CN106345394A - Method for extracting lithium from bittern and preparing high-purity lithium concentrate - Google Patents
Method for extracting lithium from bittern and preparing high-purity lithium concentrate Download PDFInfo
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- CN106345394A CN106345394A CN201610951367.0A CN201610951367A CN106345394A CN 106345394 A CN106345394 A CN 106345394A CN 201610951367 A CN201610951367 A CN 201610951367A CN 106345394 A CN106345394 A CN 106345394A
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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
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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Abstract
The invention discloses a method for extracting lithium from bittern and preparing a high-purity lithium concentrate. The method is characterized by comprising the following steps: adding a 0.5-20kg/t magnetic lithium ion sieve into a bittern conveying pipeline, and adjusting the pH value to be higher than or equal to 5.0; separating the magnetic lithium ion sieve from the bittern by a magnetic separation system; feeding the magnetic lithium ion sieve into a desorption activation link; performing magnetic separation of the ion sieve and the desorption liquid again; feeding the magnetic lithium ion sieve into the raw bittern, and extracting lithium again; circulating the desorption liquid repeatedly until the lithium concentration is higher than or equal to 3g/l, and enabling the desorption liquid to pass through a nanofiltration membrane, wherein the filtered part of the nanofiltration membrane is the high-purity concentrate with purity of higher than or equal to 99%, and a lithium carbonate product is directly prepared; repeatedly circulating the intercepted part of the nanofiltration membrane by a nanofiltration link until the manganese-lithium ratio is greater than 2:1; adding sodium bicarbonate to prepare a manganese carbonate product; separating with PP cotton; and returning the lithium liquid to feed water to the nanofiltration membrane. In the invention, high-purity lithium concentrate can be prepared by use of the magnetic lithium ion sieve and by combining the magnetic separation and membrane separation technology; and in the process, the lithium concentration links such as solarization and reverse osmosis are not needed.
Description
Technical field
The invention belongs to lithium extractive technique field, it is related to a kind of extract lithium from salt and prepare the side of high purity lithium dope
Method.
Background technology
Lithium is acknowledged as " promoting the energy metal of world's progress ", and lithium battery is widely used in the families such as mobile phone, computer
Electrical domain.The growth the surging of clean energy resource demand and low price lithium salts being produced with the mankind, the lithium energy will have a deep effect on
The life of the mankind.
In nature, mainly richness is stored in the mineral deposits such as pegmatite, salt lake bittern, sea water, GEOTHERMAL WATER to elemental lithium.Exploit profit
Lithium resource is mainly pegmatite and salt lake, particularly based on saline lake lithium resource.Lithium resource reserves about 2.6 in sea water ×
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 of the prior art and ion sieve absorption method, wherein, the salt of high Mg/Li ratio carries lithium no
Method Direct precipitation, absorption method has a clear superiority.
Absorption method salt carries in lithium prior art, has using adsorbent resin, aluminium salt type adsorbent, embedding lithium active group material
Material, mno2Adsorbent, spodumene concentrate are the absorption lithium-ion technology such as the adsorbent of raw material, lithium ion sieve.Among these again with lithium
Ion sieve is because its adsorption capacity is very big, adsorption rate is increasingly paid attention to by people the features such as fast.
With respect to lithium ion sieve technology:
In domestic technique such as, two patents of Oceanography Institute Of Zhejiang, a kind of cn201010622481.1 " magnetic Nano lithium ion sieve
Adsorbent and preparation method thereof ", and 201210394616.2 " magnetic nano lithium ion sieve adsorbents and preparation method thereof " and
The paper with regard to magnetic lithium ion sieve that they deliver, wherein magnetic Nano lithium ion sieve are with nanometer fe3o4Superparamagnetic material
It is shell for kernel, nanometer lithium-Mn oxide lithium ion sieve thin film, consist of fe3o4/lixmnyo4Nucleocapsid structure,
Method is to prepare the ferroso-ferric oxide/manganous hydroxide mixture of nucleocapsid structure by a kind of reactor of percussion flow, then moves again
It is aged in water heating kettle, generate ferroso-ferric oxide/lithium manganese spinel, subsequently wash, roasting, acid activation post-drying goes out product.
The ferroso-ferric oxide magnetic core of the magnetic lithium ion sieve so worked it out, due to there being probability directly contact sour environment, is held
Easily oxidized, and after multiple acid activation, after the to a certain degree molten damage of manganese, the dissolution rate of ferrum can be greatly improved, and then affects life
Produce, meanwhile, the solution background during synthesis ferroso-ferric oxide has and mixes with the solution background of synthesis lithium manganese spinel, and impact is sharp
Spar molding.
From external technology such as, such as zl01823738x, zl01823740.1 Patents pass through prepare graininess from
Son sieve, filling adsorbent bed carries out salt and carries lithium.These techniques there is also similar shortcoming: makes granular lithium ion sieve easy
Broken, the operational efficiency of adsorbent bed is seriously restricted, and then is much unable to reach design production capacity.
Extract lithium technology with respect to using lithium ion sieve from salt:
" micro lithium ion in sea water is extracted in a kind of scale to be all patented technology zl201110321563.7 of Oceanography Institute Of Zhejiang
Method and device ", magnetic Nano lithium ion sieve suspension is injected in the front end of passage and is dispersed in sea water fast
Speed carries lithium；The end of passage is provided with magnetic Nano lithium ion sieve concentrating recovery device, the magnetic Nano lithium ion in sea water
Sieve is progressively condensed into the concentration stream of high concentration；The sea water of clarification flows out from flow field end, magnetic Nano lithium ion sieve concentration stream
The first end being directed back into runner carries out next round circulation and carries lithium, takes turns circulation and carries after lithium through, when magnetic Nano lithium ion sieve adsorbs
Close to when balancing, implementing de- lithium operation, the magnetic Nano lithium ion sieve after desorption lithium ion is returned to more again circulates storage to lithium
Carry out new round seawater circulation in groove and propose lithium operation.
If said method being used for salt carry lithium, because lithium concentration is far above sea water in salt, putting forward lithium process and can bring halogen
Water ph declines, if not adjusting salt acid or alkali environment, the adsorption capacity of ion sieve can be significantly inhibited；Meanwhile, 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 control of purity etc. in eluent；With
When, the molten damage of said method uncontrollable magnetic lithium manganese spinel ferrum in running, and the manganese of molten damage cannot be reclaimed.
In sum, in prior art, either lithium ion sieve technology still extracts lithium skill using lithium ion sieve from salt
Art need to break through further.
Content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides one kind to extract lithium simultaneously using magnetic lithium ion sieve from salt
The method preparing high purity lithium dope.
The technical solution used in the present invention:
A kind of method extracted lithium from salt and prepare high purity lithium dope, adds 0.5-20kg/t magnetic in brine transportation pipeline
Property lithium ion sieve, and adjust ph to >=5.0, thereafter by magnetic separation system separation magnetic lithium ion sieve and salt, magnetic lithium ion
Sieve enters desorbing activation link, Magneto separate ion sieve and stripping liquid again, and magnetic lithium ion sieve feeds in former salt and carries lithium again,
Through multiple circulation until passing through NF membrane after lithium concentration >=3g/l, the filtration fraction of NF membrane is the height of purity >=99% to stripping liquid
Pure lithium dope, directly prepares lithium carbonate product；
And/or the retention part of NF membrane is through nanofiltration link iterative cycles, until manganese lithium ratio, during more than 2:1, adds sodium bicarbonate
Prepare manganese carbonate product, after separating through pp cotton, lithium liquid is back to NF membrane feedwater.
Further, ion sieve inhales lithium process using strong base substance regulation salt ph to >=5.0, and strong base substance includes hydroxide
Sodium, potassium hydroxide and sodium carbonate.
Further, Magneto separate separates for High-gradient Magnetic, and magnet includes permanent magnetism, electromagnetism or superconducting magnet, high-gradient medium bag
Include steel mesh, rod iron, steel-tooth or bristle.
Further, salt and the Magneto separate process of ion sieve comprise ion sieve trapping, ion sieve cleaning, ion sieve eluting three
Individual link, cleaning process includes magnesium, potassium impurity using tap water or deionized water eluting, utilizes acid activation liquid under the conditions of no magnetic
Eluting lithium ion sieve is to acid activation link.
Further, desorbing activation link acid concentration is 0.1-1 mol/l, and desorption time is more than 0.5h, and the acid of use is no
Machine or organic acid, including hydrochloric acid, sulphuric acid, nitric acid or carboxylic acid.
Further, enter anti-acid NF membrane during stripping liquid lithium concentration >=3g/l, the filtration fraction lithium concentration of NF membrane >=
2g/l, directly adds sodium carbonate and lithium carbonate product is obtained.
Further, control lithium manganese mixing stripping liquid in the cycle-index of NF membrane, make the retention part manganese lithium of NF membrane dense
Degree ratio, more than 2:1, adds sodium bicarbonate and/or potassium bicarbonate, and utilizes pp cotton filtration separation manganese carbonate, and lithium liquid feeds again to be received
Filter membrane feedwater end.
Further, magnetic lithium ion sieve is, in particle diameter≤50, nano ferriferrous oxide magnetic core Surface coating silicon dioxide is lazy
Property layer, generate lithium manganese spinel in silica surface thereafter, and ultimately generate nano-magnetic lithium ion sieve, wherein, ferrosilicon unit
Plain mol ratio 1:1-1:5, ferrimanganic elemental mole ratios 1:1 to 1:30, saturation quality magnetic moment is more than 5 emu/g, the absorption of saturation lithium
Ability is more than 5 mg/g.
Further, magnetic lithium ion sieve ferrosilicon ratio 1:1, ferrimanganic is more than than 1:1, saturation quality magnetic moment than 1:4, lithium manganese
20emu/g, the absorbability of saturation lithium is more than 30mg/g.
Further, described magnetic lithium ion sieve preparation method is as follows:
(1) particle diameter≤50nm ferriferrous oxide particles are prepared by adding dispersant, dispersant includes Polyethylene Glycol, polyethylene
Ketopyrrolidine or carbamide；
(2) pass through Magneto separate by the solution separating of nano ferriferrous oxide and step (1), no magnetic liquid phase reuse, to step (1), has
Magnetic component, after the washing of magnetic field situ, adds in ethanol/water mixed solution, adds tetraethyl orthosilicate uniform stirring thereafter,
The ferroso-ferric oxide solution of preparation coated with silica；Ferrosilicon ratio 1:1-1:5；
(3) pass through Magneto separate by coated with silica ferroso-ferric oxide and step (2) solution separating, no the reuse of magnetic liquid phase is to step
(2), there is magnetic component after the washing of magnetic field situ, add in manganese chloride solution, be slowly added to Lithium hydrate under agitation
Solution, and finally control mol ratio >=4:1, mol ratio=1:1 to the 1:30 of fe:mn of li:mn, lithium manganese compound is in titanium dioxide
Silicon face is formed, and obtains magnetic lithium manganese compound；
(4) pass through Magneto separate by the solution separating of magnetic lithium manganese compound and step (3), no magnetic liquid phase reuse, to step (3), has
Magnetic component, after the washing of magnetic field situ, is dried, and calcining obtains magnetic lithium manganese spinel；
(5) magnetic lithium manganese spinel is added in hydrochloric acid, nitric acid or sulfuric acid solution and stir, obtain magnetic lithium ion sieve；
(6) by Magneto separate, magnetic lithium ion sieve is separated with the acid solution of step (5), no magnetic liquid phase enters lithium manganese acid mixed solution
In collecting pit, there is magnetic component after the washing of magnetic field situ, enter the magnetic lithium ion sieve that 60-200 DEG C of drying is dried.
Further, in step (2), uniform stirring stirs 5h for 70-300rpm.
Further, in step (3), add in 1.0-5.0 mol/l manganese chloride solution, slow under 70-300rpm stirring condition
Slow addition 0.5-2.0 mol/l lithium hydroxide solution.
Further, in step (4), there is magnetic component after the washing of magnetic field situ, 60-200 DEG C of drying, and 350 DEG C of calcinings
5h.
Further, in step (5), magnetic lithium manganese spinel is added 0.1-2 mol/l hydrochloric acid, nitric acid or sulfuric acid solution
In, 70-300rpm stirs 1-24h.
Preferably, in step (2), uniform stirring stirs 5h for 70-300rpm；In step (3), add 1.0-5.0 mol/l
In manganese chloride solution, under 70-300rpm stirring condition, it is slowly added to 0.5-2.0 mol/l lithium hydroxide solution；In step (4),
There is magnetic component after the washing of magnetic field situ, 60-200 DEG C of drying, and 350 DEG C of calcining 5h；In step (5), by magnetic lithium manganese point
Spar adds in 0.1-2 mol/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 heavy through sodium bicarbonate and sodium carbonate distribution
Behind shallow lake, obtain manganese carbonate precipitation and lithium carbonate precipitation.
Further, Magneto separate adopts and includes permanent magnetism, electromagnetism, superconducting magnet Magneto separate；Fill during Magneto separate acidproof not
Rust steel high-gradient medium, or realize opening gradient separations using the own magnetic gradient of magnet；Acid-resistant stainless steel high-gradient medium includes
Steel wool, steel rod, steel mesh and steel plate.
The present invention utilizes magnetic lithium ion sieve, in conjunction with Magneto separate and membrane separation technique, can prepare high purity lithium dope.Magnetic divides
Utilize ion sieve trapping, ion sieve cleaning in magnetic field, three process procedures of stripping liquid eluting outside magnetic field from process, it is possible to achieve magnetic
Property the process goal such as ion sieve and the Impurity removal such as salt high efficiency separation, stripping liquid lithium concentration accuracy controlling, magnesium, potassium.Ion sieve
Stripping liquid directly can produce high-purity, high concentration lithium chloride dope by NF membrane, and period concentrates ring without lithiums such as Exposure to Sunlight, reverse osmosiss
Section.
The present invention compares patent 201110321563.7, has following creative contribution, and first is that lithium process profit inhaled by ion sieve
Adjust salt ph with strong base substance；Solution puies forward lithium process and declines because of salt ph, and the adsorption capacity of ion sieve is significantly inhibited
Problem；Second it is proposed that the trapping of Magneto separate process ion sieve, ion sieve cleaning in magnetic field, the integrated work of stripping liquid eluting outside magnetic field
Skill, can precisely realize lithium concentration and control of purity in eluent；3rd, can direct preparation of high-purity lithium in conjunction with Nanofiltration Membrane Separation Technology
Dope, period need not any lithium concentration link.
The magnetic lithium ion sieve of the especially present invention:
Magnetic lithium ion sieve of the present invention adopts ferroso-ferric oxide magnetic core particle diameter and coating selection aspect through repetition test, finds
The thick coating of particle diameter easily comes off, and coating easily produces as the other coatings using non-silicon dioxide, ferroso-ferric oxide core
Life is exposed, and particularly during follow-up adsorption-desorption repeatedly, ferroso-ferric oxide magnetic core can produce dissolving, therefore, warp because exposed
Cross comprehensive analysis, final choice≤50 nanometer, coating selects silicon dioxide.
Magnetic lithium ion sieve of the present invention can directly prepare magnetic lithium manganese spinel, magnetic core profit in mesolow hydrothermal reaction kettle
Use inert material Silica-coated, and lithium manganese spinel grows in inert material surface crystallization, protected by wrapping up inert material
Shield ferroso-ferric oxide magnetic core, and then the molten damage of ferrum is greatly reduced；There is provided crystallization for lithium manganese spinel in hydrothermal reaction kettle simultaneously
Interface, accelerates crystallization rate and the perfect crystalline degree of lithium manganese spinel, and then magnetic lithium ion sieve is greatly reduced to use and regenerate
During manganese molten damage.The complete alternation that synthesis technique realizes lithium uses, and the preparation cost of lithium ion sieve is greatly reduced.
Meanwhile, the not lithium of reaction and manganese completely in Magneto separate reuse lithium manganese compound building-up process, realize acid lithium manganese and mix
Close liquid to separate with magnetic lithium ion sieve, and then realize the complete utilization of dissolution lithium and manganese during acid activation.Salt lake bittern carries lithium
During, magnetic lithium ion sieve can realize the cleaning that magnesium, potassium, sodium etc. attach element, magnetic lithium ion with the sharp separation of salt
Sieve is separated with acidic activated liquid, realizes lithium ion sieve reuse.
The new technology that magnetic lithium ion sieve of the present invention proposes passes through 4 Magneto separate processes, overcome manganese systems lithium ion sieve with
A separation difficult problem for water, recycles to no magnetic liquid phase simultaneously, has such as reclaimed incomplete in magnetic manganese systems lithium ion sieve building-up process
Participate in li and mn of reaction, and complete-reclaiming manganese systems lithium ion sieve uses the molten damage manganese of process.The chlorination of this technique output
Lithium concentration and purity are all higher, and easily realize large-scale production.
Magnetic lithium ion sieve lithium manganese spinel of the present invention grows in inert material surface crystallization, is lithium in hydrothermal reaction kettle
Galaxite provides crystalizing interface, accelerates crystallization rate and the perfect crystalline degree of lithium manganese spinel.Compare existing magnetic lithium manganese
The manufacturing process of spinelle, the lithium manganese spinel lattice growth of this process route synthesis is more sophisticated, and magnetic lithium is greatly reduced
The molten damage of manganese in ion sieve use and regenerative process.Avoid it oxidized and the manganese during lithium ion sieve uses, ferrum simultaneously
Dissolution.The lithium chloride solution that lithium manganese spinel activation process produces can achieve and recycles completely, and then lithium ion is greatly reduced
The manufacturing cost of sieve.
Brief description
Fig. 1 is the preparation technology flow chart of the embodiment of the present invention 1.
Fig. 2 is the embodiment of the present invention 1 salt magnetic separation link integrated technique exploded view.
Fig. 3 is the preparation technology flow chart of magnetic lithium ion sieve of the present invention.
Specific embodiment
Tie that the present invention is described further with specific embodiment below.
Embodiment 1:
Certain salt 0.3g/l containing lithium, 100g/l containing magnesium, 0.6g/l containing potassium, 1.3g/l containing sodium, salt ph=5.0-5.3, defeated in salt
Send and in pipeline, add 10g/l magnetic manganese bioxide ionic sieve, adjust salt ph >=5.0 using sodium hydroxide, utilize thereafter bore
1.25m slurry electromagnetic motor carries out Magneto separate, magnetic field intensity 1.3t, and high-gradient medium selects rhombus medium net.Above-mentioned Magneto separate sets
Standby achievable 300 tons of brine treatment abilities per hour.Magnetic separation link is integrated with ion sieve trapping, ion sieve cleaning, magnetic in magnetic field
Three process procedures of stripping liquid eluting outside the venue, as shown in accompanying drawing 1,2.
Specific as follows: after magnetic separation, no magnetic liquid phase component is to carry salt after lithium, can directly discharge；Have magnetic part be magnetic from
Son sieve is captured in rhombus medium net surface, is passed through thereafter tap water in magnetic field, the impurity such as magnesium that washing surface attaches, potassium, sodium；
After washing terminates, magnetic separator demagnetizes, and pumps into acidic effluent liquid in magnetic separator, and is rushed magnetic lithium ion sieve by mixing wastewater with air
It is eluted to 50m from high-gradient medium chamber3Acid regeneration bucket.Above-mentioned acidic effluent liquid is the hydrochloric acid of 0.5 mol/l, and it is directly as magnetic
Select machine flushing water and recycle, until lithium concentration reaches 6g/l.The mixed system that acid regeneration liquid is sieved with magnetic ion is again
Carry out solid-liquid separation through 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 using former salt and carries out lithium absorption again in delivery pipe.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.Through NF membrane, filtration fraction is and contains lithium above-mentioned acidity lithium dope
High-purity dope, after multiple circulation, control manganese lithium mol ratio is 2:1 to retention part, adds sodium bicarbonate, prepares manganese carbonate, lithium
Solution returns to NF membrane feedwater.
Embodiment 2: preparation magnetic lithium ion sieve, as shown in Figure 3.
1 ton of magnetic manganese bioxide ionic sieve of preparation, adds 0.5 g/l concentration carbamide as dispersion, stirs in 500rpm
Under the conditions of mixing, 1:1.5 adds 0.17-0.18 t ferrous chloride and 0.26-0.27 t copperas solution in molar ratio, leads to thereafter
Cross peristaltic pump and be slowly added to 10% ammonia 900-1000 l ammonia spirit, until solution ph=7.0, black precipitate as four oxidation
Three ferromagnetic cores, its mean diameter is 20 ± 3 nm.Above-mentioned mixed solution is pumped into φ 300 mm slurry electromagnetic separator, wherein fills out
Fill rustless steel rhombus net as high-gradient medium.Magnetic group is had to be divided into ferroso-ferric oxide magnetic core, using mixing wastewater with air pulse lavage, will
Ferroso-ferric oxide magnetic core pumps into bag silicon agitator, and no magnetic liquid phase component is unreacted completely ammonia, is directly back to agitator,
This reflux course can reduce by 20% ammonia and add.
The mixed solution of second alcohol and water is added, wherein ethanol: water volume is 1:1 in bag silicon agitator.Stir in 500 rpm
Under the conditions of add 400-450 l tetraethyl orthosilicate, by controlling the addition of ferroso-ferric oxide, make silicon: ferrum mol ratio is 1:3
To between 1:4, after stirring 5 hours, mixed liquor pumps into φ 300mm slurry electromagnetic separator again, has magnetic group to be divided into silicon dioxide
The ferroso-ferric oxide magnetic core of cladding, using mixing wastewater with air pulse lavage, pumps into lithium manganese spinel agitator, no magnetic liquid phase component is
The a small amount of not tetraethyl orthosilicate of reaction, ethanol and water mixed solution completely, are directly back to bag silicon agitator, this step can reuse
95% ethanol.
It is to add the manganese chloride solution 1600-1700 l that concentration is 2 mol/l, in 500rpm in lithium manganese compound agitator
Pump into coated with silica ferroso-ferric oxide under stirring condition, and add concentration to be 2.86 mol/l lithium hydroxide solution 5600-
5700 l, control the concentration of ferroso-ferric oxide, Lithium hydrate and manganese chloride to make ferrum: manganese mol ratio is 1:2, lithium: manganese mol ratio
For 5:1.After stirring 1 hour, still aging 12h, obtain final product magnetic lithium manganese compound.Above-mentioned mixed liquor pumps into permanent magnetism scraper plate magnetic separation
Machine, is had magnetic solid phase to be magnetic lithium manganese spinel, is directly collected by scraper plate, inserts 350 DEG C of calcinings 5 in kiln little after 60 DEG C of drying
When, obtain final product magnetic lithium manganese spinel.No magnetic liquid phase is to have neither part nor lot in the Lithium hydrate of reaction, and direct reuse to lithium manganese spinel stirs
Bucket, this cyclic process can reuse 80% Lithium hydrate.
Magnetic lithium manganese spinel puts in the hcl activation bucket of 0.5 mol/l, and 200 rpm stirring 5h, thereafter by above-mentioned mixing
Solution pumps into aforementioned permanent magnetism scraper plate magnetic separator, and no magnetic component is contained lithium, a small amount of manganese and trace iron, has magnetic component to be received by link plate
Collection, obtains final product 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
Carry out distribution precipitation after certain value and then prepare lithium carbonate, manganese carbonate and three kinds of products of ferric carbonate.
The magnetic lithium ion sieve of above-mentioned preparation, up to 20 mg/g, during magnetic saturation, quality magnetic moment reaches the saturated adsorption capacity of lithium
To 10 emu/g.The molten loss rate of this magnetic lithium ion sieve single adsorptions desorption process manganese is less than 3/3rds ‰ thousand, the molten loss rate of ferrum
Less than 1 ‰；Single Magneto separate is separated from water circulation, and magnetic material non-magnetic component expulsion rate is less than 3 ‰.Follow through 50 adsorption-desorptions
Do not find after ring that adsorption capacity occurs significant change, above-mentioned magnetic manganese bioxide ionic sieve gross mass after 50 adsorption-desorptions is damaged
Consumption rate is less than 5%.
The foregoing is only presently preferred embodiments of the present invention, all made within the spirit and principles in the present invention appoint
What modification, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that in brine transportation pipeline throw
Plus 0.5-20kg/t magnetic lithium ion sieve, and adjust ph to >=5.0, thereafter by magnetic separation system separation magnetic lithium ion sieve and halogen
Water, magnetic lithium ion sieve enters desorbing activation link, Magneto separate ion sieve and stripping liquid again, and magnetic lithium ion sieve feeds former halogen
Lithium is carried again, through multiple circulation until passing through NF membrane after lithium concentration >=3g/l, the filtration fraction of NF membrane is stripping liquid in water
The high purity lithium dope of purity >=99%, directly prepares lithium carbonate product；
The retention part of NF membrane is through nanofiltration link iterative cycles, until manganese lithium ratio, during more than 2:1, adds sodium bicarbonate and prepares carbon
Sour manganese product, after separating through pp cotton, lithium liquid is back to NF membrane feedwater.
2. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Ion sieve is inhaled lithium process and utilizes strong base substance to adjust salt ph to >=5.0, and strong base substance includes sodium hydroxide, potassium hydroxide and carbon
Sour sodium.
3. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Magneto separate separates for High-gradient Magnetic, and magnet includes permanent magnetism, electromagnetism or superconducting magnet, and high-gradient medium includes steel mesh, rod iron, steel-tooth
Or bristle.
4. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Salt comprises ion sieve trapping, ion sieve cleaning, three links of ion sieve eluting, cleaning process with the Magneto separate process of ion sieve
Include magnesium, potassium impurity using tap water or deionized water eluting, utilize acid activation liquid by ion sieve from high ladder under the conditions of no magnetic
It is eluted to acid activation link in degree medium.
5. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Desorbing activation link acid concentration is 0.1-1 mol/l, and desorption time is more than 0.5h, and the acid of use is inorganic or organic acid, including
Hydrochloric acid, sulphuric acid, nitric acid or carboxylic acid.
6. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Anti-acid NF membrane is entered, the filtration fraction of NF membrane directly adds sodium carbonate and lithium carbonate is obtained during stripping liquid lithium concentration >=3g/l
Product.
7. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Control lithium manganese mixing stripping liquid in the cycle-index of NF membrane, the retention part manganese lithium concentration ratio making NF membrane, more than 2:1, adds
Sodium bicarbonate and/or potassium bicarbonate, and utilize pp cotton filtration separation manganese carbonate, lithium liquid feeds NF membrane feedwater end again.
8. according to claim 1 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
Magnetic lithium ion sieve is, in particle diameter≤50 nano ferriferrous oxide magnetic core Surface coating silicon dioxide inert layer, 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 is more than 5 emu/g, and the absorbability of saturation lithium is more than 5 mg/g.
9. according to claim 8 a kind of from salt extract lithium and prepare high purity lithium dope method it is characterised in that
The preparation method of described magnetic lithium ion is as follows:
(1) particle diameter≤50nm ferriferrous oxide particles are prepared by adding dispersant, dispersant includes Polyethylene Glycol, polyethylene
Ketopyrrolidine or carbamide；
(2) pass through Magneto separate by the solution separating of nano ferriferrous oxide and step (1), no magnetic liquid phase reuse, to step (1), has
Magnetic component, after the washing of magnetic field situ, adds in ethanol/water mixed solution, adds tetraethyl orthosilicate uniform stirring thereafter,
The ferroso-ferric oxide solution of preparation coated with silica；Ferrosilicon ratio 1:1-1:5；
(3) pass through Magneto separate by coated with silica ferroso-ferric oxide and step (2) solution separating, no the reuse of magnetic liquid phase is to step
(2), there is magnetic component after the washing of magnetic field situ, add in manganese chloride solution, be slowly added to Lithium hydrate under agitation
Solution, and finally control mol ratio >=4:1, mol ratio=1:1 to the 1:30 of fe:mn of li:mn, lithium manganese compound is in titanium dioxide
Silicon face is formed, and obtains magnetic lithium manganese compound；
(4) pass through Magneto separate by the solution separating of magnetic lithium manganese compound and step (3), no magnetic liquid phase reuse, to step (3), has
Magnetic component, after the washing of magnetic field situ, is dried, and calcining obtains magnetic lithium manganese spinel；
(5) magnetic lithium manganese spinel is added in hydrochloric acid, nitric acid or sulfuric acid solution and stir, obtain magnetic lithium ion sieve；
(6) by Magneto separate, magnetic lithium ion sieve is separated with the acid solution of step (5), no magnetic liquid phase enters lithium manganese acid mixed solution
In collecting pit, there is magnetic component after the washing of magnetic field situ, enter the magnetic lithium ion sieve that 60-200 DEG C of drying is dried.
10. a kind of method extracted lithium from salt and prepare high purity lithium dope according to claim 9, its feature exists
In,
In step (2), uniform stirring stirs 5h for 70-300rpm；
In step (3), add in 1.0-5.0 mol/l manganese chloride solution, under 70-300rpm stirring condition, be slowly added to 0.5-
2.0 mol/l lithium hydroxide solutions；
In step (4), there is magnetic component after the washing of magnetic field situ, 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
Stirring 1-24h.
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