CN110203975A - The leaching method of manganese element and the preparation method of LITHIUM BATTERY manganese sulfate - Google Patents
The leaching method of manganese element and the preparation method of LITHIUM BATTERY manganese sulfate Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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Abstract
The invention discloses a kind of leaching methods of manganese element, for pyrolusite or anode slag, powder is made in pyrolusite or anode slag, powder is reacted with the acid solution containing reducing agent, it is separated by solid-liquid separation after reaction, obtains leachate and slag, realize the leaching of manganese element, the reducing agent contains at least two hydroxyls, and two hydroxyls therein must be located on adjacent carbon atom；A kind of preparation method of LITHIUM BATTERY manganese sulfate is also disclosed, including ore reduction, miberal powder ball milling, chemical combination drill traverse go out, except cleaning, crystallizing, dry all steps again, wherein joined foregoing reducing agent.The reducing agent source that the present invention uses is wide, and cheap, reactivity is big, and non-toxic to humans；Low energy consumption for preparation process, and output waste residue is few, no exhaust gas, waste water, effectively obtains leaching and the LITHIUM BATTERY manganese sulfate product of manganese element.
Description
Technical field
The present invention relates to the systems of the leaching method and LITHIUM BATTERY manganese sulfate of battery technology field more particularly to a kind of manganese element
Preparation Method.
Background technique
In recent years, domestic and international new-energy automobile industry development is swift and violent, and multiple countries have put into effect the fuel vehicle regulation that prohibits selling, the whole world
Power battery demand is continued vigorous.11-13 days in January, 2019, hundred people of Electric Cars in China understand what Forum was inquired into jointly
Theme is " global zero-emission and comprehensive motorized ", and Chinese electric vehicle market will welcome more large-scale outbreak.Positive electrode is lithium
The most key material in ion secondary battery, accounting is up to 40% in battery cost, accounts in new energy passenger car cost
It is the maximum material cell of the magnitude of value in new energy passenger car than 8%~14%.Estimate according to Gaosheng (Goldman Sachs), arrives
2025, the scale in this market was up to 40,000,000,000 dollars, and leading by China.If pressing positive electrode cost accounting battery
For totle drilling cost in terms of 40%, positive electrode market scale is up to 16,000,000,000 dollars.Wherein, tertiary cathode material (nickeliferous, cobalt, manganese three
Kind element) have many advantages, such as that capacity is high, cost is relatively low, harmonious preferable, it is the mainstream positive electrode of power battery.By power electric
Pond market pulls, and will be substantially increased in industry to the demand of LITHIUM BATTERY manganese sulfate product, it is contemplated that the year two thousand twenty demand reaches 16
Ten thousand tons, the output value reaches 1,100,000,000 RMB.
China is used to leach the manganese spar grade of Sulphuric acid manganese previously, is mostly 20% or so.As manganese ore is constantly opened
It adopts, the grade of manganese ore is also lower and lower, and the grade of the manganese spar generally used now is in the section 12-16%.If with low-grade
Manganese spar prepares manganese sulfate, and 1 ton of LITHIUM BATTERY manganese sulfate needs to consume about 2.7 tons of ore, generates about 3 tons of waste residue, and waste residue by
Unqualified in the performance indicator that will lead to final products cement in cement raw material containing a large amount of calcium sulfate and being added to, waste residue cannot
Raw material as cement baking.In addition, in the manganese sulfate product as made from low-grade Leaching of rhodochrosite ore and its downstream industry
Between in product, potassium, sodium, calcium, magnesium, iron, the content of zinc and other objectionable impurities are high, except the impurity such as sodium, potassium, calcium, magnesium are always sulfuric acid
The technical problem of manganese production.LITHIUM BATTERY manganese sulfate is produced just because of using low-grade manganese spar, needs to consume a large amount of mine
Stone, while the complex process for generating largely without the waste residue of commercial value, and cleaning, the impurity content in product are high；Ye You producer
Once using the technology path for preparing LITHIUM BATTERY manganese sulfate by manganese metal and sulfuric acid reaction, but the technique can generate a large amount of acid mists
And it is larger to surrounding environment influence.
The grade of pyrolusite is high, and generally higher than 40%, leaching preparation LITHIUM BATTERY manganese sulfate by pyrolusite is one relatively reasonable
Route.Domestic producer prepares LITHIUM BATTERY manganese sulfate by two mine one-step method as raw material using high-grade pyrolusite, still
The shortcomings that two mine one-step method is more: reduction rate and leaching rate are lower, a large amount of ferric hydroxide colloids of by-product；Colloidal iron hydroxide is useless
Slag, large specific surface area adsorb a large amount of manganese ions, affect the rate of recovery of manganese；Impurity removal process is more difficult to control in purification process, especially
It is required that the mineral resources stable components of pyrolusite and pyrite.
In addition, pyrolusite it is existing leaching method it is main further include:
(1) sulfur dioxide lixiviation process.SO2It is a kind of mature technology probably already existed that gas, which directly leaches pyrolusite, due to
Side reaction is had in the leaching reaction process generates manganous dithionate (MnS2O6) and influence leaches the matter of manganese sulfate in product
Amount, thus be not used widely yet in the production of manganese product so far.
(2) calcium dithionate method leaches pyrolusite.By pyrolusite powder and calcium dithionate (CaS in leaching tanks206) mixing
At ore pulp, it is passed through SO2To generate manganese sulfate and manganous dithionate.Calcium dithionate method leaches pyrolusite, in reduction mechanism reality
On be still SO2Reduction leaching process, the quantity of slag are its main disadvantage greatly.
(3) ferrous sulfate lixiviation process.Ferrous sulfate can be used as reducing agent and leach pyrolusite in an acidic solution, make pyrolusite
In tetravalent manganese be reduced into manganese sulfate.But iron-content is higher in the leachate of this method, if using current Fe (OH)3In
Iron is removed with the precipitation method can generate a large amount of colloidal precipitation, to cause the adsorption loss of filtration difficulty and manganese.
(4) iron direct leaching.It is external recently studies have shown that being directly added into sponge iron, energy in acid pyrolusite pulp
The tetravalent manganese in pyrolusite is enough set promptly to be reduced into bivalent manganese, it is more more efficient than with ferrous sulfate.But iron filings are acid molten
It is reacted soon with acid in liquid and generates ferrous sulfate, actually play reduction or in ferrous sulfate ferrous ion.
(5) direct-reduction process.In acid condition, coal can be reacted with pyrolusite, make MnO therein2Be reduced into MnO and into
Enter solution.But this method there are flue dust it is more, energy consumption is high the problems such as.
(6) oxalic acid direct leaching.In acid medium, with manganese dioxide redox reaction can occur for oxalic acid, realize
Manganese ion leaches.But oxalic acid price is higher, it is economically not cost-effective.
(7) methanol direct leaching.In recent years in the leaching process of research deepwater station, has and used in acid medium
The report of ethyl alcohol or methanol as leaching agent.
(8) agriculture and forestry by-product direct leaching.The cellulose of one of crop products or its byproduct main component, can make
For the reducing agent of pyrolusite, be a kind of source it is wide, without toxic element, cheap renewable resource.But agricultural by-product
Object source is by territory restriction, and slag after being oxidized and filter residue form mixture, not environmentally.
In addition to the method for the above existing common various leaching pyrolusites, there are many more the studied exploitations of lixiviation process, such as
Reduction roasting-ammonia leaching process, reduction roasting-carbaminate method, hydrogen peroxide reduction method, sucrose or method of glucose reduction, phenol
Reduction method, chloridising and nitrate process etc..But the big multipaths complexity of these leaching methods or high production cost or material
Corrosivity is strong, pollutes environment, and is not suitable for the processing of low-grade pyrolusite.
Summary of the invention
The present invention proposes a kind of leaching method of manganese element and the preparation method of LITHIUM BATTERY manganese sulfate, to solve above-mentioned technology
Problem.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
According to a first aspect of the embodiments of the present invention, a kind of leaching method of manganese element is provided, pyrolusite or sun are used for
Powder is made in pyrolusite or anode slag by pole slag, and powder is reacted with the acid solution containing reducing agent, is reacted laggard
Row is separated by solid-liquid separation, and is obtained leachate and filter residue, is realized the leaching of manganese element；
The reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2,
R3, R4 are independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；Its
In, R1, R2, R3, R4 are independent substituent group or in which two adjacent group joint cyclization.
Preferably, the particle size of the powder is 40~400 mesh.The powder is pyrolusite powder or anode slag
Powder.
Preferably, R1, R2, R3, R4 are independent substituent group in the molecular structural formula of the compound, and R1, R2,
The alkyl that R3, R4 are respectively hydrogen or carbon atom number is 1~4.
Preferably, the reducing agent further includes that following substance is any one or more of: iron powder, sulfur dioxide, sulfurous
Acid, sodium sulfite, ammonium sulfite, ferrous sulfate, sodium thiosulfate, calcium dithionate, hydrogen peroxide, oxalic acid, glucose, sugarcane
Sugar, cellulose, cornstalk, methanol, formaldehyde, phenol.
Preferably, the acid solution is inorganic acid.
As a further preference, the inorganic acid is that sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid are any one or more of.
As it is another preferably, the acid solution also contains organic acid；The organic acid is oxalic acid, formic acid, acetic acid, trichlorine
Acetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
Preferably, being further comprised the steps of: after obtaining leachate and filter residue by phase analysis washing several times, washing lotion is obtained after washing
And washed-residue, washing lotion, which is put into leachate mixing or ball mill processing powder is added, is made slurry.
Washed-residue is reacted with the acid solution containing reducing agent preferably, further comprising the steps of:, stir and is added
Heat is separated by solid-liquid separation after reaction, obtains secondary leachate and secondary response filter residue, realizes the leaching of manganese element in washed-residue.
Preferably, the solid-to-liquid ratio of the powder and the acid solution containing reducing agent is 10~2000g/L.
Preferably, reaction temperature is 0~150, DEG C reaction time is 0.1~24 hour.
According to a second aspect of the embodiments of the present invention, a kind of preparation method of LITHIUM BATTERY manganese sulfate is provided, feature exists
In including the following steps:
(1) powder ore reduction: is made in pyrolusite or anode slag；
(2) miberal powder ball milling: it is further processed powder with ball mill, slurry is made；
(3) chemical combination drill traverse goes out: slurry injects chemical combination slot, and the reducing agent and sulphur as described in claim 1-3 is added to slurry
Acid solution is passed through steam heating feed liquid, is stirred to react to obtain leachate and filter residue；
(4) except removal of impurities again: leachate being separated, blender is added and adjusts pH value, and impurity removal reagents are added to clean
Matter is purified liquid and filter residue after feed liquid separation；
(5) it crystallizes: after scavenging solution stands a few hours, the manganese sulfate solution of purification is obtained by filtration, it is brilliant that crystallization obtains manganese sulfate
Body；
(6) dry: manganese sulfate crystal obtains the LITHIUM BATTERY manganese sulfate of finished product through drying.
Preferably, the blender is manganese carbonate, manganese oxide, calcium oxide, calcium hydroxide, hydroxide in step (4)
At least one of sodium.
Preferably, the impurity removal reagents include ferric sulfate and/or manganous fluoride in step (4).
Preferably, the method that the crystallization obtains manganese sulfate crystal is high temperature crystallization in step (5).
Compared with prior art, the reducing agent source that the present invention uses is wide, and cheap, reactivity is big, and to people
Body is nontoxic；Low energy consumption for preparation process, and output waste residue is few, no exhaust gas, waste water, effectively obtains the leaching and LITHIUM BATTERY of manganese element
Manganese sulfate product.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the leaching method of manganese element of the present invention；
Fig. 2 is a kind of flow chart of LITHIUM BATTERY manganese sulfate preparation method of the present invention.
Specific embodiment
Below with reference to specific embodiment shown in the drawings, the present invention will be described in detail.But these embodiments are simultaneously
The present invention is not limited, structure that those skilled in the art are made according to these embodiments, method or functionally
Transformation is included within the scope of protection of the present invention.
It is only to be not intended to limit the invention merely for for the purpose of describing particular embodiments in terminology used in the present invention.
It is also intended in the present invention and the "an" of singular used in the attached claims, " described " and "the" including majority
Form, unless the context clearly indicates other meaning.It is also understood that term "and/or" used herein refers to and wraps
It may be combined containing one or more associated any or all of project listed.
The embodiment of the present invention in a first aspect, propose a kind of leaching method of manganese element, be used for pyrolusite or anode slag, packet
Include following steps:
(a) powder is made in pyrolusite or anode slag, powder is reacted with the acid solution containing reducing agent；
(b) it is separated by solid-liquid separation after reacting, obtains leachate and filter residue, realize the leaching of manganese element.
Wherein, the reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2,
R3, R4 are independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；Its
In, R1, R2, R3, R4 are independent substituent group or in which two adjacent group joint cyclization.In step (a) powder with contain
It can accelerate reaction after thering is the acid solution of reducing agent to mix with agitating and heating.
Under the action of acidic environment and above-mentioned reducing agent, the manganese element in pyrolusite is leached the present invention, and leaching rate
Height can achieve 98% or more.
The present invention above-mentioned reducing agent contains at least two hydroxyls in molecule, and two hydroxyls therein must distinguish position
In on adjacent carbon atom, including but not limited to following compounds:
Wherein, independent substituent group R1, R2, R3, R4 can distinguish in the molecular structural formula as the compound of reducing agent
The alkyl for being 1~4 for hydrogen or carbon atom number.The reducing agent of above structure on the market be easy purchase and it is at low cost, meet work
Industry production requirement；The reducing agent of above structure be oxidized after product, molecule is small and structure is simple, such as gas molecule passes through
The method of gas-liquid separation can remove by-product, for another example low-boiling compound can by the method distilling or be evaporated under reduced pressure from
It is removed in system.
In addition, reducing agent can be one of above compound or a variety of, it can also include any in following substance
Kind is a variety of: iron powder, sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, ferrous sulfate, sodium thiosulfate, dithionic acid
Calcium, hydrogen peroxide, oxalic acid, glucose, sucrose, cellulose, cornstalk, methanol, phenol, formaldehyde etc..For example, reducing agent can be
Single compound glycerine is also possible to the mixture of ethylene glycol and 1,2-PD, can also be ethylene glycol and sulfur dioxide
Or glycerine and hydrogen peroxide etc. combine.The selection of reducing agent, with environmental protection, efficiently for standard.
Pyrolusite, main component MnO2, manganese content is not less than 10%.Following two from Nigeria mining area
The content of pyrolusite sample, manganese respectively reaches 41.2% and 52.4%, is high-quality rich manganese ore, also containing potassium, sodium, iron, copper,
The impurity elements such as barium, zinc, aluminium, unit ppm.
Sample 1:Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；
Cu, 1889.0；Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
Sample 2:Mn, 523700.0；Ca, 4736.0；K, 10910.0；Mg, 2955.0；Na, 2087.0；Fe, 37660.0；
Cu, 3007.0；Ni, 128.7；Ba, 368.6；Zn, 1254.0；Al, 7191.0.
Generally, manganese content is higher, and mine grade is higher, is more advantageous for method of the invention.Make in the present invention
Reducing agent reduction activation is big, and by taking ethylene glycol as an example, as shown in chemical equation (1), the molecular weight for restoring agent molecule is small, and
Each molecule can contribute multiple electronics, and reaction efficiency is very high.Even if the content of manganese dioxide is very low in manganese ore, can also
It is efficiently leached with realizing.China's low-grade pyrolusite reserves are more, and from the point of view of strategic height, deep people's research and development is low-grade
The various novel techniques of pyrolusite reduction process, to improve increasingly the manganese Utilization Rate of Mineral Resources of dilution, further develop me
The new road toward industrialization that state's manganese systems product is industrial, reduces environmental pollution, walks sustainable development all has very real meaning.
In addition, researcher of the invention also found that method of the invention is also fitted in developing technical process of the invention
For leaching recycling manganese from electrolytic manganese anode slag, electrolytic zinc anode slag.Anode slag is one of production electrolytic process solid
Waste is the divalent manganesetion (Mn in electrolytic process in feed liquid2+) in anode chamber with MnO2Or the hydrous oxide shape of manganese
Formula precipitates in a cell, while also containing electrolytic catalyst SeO2With the elements such as Pb, Ag, Sn for being dissolved out by electrode plate, master
Wanting ingredient is the compound containing manganese, including manganese sulfate (MnSO4), manganese dioxide (MnO2) etc., manganese content is often as high as 40~
50%, while also containing a small amount of other valuable elements, such as lead, silver, selenium, tin etc..
The particle size of powder used in the present invention is typically chosen in 40~400 mesh.Generally, particles of powder is smaller,
Reactivity is bigger, and leaching rate is higher.But the problems such as considering cost and fugitive dust, selection is suitably sized, further excellent
It is selected as 80~200 mesh.
The present invention for the acid solution that reducing agent provides reaction media can be inorganic acid, organic acid or organic acid with it is inorganic
The mixture of acid.
Here inorganic acid can be carborane acid (H [CHB11Cl11]), hydrosulphuric acid (H2S), Perthiocarbonate
(H2CS4), thiocarbonic acid (H2CS3), hydrogen cyanide (HCN), selenium cyanic acid (HSeCN), thiocyanic acid (HSCN), fluoboric acid (HBF4), fluorine
Silicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), hydrofluoric acid (HF), hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), inclined aluminium
Acid (HAlO2), tetrahydroxy close aluminium (III) acid (HAl (OH)4), arsenic acid (H3AsO4), metaarsenous acid (HAsO2), arsenious acid
(H3AsO3), pyroarsenic acid (H4As2O7), boric acid (H3BO3), metaboric acid ((HBO2)n), tetraboric acid (H2B4O7), perboric acid (HBO3)、
12 tungsten boric acid (H5BW12O40), bromic acid (HBrO3), bromous acid (HBrO2), hypobromous acid (HBrO), hyperbromic acid (HBrO4), former carbon
Acid (H4CO4), cross two carbonic acid (H2C2O6), percarbonic acid (H2CO4Or H2CO3·H2O2), chloric acid (HClO3), perchloric acid (HClO4),
Chlorous acid (HClO2), hypochlorous acid (HClO), fulminic acid (HONC), cyanic acid (HOCN), isocyanic acid (HNCO), acid iodide (HIO3), secondary iodine
Acid (HIO or IOH), metaperiodic acid (HIO4), periodic acid (H5IO6), burnt periodic acid (H4I2O9), nitric acid (HNO3), nitrous acid
(HNO2), phosphoric acid (H3PO4), former phosphoric acid (H5PO5), metaphosphoric acid (HPO3)n, phosphorous acid (H3PO3), pyrophosphorous acid (H4P2O5), partially
Phosphorous acid (HPO2), hypophosphorous acid (H3PO2), hypophosphoric acid (H4P2O6), pyrophosphoric acid (H4P2O7), sulfuric acid (H2SO4), sulfurous acid
(H2SO3), thiosulfuric acid (H2S2O3), pyrosulfuric acid (H2S2O7), sulphoxylic acid (H2SO2), polythionic acid (H2SxO6, x=2~6), it is former
Sulfuric acid (H6SO6), hydrosulfurous acid (H2S2O4), permonosulphuric acid (H2SO5), peroxy-disulfuric acid (H2S2O8), chlorosulfonic acid (HSO3Cl), fluorine
Sulfonic acid (HSO3F), metasilicic acid (H2SiO3Or SiO2·H2O), orthosilicic acid (H4SiO4), two metasilicic acid (H2Si2O5Or 2SiO2·
H2) and disilicic acid (H O6Si2O7Or 2SiO2·3H2O) any one or more of, preferably sulfuric acid, hydrochloric acid, nitric acid, in phosphoric acid
It is any one or more.
Here organic acid can be oxalic acid, formic acid, acetic acid, propionic acid, succinic acid, trifluoracetic acid, trifluoromethanesulfonic acid, first
Sulfonic acid, mandelic acid, methylsulfuric acid, ethyl sulfuric acid, oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, bis- (catechol) boron
Sour, double oxalic acid boric acid, dimalonic acid boric acid, three (pentafluoroethyl group) three fluorophosphoric acid, three fluorophosphoric acid of triethyl group, four cyano boric acid, wine
At least one in stone acid, malic acid, citric acid, ascorbic acid, benzoic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid and caffeic acid
Kind, preferably oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
The usage amount of acid is related to the content of manganese dioxide in pyrolusite.Generally, excessive acid is conducive to mentioning for leaching rate
It is high.But it neutralizes excessive acid to need to consume alkali and generate solid by-product such as sodium sulphate, ammonium sulfate.It is different for various grades
Pyrolusite, sour usage amount is one of the main technologic parameters that must optimize.
The solid-to-liquid ratio of powder and the acid solution containing reducing agent can be 10~2000g/L, preferably 100~
1000g/L, further preferably 500~1000g/L.Although solid-to-liquid ratio is low can to accelerate reaction progress, be conducive to metallic element
Leaching, but water consumption is big, worth choosing；Solid-to-liquid ratio is too high, then may cause reaction not exclusively, metallic element cannot all be soaked
Out.
Reducing leaching carries out in the acid solution containing reducing agent, the usage amount of reducing agent and pyrolusite grade and also
Former agent molecule structure is related, and the amount for the reducing agent that the pyrolusite of different grades needs is different.The additive amount of reducing agent is according to also
The reaction equation of former agent and manganese dioxide stoichiometrically calculates.In order to guarantee that Leach reaction carries out completely it is contemplated that reducing agent
It is slightly excessive.Extra reducing agent can be removed after fully reacting by way of distilling or being evaporated under reduced pressure.If reducing agent
Boiling point is higher, is not easy to remove by the method distilled or be evaporated under reduced pressure, it may be considered that miberal powder is suitably excessive.
Leach reaction temperature may be controlled to 0~150 DEG C, preferably 25~120 DEG C, further preferably 45~110 DEG C.
Generally, reducing leaching reaction is exothermic reaction, maintains reaction less energy intensive.If exothermic heat of reaction is obvious, reducing agent is controlled
Speed is added, reducing agent is preferably added portionwise, or give and cool down.
The Leach reaction time may be controlled to 0.1~24 hour, preferably 1~6 hour, and further preferably 2~4 is small
When.Reaction rate is big, and reaction usually can be completed within a very short time, general that reaction is appropriately extended in order to ensure fully reacting
Time.
Leach reaction can carry out under stiring, and agitating mode and mixing speed are not particularly limited.
Consersion unit used in Leach reaction, however, it would be possible to use all applicable containers and pressure vessel, container
Material need to be selected according to the physico-chemical property of reactant, preferably with the material with acid-resistant property.The reducing leaching reaction
Can in batches, it is semicontinuous or be carried out continuously.By reaction equation (1) it is found that reducing leaching may generate by-product CO2.With
Reaction continuous progress, CO2Amount be continuously increased, will lead to pressure in reaction vessel and constantly rise.Consider safety in production simultaneously
The manufacturing cost for reducing equipment can be slowly added into a certain reactant on one side to control reaction rate, pass through release CO on one side2
Method so that pressure in reaction vessel is stablized in certain level.
In addition, can also include the following steps (c) after obtaining leachate and filter residue: several times by residue washing, washing
After obtain washing lotion and washed-residue, washing lotion, which is put into leachate mixing or ball mill processing miberal powder is added, is made slurry.
Further, it can also include step (d): washed-residue being reacted with the acid solution containing reducing agent, is stirred
It mixes and heats, be separated by solid-liquid separation after reaction, obtain secondary leachate and secondary response filter residue, realize manganese element in washed-residue
It leaches.
Step (c) and step (d) can be repeated several times, and with the leaching as much as possible for realizing manganese element, avoid wave as far as possible
Take.
It is described further below by leaching method of the specific embodiment to above-mentioned manganese element.
Embodiment 1
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 120
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 1200mL mass percentage is 25% is added,
Reaction mixture solid content is about 833g/L；It opens and stirs and heat；When temperature rises to 110 DEG C, start be added dropwise glycerine and
Formalin, reaction acutely, generate a large amount of bubbles；After about 2 hours, it is added dropwise；Glycerine about 70g and formaldehyde are added in total
About 10g.It is being added in the liquid phase acid solution to reactor, the concentration of glycerine is about 60g/L.The reaction was continued after charging
0.5 hour, to ensure fully reacting.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
As it is another preferably, the acid solution also contains organic acid；The organic acid is oxalic acid, formic acid, acetic acid, trichlorine
Acetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 98.6%.
Embodiment 2
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 40
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 980mL mass percentage is 30% is added,
About 80g ethylene glycol is added, is uniformly mixed.It is being added in the liquid phase acid solution to reactor, the concentration of ethylene glycol is about 80g/
L.Reaction mixture solid content is about 1000g/L.It opens and stirs and heat；When temperature rises to 150 DEG C, about 1 hour is kept the temperature.To
After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 98.7%.
Embodiment 3
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 200
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 600mL mass percentage is 50% is added,
About 73.5g 1,2-PD is added, is uniformly mixed.In liquid phase acid solution to reactor is added, 1,2-PD it is dense
Degree is about 120g/L.Reaction mixture solid content is about 1500g/L.It opens and stirs and heat；When temperature rises to 45 DEG C, heat preservation
About 12 hours.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is about 45.3%.
Embodiment 4
Fetch the pyrolusite sample 2 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 523700.0；Ca, 4736.0；K, 10910.0；Mg, 2955.0；Na, 2087.0；Fe, 37660.0；Cu,
3007.0；Ni, 128.7；Ba, 368.6；Zn, 1254.0；Al, 7191.0.
1000g pyrolusite sample 2 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 120
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 1500mL mass percentage is 25% is added,
Reaction mixture solid content is about 670g/L；It opens and stirs and heat；When temperature rises to 95 DEG C, start that ethylene glycol and third is added dropwise
Triol, reaction acutely, generate a large amount of bubbles, wherein VEthylene glycol:VGlycerine=1:1；After about 4 hours, ethylene glycol and glycerine are dripped
Finish；Ethylene glycol and glycerine about 94.0g are added in total.In liquid phase acid solution to reactor is added, ethylene glycol and the third three
The concentration of alcohol is about 63g/L.The reaction was continued after charging 2 hours, to ensure fully reacting.After cooling, implement solid-liquid point
From.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 95.3%.
Embodiment 5
The pyrolusite sample 3 from China somewhere is fetched, through analyzing, the main chemical compositions of the mine are following (unit: %):
Mn, 18.6；MnO2, 28.0；CaO, 2.1；MgO, 1.9；Fe2O3, 8.2；SiO2, 39.2；Al2O3, 3.7.
1000g pyrolusite sample 3 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 120
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 980mL mass percentage is 30% is added,
About 80.0g ethylene glycol is added, is uniformly mixed.Reaction mixture solid content is about 1000g/L；It opens and stirs and heat；Work as temperature
When rising to 120 DEG C, about 2 hours are kept the temperature.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate and filter residue are divided
From.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 99.7%.Leachate is merged with wash filtrate molten
Liquid is re-used for the leaching of pyrolusite, until the acid solution containing reducing agent loses activity.
Embodiment 6
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 120
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 1000mL mass percentage is 30% is added,
About 100g glycerine is added；It is uniformly mixed；Reaction mixture solid content is about 1000g/L；It opens and stirs and heat；When temperature liter
When to 150 DEG C, about 8 hours are kept the temperature.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 92.7%.
Embodiment 7
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 120
Purpose pyrolusite powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 1000mL mass percentage is 30% is added,
The mixture (the two ratio, volume ratio 1:3) of about 100g glycerine and ethylene glycol is added；It is being added to the liquid phase acidity of reactor
In solution, the concentration of reducing agent is about 100g/L；It is uniformly mixed；Reaction mixture solid content is about 1000g/L；Open stirring simultaneously
Heating；When temperature rises to 150 DEG C, about 8 hours are kept the temperature.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, will leach
Liquid is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 95.7%.
Embodiment 8
Fetch the pyrolusite sample 1 from African somewhere, through analyzing, the main chemical compositions of the mine it is following (unit:
Ppm): Mn, 412100.0；Ca, 4818.0；K, 10220.0；Mg, 2189.0；Na, 954.2；Fe, 34860.0；Cu, 1889.0；
Co, 27.4；Ni, 89.2；Ba, 372.3；Zn, 1119.0；Al, 10030.0.
1000g pyrolusite sample 1 is weighed, particle size is obtained by the methods of mechanical crushing, wet ball grinding and is about 80
Purpose miberal powder；Miberal powder is transferred to reaction vessel, the aqueous sulfuric acid that about 1000mL mass percentage is 30% is added, is added
About 120g 2,3- butanediol；It is being added in the liquid phase acid solution to reactor, the concentration of 2,3-butanediol is about 120g/L；
It is uniformly mixed；Reaction mixture solid content is about 1000g/L；It opens and stirs and heat；When temperature rises to 150 DEG C, heat preservation about 8
Hour.After cooling, implement to be separated by solid-liquid separation.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 80.7%.
Embodiment 9
Fetch certain electrolytic manganese anode slag sample 4 from China manganese tessellated region, through analyzing, the anode slag sample 4 it is main
Chemical component are as follows: the content of manganese is 36.6~47.2%, also containing impurity elements such as lead, calcium, magnesium, selenium, antimony, strontium, arsenic, wherein having
Valence metal lead content is 6.3~7.6%, and Se content is 0.26~0.30%, and content of strontium is 0.11~0.14%.Because its composition is multiple
It is miscellaneous, it is big to recycle difficulty, therefore in addition to aoxidizing ferrous iron for electrolytic manganese factory on a small quantity, the overwhelming majority becomes waste, long-term heap
Put or cheap selling to manganeisen smelting enterprise as production manganeisen raw material.If the earth of positive pole is stacked for a long time without
It is used, necessarily leads to serious environmental pollution and the waste of resource.
1000g electrolytic manganese anode slag sample 4 is weighed, it is big to obtain particle size by the methods of mechanical crushing, wet ball grinding
General is the anode ground-slag of 120 mesh；Anode ground-slag is transferred to reaction vessel, it is 30% that about 1000mL mass percentage, which is added,
Aqueous sulfuric acid；About 200g glycol water substandard products (waste products) is added, and (the glycol water ingredient is more complex, contains second
Glycol is about 40%)；It opens and stirs and heat；When temperature rises to 120 DEG C, about 4 hours are kept the temperature.After cooling, implement solid-liquid point
From.With the mode of suction filtration, leachate is separated with filter residue.
The acid solution used herein be sulfuric acid, could alternatively be any one of inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid or
It is a variety of；Alternatively, the organic acids such as oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of；Or
The mixing of person above-mentioned inorganic acid and organic acid.
Cleaning filter residue simultaneously filters, and obtains filtrate and filter residue, weighs after filter residue and drying.Leachate is merged with wash filtrate,
With the content of manganese element in icp analysis solution, the leaching rate for calculating manganese is 98.9%.
It is nontoxic in conclusion the reducing agent reactivity that the present invention uses is big, it is environmentally protective, it can will be in pyrolusite
The less soluble manganese element of high-valence state is reduced into the divalent manganesetion soluble easily in water of lower valency, after reaction by-product be gas or
Person's low boiling point small organic molecule is easy to remove from system, and the reducing agent；It is short and at low cost to leach recovery process route,
The manganese ion in pyrolusite can be leached by single step reaction, leaching rate is high, and extraction time is short.
Manganese sulfate is that tertiary cathode material is most important, most basic manganese source material, LITHIUM BATTERY manganese sulfate product specification such as table 1
It is shown.The impurity such as potassium, sodium, calcium, magnesium in raw material have a major impact the chemical property of lithium ion battery, power battery row
Requirement of the industry client to impurity content in manganese sulfate is quite harsh, it is desirable that the content of the impurity such as potassium, sodium, calcium, magnesium must control
100ppm or less.It is difficult to make the impurity content in manganese sulfate to reach this requirement using traditional impurity-removing method, it is necessary to carry out deep
Degree removal of impurities, can just produce the high purity manganese sulfate raw material for being suitable for power lithium-ion battery positive electrode.
1 LITHIUM BATTERY manganese sulfate product specification of table
The second aspect of the embodiment of the present invention provides a kind of preparation method of LITHIUM BATTERY manganese sulfate, includes the following steps.
(1) miberal powder ore reduction: is made in pyrolusite or anode slag.
Wherein, the equipment for being crushed pyrolusite or anode slag can be using crusher, wet ball mill etc..Miberal powder after broken
Particle size is typically chosen in 40~400 mesh, further preferably 80~200 mesh.
(2) miberal powder ball milling: it is further processed miberal powder with ball mill, slurry is made.
(3) chemical combination drill traverse goes out: slurry injects chemical combination slot, and reducing agent and sulfuric acid solution as described above is added to slurry, leads to
Enter steam heating feed liquid, is stirred to react to obtain leachate and filter residue.
Specifically, slurry is sent to chemical combination slot with shurry pump, reducing agent is added, from acid from raw material tank respectively according to a certain ratio
The dilute sulfuric acid that the concentrated sulfuric acid or sulfuric acid plant come and mother liquor, returning charge etc. is added in measuring tank, is passed through steam heating feed liquid, is stirred to react
To leachate.
(4) except removal of impurities again: leachate being separated, blender is added and adjusts pH value, and impurity removal reagents are added to clean
Matter is purified liquid and filter residue after feed liquid separation.
Specifically, feed liquid can separate leachate and filter residue through operations such as filters pressings after Leach reaction.Leachate send to
Purification and impurity removal reactive tank adjusts pH value, and impurity removal reagents are added except impurity.After reaction by the isolated scavenging solution of feed liquid and filter
Slag, scavenging solution are sent to purification and impurity removal reactive tank, are added impurity removal reagents and are cleaned, and foreign ion is removed.Feed liquid separation and net
Eliminate it is miscellaneous can operate repeatedly for several times, until impurity content meet product specification requirement.
Wherein, the blender is used for heightening pH value, can be manganese carbonate, manganese oxide, calcium oxide, calcium hydroxide, hydrogen
At least one of sodium oxide molybdena.The impurity removal reagents may include ferric sulfate and/or manganous fluoride.Wherein, ferric sulfate is for removing
Impurity be the elements such as Na, K ion, manganous fluoride is the ion of the elements such as Ca, Mg for the impurity of removing.
(5) it crystallizes: after scavenging solution stands a few hours, the manganese sulfate solution of purification is obtained by filtration, it is brilliant that crystallization obtains manganese sulfate
Body.Wherein, scavenging solution, which can be placed in stand in pond, stands a few hours；The method that the crystallization obtains manganese sulfate crystal can be height
Temperature crystallization.
(6) dry: manganese sulfate crystal obtains the LITHIUM BATTERY manganese sulfate of finished product through drying.Manganese sulfate is crystallized through drying, is obtained
Finished product, then weighing, packaging.
One of process flow is enumerated below, is described as follows:
Pyrolusite is sent through clamshell crane to hopper, is sent into crusher, wet ball mill by belt feeder through disk feeder, will
Mineral are crushed to~120 mesh.Ball mill is with water come inherent filtration slag washing water.Ball mill flows out ore pulp and enters slurry through grinding machine vibrating screen
Pond.Slurry is sent to chemical combination slot with shurry pump, is added respectively from raw material tank addition reducing agent, from sour measuring tank according to a certain ratio dense
The dilute sulfuric acid and mother liquor, returning charge etc. of sulfuric acid or sulfuric acid plant are passed through steam and heat feed liquid to stopping heating after 95 DEG C of temperature, stir
It mixes and obtains within reaction 2~4 hours reaction leachate.
Feed liquid is pumped to program controlled automatic filter press separation leachate and filter residue with reaction solution after reaction.Leachate send to
Manganese carbonate tune pH value is added in purification and impurity removal reactive tank, and ferric sulfate is added except sodium, potassium.Feed liquid separation and purification and impurity removal can be anti-
Multiple operation is for several times.Number of repetition can make impurity content meet product specification requirement determine according to actual needs.Filter residue is through washing
Drying discharge, slag washing water are sent to washery slag pond afterwards.
After finally obtained scavenging solution stands a few hours in standing pond, with the filtering of program controlled automatic filter press is pumped to, obtain
To the manganese sulfate solution of purification；It is sent again into refined filtration liquid pool, the pH value of solution is adjusted with the concentrated sulfuric acid.With pump the sulfuric acid of purification
Manganese solution is sent to evaporative crystallization tank condensing crystallizing, is discharged to automatic continuous conveyer centrifugal when material liquid-solid ratio in tank is 1:1
Separate manganese sulfate crystallization and mother liquor.Manganese sulfate crystallization is delivered to pneumatic drier drying through screw conveyor, obtains finished product, then
Weighing, packaging.Mother liquor is sent to mother liquor pond, is transferred back to evaporative crystallization tank.
Based on the leachate of previous embodiment 2, acid solution takes sulfuric acid, it can is successively prepared according to above-mentioned process flow
LITHIUM BATTERY manganese sulfate: the pH value that appropriate manganese carbonate adjusts leachate is added；Then ferric sulfate and manganese carbonate is added, removes potassium, sodium
Ion；Implement to be separated by solid-liquid separation；Then manganese carbonate is added, removes iron ion；Implement to be separated by solid-liquid separation；Then calcium oxide is added, until pH
=5, remove heavy metal ion；Implement to be separated by solid-liquid separation；Then manganous fluoride is added, reacts 4 hours, removes calcium and magnesium ion；Implement solid
Liquid separation.After removal of impurities is completed except weight, high temperature crystallization；Centrifuge separation, and dry crystal；Last battery pack grade manganese sulfate crystal,
Obtain product.
In order to effectively remove sodium, potassium ion, need to introduce Fe3+Ion (Fe2(SO4)3).If pH control is excessively high, it will lead to and draw
The Fe entered3+Ion conversion is Fe (OH)3Precipitating, is unfavorable for reacting, if pH control is too low, is unfavorable for the progress of reaction.
According to the hydroxide of each heavy metal ion, solubility product is smaller in water, while passing through many experiments, leachate
In metal impurities precipitated substantially in the form of hydroxide in pH=6 or so.Pb can be effectively removed by adjusting pH value2+、Sb3 +、Cu2+、Co2+、Ni2+、Sn2+、Ag+、Sr2+、As3+、Zn2+、Al3+Equal impurity elements.Fluoride according to part metals is in water
Solubility product is smaller, and selection uses MnF2Remove the calcium and magnesium ion in solution.
When carrying out high temperature crystallization process, will removal of impurities except the solution after weight, be evaporated under reduced pressure under the conditions of 70 DEG C, when there is crystalline substance
Stop distillation when body is precipitated；Temperature rises to 100 DEG C of holding a period of times, sufficiently to precipitate crystal.
To obtained crystal equivalent acquisition sample (sample Y1, sample Y2) twice, carry out respectively Elemental Composition analysis and with
The product specification of table 1 compares, and obtains the analysis result such as table 2.As shown in Table 2, LITHIUM BATTERY manganese sulfate product obtained by embodiment
Main content and impurity content touch the mark requirement, and partial impurities content is lower than instrument Monitoring lower-cut.
LITHIUM BATTERY manganese sulfate product each element component analysis (unit: ppm) obtained by 2 embodiment of table
Low energy consumption for preparation process of the present invention, and reduction is leached and purified and can complete in same reactive tank, and equipment investment is few；
Output waste residue is few, no exhaust gas, waste water；The reducing agent source used is wide, and cheap, reactivity is big, and nothing nontoxic to the human body
Evil；It is driven by reaction thermodynamics and kinetics, reduction rate and leaching rate are high (reaching 98% or more)；Reducing agent is a kind of simple
Compound, metals content impurity is extremely low, and the impurity of introducing can be ignored, and the manganese sulfate solution purification process of leaching is simple
And it is easy to control, popularity application can be obtained in each industry in downstream, such as there is the LITHIUM BATTERY of strict demand to metals content impurity
Sulfuric acid manganese industry and high pure metal manganese industry.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by the application
Claim point out.
It should be understood that the present invention is not limited to the precise structure already described above and shown in the accompanying drawings, and
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.
Claims (14)
1. a kind of leaching method of manganese element is used for pyrolusite or anode slag, which is characterized in that pyrolusite or anode slag are made
Powder, powder are reacted with the acid solution containing reducing agent, are separated by solid-liquid separation after reaction, and leachate and filter are obtained
Slag realizes the leaching of manganese element；
The reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2, R3, R4
It is independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；R1,R2,
R3, R4 are independent substituent group or in which two adjacent group joint cyclization.
2. the leaching method of manganese element according to claim 1, which is characterized in that in the molecular structural formula of the compound
R1, R2, R3, R4 are independent substituent group, and the alkyl that R1, R2, R3, R4 are respectively hydrogen or carbon atom number is 1~4.
3. the leaching method of manganese element according to claim 1, which is characterized in that the reducing agent further includes following substance
It is any one or more of: iron powder, sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, ferrous sulfate, sodium thiosulfate,
Calcium dithionate, hydrogen peroxide, oxalic acid, glucose, sucrose, cellulose, cornstalk, methanol, formaldehyde, phenol.
4. the leaching method of manganese element according to claim 1, which is characterized in that the acid solution is inorganic acid.
5. the leaching method of manganese element according to claim 4, which is characterized in that the inorganic acid is sulfuric acid, hydrochloric acid, nitre
Acid, phosphoric acid are any one or more of.
6. the leaching method of manganese element according to claim 4, which is characterized in that the acid solution also contains organic
Acid；The organic acid is that oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
7. the leaching method of manganese element according to claim 1, which is characterized in that further include after obtaining leachate and filter residue
Step:
Several times by residue washing, washing lotion and washed-residue are obtained after washing；
Washing lotion is put into leachate mixing, alternatively, ball mill processing powder, which is added, in washing lotion is made slurry.
8. the leaching method of manganese element according to claim 7, which is characterized in that further comprise the steps of: by washed-residue with contain
There is the acid solution of reducing agent to be reacted, stir and heat, be separated by solid-liquid separation after reaction, obtains secondary leachate and secondary
Filter residue is reacted, realizes the leaching of manganese element in washed-residue.
9. according to claim 1 to the leaching method of manganese element described in 8 any one, which is characterized in that the powder with
The solid-to-liquid ratio of acid solution containing reducing agent is 10~2000g/L.
10. according to claim 1 to the leaching method of manganese element described in 8 any one, which is characterized in that reaction temperature 0
~150 DEG C, the reaction time is 0.1~24 hour.
11. a kind of preparation method of LITHIUM BATTERY manganese sulfate, which comprises the steps of:
(1) powder ore reduction: is made in pyrolusite or anode slag；
(2) miberal powder ball milling: it is further processed powder with ball mill, slurry is made；
(3) chemical combination drill traverse goes out: slurry injects chemical combination slot, and reducing agent as described in claim 1-3 is added to slurry and sulfuric acid is molten
Liquid is passed through steam heating feed liquid, is stirred to react to obtain leachate and filter residue；
(4) except removal of impurities again: leachate being separated, blender is added and adjusts pH value, and impurity removal reagents are added except impurity, material
Liquid and filter residue are purified after liquid separation；
(5) it crystallizes: after scavenging solution stands a few hours, the manganese sulfate solution of purification is obtained by filtration, crystallization obtains manganese sulfate crystal；
(6) dry: manganese sulfate crystal obtains the LITHIUM BATTERY manganese sulfate of finished product through drying.
12. the preparation method of LITHIUM BATTERY manganese sulfate according to claim 11, which is characterized in that described in step (4)
Blender is at least one of manganese carbonate, manganese oxide, calcium oxide, calcium hydroxide, sodium hydroxide.
13. the preparation method of LITHIUM BATTERY manganese sulfate according to claim 11, which is characterized in that described to remove in step (4)
It include ferric sulfate and/or manganous fluoride in miscellaneous reagent.
14. the preparation method of LITHIUM BATTERY manganese sulfate according to claim 11, which is characterized in that in step (5), the knot
The method that crystalline substance obtains manganese sulfate crystal is high temperature crystallization.
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Cited By (6)
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| CN112777642A (en) * | 2021-01-26 | 2021-05-11 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
| CN112939090A (en) * | 2021-05-14 | 2021-06-11 | 蜂巢能源科技有限公司 | Manganese sulfate purification and crystallization method |
| CN114162796A (en) * | 2021-12-09 | 2022-03-11 | 宁波行殊新能源科技有限公司 | Method for recycling and regenerating phosphate waste |
| CN114162872A (en) * | 2021-12-31 | 2022-03-11 | 湖南烯富环保科技有限公司 | Method for preparing battery-grade manganese sulfate from manganese oxide ore |
| CN114684858A (en) * | 2022-01-14 | 2022-07-01 | 内蒙古大学 | Preparation process of small-particle-size and high-dispersion manganese fluoride nanocrystalline |
| CN115057475A (en) * | 2022-06-30 | 2022-09-16 | 夏江(乌兰察布)环保科技有限公司 | Industrial waste dephosphorization steel slag environment-friendly treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112777642A (en) * | 2021-01-26 | 2021-05-11 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
| CN112777642B (en) * | 2021-01-26 | 2023-03-14 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
| CN112939090A (en) * | 2021-05-14 | 2021-06-11 | 蜂巢能源科技有限公司 | Manganese sulfate purification and crystallization method |
| CN112939090B (en) * | 2021-05-14 | 2021-08-24 | 蜂巢能源科技有限公司 | Manganese sulfate purification and crystallization method |
| CN114162796A (en) * | 2021-12-09 | 2022-03-11 | 宁波行殊新能源科技有限公司 | Method for recycling and regenerating phosphate waste |
| CN114162872A (en) * | 2021-12-31 | 2022-03-11 | 湖南烯富环保科技有限公司 | Method for preparing battery-grade manganese sulfate from manganese oxide ore |
| CN114684858A (en) * | 2022-01-14 | 2022-07-01 | 内蒙古大学 | Preparation process of small-particle-size and high-dispersion manganese fluoride nanocrystalline |
| CN115057475A (en) * | 2022-06-30 | 2022-09-16 | 夏江(乌兰察布)环保科技有限公司 | Industrial waste dephosphorization steel slag environment-friendly treatment method |
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