CN107964597A - A kind of method for handling lepidolite extraction alkali metal - Google Patents
A kind of method for handling lepidolite extraction alkali metal Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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Abstract
The present invention provides a kind of method for handling lepidolite extraction alkali metal, this method comprises the following steps：First the lepidolite after mechanical activation is uniformly mixed with reconstructors, obtains mixture, then mixture and acidic activator are uniformly mixed, 1~4h is reacted at 50~100 DEG C；500~800 DEG C are then heated to, 10~60s is reacted, is cooled to 150~250 DEG C, obtains reconstruct clinker；Finally reconstruct clinker is added in alkaline leaching agent, alkali metal ion is leached and is synchronously cleaned by separation of solid and liquid, obtain the lithium salt solution and solid impurity rich in alkali metal.The method of the present invention, the ice crystal of potassium, sodium, aluminium element and fluorine element generation insoluble in acid in lepidolite is made full use of as fluxing agent, sodium, sylvite are used as reconstructors by the use of in mica and in system, it need not in addition increase the raw materials such as potassium, sodium and aluminium in whole technical process, have the characteristics that flow is short, remodeling temperature is low, energy consumption is low, the alkali metal rate of recovery is high.
Description
Technical field
The invention belongs to technical field of mineral processing, more particularly to a kind of lepidolite ore raw material that handles to extract alkali metal
Method.
Background technology
The mineral containing lithium are more at present, and have industrial value mainly has spodumene (Li2O·Al2O3·4SiO2), lithium cloud
Female KLi1.5Al1.5[AlSi3O10](OH,F)2, petalite (Li2O·Al2O3·8SiO2), phosphorus lepidolite LiAl [PO4](OH,
) and zinnwaldite K (Li, Al, Fe) [AlSi F3O10](OH,F)2.Salt lake bittern is the important sources for carrying lithium at the same time, due to bittern
In to carry lithium of low cost, existing many producers at present, but due in bittern the impurity content such as Mg it is high, later stage removal of impurities is cumbersome, leads
Cause product purity it is not high, and with lithium demand increase, carried since ore lithium by some producers favor and progressively produce,
So that it is gradually ripe that lithium technique is put forward in ore.
Lithium carbonate is a kind of important industrial chemicals, as country supports that lithium electricity is green in high energy to the emphasis of lithium electric material
The wide application of color energy field, both at home and abroad constantly increases lithium carbonate demand, price is gradually surging.And Rb, Cs are only because of its
Special photoelectric effect is applied to photocatalysis and military industry field, and Rb does not have single ore to exploit, scarcity of resources, far from
Meet demand, thus how comprehensive development and utilization lepidolite resource, there is considerable economy and strategic importance.
Contain a variety of metal values and the nonmetallic members such as Li, Na, K, Rb, Cs, Al and F in the lepidolite ore of Yichuan
Element, has a great economic value, and Li2O contents are only second to 6~8wt.% of spodumene in 4~5wt.% in lepidolite ore,
K2O contents may be up to 8.5wt.% and Rb contents and can reach 1~1.5wt.%, since Rb does not find its individualism so far
Ore, therefore Rb has very big extraction value, therefore the great favourable resources advantage of lepidolite extracted lithium.
At present processing lepidolite ore method be mainly conventional limestone roasting method, sulfuric acid process, sulfate process, chloridising roasting and
Autoclaving method etc..Lime burning method, chlorinating roasting, traditional sulfuric acid process etc., carry out the side of ore phase reconstruction using high temperature sintering
Formula, because the resource such as its high energy consumption, material circulation is big, Li et al. alkali metal recovery rate is low, valuable metal rubidium and caesium cannot be filled
Divide and utilize, can not embody the advantage and value of the lepidolite ore utilization of resources；Sulfuric acid process extracts alkali metal, since its sulfuric acid dosage is big
Cause its plumper dosage big, mainly with Al in solution3+And F-Based on, in slag subsidiary alkali gold larger with alkali metal separating difficulty
Category amount is big, so as to reduce the rate of recovery of alkali metal in lepidolite.
In the research work for carrying out Jiangxi lepidolite comprehensive utilization of resources exploitation, lepidolite mineral are usually used into ore deposit phase
Reconstruct, valuable metal are converted into corresponding product and carry out segmentation separation, prepare respective objects product.Ore phase reconstruction is former by handling
The Mineral pairs wherein mineral structure containing valuable constituent is reconfigured, and is converted into valuable constituent extractable and can be disconnected from each other
State, so as to fulfill efficiently separating.Such as Chinese patent CN201210080657.4 provides a kind of processing lepidolite ore
Method, this method are directed to the component and mineral structure of lepidolite, design specific ore phase reconstruction target, turn alkali metal etc.
Compound soluble easily in water is turned to, but this method needs high-temperature steam defluorinate, it is mutually overlapping with carrying out ore deposit after reconstructors mixed-forming
Structure, program is complicated, and energy consumption is higher.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
The method of kind processing lepidolite extraction alkali metal, this method flow is short, energy consumption is low, it can be achieved that step removal of impurities extraction alkali metal is first
Element, and the rate of recovery of alkali metal is high.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of method for handling lepidolite extraction alkali metal, comprises the following steps：
First the lepidolite after mechanical activation is uniformly mixed with reconstructors, obtains mixture, then mixture and acidity are lived
Agent is uniformly mixed, and 1~4h is reacted at 50~100 DEG C, helping beneficial to boiling reconstruct reaction can be generated in this reaction process
Molten auxiliary agent, can reduce the temperature of boiling reconstruct reaction, save energy consumption；Then heat to 500~800 DEG C and carry out boiling reconstruct instead
Should, 10~60s is reacted, makes alkali metal in lepidolite that ion-exchange reactions occur with reconstructors, is changed into solvable lithium salts
And alkali metal salt, and reconstructors are then combined production sodium silicoaluminate and potassium aluminosilicate etc. with silicon, aluminium, by reconstructing, the material after reacting is cold
But absorb water to 150~250 DEG C to avoid alkali metal salt and promote the progress of follow-up Leach reaction using waste heat at the same time, obtain reconstructing ripe
Material；Finally reconstruct clinker is added in alkaline leaching agent, the impurity such as iron removaling, aluminium, fluorine, nickel, cobalt, manganese, sulfate ion is removed, leaches
Alkali metal ion is simultaneously synchronously cleaned by separation of solid and liquid, obtains the lithium salt solution and solid impurity rich in alkali metal.
In the present invention, boiling reconstruct refers to that the reaction mass in reaction system is microspheroidal slurry, and microspheroidal slurry passes through
After heating is with moisture evaporation, the progress ore phase reconstruction reaction under the conditions of the tumbling state that seethe with excitement, alkali metal and reconstructors in lepidolite
There is a phenomenon where ion exchange.The temperature and time control of boiling reconstruct reaction need to control within the scope of the invention, if low
Reaction is then reconstructed in the scope of the present invention not exclusively, causes the reduction of alkali metal recovery rate, if beyond the scope of this invention, alkali
Double sintering can occur for metal salt, cause soluble lithium salt to be changed into slightly solubility lithium salts or be wrapped by, so as to reduce yield.
The method of the present invention, mainly passes through low-temperature boiling reconstruct extraction alkali metal in lepidolite, including lepidolite ore machinery
The processing step such as activation, low temperature dispensing, chemical activation, boiling reconstruct, dissolution separation alkali metal salt.Alkali metal is converted to solvable
Low temperature ore phase reconstruction during salt carries out, makes the impurity such as remaining fluorine, sulfate radical and leaching agent reaction in dissolution alkali metal salt generate not
Molten complex compound, reconstruct waste residue exist with aluminosilicate form, realize step removal of impurities extraction alkali metal, and reconstruct waste residue may be used also
Directly recycling reconstructors recycle or are directly used as the basic material of building trade, for lepidolite processing provides one kind economy,
Efficient Development and the new method utilized.
Above-mentioned method, it is preferred that the reconstructors are sodium, the sulfate and/or villaumite of potassium.Due to activation process and again
Structure can produce the sulfate and/or villaumite of a large amount of sodium, potassium during reacting, be reduced at the same time in order to avoid bringing other impurities into
Material circulation in reaction system, and realize recycling for resource, method of the invention addition sodium, potassium sulfate and/
Or villaumite is as reconstructors.
Above-mentioned method, it is preferred that the acidic activator is sulfuric acid, hydrochloric acid, nitric acid and/or hydrofluoric acid.
Above-mentioned method, it is preferred that the lepidolite and the mass ratio of reconstructors are (2~5):1.Lepidolite and reconstructors
Mass ratio need to control within the scope of the invention, beyond the scope of this invention, then the additive amount of reconstructors is very few, be unfavorable for weight
Structure reaction fully carries out, and less than the scope of the present invention, then reconstructors excessively cause in reaction system that material is excessive, are unfavorable for controlling
Cost.
Above-mentioned method, it is preferred that the mass ratio of the acidic activator and mixture is (1~3):1.Acidic activator
It need to be controlled within the scope of the invention with the mass ratio of mixture, beyond the scope of this invention, then acidic activator additive amount mistake
It is cause to go back residual fraction acidic materials in reconstruct reaction system more, equipment is caused to corrode as reconstructed tower, while increase cost, it is low
In the scope of the present invention, then lepidolite activation degree is inadequate, is unfavorable for the progress of reconstruct reaction.
Above-mentioned method, it is preferred that the alkaline leaching agent is calcium hydroxide and/or sodium hydroxide solution, the alkalescence
The pH value of leaching agent is 10~12.The pH value of alkaline leaching agent need to control within the scope of the invention, and pH value is excessive, can cause aluminium
Compound Deng tellurium dissolves under strongly alkaline conditions, and pH value is too low, then cannot eliminate the impurity such as magnesium, manganese member completely
Element.
Above-mentioned method, it is preferred that the content of lithia is 15~20g/L in the lithium salt solution.
Above-mentioned method, it is preferred that the mechanical activation processing refers to will using ball mill, Raymond mill and/or micropowder grinding
Lepidolite is milled to particle mean size less than 20 μm.The method of the present invention, lepidolite is handled using mechanical activation, make mica and feldspar,
The peel separations such as quartz, while broken increase surface area, mechanical activation reduce activation energy, advantageously reduce boiling reconstruct reaction
Temperature.
Technical scheme relates generally to following chemical equation：
Lepidolite chemical formula is K (Li, Al)2.5-3[Si3.5-3Al0.5-1O10](OH,F)2, can be abbreviated as：MeF·MeOH·
Al2O3·3SiO2；Wherein Me is Li, Na, K, Rb, Cs；
(a) cryochemistry activation stage：
MeF·MeOH·Al2O3·3SiO2+4H2SO4→Me2SO4+Al2(SO4)3+HF↑+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+8HCl→2MeCl+2AlCl3+HF↑+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+7HF→2MeF+2AlF3+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+8HNO3→2MeNO3+2Al(NO3)3+HF↑+3SiO2+4H2O；
MO+H2SO4→H2O+MSO4(M Fe, Cu, Mn, Mg, Ca), divalent metal element and other inorganic acid reaction equations
Formula is as described above.
(b) medium temperature roast reduction phase is thought of as complex salt, therefore by taking sodium salt as an example, it is as follows to be related to chemical equation：
2[MeF·MeOH·Al2O3·3SiO2]+2Na2SO4→2Me2SO4+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaCl→4MeCl+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaNO3→4MeNO3+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaF→4MeF+3NaAlSi2O6+NaAlF2(OH)2；
Al2(SO4)3·18H2O→Al2O3+3SO3+18H2O (medium temperature decomposition)；
2AlCl3·6H2O→Al2O3+6HCl+3H2O (medium temperature decomposition)；
It is more due to being related to inorganic acid, reconstructors species, it is related to reactive chemistry equation only for example, not listing one by one.
(c) leaching stage is related to following chemical equation：
Me2SO4+Al2(SO4)3→2MeAl(SO4)2(Me Na, K, Rb, Cs, NH4 +)；
Once leach dedoping step and be related to chemical equation, by taking villaumite and sulfate impurities as an example, using sodium hydroxide gradually
Leached into leaching agent：
MCl2+2NaOH→M(OH)2+2NaCl；
MSO4+2NaOH→M(OH)2+Na2SO4。
Compared with prior art, the advantage of the invention is that：
The method of the present invention, the two steps activation of use, mechanical activation are combined with chemical activation, subtracted first using mechanical activation
Small material particular diameter, increase specific surface area, reduce reaction activity, then carry out low temperature and simple acidifying in conjunction with chemical activation
Processing, destroys mica surface densification protective film, enters beneficial to reconstructors in boiling restructuring procedure in mica layer laminated structure, quickly
Generation ion-exchange reactions.
The method of the present invention, improves the recovery rate of valuable metal element in lepidolite and carries waste residue after the alkali metal such as lithium
Comprehensive value, reduces reconstruct reaction temperature and time, realizes the utilization of reconstructors feedstock circulation, the efficient dissolution of alkali metal salt
With the separated in synchronization of the impurity such as iron, aluminium, manganese.
The present invention, as background, makes full use of lithium cloud using " ore phase reconstruction method processing lepidolite extraction battery-level lithium carbonate " technology
The ice crystal of potassium, sodium, aluminium element and fluorine element generation insoluble in acid in mother is as fluxing agent, using in mica and in system
In addition sodium, sylvite need not increase the raw materials such as potassium, sodium and aluminium, compared with by calcium chloride " ore deposit phase as reconstructors in whole technical process
The technique of reconstruct ", has the characteristics that flow is short, remodeling temperature is low, energy consumption is low, meanwhile, the present invention is to producing each technique, each operation
Be precisely controlled with when reaction time, the alkali metal rate of recovery is high.Each step mutually cooperates with, and realizes lepidolite jointly
Economic, efficiently utilization, easy to large-scale develop and utilize lepidolite resource.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the process flow chart that lepidolite extraction alkali metal is handled in the embodiment of the present invention 1.
Embodiment
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment to invent herein do it is more complete
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The tantalum niobium lithium ore deposit for selecting Yichuan to produce in each embodiment, main component is shown in Table 1 in lepidolite.
1 lepidolite ore of table forms
| K | Na | Rb | Cs | Fe | Mn | Li2O | CaO | F | SiO2 | Al2O3 | |
| Wt/% | 6.45 | 1.25 | 1 | 0.2 | 0.13 | 0.24 | 4.2 | 0.14 | 4.46 | 50.78 | 26.93 |
Embodiment 1：
A kind of method of processing lepidolite extraction alkali metal of the invention, comprises the following steps：
According to technological process as shown in Figure 1, lepidolite is first milled to less than 20 μm by particle mean size using ball mill, by machine
Lepidolite after tool activation (presses 1 with reconstructors by sodium sulphate and potassium sulfate:1 mass ratio mixing composition) mixed
Close and expect, the mass ratio of lepidolite and reconstructors is 2:1, then mixture and mass fraction are uniformly mixed for 50% sulfuric acid, sulphur
The mass ratio of acid and mixture is 1:1, react 2h at 80 DEG C；700 DEG C are then heated to, 60s is reacted, after being cooled to 150 DEG C
Obtain reconstruct clinker；Clinker will finally be reconstructed to add in the alkaline calcium hydroxide solution that pH value is 12, leach alkali metal ion simultaneously
Synchronously cleaned by separation of solid and liquid, obtain the lithium salt solution and solid impurity rich in alkali metal.Lithium content is aoxidized in lithium salt solution
Up to 17g/L, and aluminium, iron, nickel, cobalt, manganese, content of fluoride ion are relatively low, in solid impurity mainly include sodium silicoaluminate, potassium aluminosilicate,
A small amount of calcium sulfate and calcirm-fluoride.
The dissolution yield of alkali metal is respectively in lepidolite concentrate after boiling reconstruct：Li 93.18%, K 94.25%, Rb
92.01%th, Cs 91.15%.
Lithium content is aoxidized in obtained lithium salt solution and reaches 17g/L, other impurities content is relatively low, and specific testing result is shown in Table 2
It is shown.
Lithium salt solution component in 2 embodiment 1 of table
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 17.01 | 10.13 | 12.75 | 1.65 | 0.14 | 0.05 | 0.33 | 0.01 | 0.01 | 0.01 | -- |
Embodiment 2：
A kind of method of processing lepidolite extraction alkali metal of the invention, comprises the following steps：
Lepidolite is milled to less than 20 μm by particle mean size using Raymond mill and ball mill Combined Treatment, after mechanical activation
Lepidolite (presses 1 with reconstructors by sodium sulphate and potassium sulfate:1 mass ratio mixing composition) be uniformly mixed obtain mixture, lithium cloud
Female and reconstructors mass ratioes are 2.5:1, then mixture and mass fraction are uniformly mixed for 50% sulfuric acid, sulfuric acid is with mixing
The mass ratio of material is 1.5:1, react 3h at 60 DEG C；800 DEG C are then heated to, reacts 30s, weight is obtained after being cooled to 200 DEG C
Structure clinker；Clinker will finally be reconstructed to add in the alkaline calcium hydroxide solution that pH value is 12, leach alkali metal ion and by solid
The synchronous removal of impurities of liquid separation, obtains the lithium salt solution and solid impurity rich in alkali metal.Lithium content is aoxidized in lithium salt solution to reach
15.65g/L, and aluminium, iron, nickel, cobalt, manganese, content of fluoride ion are relatively low, mainly include in solid impurity sodium silicoaluminate, potassium aluminosilicate,
A small amount of calcium sulfate and calcirm-fluoride.
The dissolution yield of alkali metal is respectively in lepidolite concentrate after boiling reconstruct：Li 95.72%, K 95.04%, Rb
93.11%th, Cs 91.88%.
Lithium content is aoxidized in obtained lithium salt solution and reaches 15.65g/L, other impurities content is relatively low, and specific testing result is shown in
Shown in table 3.
Lithium salt solution component in 3 embodiment 2 of table
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 15.65 | 9.43 | 10.17 | 1.22 | 0.13 | 0.02 | 0.29 | -- | 0.01 | 0.01 | -- |
Embodiment 3：
A kind of method of processing lepidolite extraction alkali metal of the invention, comprises the following steps：
Lepidolite is milled to less than 20 μm by particle mean size using micropowder grinding, by the lepidolite and reconstructors after mechanical activation
(press 1 by sodium sulphate and potassium sulfate:1 mass ratio mixing composition) be uniformly mixed obtain the matter of mixture, lepidolite and reconstructors
Amount is than being 3:1, then mixture and mass fraction are uniformly mixed for 50% sulfuric acid, the mass ratio of sulfuric acid and mixture is 2:1,
4h is reacted at 100 DEG C；750 DEG C are then heated to, reacts 40s, reconstruct clinker is obtained after being cooled to 250 DEG C；Finally will reconstruct
Clinker is added in the alkaline calcium hydroxide solution that pH value is 12, is leached alkali metal ion and is synchronously cleaned by separation of solid and liquid, is obtained
To lithium salt solution and solid impurity rich in alkali metal.Lithium content is aoxidized in lithium salt solution and reaches 18.52g/L, and aluminium, iron, nickel,
Cobalt, manganese, content of fluoride ion are relatively low, mainly include sodium silicoaluminate, potassium aluminosilicate, a small amount of calcium sulfate and calcirm-fluoride in solid impurity.
The dissolution yield of alkali metal is respectively in lepidolite concentrate after boiling reconstruct：Li 94.55%, K 93.82%, Rb
91.93%th, Cs 91.00%.
Lithium content is aoxidized in obtained lithium salt solution and reaches 18.52g/L, other impurities content is relatively low, and specific testing result is shown in
Shown in table 4.
Lithium salt solution component in 4 embodiment 3 of table
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 18.52 | 11.21 | 14.06 | 1.75 | 0.19 | 0.06 | 0.37 | 0.02 | 0.02 | 0.02 | -- |
Embodiment 4：
A kind of method of processing lepidolite extraction alkali metal of the invention, comprises the following steps：
Lepidolite is milled to less than 20 μm by particle mean size using Raymond mill and micropowder grinding Combined Treatment, after mechanical activation
Lepidolite (presses 1 with reconstructors by sodium chloride and potassium chloride:1 mass ratio mixing composition) be uniformly mixed obtain mixture, lithium cloud
Female and reconstructors mass ratioes are 5:1, then uniform, hydrochloric acid and mixture by the mixed in hydrochloric acid that mixture and mass fraction are 33%
Mass ratio be 1:1, react 2h at 60 DEG C；550 DEG C are then heated to, 60s is reacted, obtains reconstructing after being cooled to 180 DEG C ripe
Material；Clinker will finally be reconstructed to add in the alkaline calcium hydroxide solution that pH value is 12, leach alkali metal ion and by solid-liquid point
From synchronous removal of impurities, the lithium salt solution and solid impurity rich in alkali metal are obtained.Lithium content is aoxidized in lithium salt solution and reaches 10.78g/L,
And aluminium, iron, nickel, cobalt, manganese, content of fluoride ion are relatively low, sodium silicoaluminate, potassium aluminosilicate, a small amount of sulfuric acid are mainly included in solid impurity
Calcium and calcirm-fluoride.
The dissolution yield of alkali metal is respectively in lepidolite concentrate after boiling reconstruct：Li 90.52%, K 89.78%, Rb
87.51%th, Cs 87.17%.
Lithium content is aoxidized in obtained lithium salt solution and reaches 10.78g/L, other impurities content is relatively low, and specific testing result is shown in
Shown in table 5.
Lithium salt solution component in 5 embodiment 4 of table
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 10.78 | 7.52 | 9.16 | 1.03 | 0.11 | 0.07 | 0.21 | 0.98 | 0.01 | 0.01 | -- |
Embodiment 5：
A kind of method of processing lepidolite extraction alkali metal of the invention, comprises the following steps：
Lepidolite is milled to less than 20 μm by particle mean size using Raymond mill and micropowder grinding Combined Treatment, after mechanical activation
Lepidolite (presses 1 with reconstructors by sodium chloride and potassium chloride:1 mass ratio mixing composition) be uniformly mixed obtain mixture, lithium cloud
Female and reconstructors mass ratioes are 4:1, then mixture and acidic activator are uniformly mixed, acidic activator is specially 33% salt
Acid and 40% hydrofluoric acid, the mass ratio of hydrochloric acid, hydrofluoric acid and mixture is 1:0.5:1, react 4h at 60 DEG C；Then heat to
750 DEG C, 45s is reacted, reconstruct clinker is obtained after being cooled to 200 DEG C；Clinker will finally be reconstructed and add the alkaline hydrogen-oxygen that pH value is 12
Change in calcium solution, leach alkali metal ion and simultaneously synchronously cleaned by separation of solid and liquid, obtain lithium salt solution rich in alkali metal and solid
Body impurity.Lithium content is aoxidized in lithium salt solution and reaches 12.55g/L, and aluminium, iron, nickel, cobalt, manganese, content of fluoride ion are relatively low, solid is miscellaneous
Mainly include sodium silicoaluminate, potassium aluminosilicate, a small amount of calcium sulfate and calcirm-fluoride in matter.
The dissolution yield of alkali metal is respectively in lepidolite concentrate after boiling reconstruct：Li 91.19%, K 91.07%, Rb
89.58%th, Cs 88.72%.
Lithium content is aoxidized in obtained lithium salt solution and reaches 12.55g/L, other impurities content is relatively low, and specific testing result is shown in
Shown in table 6.
Lithium salt solution component in 6 embodiment 5 of table
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 12.55 | 9.78 | 11.77 | 1.28 | 0.16 | 0.01 | 0.28 | 0.07 | 0.01 | 0.01 | -- |
Claims (8)
- A kind of 1. method for handling lepidolite extraction alkali metal, it is characterised in that comprise the following steps：First the lepidolite after mechanical activation is uniformly mixed with reconstructors, obtains mixture, then by mixture and acidic activator It is uniformly mixed, 1~4h is reacted at 50~100 DEG C；500~800 DEG C are then heated to, 10~60s is reacted, is cooled to 150 ~250 DEG C, obtain reconstruct clinker；Finally reconstruct clinker is added in alkaline leaching agent, alkali metal ion is leached and passes through solid-liquid The synchronous removal of impurities of separation, obtains the lithium salt solution and solid impurity rich in alkali metal.
- 2. according to the method described in claim 1, it is characterized in that, the reconstructors are sodium, the sulfate and/or villaumite of potassium.
- 3. according to the method described in claim 1, it is characterized in that, the acidic activator for sulfuric acid, hydrochloric acid, nitric acid and/or Hydrofluoric acid.
- 4. according to the method described in claim 1, it is characterized in that, the lepidolite and the mass ratio of reconstructors are (2~5): 1。
- 5. according to the method described in claim 1, it is characterized in that, the mass ratio of the acidic activator and mixture for (1~ 3):1。
- 6. according to the method described in claim 1, it is characterized in that, the alkaline leaching agent is calcium hydroxide and/or hydroxide Sodium solution, the pH value of the alkaline leaching agent is 10~12.
- 7. according to the method described in claim 1, it is characterized in that, the content of lithia is 15~20g/ in the lithium salt solution L。
- 8. according to the method described in claim 1, it is characterized in that, mechanical activation processing refers to using ball mill, Lei Meng Lepidolite is milled to particle mean size less than 20 μm by mill and/or micropowder grinding.
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| CN110482576A (en) * | 2019-09-26 | 2019-11-22 | 福州大学 | A kind of method that lepidolite hydro-thermal prepares lithium salts |
| CN111534705A (en) * | 2020-04-21 | 2020-08-14 | 华南理工大学 | Composite additive for treating lepidolite ore and application thereof |
| CN114737066A (en) * | 2022-04-20 | 2022-07-12 | 北京中科云腾科技有限公司 | Method for extracting lithium from lithium ore leaching slag |
| CN114875250A (en) * | 2022-05-18 | 2022-08-09 | 北京机械力化学研究院有限公司 | Method for purifying lithium from lithium-containing clay |
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| CN114875250B (en) * | 2022-05-18 | 2023-08-01 | 北京机械力化学研究院有限公司 | Method for purifying lithium from lithium-containing clay |
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