CN106345394B - A method of it extracting lithium from brine and prepares high purity lithium dope - Google Patents
A method of it extracting lithium from brine and prepares high purity lithium dope Download PDFInfo
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- CN106345394B CN106345394B CN201610951367.0A CN201610951367A CN106345394B CN 106345394 B CN106345394 B CN 106345394B CN 201610951367 A CN201610951367 A CN 201610951367A CN 106345394 B CN106345394 B CN 106345394B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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Abstract
The method that the invention discloses a kind of to extract lithium from brine and prepare high purity lithium dope, it is characterized in that, 0.5-20kg/t magnetism lithium ion sieve is added in brine transportation pipeline, and pH is adjusted to >=5.0, magnetic lithium ion sieve and brine are separated thereafter by magnetic separation system, magnetic lithium ion sieve enters desorption activation link, Magneto separate ion sieve and stripping liquid again, magnetic lithium ion sieve feeds in former brine and mentions lithium again, stripping liquid is through repeatedly circulation until passing through nanofiltration membrane after lithium concentration >=3g/l, the filtration fraction of nanofiltration membrane is the high purity lithium dope of purity >=99%, directly prepare lithium carbonate product；The retention part of nanofiltration membrane is through nanofiltration link iterative cycles, until adding sodium bicarbonate when manganese lithium ratio is greater than 2:1 and preparing manganese carbonate product, after the separation of PP cotton, lithium liquid is back to nanofiltration membrane water supply.The present invention can prepare high purity lithium dope in conjunction with Magneto separate and membrane separation technique using magnetic lithium ion sieve.Link is concentrated without the lithiums such as solarization, reverse osmosis in period.
Description
Technical field
The invention belongs to lithium extractive technique fields, are related to a kind of side for extracting lithium from brine and prepare high purity lithium dope
Method.
Background technique
Lithium is acknowledged as " pushing the energy metal of world's progress ", and lithium battery is widely used in the families such as mobile phone, computer
Electrical domain.Growth with the mankind to the surging and low price lithium salts production of clean energy resource demand, the lithium energy will have a deep effect on
The life of the mankind.
The main richness of elemental lithium is stored in the mineral deposits such as pegmatite, salt lake bittern, seawater, GEOTHERMAL WATER in nature.Benefit is exploited
Lithium resource is mainly pegmatite and salt lake, especially based on saline lake lithium resource.Lithium resource reserves about 2.6 in seawater ×
1011T is more than 10,000 times of land lithium resource total amount.Therefore, salt lake bittern and Extracting Lithium from Seawater technical research cause extensive pass
Note.
Main technique Direct precipitation in the prior art and ion sieve absorption method, wherein the brine of high Mg/Li ratio mention lithium without
Method Direct precipitation, absorption method have a clear superiority.
Absorption method brine mentions lithium in the prior art, has using absorption resin, aluminium salt type adsorbent, embedding lithium active group material
Material, MnO2The absorption lithium-ion technologies such as adsorbent, adsorbent, the lithium ion sieve that spodumene concentrate is raw material.Among these again with lithium
Ion sieve is increasingly paid attention to by people because of the features such as its adsorption capacity is very big, adsorption rate is fast.
Relative to lithium ion sieve technology:
In domestic technique such as, two patents of Oceanography Institute Of Zhejiang, CN201010622481.1 " a kind of magnetic Nano lithium from
Sub- sieve adsorbant and preparation method thereof " and 201210394616.2 " magnetic nano lithium ion sieve adsorbents and preparation method thereof "
And their papers about magnetic lithium ion sieve for delivering, wherein magnetic Nano lithium ion sieve is with nanometer Fe3O4Superparamagnetism
Material is kernel, nanometer lithium-Mn oxide lithium ion sieve film is shell, and group becomes Fe3O4/LixMnyO4Core-shell structure,
Method is ferroso-ferric oxide/manganous hydroxide mixture that core-shell structure is prepared by a kind of reactor of percussion flow, then
It moves on in water heating kettle and is aged again, generate ferroso-ferric oxide/lithium manganese spinel, subsequently wash, roast, drying is produced after acid activation
Product.
The ferroso-ferric oxide magnetic core for the magnetic lithium ion sieve worked it out in this way is held due to there is probability directly to contact acidic environment
It is easily oxidized, and after multiple acid activation, after manganese damage molten to a certain degree, the dissolution rate of iron can be greatly improved, and then influence life
It produces, meanwhile, the solution background of solution background and synthesis lithium manganese spinel during synthesis ferroso-ferric oxide, which has, to be mixed, and point is influenced
Spar molding.
Such as from external technology, for example, ZL01823738X, ZL01823740.1 related patents by preparation graininess from
Son sieve, filling adsorbent bed carry out brine and mention lithium.There is also similar disadvantages for these techniques: being made into granular lithium ion sieve and is easy
Broken, the operational efficiency of adsorbent bed is seriously restricted, and then is much unable to reach design production capacity.
Lithium technology is extracted from brine relative to using lithium ion sieve:
It is all that " trace lithium in seawater is extracted in a kind of scale by the patented technology ZL201110321563.7 of Oceanography Institute Of Zhejiang
The method and device of ion ", magnetic Nano lithium ion sieve suspension is injected in the front end in channel and is dispersed in seawater
In quickly mention lithium；The end in channel is provided with magnetic Nano lithium ion sieve concentrating recovery device, the magnetic Nano lithium in seawater
Ion sieve is gradually condensed into the concentration stream of high concentration；Clear seawater is flowed out from flow field end, and magnetic Nano lithium ion sieve is dense
The first end that contracting stream is directed back into runner carries out next round circulation and mentions lithium, is taken turns after circulation mentions lithium, when magnetic Nano lithium ion sieve more
When adsorbing lithium close to balance, implement de- lithium operation, the magnetic Nano lithium ion sieve after lithium ion is desorbed is returned again again to following
New round seawater circulation is carried out in ring storage tank proposes lithium operation.
If the above method, which is used for brine, mentions lithium, since lithium concentration is much higher than seawater in brine, halogen can be brought by proposing lithium process
Water pH decline, if not adjusting brine acid or alkali environment, the adsorption capacity of ion sieve, which will receive, to be significantly inhibited；Meanwhile it is above-mentioned single
Magneto separate process is difficult to realize the preparation of high purity lithium product, it is difficult to precisely realize lithium concentration and Pureness control etc. in eluent；Together
When, the above method is unable to control the molten damage of magnetic lithium manganese spinel iron in the process of running, and can not recycle the manganese of molten damage.
In conclusion either lithium ion sieve technology still uses lithium ion sieve to extract lithium skill from brine in the prior art
Art need further to break through.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention, which provides, a kind of extracts lithium simultaneously from brine using magnetic lithium ion sieve
The method for preparing high purity lithium dope.
The technical solution adopted by the present invention:
A method of it extracting lithium from brine and prepares high purity lithium dope, 0.5- is added in brine transportation pipeline
20kg/t magnetism lithium ion sieve, and pH to >=5.0 is adjusted, magnetic lithium ion sieve and brine, magnetic are separated thereafter by magnetic separation system
Property lithium ion sieve enter desorption activation link, Magneto separate ion sieve and stripping liquid, magnetic lithium ion sieve are fed in former brine again
Lithium is mentioned again, and stripping liquid is through repeatedly circulation until by nanofiltration membrane after lithium concentration >=3g/l, the filtration fraction of nanofiltration membrane is purity
>=99% high purity lithium dope, directly prepares lithium carbonate product；
And/or the retention part of nanofiltration membrane adds carbonic acid when manganese lithium ratio is greater than 2:1 through nanofiltration link iterative cycles
Hydrogen sodium prepares manganese carbonate product, and after the separation of PP cotton, lithium liquid is back to nanofiltration membrane water supply.
Further, ion sieve inhales lithium process using strong base substance adjusting brine pH to >=5.0, and strong base substance includes hydroxide
Sodium, potassium hydroxide and sodium carbonate.
Further, Magneto separate is High-gradient Magnetic separation, and magnet includes permanent magnetism, electromagnetism or superconducting magnet, high-gradient medium packet
Include steel mesh, rod iron, steel-tooth or bristle.
Further, the Magneto separate process of brine and ion sieve includes ion sieve trapping, ion sieve cleaning, ion sieve elution three
A link, cleaning process include magnesium, potassium impurity using tap water or deionized water elution, and acid activation liquid is utilized under the conditions of no magnetic
Lithium ion sieve is eluted to acid activation link.
Further, desorption activation link acid concentration is 0.1-1mol/L, and desorption time is greater than 0.5h, and the acid used is inorganic
Or organic acid, including hydrochloric acid, sulfuric acid, nitric acid or carboxylic acid.
Further, enter anti-acid nanofiltration membrane when stripping liquid lithium concentration >=3g/l, the filtration fraction lithium concentration of nanofiltration membrane >=
2g/l is added directly sodium carbonate and lithium carbonate product is made.
Further, control lithium manganese mixing stripping liquid keeps the retention part manganese lithium of nanofiltration membrane dense in the cycle-index of nanofiltration membrane
Degree adds sodium bicarbonate and/or saleratus, and be separated by filtration manganese carbonate using PP cotton, lithium liquid is fed again to be received than being greater than 2:1
Filter membrane is to water end (W.E.).
Further, magnetic lithium ion sieve is, lazy in partial size≤50 nano ferriferrous oxide magnetic core surface coated silicas
Property layer, generate lithium manganese spinel in silica surface thereafter, and ultimately generate nano-magnetic lithium ion sieve, wherein ferrosilicon member
Plain molar ratio 1:1-1:5, ferrimanganic elemental mole ratios 1:1 to 1:30, saturation quality magnetic moment are greater than 5 emu/g, are saturated the absorption of lithium
Ability is greater than 5 mg/g.
Further, magnetic lithium ion sieve ferrosilicon ratio 1:1, ferrimanganic ratio 1:4, lithium manganese ratio 1:1, saturation quality magnetic moment are greater than
20emu/g, the adsorption capacity for being saturated lithium are greater than 30mg/g.
Further, the magnetic lithium ion sieve the preparation method is as follows:
(1) partial size≤50nm ferriferrous oxide particles are prepared by adding dispersing agent, dispersing agent includes polyethylene glycol, gathers
Vinylpyrrolidone or urea；
(2) nano ferriferrous oxide is separated with the solution of step (1) by Magneto separate, no magnetic liquid phase reuse to step
(1), it after thering is magnetic component to wash in situ in magnetic field, is added in ethanol/water mixed solution, ethyl orthosilicate and uniform is added thereafter
Stirring, prepares the ferroso-ferric oxide solution of coated with silica；Ferrosilicon ratio 1:1-1:5；
(3) coated with silica ferroso-ferric oxide is separated with step (2) solution by Magneto separate, no magnetic liquid phase reuse is extremely
Step (2) after having magnetic component to wash in situ in magnetic field, is added in manganese chloride solution, is slowly added to hydrogen-oxygen under agitation
Change lithium solution, and finally control molar ratio >=4:1 of Li:Mn, molar ratio=1:1 to 1:30 of Fe:Mn, lithium manganese compound is two
Silicon oxide surface is formed, and magnetic lithium manganese compound is obtained；
(4) magnetic lithium manganese compound is separated with the solution of step (3) by Magneto separate, no magnetic liquid phase reuse to step
(3), it after thering is magnetic component to wash in situ in magnetic field, dries, calcining obtains magnetic lithium manganese spinel；
(5) magnetic lithium manganese spinel is added in hydrochloric acid, nitric acid or sulfuric acid solution and is stirred, obtain magnetic lithium ion sieve；
(6) magnetic lithium ion sieve is separated with the acid solution of step (5) by Magneto separate, it is mixed that no magnetic liquid phase enters lithium mangaic acid
It closes in liquid collecting pit, after thering is magnetic component to wash in situ in magnetic field, into the magnetic lithium ion of 60-200 DEG C of drying obtained by drying
Sieve.
Further, in step (2), uniform stirring is that 70-300rpm stirs 5h.
Further, it in step (3), is added in 1.0-5.0mol/L manganese chloride solution, under 70-300rpm stirring condition slowly
0.5-2.0mol/L lithium hydroxide solution is added.
Further, in step (4), after thering is magnetic component to wash in situ in magnetic field, 60-200 DEG C of drying, and 350 DEG C of calcinings
5h。
Further, in step (5), 0.1-2mol/L hydrochloric acid, nitric acid or sulfuric acid solution is added in magnetic lithium manganese spinel
In, 70-300rpm stirs 1-24h.
It is preferred that uniform stirring is that 70-300rpm stirs 5h in step (2)；In step (3), 1.0-5.0mol/L chlorine is added
Change in manganese solution, 0.5-2.0mol/L lithium hydroxide solution is slowly added under 70-300rpm stirring condition；In step (4), have
After magnetic component is washed in situ in magnetic field, 60-200 DEG C of drying, and 350 DEG C of calcining 5h；It is in step (5), magnetic lithium manganese point is brilliant
Stone is added in 0.1-2mol/L hydrochloric acid, nitric acid or sulfuric acid solution, and 70-300rpm stirs 1-24h.
Further, the lithium manganese acid mixed solution in lithium manganese acid mixed solution collecting pit is distributed heavy through sodium bicarbonate and sodium carbonate
Behind shallow lake, manganese carbonate precipitating and lithium carbonate precipitating are obtained.
Further, it includes permanent magnetism, electromagnetism, superconducting magnet Magneto separate that Magneto separate, which uses,；Fill during Magneto separate it is acidproof not
Rust steel high-gradient medium, or gradient separations are opened using the own magnetic gradient realization of magnet；Acid-resistant stainless steel high-gradient medium includes
Steel wool, steel rod, steel mesh and steel plate.
The present invention can prepare high purity lithium dope in conjunction with Magneto separate and membrane separation technique using magnetic lithium ion sieve.Magnetic point
It is cleaned from process using ion sieve in ion sieve trapping, magnetic field, three process procedures of stripping liquid elution outside magnetic field, magnetic may be implemented
Property ion sieve and brine efficiently separate, the process goals such as the impurity removal such as stripping liquid lithium concentration accuracy controlling, magnesium, potassium.Ion sieve
Stripping liquid directly can produce high-purity, high concentration lithium chloride dope by nanofiltration membrane, and ring during which is concentrated without the lithiums such as solarization, reverse osmosis
Section.
The present invention compares patent 201110321563.7, there is following creative contribution, and first is that ion sieve inhales lithium process benefit
Brine pH is adjusted with strong base substance；Solution mention lithium process because brine pH decline, what the adsorption capacity of ion sieve was significantly inhibited
Problem；Second, propose that the trapping of Magneto separate process ion sieve, ion sieve cleaning, the outer stripping liquid elution in magnetic field integrate work in magnetic field
Skill can precisely realize lithium concentration and Pureness control in eluent；Third, can direct preparation of high-purity lithium in conjunction with Nanofiltration Membrane Separation Technology
During which dope is not necessarily to the concentration link of any lithium.
Magnetic lithium ion sieve especially of the invention:
Magnetism lithium ion sieve of the invention passes through repetition test using ferroso-ferric oxide magnetic core partial size and coating selection aspect,
It was found that the thick coating of partial size is easy to fall off, coating such as other coatings using non-silica, ferroso-ferric oxide core hold
It is also easy to produce exposed, especially during subsequent adsorption-desorption repeatedly, ferroso-ferric oxide magnetic core can be dissolved because of exposed generation, because
This, by comprehensive analysis, final choice≤50 nanometer, coating selects silica.
Magnetism lithium ion sieve of the invention can directly prepare magnetic lithium manganese spinel, magnetic core benefit in mesolow hydrothermal reaction kettle
With inert material Silica-coated, and lithium manganese spinel is grown in inert material surface crystallization, is passed through package inert material and is protected
Ferroso-ferric oxide magnetic core is protected, and then the molten damage of iron is greatly reduced；Crystallization is provided for lithium manganese spinel in hydrothermal reaction kettle simultaneously
Interface, accelerates the crystallization rate and crystallization integrity degree of lithium manganese spinel, and then magnetic lithium ion sieve is greatly reduced and uses and regenerates
The molten damage of manganese in the process.Synthesis technology realizes that the complete alternation of lithium uses, and the preparation cost of lithium ion sieve is greatly reduced.
Meanwhile the lithium and manganese not reacted completely in Magneto separate reuse lithium manganese compound synthesis process, realize that acid lithium manganese is mixed
The separation of liquid and magnetic lithium ion sieve is closed, and then realizes that acid activation dissolves out the complete utilization of lithium and manganese in the process.Salt lake bittern mentions lithium
In the process, magnetic lithium ion sieve can realize that magnesium, potassium, sodium etc. attach the cleaning of element, magnetic lithium ion with the quick separating of brine
Lithium ion sieve reuse is realized in the separation of sieve and acidic activated liquid.
The new process that magnetism lithium ion sieve of the invention proposes by 4 Magneto separate processes, overcome manganese systems lithium ion sieve with
The separation problem of water, while no magnetic liquid phase is recycled, it has such as recycled incomplete in magnetic manganese systems lithium ion sieve synthesis process
Participate in the Li and Mn of reaction, and the complete-reclaiming molten damage manganese of manganese systems lithium ion sieve use processes.The chlorination of the technique output
Lithium concentration and purity are higher, and easily realize large-scale production.
Magnetism lithium ion sieve lithium manganese spinel of the invention is grown in inert material surface crystallization, is lithium in hydrothermal reaction kettle
Galaxite provides crystalizing interface, accelerates the crystallization rate and crystallization integrity degree of lithium manganese spinel.Compared to existing magnetic lithium manganese
The lithium manganese spinel lattice development of the manufacturing process of spinelle, this process route synthesis is more perfect, and magnetic lithium is greatly reduced
The molten damage of manganese in ion sieve use and regenerative process.It is avoided to be oxidized and the manganese in lithium ion sieve use process, iron simultaneously
Dissolution.The lithium chloride solution that lithium manganese spinel activation process generates can realize complete recycling, and then lithium ion is greatly reduced
The manufacturing cost of sieve.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of the embodiment of the present invention 1.
Fig. 2 is 1 brine magnetic separation link integrated technique exploded view of the embodiment of the present invention.
Fig. 3 is the preparation technology flow chart of magnetic lithium ion sieve of the invention.
Specific embodiment
Tie that the present invention is described further with specific embodiment below.
Embodiment 1:
Certain brine 0.3g/l containing lithium, 100g/l containing magnesium, 0.6g/l containing potassium, 1.3g/l containing sodium, brine pH=5.0-5.3, in halogen
10g/l magnetism manganese bioxide ionic sieve is added in water conveyance conduit, is adjusted brine pH >=5.0 using sodium hydroxide, is utilized thereafter
Bore 1.25m slurry electromagnetic motor carries out Magneto separate, magnetic field strength 1.3T, and high-gradient medium selects diamond shape medium net.Above-mentioned magnetic point
300 tons of brine treatment abilities per hour can be realized from equipment.Magnetic separation link is integrated with that ion sieve trapping, ion sieve is clear in magnetic field
It washes, three process procedures of stripping liquid elution outside magnetic field, as shown in attached drawing 1,2.
Specific as follows: after magnetic separation, no magnetic liquid phase component is to mention brine after lithium, can direct emission；Have magnetic part it is i.e. magnetic from
Son sieve is captured in diamond shape medium net surface, is passed through tap water, the impurity such as magnesium, potassium, sodium that washing surface attaches in magnetic field thereafter；
After washing, magnetic separator demagnetization is pumped into acidic effluent liquid in magnetic separator, and is rushed by mixing wastewater with air by magnetic lithium ion sieve
50m is eluted to from high-gradient medium chamber3Acid regeneration bucket.Above-mentioned acidic effluent liquid is the hydrochloric acid of 0.5 mol/L, directly as magnetic
It selects machine flushing water and recycles, until lithium concentration reaches 6g/l.The mixed system of acid regeneration liquid and magnetic ion sieve is again
It is separated by solid-liquid separation by above-mentioned slurry electromagnetic motor, no magnetic liquid phase component is acid lithium dope, has magnetic group to be divided into regenerant ions
Sieve is directly poured in delivery pipe using former brine and carries out lithium absorption again.There is a small amount of magnetic titanium dioxide in above-mentioned acidity lithium dope
Manganese ion sieves the manganese ion of molten damage, and concentration is about 2-3g/l.Above-mentioned acidity lithium dope passes through nanofiltration membrane, and filtration fraction is to contain lithium
High-purity dope, for retention part after repeatedly recycling, control manganese lithium molar ratio is 2:1, and sodium bicarbonate is added, prepares manganese carbonate, lithium
Solution returns to nanofiltration membrane water supply.
Embodiment 2: magnetic lithium ion sieve is prepared, as shown in Fig. 3.
1 ton of magnetic manganese bioxide ionic sieve is prepared, 0.5 g/l concentration urea is added as dispersion, is stirred in 500rpm
1:1.5 adds 0.17-0.18 t frerrous chloride and 0.26-0.27 t ferrous sulfate solution in molar ratio under the conditions of mixing, and leads to thereafter
It crosses peristaltic pump and is slowly added to 10% ammonium hydroxide 900-1000 L ammonia spirit, until pH value of solution=7.0, black precipitate is four oxidations
Three ferromagnetic cores, average grain diameter are 20 ± 3 nm.Above-mentioned mixed solution is pumped into 300 mm slurry electromagnetic separator of φ, wherein filling out
Stainless steel rhombus net is filled as high-gradient medium.There is magnetic group to be divided into ferroso-ferric oxide magnetic core, it, will using mixing wastewater with air pulse lavage
Ferroso-ferric oxide magnetic core is pumped into packet silicon agitator, and no magnetic liquid phase component is the complete ammonium hydroxide of unreacted, is directly back to agitator,
The reflux course can reduce by 20% ammonium hydroxide and add.
The mixed solution of second alcohol and water is added in packet silicon agitator, wherein ethyl alcohol: water volume 1:1.It is stirred in 500 rpm
Under the conditions of be added 400-450 L ethyl orthosilicate, by control ferroso-ferric oxide additional amount, make silicon: iron molar ratio 1:3
To between 1:4, after stirring 5 hours, mixed liquor is pumped into φ 300mm slurry electromagnetic separator again, has magnetic group to be divided into silica
The ferroso-ferric oxide magnetic core of cladding is pumped into lithium manganese spinel agitator using mixing wastewater with air pulse lavage, and no magnetic liquid phase component is
Ethyl orthosilicate, ethyl alcohol and the water mixed solution not reacted completely on a small quantity, are directly back to packet silicon agitator, which can reuse
95% ethyl alcohol.
It is to add the manganese chloride solution 1600-1700 L that concentration is 2mol/L in lithium manganese compound agitator, in 500rpm
Coated with silica ferroso-ferric oxide is pumped under stirring condition, and it is 2.86 mol/L lithium hydroxide solution 5600- that concentration, which is added,
The concentration of 5700 L, control ferroso-ferric oxide, lithium hydroxide and manganese chloride make iron: manganese molar ratio is 1:2, lithium: manganese molar ratio
For 5:1.After stirring 1 hour, still aging 12h is to get magnetic lithium manganese compound.Above-mentioned mixed liquor is pumped into permanent magnetism scraper plate magnetic separation
Machine has magnetic solid phase for magnetic lithium manganese spinel, is directly collected by scraper plate, and it is small that 350 DEG C of calcinings 5 in kiln are placed in after 60 DEG C of drying
When to get magnetic lithium manganese spinel.No magnetic liquid phase is the lithium hydroxide for having neither part nor lot in reaction, and direct reuse to lithium manganese spinel stirs
Bucket, which can 80% lithium hydroxide of reuse.
In the HCl activation bucket of magnetic lithium manganese spinel investment 0.5mol/L, 200 rpm stir 5h, thereafter by above-mentioned mixing
Solution is pumped into aforementioned permanent magnetism scraper plate magnetic separator, and no magnetic component contains lithium, a small amount of manganese and trace iron, has magnetic component to receive by hanging plate
Collection, up to magnetic lithium ion sieve after 60 DEG C of drying.The acid solution of above-mentioned no magnetic component can be recycled for multiple times, until lithium concentration reaches
Distribution is carried out after certain value precipitates and then prepare three kinds of lithium carbonate, manganese carbonate and ferric carbonate products.
The magnetic lithium ion sieve of above-mentioned preparation, the saturated adsorption capacity of lithium is up to 20 mg/g, and quality magnetic moment reaches when magnetic saturation
To 10 emu/g.The molten loss rate of the magnetism lithium ion sieve single adsorptions desorption process manganese is less than 3/3rds ‰ thousand, the molten loss rate of iron
Less than 1 ‰；Single Magneto separate is separated from water circulation, and the non-magnetic component expulsion rate of magnetic material is less than 3 ‰.It is followed through 50 adsorption-desorptions
Do not find that significant change occurs for adsorption capacity after ring, above-mentioned magnetism manganese bioxide ionic sieve gross mass after 50 adsorption-desorptions is damaged
Consumption rate is less than 5%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, and done within the spirit and principles of the present invention
What modifications, equivalent substitutions and improvements etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of method extracted lithium from brine and prepare high purity lithium dope, which is characterized in that thrown in brine transportation pipeline
Add 0.5-20kg/t magnetism lithium ion sieve, and adjust pH to >=5.0, separates magnetic lithium ion sieve and halogen thereafter by magnetic separation system
Water, magnetic lithium ion sieve enter desorption activation link, and Magneto separate ion sieve and stripping liquid, magnetic lithium ion sieve feed former halogen again
Lithium is mentioned in water again, stripping liquid is through repeatedly circulation until by nanofiltration membrane after lithium concentration >=3g/l, the filtration fraction of nanofiltration membrane is
The high purity lithium dope of purity >=99%, directly prepares lithium carbonate product, wherein Magneto separate is High-gradient Magnetic separation, and magnet includes forever
Magnetic, electromagnetism or superconducting magnet；
The retention part of nanofiltration membrane is through nanofiltration link iterative cycles, until adding sodium bicarbonate system when manganese lithium molar ratio is greater than 2:1
Standby manganese carbonate product, after the separation of PP cotton, lithium liquid is back to nanofiltration membrane water supply；
Ion sieve inhales lithium process and adjusts brine pH to >=5.0 using strong base substance, and strong base substance includes sodium hydroxide, potassium hydroxide
And sodium carbonate；
Desorption activation link acid concentration is 0.1-1 mol/L, and desorption time is greater than 0.5h, and the acid used is inorganic or organic acid,
Including hydrochloric acid, sulfuric acid, nitric acid or carboxylic acid;
The Magneto separate process of brine and ion sieve includes ion sieve trapping, ion sieve cleaning, ion sieve three links of elution, cleaning
Process using tap water or deionized water elution include magnesium, potassium impurity, under the conditions of no magnetic using acid activation liquid by ion sieve from
Acid activation link is eluted in high-gradient medium.
2. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 1, which is characterized in that
High-gradient medium includes steel mesh, rod iron, steel-tooth or bristle.
3. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 1, which is characterized in that
Enter anti-acid nanofiltration membrane when stripping liquid lithium concentration >=3g/l, the filtration fraction of nanofiltration membrane is added directly sodium carbonate and lithium carbonate is made
Product.
4. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 1, which is characterized in that
Lithium manganese mixing stripping liquid is controlled in the cycle-index of nanofiltration membrane, so that the retention part manganese lithium concentration ratio of nanofiltration membrane is greater than 2:1, adds
Sodium bicarbonate and/or saleratus, and it is separated by filtration manganese carbonate using PP cotton, lithium liquid feeds nanofiltration membrane to water end (W.E.) again.
5. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 1, which is characterized in that
Magnetic lithium ion sieve is, in partial size≤50 nano ferriferrous oxide magnetic core surface coated silica inert layers, thereafter in dioxy
SiClx Surface Creation lithium manganese spinel, and ultimately generate nano-magnetic lithium ion sieve, wherein ferrosilicon elemental mole ratios 1:1-1:5,
Ferrimanganic elemental mole ratios 1:1 to 1:30, saturation quality magnetic moment are greater than 5 emu/g, and the adsorption capacity for being saturated lithium is greater than 5 mg/g.
6. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 5, which is characterized in that
It is described magnetism lithium ion the preparation method is as follows:
(1) partial size≤50nm ferriferrous oxide particles are prepared by adding dispersing agent, dispersing agent includes polyethylene glycol, polyethylene
Pyrrolidones or urea；
(2) nano ferriferrous oxide is separated with the solution of step (1) by Magneto separate, no magnetic liquid phase reuse has to step (1)
It after magnetic component is washed in situ in magnetic field, is added in ethanol/water mixed solution, ethyl orthosilicate and uniform stirring is added thereafter,
Prepare the ferroso-ferric oxide solution of coated with silica；Ferrosilicon molar ratio 1:1-1:5；
(3) coated with silica ferroso-ferric oxide is separated with step (2) solution by Magneto separate, no magnetic liquid phase reuse to step
(2), it after thering is magnetic component to wash in situ in magnetic field, is added in manganese chloride solution, is slowly added to lithium hydroxide under agitation
Solution, and molar ratio >=4:1 of Li:Mn is finally controlled, molar ratio=1:1 to 1:30 of Fe:Mn, lithium manganese compound is in titanium dioxide
Silicon face is formed, and magnetic lithium manganese compound is obtained；
(4) magnetic lithium manganese compound is separated with the solution of step (3) by Magneto separate, no magnetic liquid phase reuse has to step (3)
It after magnetic component is washed in situ in magnetic field, dries, calcining obtains magnetic lithium manganese spinel；
(5) magnetic lithium manganese spinel is added in hydrochloric acid, nitric acid or sulfuric acid solution and is stirred, obtain magnetic lithium ion sieve；
(6) magnetic lithium ion sieve is separated with the acid solution of step (5) by Magneto separate, no magnetic liquid phase enters lithium manganese acid mixed solution
In collecting pit, after thering is magnetic component to wash in situ in magnetic field, into the magnetic lithium ion sieve of 60-200 DEG C of drying obtained by drying.
7. a kind of method extracted lithium from brine and prepare high purity lithium dope according to claim 6, which is characterized in that
In step (2), uniform stirring is that 70-300rpm stirs 5h；
In step (3), it is added in 1.0-5.0 mol/L manganese chloride solution, is slowly added to 0.5- under 70-300rpm stirring condition
2.0 mol/L lithium hydroxide solutions；
In step (4), after thering is magnetic component to wash in situ in magnetic field, 60-200 DEG C of drying, and 350 DEG C of calcining 5h；
In step (5), magnetic lithium manganese spinel is added in 0.1-2 mol/L hydrochloric acid, nitric acid or sulfuric acid solution, 70-300rpm
Stir 1-24h.
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| BR112021011997A2 (en) * | 2018-12-18 | 2021-09-21 | Standard Lithium Ltd. | PROCESS FOR RECOVERING LITHIUM FROM BRINE WITH ADDED ALKALY |
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| CN116272846A (en) * | 2021-12-20 | 2023-06-23 | 比亚迪股份有限公司 | Magnetic titanium-based lithium adsorbent and preparation method thereof |
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