 11g manganous fluorides, using manganous fluoride, which removes
Calcium and magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polyacrylamide
Amine is pre-configured to the solution of 3g/L, and aluminium polychlorid is configured to the solution of 50g/L, and its adding proportion is every liter of solid-liquid mixing
Thing adds polyacrylamide 1.5mL, aluminium polychlorid 1mL, then stirs 35 minutes.Then the solidliquid mixture after stirring is entered
Row solid-liquid separation, obtains pure manganese sulfate solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing,
Then solid-liquid separation is carried out again, wet manganese sulfate semi-finished product are obtained, and the wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY is obtained
High purity manganese sulfate.The light metal impurity ＜ such as manganese content ＞ 99.2% in the LITHIUM BATTERY high-purity sulphuric acid manganese product for obtaining after testing, calcium and magnesium
25ppm, iron content ＜ 2ppm, other beavy metal impurities are respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as preparing mangaic acid
The high-purity manganio raw material of excellent LITHIUM BATTERY of lithium and Li-Ni-Mn-Co-O.
Embodiment 5：
It is manganese ore raw material from the low-grade manganese that manganese content is 24%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.3：0.35 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.5, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 0.7g diethyldithiocarbamates.Add in solidliquid mixture again
Enter manganous fluoride, in solution calcium content be 600mg/L, content of magnesium be 750 mg/L, add 7g manganous fluorides, using manganous fluoride, which removes
Calcium and magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polyacrylamide
Amine is pre-configured to the solution of 3g/L, and aluminium polychlorid is configured to the solution of 50g/L, and its adding proportion is every liter of solid-liquid mixing
Thing adds polyacrylamide 1.5mL, aluminium polychlorid 1mL, then stirs 35 minutes.Then the solidliquid mixture after stirring is entered
Row solid-liquid separation, obtains pure manganese sulfate solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing,
Then solid-liquid separation is carried out again, wet manganese sulfate semi-finished product are obtained, and the wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY is obtained
High purity manganese sulfate.The light metal impurity ＜ such as manganese content ＞ 99.2% in the LITHIUM BATTERY high-purity sulphuric acid manganese product for obtaining after testing, calcium and magnesium
25ppm, iron content ＜ 2ppm, other beavy metal impurities are respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as preparing mangaic acid
The high-purity manganio raw material of excellent LITHIUM BATTERY of lithium and Li-Ni-Mn-Co-O.
Embodiment 6：
It is manganese ore raw material from the low-grade manganese that manganese content is 23%, low-grade manganese, troilite, industrial sulphuric acid is pressed into quality
Than for 1：0.3：0.35 ratio carries out dispensing, and the material for preparing is put in batch extractor carries out Chemical Leaching, then solid-liquid separation
Afterwards, primary manganese sulfate solution is obtained, the primary manganese sulfate concentration is 250～280g/L.Add in the primary manganese sulfate solution
Enter manganese dioxide, and adjust the pH value of solution to 4.4, add manganese dioxide as iron removal by oxidation agent, by it is ferrous oxidising be three
Valency ferrum regeneration ferric hydroxide precipitate removes ferrum, good iron removal effect；Then solid-liquid separation is carried out again, obtains secondary manganese sulfate molten
Liquid.Diethyldithiocarbamate is added in the secondary manganese sulfate solution, according to content of beary metal in secondary manganese sulfate solution, diethyldithiocarbamate adds
Plus ratio is that every liter of solution adds 0.5～1.5g diethyldithiocarbamates, the embodiment adds 0.9g diethyldithiocarbamates.Add in solidliquid mixture again
Enter manganous fluoride, in solution calcium content be 650mg/L, content of magnesium be 900 mg/L, add 9g manganous fluorides, using manganous fluoride, which removes
Calcium and magnesium effect is good.Polyacrylamide and aluminium polychlorid are added in solidliquid mixture again, its feed postition is, by polyacrylamide
Amine is pre-configured to the solution of 3g/L, and aluminium polychlorid is configured to the solution of 50g/L, and its adding proportion is every liter of solid-liquid mixing
Thing adds polyacrylamide 1.5mL, aluminium polychlorid 1mL, then stirs 40 minutes.Then the solidliquid mixture after stirring is entered
Row solid-liquid separation, obtains pure manganese sulfate solution, then the pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing,
Then solid-liquid separation is carried out again, wet manganese sulfate semi-finished product are obtained, and the wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY is obtained
High purity manganese sulfate.The light metal impurity ＜ such as manganese content ＞ 99.2% in the LITHIUM BATTERY high-purity sulphuric acid manganese product for obtaining after testing, calcium and magnesium
25ppm, iron content ＜ 2ppm, other beavy metal impurities are respectively less than 5ppm.The LITHIUM BATTERY high purity manganese sulfate can be used as preparing mangaic acid
The high-purity manganio raw material of excellent LITHIUM BATTERY of lithium and Li-Ni-Mn-Co-O.
Preparation process is simple of the present invention, it is easy to operate, producing process are not required to a large amount of outer adding medicines, will not bring two to environment
Secondary pollution, low production cost, it is easy to accomplish industrial-scale production, the low-grade manganese for overcoming prior art completely produce electricity
The deficiency that pond level high purity manganese sulfate method is present.The product purity of preparation is high, and impurity content is few, and the LITHIUM BATTERY high purity manganese sulfate can
As the high-purity manganio raw material of excellent LITHIUM BATTERY for preparing LiMn2O4 and Li-Ni-Mn-Co-O.
The ultimate principle and principal character and advantages of the present invention of the present invention, the technology of the industry has been shown and described above
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement both fallen within scope of the claimed invention, the claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (10)
1. a kind of method that utilization low-grade manganese prepares LITHIUM BATTERY high purity manganese sulfate, comprises the following steps：
（1）Low-grade manganese, troilite, industrial sulphuric acid are put in batch extractor carries out Chemical Leaching, then after solid-liquid separation, obtains
Obtain primary manganese sulfate solution；
（2）Add manganese dioxide in the primary manganese sulfate solution, and adjust the pH value of solution, then carry out solid-liquid point again
From the secondary manganese sulfate solution of acquisition；
（3）Diethyldithiocarbamate is added in the secondary manganese sulfate solution；
（4）To step（3）Manganous fluoride is added in the solidliquid mixture for obtaining；
（5）To step（4）Polyacrylamide and aluminium polychlorid, stirring a period of time are added in the solidliquid mixture for obtaining；
（6）By step（5）The solidliquid mixture for obtaining carries out solid-liquid separation, obtains pure manganese sulfate solution；
（7）The pure manganese sulfate solution is placed in crystallization kettle carries out condensing crystallizing；
（8）By step（7）The solidliquid mixture of gained carries out solid-liquid separation again, obtains wet manganese sulfate semi-finished product；
（9）The wet manganese sulfate semi-finished product are dried, LITHIUM BATTERY high purity manganese sulfate is obtained.
2. method according to claim 1, step（1）Described in low-grade manganese manganese content be 18%～25%.
3. method according to claim 1 and 2, step（1）Middle-low grade manganese ore, troilite, industrial sulphuric acid are in mass ratio
For 1：（0.26～0.3）：（0.30～0.35）Ratio carry out dispensing.
4. method according to claim 1, the primary manganese sulfate solution concentration are 250～280g/L.
5. method according to claim 1, step（2）The middle pH value for adjusting solution is to 4.2～4.5.
6. method according to claim 1, step（3）The adding proportion of middle diethyldithiocarbamate be every liter of solution add 0.5～
1.5g diethyldithiocarbamate.
7. method according to claim 1, step（4）The adding proportion of middle manganous fluoride is that every liter of solution adds 6～12g fluorine
Change manganese.
8. method according to claim 1, step（5）Described in polyacrylamide concentration be 3g/L, the polymerization chlorine
The concentration for changing aluminum is 50g/L.
9. the method according to claim 8 or 1, step（5）Described in polyacrylamide and the aluminium polychlorid addition
Ratio is that every liter of solution adds polyacrylamide 1.5mL, aluminium polychlorid 1mL.
10. method according to claim 1, step（5）Described in mixing time be 30～40 minutes.
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| CN115010179A (en) * | 2021-03-05 | 2022-09-06 | 中南大学 | Method for preparing fluorine-free battery-grade high-purity manganese sulfate by fluorination method |
| CN114988478A (en) * | 2022-06-09 | 2022-09-02 | 四川大学 | Method for preparing battery-grade manganese sulfate by synergistic elution crystallization of chelating agent |
| CN114988478B (en) * | 2022-06-09 | 2024-03-22 | 四川大学 | Method for preparing battery-grade manganese sulfate by synergistic dissolution crystallization of chelating agent |
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