CN108910851A - A method of lithium-containing compound is prepared by amblygonite - Google Patents
A method of lithium-containing compound is prepared by amblygonite Download PDFInfo
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- CN108910851A CN108910851A CN201811109579.XA CN201811109579A CN108910851A CN 108910851 A CN108910851 A CN 108910851A CN 201811109579 A CN201811109579 A CN 201811109579A CN 108910851 A CN108910851 A CN 108910851A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
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- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention provides a kind of method for preparing lithium-containing compound by amblygonite, the described method comprises the following steps：Amblygonite is mixed with acid and hydrogen fluoride, the acid does not include hydrofluoric acid, obtains mixed liquor；PH adjusting agent is added into the mixed liquor, adjusts the mixed solution pH, separation of solid and liquid obtains lithium-containing solution；Or pH adjusting agent is added into the mixed liquor, the mixed solution pH is adjusted, the mixed liquor is heated, separation of solid and liquid obtains lithium-containing solution；The lithium-containing solution pH is adjusted, separation of solid and liquid obtains lithium phosphate, or source of iron is added into the lithium-containing solution, and separation of solid and liquid obtains ferric lithium phosphate precursor, and the ferric lithium phosphate precursor is sintered to obtain LiFePO4.The method process flow is simple, easy to operate, can sufficiently extract the elemental lithium in amblygonite, the lithium-containing compound purity is high being prepared.The method can substantially reduce cost with one-step synthesis LiFePO4, and the LiFePO4 purity is high being prepared.
Description
Technical field
The invention belongs to field of compound preparation, be related to a kind of preparation method of lithium-containing compound, more particularly to it is a kind of by
The method that amblygonite prepares lithium-containing compound.
Background technique
Lithium is a kind of most light metal, lithium metal and its alloy and compound nuclear energy power generation, lightweight height than strong alloy,
Metallurgy, aluminium metallurgy, high-energy battery, medicine, glass, ceramics, lubricating grease, petroleum, chemical industry, organic synthesis, light metal weld, are nonmetallic
It is widely applied in the various fields such as mineral surface modification and daily necessities production.In recent decades, American and Britain, moral, method, day
Substantial contribution and human and material resources are successively put into states such as Russia, carries out the depth of aluminium lithium alloy, magnesium lithium alloy development and lithium resource
Gradation development application study, and the achievement to catch people's attention and successfully is obtained in succession, promote development and application, the life of world's lithium resource
Production and consumption and trade, produce important role to world's lithium industrial development.
Lithium resource is relatively abundanter in the world, and lithium resource is mainly distributed on south, North America, Asia, Australia and Africa.In glass benefit
Wei Ya only ties up the Li2O reserves of Buddhist nun's salt basin i.e. up to 1913.5 ten thousand t；The silver-colored peak (Silver Peak) and Jia Lifu of Nevada, USA
The Li2O reserves in both lakes Xi Er in Buddhist nun Asia state are more than 10,000,000 t；The ChaErHan salt lake in China Qinghai and bavin denier salt lake and
In many places brine in Sichuan Province, lithium resource reserves are estimated up to 10,000,000 t or so.The bittern mineral deposit lithium money that Argentinian Ka Tabaka is saved
Source reserves are also considerable, estimate its Li2O reserves up to millions of t.The reserves calculated in pegmatite lithium deposite by Li2O, beauty
634.8 ten thousand t of state, 4,260,000 t of Chile, 6,600,000 t of Canada, general assorted (Greenbushes) spodumene of the Green of western australia
Mine Li2O reserves are up to 6,000,000 t, and the amblygonite Li2O reserves of Zimbabwe and Namibia are also bigger, Xinjiang of China cocoa
Lepidolite reserves in the mineral deposits such as support sea, the spodumene of northwestern Sichuan and Yichuan tantalum niobium lithium rubidium caesium polymetallic ore
It is very abundant.
Spodumene, petalite, lepidolite the lithium method that mentions had many reports, but mentioning for amblygonite
Lithium, the research that people carry out are seldom.
CN107188205A discloses the technique that a kind of acidization extracts lithium sulfate from amblygonite, the technique include with
Lower step：(1) raw material is levigate：Raw material in amblygonite is carried out levigate；(2) ingredient：By lithium phosphorus aluminium of the step (1) after levigate
Stone and the concentrated sulfuric acid are mixed；(3) it roasts：Step (2) mixed material is roasted；(4) it sizes mixing leaching：To step
(3) clinker, which is placed in reaction kettle, is added water progress heating stirring；(5) purification and impurity removal：To being removed in the solution leached in step (4)
The impurity such as aluminium or calcium；(6) solution in step (5) after the reaction was completed is evaporated concentration.
CN107162024A discloses the technique that a kind of acidization extracts lithium carbonate from amblygonite, the technique include with
Lower step：Raw material is levigate, and-amblygonite and the concentrated sulfuric acid after ingredient-is levigate mix-roasts-sizes mixing leaching-purification and remove
It is miscellaneous-to remove the impurity such as aluminium or calcium-sinker of evaporation and concentration-one time-and once stir and wash-secondary stir is washed-and dry to obtain lithium carbonate product.
CN107200338A discloses the technique that a kind of acidization extracts lithium hydroxide from amblygonite, process route
For：Amblygonite by levigate and ingredient → roasting → clinker is levigate and leach together with the concentrated sulfuric acid → purification and impurity removal → evaporation is dense
Sodium → evaporative crystallization → recrystallization → drying and packaging is analysed in contracting → causticization → freezing.It, can be from lithium using technology of the invention
Lithium is extracted in peganite, becomes standard compliant monohydrate lithium hydroxide product, the yield of lithium can achieve 86% or more.
CN107188204A discloses a kind of lime method and extracts the technique of lithium hydroxide from amblygonite, including walks as follows
Suddenly：The grinding of S1 raw material, it is levigate to 100~200 mesh；S2 ingredient, is uniformly mixed into raw material；S3 roasting, high-temperature roasting are formed ripe
Material；S4 leaches filtering, obtains lithium hydroxide solution；S5 is concentrated by evaporation, and obtains lithium hydroxide clear liquid；S6 crystallization, obtains hydroxide
Lithium crystallization.
Although the above method can be realized mentions lithium from amblygonite, its process route is long, while mentioning lithium
Recovery rate is to be improved, and the purity of the product containing lithium is also required to further improve, and furthermore the iron in amblygonite and phosphorus do not obtain
Adequately utilize.
Summary of the invention
To solve the technical problems existing in the prior art, the present invention provides one kind and prepares lithium-containing compound by amblygonite
Method, the method process flow is simple, easy to operate, can sufficiently extract the elemental lithium in amblygonite, be prepared
Lithium-containing compound purity is high.
In order to achieve the above objectives, the present invention uses following technical scheme：
The present invention provides a kind of method that amblygonite prepares lithium-containing compound, the described method comprises the following steps：
Amblygonite is mixed with acid and hydrogen fluoride, the acid does not include hydrofluoric acid, obtains mixed liquor；
PH adjusting agent is added into the mixed liquor, adjusts the mixed solution pH, separation of solid and liquid obtains lithium-containing solution；
Or pH adjusting agent is added into the mixed liquor, the mixed solution pH is adjusted, the mixed liquor, solid-liquid point are heated
From obtaining lithium-containing solution；
The lithium-containing solution pH is adjusted, separation of solid and liquid obtains lithium phosphate, or source of iron, solid-liquid are added into the lithium-containing solution
Isolated ferric lithium phosphate precursor, the ferric lithium phosphate precursor are sintered to obtain LiFePO4.
In the present invention, the method generates hexafluoro aluminic acid by hydrofluoric acid dissolution aluminium element, then is adjusted by pH adjusting agent
PH generates hexafluoro sodium aluminate or potassium hexafluoroaluminate precipitating, or generates hexafluoro-ammonium aluminate soluble easily in water, passes through the side of heat resolve
Formula generates fluorination aluminum precipitation and ammonia and hydrogen fluoride, achievees the purpose that separate aluminium element.
As currently preferred technical solution, the mass ratio of the amblygonite and hydrogen fluoride is 1:(0.8~2.0),
Such as 1:0.8,1:0.9,1:1.0,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:
2.0 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 1:
(1.0~1.5).
Wherein, when the mass ratio of the amblygonite and hydrogen fluoride is greater than 1:When 0.8, aluminium element has part and generates tetrafluoro
Aluminic acid can not pass through precipitation and separation from solution；And when the mass ratio of amblygonite and hydrogen fluoride is less than 1:When 2.0, fluorine ion
Product purity can be reduced in conjunction with the other impurities element in amblygonite.
As currently preferred technical solution, the mass ratio of the acid and hydrogen fluoride is (0.1~1.0):1, the acid
It does not include hydrofluoric acid, such as 0.1:1,0.2:1,0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1,0.9:1 or 1.0:1
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
In the present invention, the purpose that acid is added is to promote elemental lithium, aluminium element and the dissolution of phosphate radical, acid and hydrofluoric acid
Mass ratio less than 0.1:1, the amount of dissolution that will cause elemental lithium is reduced, and when the mass ratio of acid and hydrogen fluoride is greater than 1.0:When 1,
It can promote the dissolution of a large amount of impurity elements, therefore the present invention is controlling the same of the additional amount of hydrogen fluoride with fluorine ion collective effect
When, need to carry out the control of sour additional amount.
As currently preferred technical solution, the acid includes organic and or inorganic acids.
Preferably, the acid is pure acid or acid solution.
Wherein, when heretofore described amblygonite is mixed with acid solution, the mass ratio of hydrogen fluoride and acid is lithium phosphorus aluminium
The ratio of the gross mass of contained acid in stone and acid solution.
Preferably, the inorganic acid include in sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid any one or at least two group
It closes, the combination is typical but non-limiting example has：The combination of sulfuric acid and hydrochloric acid, the combination of nitric acid and sulfuric acid, nitric acid and hydrochloric acid
Combination, the combination or sulfuric acid of hydrochloric acid and phosphoric acid, the combination of nitric acid and hydrochloric acid etc..
Wherein, it when heretofore described acid is inorganic acid, is mainly mixed in the form of acid solution with amblygonite.
Preferably, the organic acid includes any one in formic acid, acetic acid, oxalic acid or trifluoroacetic acid or at least two
Combination, the combination is typical but non-limiting example has：The combination of formic acid and acetic acid, the combination of acetic acid and oxalic acid, oxalic acid and three
The combination of fluoroacetic acid, trifluoroacetic acid and the combination added or the combination of acid, acetic acid and oxalic acid etc..
As currently preferred technical solution, the addition pH adjusting agent adjusts pH of mixed to 4~6, such as 4,4.2,
4.5,4.8,5,5.2,5.5,5.8 or 6 etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Preferably, the pH adjusting agent include in liquefied ammonia, sodium hydrate solid or potassium hydroxide solid any one or
In at least two combination or ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution any one or at least two combination,
The combination is typical but non-limiting example has：Combination, sodium hydrate solid and the potassium hydroxide of liquefied ammonia and sodium hydrate solid
The combination of solid, the combination of potassium hydroxide solid and liquefied ammonia, ammonium hydroxide and sodium hydroxide solution combination, sodium hydroxide solution and hydrogen
Combination, potassium hydroxide solution and combination of ammonium hydroxide of potassium oxide solution etc..
In the present invention, when the pH adjusting agent is non-liquefied ammonia or ammonium hydroxide, the hexafluoro aluminic acid for being slightly soluble in water can be generated in solution
Salt, by being separated by solid-liquid separation i.e. separable aluminium element, although still containing a small amount of hexafluoro aluminate in solution, due to subsequent heavy
It forms sediment during adjusting pH precipitate phosphoric acid lithium, the dissolubility of hexafluoro aluminate is poor to the responsiveness of pH, and pH raising will not analyse
Out, therefore it will not influence the purity of product.
Preferably, after adjusting the dissolution fluid pH, buffer is added into the dissolution fluid.
Preferably, the buffer includes sodium dihydrogen phosphate-disodium hydrogen phosphate, citric acid-sodium citrate, phthalic acid
Any one in hydrogen potassium-sodium hydroxide or hexa-hydrochloric acid.
In the present invention, in order to precipitate aluminum phosphate sufficiently, therefore dissolution fluid needs standing a period of time after pH is adjusted, in order to
Guarantee dissolution fluid pH stable, after adjusting the dissolution fluid pH, a small amount of buffer is added into dissolution fluid, the buffer is not
It is limited to above-mentioned cited buffering pair, the buffer that can be used in the range of pH4~6 is suitable for the present invention.The buffer
It can be added in the form of solid or buffer.
As currently preferred technical solution, the temperature of the heating mixed liquor is 300~500 DEG C, such as 300
DEG C, 320 DEG C, 350 DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 450 DEG C, 480 DEG C or 500 DEG C etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Wherein, above-mentioned reaction temperature has been more than the boiling point of water in solution, above-mentioned in order to guarantee the stabilization of reactant quality ratio
Reaction need to carry out in the closed reactor that can bear high pressure, such as autoclave.
In the present invention, when less than 300 DEG C, hexafluoro-ammonium aluminate can not decompose the heating temperature completely, work as heating temperature
When greater than 500 DEG C, uncontrollable side reaction can occur in system, influence product purity.It is worth noting that, when the model of pH adjusting
When enclosing not in 4~6 range, reaction temperature is controlled anyway, has a large amount of aluminium element to remain in solution, therefore solution
PH and reaction temperature have codetermined the separation degree of aluminium.
Preferably, the mixed liquor is heated when the pH adjusting agent is liquefied ammonia or ammonium hydroxide.
Preferably, the temperature that the mixed liquor is kept after the heating is 80~100 DEG C, such as 80 DEG C, 82 DEG C, 85
DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C or 100 DEG C etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable.
In the present invention, hexafluoro-ammonium aluminate heat resolve can generate ammonia and hydrogen fluoride, in order to reduce ammonia and hydrogen fluoride mistake
Amount dissolution, which enters in solution, brings excessive levels of impurities to the settling step of subsequent elemental lithium, and need to control solution temperature is 80~100 DEG C,
As currently preferred technical solution, the adjusting lithium-containing solution pH to 8~14, such as 8,9,10,11,12,13
Or 14 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 10
~12.
In the present invention, if carried out under the conditions of supercooling, the impurity content that will lead to the lithium phosphate being settled out is excessively high, therefore
Preamble controls solution temperature, has great influence to sinker step.
Preferably, before the adjusting lithium-containing solution pH, lithium-containing compound is added into lithium-containing solution.
Preferably, the lithium-containing compound include in lithium sulfate, lithium chloride, lithium nitrate or lithium hydroxide any one or
At least two combination, the combination is typical but non-limiting example has：Combination, lithium chloride and the nitric acid of lithium sulfate and lithium chloride
The combination of lithium, the combination or lithium sulfate of lithium nitrate and lithium hydroxide, the combination of lithium chloride and lithium nitrate etc..
Preferably, pH adjusting agent is added into solution in the adjusting lithium-containing solution pH.
Preferably, the pH adjusting agent include in liquefied ammonia, sodium hydrate solid or potassium hydroxide solid any one or
In at least two combination or ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution any one or at least two combination,
The combination is typical but non-limiting example has：Combination, sodium hydrate solid and the potassium hydroxide of liquefied ammonia and sodium hydrate solid
The combination of solid, the combination of potassium hydroxide solid and liquefied ammonia, ammonium hydroxide and sodium hydroxide solution combination, sodium hydroxide solution and hydrogen
Combination, potassium hydroxide solution and combination of ammonium hydroxide of potassium oxide solution etc..
Preferably, after adjusting the dissolution fluid pH, buffer is added into the dissolution fluid；
Preferably, the buffer includes boric acid-potassium chloride-sodium hydroxide, ammonium chloride-ammonium hydroxide, disodium hydrogen phosphate-hydrogen-oxygen
Change any one in sodium, sodium bicarbonate-sodium hydroxide or Tris-HCl.
In the present invention, in order to precipitate lithium phosphate sufficiently, therefore dissolution fluid needs standing a period of time after pH is adjusted, in order to
Guarantee dissolution fluid pH stable, after adjusting the dissolution fluid pH, a small amount of buffer is added into dissolution fluid, the buffer is not
It is limited to above-mentioned cited buffering pair, the buffer that can be used in the range of pH8~14 is suitable for the present invention.The buffer
It can be added in the form of solid or buffer.
As currently preferred technical solution, the source of iron includes ferrous sulfate, frerrous chloride, ferrous nitrate, sulfuric acid
Any one in iron, iron chloride or ferric nitrate or the combination at least connecting, the combination is typical but non-limiting example has：Sulphur
The sour ferrous and combination of frerrous chloride, the combination of frerrous chloride and ferrous nitrate, ferrous nitrate and ferrous sulfate combination, sulfuric acid
The combination of iron and iron chloride, the combination of iron chloride and ferric nitrate, ferric nitrate and combination of ferric sulfate etc..
Preferably, the ferro element in the source of iron be positive trivalent when, while reducing agent is added.
Preferably, the reducing agent includes any in iron powder, potassium borohydride, sodium borohydride, hypophosphorous acid or sodium hypophosphite
It is a kind of or at least two combination, the combination is typical but non-limiting example has：The combination of iron powder and potassium borohydride, hydroboration
The combination of potassium and sodium borohydride, the combination of sodium borohydride and hypophosphorous acid, hypophosphorous acid and sodium hypophosphite combination or iron powder, hydroboration
Potassium and the combination of sodium borohydride etc..
In the present invention, since ferrous ion can be restored to obtain by iron ion, can be used in principle iron ion salt with
The form that reducing agent adds altogether replaces ferrous ion salt, but in order to improve the production efficiency, in advance by reducing agent and iron ion
The method that reactant salt obtains corresponding ferrous ion salt is more applicable.
Preferably, the sintering carries out under protective atmosphere.
Preferably, the protective atmosphere include in nitrogen, helium, neon or argon gas any one or at least two group
It closes, the combination is typical but non-limiting example has：The combination of nitrogen and helium, the combination of helium and neon, neon and argon gas
Combination, the combination or nitrogen of argon gas and nitrogen, the combination of helium and argon gas etc..
Preferably, the temperature of the sintering is 500~900 DEG C, such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750
DEG C, 800 DEG C, 850 DEG C or 900 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value in the numberical range
It is equally applicable.
Preferably, the time of the sintering is 10~30h, such as 10h, 12h, 15h, 18h, 20h, 22h, 25h, 28h or 30h
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, carbon coating is carried out to the LiFePO4, obtains the LiFePO4 containing carbon coating layer.
Wherein, carrying out carbon coating to the LiFePO4 can be sintered using ball-milling method, vapour deposition process or organic carbon source
Method etc., the above method is the routine operation of this field, therefore is repeated no more in specification.
As currently preferred technical solution, a kind of method that lithium-containing compound is prepared by amblygonite include with
Lower step：
Amblygonite is mixed with acid and hydrogen fluoride, the acid does not include hydrofluoric acid, the amblygonite and hydrogen fluoride
Mass ratio be 1:The mass ratio of (0.8~2), the acid and hydrogen fluoride is (0.1~1):1, obtain mixed liquor；
PH adjusting agent is added into the mixed liquor, adjusts the mixed solution pH to 4~6, separation of solid and liquid is obtained containing lithium
Solution；
Or pH adjusting agent is added into the mixed liquor, the mixed solution pH to 4~6 is adjusted, when the pH adjusting agent
When for liquefied ammonia or ammonium hydroxide, the mixed liquor is heated to 300~500 DEG C, and it is 80 that the temperature of the mixed liquor is kept after heating
~100 DEG C, separation of solid and liquid obtains lithium-containing solution；
Lithium-containing solution pH8~14 are adjusted, separation of solid and liquid obtains lithium phosphate, or iron is added into the lithium-containing solution
Source, separation of solid and liquid obtain ferric lithium phosphate precursor, and the ferric lithium phosphate precursor is sintered to obtain LiFePO4.
In the present invention, the separation of solid and liquid is independently selected from any one in the methods of filtering, centrifugation, evaporation or sedimentation
Kind or at least two combination.And corresponding operating method is well known in the art, therefore repeats no more.
In the present invention, when the adjusting pH, it can be used that pH test paper carries out test or pH instrument carries out the real time measure, as the pH
It can stop the addition of pH adjusting agent when reaching the respective range that the present invention limits, therefore the present invention does not add pH adjusting agent
Dosage is specifically limited.
In the present invention, the purification processes that obtained product need to be crushed, recrystallized or be washed etc., to remove in product
A small amount of impurity, the above method is the routine operation of this field, and specific method repeats no more.
Compared with prior art, the present invention at least has the advantages that：
(1) the present invention provides a kind of method for preparing lithium-containing compound by amblygonite, the method uses lithium phosphorus aluminium
The dissolution mode of stone and acid and hydrofluoric acid, improves the dissolution rate of elemental lithium in amblygonite, while being conducive to subsequent lithium member
The separation of element；
(2) the present invention provides a kind of methods for preparing lithium-containing compound by amblygonite, and the present invention is using adjusting pH's
Mode separates the aluminium element in mixed liquor by the hexafluoro aluminate that hydrofluoric acid and aluminium element generate, reduces elemental lithium and exist
Loss in separation process improves the separation rate of aluminium element；
(3) the present invention provides a kind of method for preparing lithium-containing compound by amblygonite, liquefied ammonia is also can be used in the present invention
PH of mixed is adjusted with ammonium hydroxide, aluminum fluoride is generated by the mode of heating, removes the aluminium element in mixed liquor, reduces lithium member
The loss of element during the separation process, improves the separation rate of aluminium element；
(4) the present invention provides a kind of method for preparing lithium-containing compound by amblygonite, the method separates aluminium element
The step of, so that elemental lithium is sufficiently separated with aluminium element, improve the purity of lithium-containing compound in product；
(5) the present invention provides a kind of method for preparing lithium-containing compound by amblygonite, the method process flow letters
It is single, it is easy to operate, the elemental lithium in amblygonite can be sufficiently extracted, the lithium salts purity is high being prepared.The lithium of lithium phosphate product
Recovery rate up to 95% or more, product purity is up to 99% or more；The recovery rate of the lithium of LiFePO4 product up to 95% with
On, product purity is up to 99% or more.
Detailed description of the invention
Fig. 1 is a kind of flow chart of method that lithium-containing compound is prepared by amblygonite provided by the invention.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:0.8,
The mass ratio of hydrogen chloride and hydrogen fluoride in the concentrated hydrochloric acid is 0.1:1, obtain mixed liquor；
Sodium hydrate solid is added into the mixed liquor, adjusts the mixed solution pH to 4, lithium-containing solution is obtained by filtration
And hexafluoro sodium aluminate solid；
The lithium-containing solution pH to 8 is adjusted using sodium hydrate solid, lithium chloride is added and is generated into solution without precipitating, mistake
Filter, makes to be washed with deionized filter residue 3 times, obtains lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 95.2%, and the purity for the lithium phosphate being prepared is 99.1%.
Embodiment 2
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated nitric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:2, institute
The mass ratio for stating the nitric acid and hydrogen fluoride in concentrated nitric acid is 1:1, obtain mixed liquor；
Potassium hydroxide solid is added into the mixed liquor, adjusts the mixed solution pH to 6, lithium-containing solution is obtained by filtration
And potassium hexafluoroaluminate solid；
The lithium-containing solution pH to 14 is adjusted using potassium hydroxide solid, lithium chloride is added and is generated into solution without precipitating,
Filtering is washed filter residue 3 times using phosphoric acid solution, is washed filter residue 3 times reusing deionized water, is obtained lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 95.9%, and the purity for the lithium phosphate being prepared is 99.3%.
Embodiment 3
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1, institute
The mass ratio for stating the hydrogen chloride and hydrogen fluoride in concentrated hydrochloric acid is 0.5:1, obtain mixed liquor；
1mol/L sodium hydroxide solution is added into the mixed liquor, adjusts the mixed solution pH to 5, is obtained by filtration and contains
Lithium solution and hexafluoro sodium aluminate solid；
The lithium-containing solution pH to 10 is adjusted using 1mol/L sodium hydroxide solution, lithium chloride is added into solution without precipitating
It generates, filtering makes to be washed with deionized filter residue 3 times, obtains lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 96.1%, and the purity for the lithium phosphate being prepared is 99.0%.
Embodiment 4
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated nitric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1.5
The mass ratio of nitric acid and hydrogen fluoride in the concentrated nitric acid is 1:0.8, obtain mixed liquor；
1mol/L potassium hydroxide solution is added into the mixed liquor, adjusts the mixed solution pH to 6, is separated by solid-liquid separation
To lithium-containing solution and potassium hexafluoroaluminate solid；
The lithium-containing solution pH to 12 is adjusted using 1mol/L potassium hydroxide solution, lithium chloride is added into solution without precipitating
It generates, filtering is washed filter residue 3 times using phosphoric acid solution, is washed filter residue 3 times reusing deionized water, is obtained lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 95.7%, and the purity for the lithium phosphate being prepared is 99.2%.
Embodiment 5
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1, institute
The mass ratio for stating the hydrogen chloride and hydrogen fluoride in concentrated hydrochloric acid is 0.5:1, obtain mixed liquor；
Ammonium hydroxide is added into the mixed liquor, adjusts the mixed solution pH to 5, the solution is placed in autoclave
In, the solution is heated to 300 DEG C, keeps the solution to 80 DEG C after reaction, lithium-containing solution and fluorination is obtained by filtration
Aluminium solid；
The lithium-containing solution pH to 10 is adjusted using 1mol/L sodium hydroxide solution, lithium chloride is added into solution without precipitating
It generates, filtering makes to be washed with deionized filter residue 3 times, obtains lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 96.5%, and the purity for the lithium phosphate being prepared is 99.1%.
Embodiment 6
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1.5
The mass ratio of hydrogen chloride and hydrogen fluoride in the concentrated hydrochloric acid is 0.8:1, obtain mixed liquor；
Ammonium hydroxide is added into the mixed liquor, adjusts the mixed solution pH to 5, the solution is placed in autoclave
In, the solution is heated to 500 DEG C, keeps the solution to 100 DEG C after reaction, lithium-containing solution and fluorination is obtained by filtration
Aluminium solid；
The lithium-containing solution pH to 12 is adjusted using 1mol/L sodium hydroxide solution, lithium chloride is added into solution without precipitating
It generates, filtering is washed filter residue 3 times using phosphoric acid solution, is washed filter residue 3 times reusing deionized water, is obtained lithium phosphate.
Wherein, the recovery rate of the method elemental lithium is 96.1%, and the purity for the lithium phosphate being prepared is 99.3%.
Embodiment 7
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1, institute
The mass ratio for stating the hydrogen chloride and hydrogen fluoride in concentrated hydrochloric acid is 0.5:1, obtain mixed liquor；
1mol/L sodium hydroxide solution is added into the mixed liquor, adjusts the mixed solution pH to 5, is obtained by filtration and contains
Lithium solution and hexafluoro sodium aluminate solid；
Frerrous chloride is added into lithium-containing solution to generate to without precipitating, filtering is obtained by filtration using deionized water washing
Solid 3 times, obtain ferric lithium phosphate precursor, the ferric lithium phosphate precursor is under nitrogen protection sintered 30h at 500 DEG C
To LiFePO4.
Wherein, the recovery rate of the method elemental lithium is 96.6%, and the purity for the LiFePO4 being prepared is 99.5%.
Embodiment 8
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated nitric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1.5
The mass ratio of nitric acid and hydrogen fluoride in the concentrated nitric acid is 1:0.8, obtain mixed liquor；
1mol/L potassium hydroxide solution is added into the mixed liquor, adjusts the mixed solution pH to 6, is separated by solid-liquid separation
To lithium-containing solution and potassium hexafluoroaluminate solid；
Ferrous sulfate is added into lithium-containing solution to generate to without precipitating, filtering is obtained by filtration using deionized water washing
Solid 3 times, obtain ferric lithium phosphate precursor, the ferric lithium phosphate precursor is under nitrogen protection sintered 10h at 900 DEG C
To LiFePO4.
Wherein, the recovery rate of the method elemental lithium is 96.9%, and the purity for the LiFePO4 being prepared is 99.6%.
Embodiment 9
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1, institute
The mass ratio for stating the hydrogen chloride and hydrogen fluoride in concentrated hydrochloric acid is 0.5:1, obtain mixed liquor；
Ammonium hydroxide is added into the mixed liquor, adjusts the mixed solution pH to 5, the solution is placed in autoclave
In, the solution is heated to 300 DEG C, keeps the solution to 80 DEG C after reaction, lithium-containing solution and fluorination is obtained by filtration
Aluminium solid；
Iron chloride and iron powder (molar ratio 1.1 are added into lithium-containing solution:1) to without precipitating generate, filtering, using go from
Be obtained by filtration solid 3 times of sub- water washing, obtain ferric lithium phosphate precursor, the ferric lithium phosphate precursor is under nitrogen protection
It is sintered sintering for 24 hours at 600 DEG C and obtains LiFePO4.
Wherein, the recovery rate of the method elemental lithium is 96.2%, and the purity for the LiFePO4 being prepared is 99.3%.
Embodiment 10
The present embodiment provides a kind of methods for preparing lithium-containing compound by amblygonite to include the following steps：
Amblygonite is mixed with concentrated hydrochloric acid and hydrogen fluoride, the mass ratio of the amblygonite and hydrogen fluoride is 1:1.5
The mass ratio of hydrogen chloride and hydrogen fluoride in the concentrated hydrochloric acid is 0.8:1, obtain mixed liquor；
Ammonium hydroxide is added into the mixed liquor, adjusts the mixed solution pH to 5, the solution is placed in autoclave
In, the solution is heated to 500 DEG C, keeps the solution to 100 DEG C after reaction, lithium-containing solution and fluorination is obtained by filtration
Aluminium solid；
Ferric nitrate and sodium hypophosphite (molar ratio 4.1 are added into lithium-containing solution:1) it generates, filters to without precipitating, use
Deionized water washs solid 3 times be obtained by filtration, obtains ferric lithium phosphate precursor, the ferric lithium phosphate precursor is in nitrogen protection
12h is sintered at lower 800 DEG C to be sintered to obtain LiFePO4.
Wherein, the recovery rate of the method elemental lithium is 96.6%, and the purity for the LiFePO4 being prepared is 99.5%.
Comparative example 1
In this comparative example, in addition to the mass ratio of amblygonite and hydrogen fluoride is 1:Outside 0.5, other conditions with embodiment 6
It is identical.
Wherein, the recovery rate of the method elemental lithium is 75.2%, and the purity for the lithium phosphate being prepared is 81.3%.
Comparative example 2
In this comparative example, in addition to the mass ratio of amblygonite and hydrogen fluoride is 1:Outside 3, other conditions with 6 phase of embodiment
Together.
Wherein, the recovery rate of the method elemental lithium is 72.3%, and the purity for the lithium phosphate being prepared is 79.6%.
Comparative example 3
In this comparative example, other than being added without concentrated hydrochloric acid, other conditions are same as Example 6.
Wherein, the recovery rate of the method elemental lithium is 39.5%, and the purity for the lithium phosphate being prepared is 91.2%.
Comparative example 4
In this comparative example, in addition to the mass ratio of hydrogen chloride and hydrogen fluoride is 2 in concentrated hydrochloric acid:Outside 1, other conditions with implementation
Example 6 is identical.
Wherein, the recovery rate of the method elemental lithium is 89.6%, and the purity for the lithium phosphate being prepared is 51.2%.
Comparative example 5
In this comparative example, in addition to pH adjusting agent is added, adjust pH of mixed to outside 2, other conditions with 6 phase of embodiment
Together.
Wherein, the recovery rate of the method elemental lithium is 77.7%, and the purity for the lithium phosphate being prepared is 84.6%.
Comparative example 6
In this comparative example, in addition to pH adjusting agent is added, adjust pH of mixed to outside 8, other conditions with 6 phase of embodiment
Together.
Wherein, the recovery rate of the method elemental lithium is 82.8%, and the purity for the lithium phosphate being prepared is 71.5%.
Comparative example 7
In this comparative example, other than the heating temperature of mixed liquor is 150 DEG C, other conditions are same as Example 6.
Wherein, the recovery rate of the method elemental lithium is 81.6%, and the purity for the lithium phosphate being prepared is 54.6%.
Comparative example 8
In this comparative example, other than the heating temperature of mixed liquor is 700 DEG C, other conditions are same as Example 6.
Wherein, the recovery rate of the method elemental lithium is 85.2%, and the purity for the lithium phosphate being prepared is 66.3%.
The Applicant declares that the present invention is explained by the above embodiments detailed construction feature of the invention, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention must rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And increase, selection of concrete mode of accessory etc., all of which fall within the scope of protection and disclosure of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method for preparing lithium-containing compound by amblygonite, which is characterized in that the described method comprises the following steps：
Amblygonite is mixed with acid and hydrogen fluoride, the acid does not include hydrofluoric acid, obtains mixed liquor；
PH adjusting agent is added into the mixed liquor, adjusts the mixed solution pH, separation of solid and liquid obtains lithium-containing solution；
Or pH adjusting agent is added into the mixed liquor, the mixed solution pH is adjusted, the mixed liquor is heated, is separated by solid-liquid separation
To lithium-containing solution；
The lithium-containing solution pH is adjusted, separation of solid and liquid obtains lithium phosphate, or source of iron is added into the lithium-containing solution, is separated by solid-liquid separation
Ferric lithium phosphate precursor is obtained, the ferric lithium phosphate precursor is sintered to obtain LiFePO4.
2. the method according to claim 1, wherein the mass ratio of the amblygonite and hydrogen fluoride is 1:(0.8
~2), preferably 1:(1~1.5).
3. method according to claim 1 or 2, which is characterized in that the mass ratio of the acid and hydrogen fluoride is (0.1~1):
1, the acid does not include hydrofluoric acid.
4. method according to claim 1-3, which is characterized in that the acid includes organic and or inorganic acids；
Preferably, the acid is pure acid or acid solution；
Preferably, the inorganic acid include in sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid any one or at least two combination；
Preferably, the organic acid include in formic acid, acetic acid, oxalic acid or trifluoroacetic acid any one or at least two group
It closes.
5. method according to claim 1-4, which is characterized in that the addition pH adjusting agent adjusts mixed liquor
PH to 4~6；
Preferably, the pH adjusting agent include in liquefied ammonia, sodium hydrate solid or potassium hydroxide solid any one or at least
In two kinds of combination or ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution any one or at least two combination；
Preferably, after adjusting the dissolution fluid pH, buffer is added into the dissolution fluid；
Preferably, the buffer includes sodium dihydrogen phosphate-disodium hydrogen phosphate, citric acid-sodium citrate, hydrogen phthalate
Any one in potassium-sodium hydroxide or hexa-hydrochloric acid.
6. method according to claim 1-5, which is characterized in that the temperature of the heating mixed liquor is
300~500 DEG C；
Preferably, the mixed liquor is heated when the pH adjusting agent is liquefied ammonia or ammonium hydroxide；
Preferably, the temperature that the mixed liquor is kept after the heating is 80~100 DEG C.
7. method according to claim 1-6, which is characterized in that the adjusting lithium-containing solution pH to 8~14, it is excellent
It is selected as 10~12；
Preferably, before the adjusting lithium-containing solution pH, lithium-containing compound is added into lithium-containing solution；
Preferably, the lithium-containing compound include in lithium sulfate, lithium chloride, lithium nitrate or lithium hydroxide any one or at least
Two kinds of combination；
Preferably, after adjusting the dissolution fluid pH, buffer is added into the dissolution fluid；
Preferably, the buffer includes boric acid-potassium chloride-sodium hydroxide, ammonium chloride-ammonium hydroxide, disodium hydrogen phosphate-hydroxide
Any one in sodium, sodium bicarbonate-sodium hydroxide or Tris-HCl.
8. the method according to the description of claim 7 is characterized in that pH is added into solution in the adjusting lithium-containing solution pH
Regulator；
Preferably, the pH adjusting agent include in liquefied ammonia, sodium hydrate solid or potassium hydroxide solid any one or at least
In two kinds of combination or ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution any one or at least two combination.
9. method according to claim 1-8, which is characterized in that the source of iron includes ferrous sulfate, protochloride
In iron, ferrous nitrate, ferric sulfate, iron chloride or ferric nitrate any one or at least two combination；
Preferably, the ferro element in the source of iron be positive trivalent when, while reducing agent is added；
Preferably, the reducing agent includes any one in iron powder, potassium borohydride, sodium borohydride, hypophosphorous acid or sodium hypophosphite
Or at least two combination；
Preferably, the sintering carries out under protective atmosphere；
Preferably, the protective atmosphere include in nitrogen, helium, neon or argon gas any one or at least two combination；
Preferably, the temperature of the sintering is 500~900 DEG C；
Preferably, the time of the sintering is 10~30h；
Preferably, carbon coating is carried out to the LiFePO4, obtains the LiFePO4 containing carbon coating layer.
10. -9 described in any item methods according to claim 1, which is characterized in that the described method comprises the following steps：
Amblygonite is mixed with acid and hydrogen fluoride, the acid does not include hydrofluoric acid, the matter of the amblygonite and hydrogen fluoride
Amount is than being 1:The mass ratio of (0.8~2), the acid and hydrogen fluoride is (0.1~1):1, obtain mixed liquor；
PH adjusting agent is added into the mixed liquor, adjusts the mixed solution pH to 4~6, separation of solid and liquid obtains lithium-containing solution；
Or pH adjusting agent is added into the mixed liquor, the mixed solution pH to 4~6 is adjusted, when the pH adjusting agent is liquid
When ammonia or ammonium hydroxide, the mixed liquor is heated to 300~500 DEG C, and it is 80~100 that the temperature of the mixed liquor is kept after heating
DEG C, separation of solid and liquid obtains lithium-containing solution；
Lithium-containing solution pH8~14 are adjusted, separation of solid and liquid obtains lithium phosphate, or iron is added into second lithium-containing solution
Source, separation of solid and liquid obtain ferric lithium phosphate precursor, and the ferric lithium phosphate precursor is sintered to obtain LiFePO4.
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| PCT/CN2019/073872 WO2020057043A1 (en) | 2018-09-21 | 2019-01-30 | Method for using amblygonite to prepare lithium-containing compound |
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| WO2020057043A1 (en) * | 2018-09-21 | 2020-03-26 | 深圳市德方纳米科技股份有限公司 | Method for using amblygonite to prepare lithium-containing compound |
| CN111137868A (en) * | 2020-01-21 | 2020-05-12 | 曲靖市德方纳米科技有限公司 | Preparation method of lithium phosphate |
| CN111204726A (en) * | 2020-01-21 | 2020-05-29 | 曲靖市德方纳米科技有限公司 | Method for preparing lithium phosphate from lithium-phosphorus-aluminum |
| CN111252749A (en) * | 2020-01-21 | 2020-06-09 | 曲靖市德方纳米科技有限公司 | Method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum |
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| CN112626357B (en) * | 2020-12-14 | 2022-09-27 | 赣州有色冶金研究所有限公司 | Method for extracting lithium from waste lithium iron phosphate powder |
| CN114455569B (en) * | 2022-02-11 | 2023-05-02 | 齐鲁工业大学 | Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof |
| CN114735670B (en) * | 2022-04-12 | 2023-11-03 | 宜昌邦普时代新能源有限公司 | Preparation method and application of high-performance lithium iron phosphate |
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