CN104310446B - A kind of technique and device being extracted battery grade lithium by salt - Google Patents
A kind of technique and device being extracted battery grade lithium by salt Download PDFInfo
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Abstract
The present invention relates to a kind of technique and device being extracted battery grade lithium by salt, this technique comprises the steps: to add in salt the lithium ion in adsorbent salt, adsorbent is retained again through purpose ceramic-film filter, ceramic membrane concentrated solution obtains adsorbent filter cake through filter press, adsorbent filter cake obtains stripping liquid after washing and desorbing, stripping liquid carries out demagging through nanofiltration membrane system, NF membrane permeate enters exchange resin tower and carries out degree of depth demagging, concentrate through reverse osmosis membrane again, enter DTRO film afterwards or electrodialysis plant carries out degree of depth concentration, concentrated solution is after evaporation, it is added thereto to BaCl2、Na2CO3And entrance purpose ceramic-film filter filters after being stirred after NaOH, ceramic membrane dope enters filter press, adds Na in clear liquid2CO3Li is prepared after solution2CO3, Li2CO3LITHIUM BATTERY Li is obtained after being centrifuged after ceramic membrane washs and drying2CO3Finished product.
Description
Technical field
The present invention relates to a kind of technique and device being extracted battery grade lithium by salt, particularly relate to use membrane technology to extract halogen
In water, the method and device of high-purity lithium, belongs to technical field of membrane separation.
Background technology
Lithium is one of national economy and the closely bound up important rare metal of people's lives, glass ceramics, petrochemical industry,
The traditional field such as metallurgy, weaving, synthetic rubber, lubriation material, medical treatment are widely applied.And lithium carbonate is lithium chemical industry
Basic compound, have multiple use, can be widely used for the field such as medicine, battery.
Lithium resource is abundanter in the world, is mainly distributed on south, North America, Asia, Australia and Africa.Open the most in the world
Adopt the most lithium minerals of application to be the salt lakes such as spodumene, petalite, lepidolite and amblygonite, containing lithium salt and well water be also
Important lithium resource, western countries utilize bittern water to produce lithium compound (such as lithium carbonate) and have accounted for the 30% of lithium production throughput
Left and right.China is lithium resource big country, and explored lithium resource reserves occupy second place of the world, and wherein salt lithium content accounts for gross reserves
79%, it is distributed mainly in the salt lake of Tibet, two places, Qinghai.In the brightness salt of Chaidamu Basin, Qinghai Province Asia, the reserves of lithium have accounted for entirely
About the 58% of state's total amount.
Salt puies forward the main method of lithium the sedimentation method, solvent extraction, ion exchange adsorption and calcining leaching method etc..
In prior art, patent CN102432044A have employed absorption method and concentrates the lithium chloride in salt, uses precipitation afterwards
Method prepares lithium carbonate product.Patent CN102275956A use extraction and back extraction fetch obtain NaCl and LiCl anti-stripping agent with
And NH4Cl and LiCl anti-stripping agent, use the sedimentation method to prepare nanoscale and micron-sized lithium carbonate product afterwards.Patent
CN102963914A uses evaporation and concentration, alkaline chemical precipitation foreign ion, filters and add precipitant and prepare lithium carbonate, and scrubbed
With obtain pure Lithium Carbonate after calcination.These methods exist in salt that lithium chloride cycles of concentration is the highest, precipitation is the longest
And the problem such as in lithium carbonate impurity content is higher.
Summary of the invention
The technical problem to be solved is: improve extract from salt in the technique of lithium time-consumingly long, lithium chloride is dense
The problem that demagnification number is the highest, yield is low, amount of reagent is big, impurity content is high in lithium carbonate product, it is proposed that a kind of by salt
Extract technique and the device of battery grade lithium.
Technical scheme:
According to an aspect of the present invention:
A kind of technique being extracted battery grade lithium by salt, comprises the steps:
1st step, with lithium adsorbent, salt is adsorbed, then lithium adsorbent is carried out desorbing, obtain stripping liquid；
2nd step, by stripping liquid demagging, obtain the stripping liquid of demagging；
3rd step, concentrates the stripping liquid of demagging, obtains containing lithium concentrated brine.
According to an embodiment of the invention:
Mg in described salt2+And Li+Weight ratio be preferably 1:1～400:1, more preferably 2:1～200:1, optimum
Elect 2:1～150:1 as.
Li+Mass percent concentration be preferably 0.1～15.0g/L, more preferably 0.3～10.0g/L, most preferably
0.5～8.0g/L.
According to an embodiment of the invention:
Lithium adsorbent refers in aluminium salt lithium adsorbent, hydroxide adsorbent, metaantimmonic acid type adsorbent, ion-sieve type adsorbent
The mixture of one or more.
According to an embodiment of the invention:
In 1st step, it is that lithium adsorbent is dispersed in salt, obtains mixed liquor, then mixed liquor is carried out solid-liquid separation, right
Lithium adsorbent after separation carries out desorbing.
The addition in salt preferably 0.05～5g/L of lithium adsorbent, more excellent 0.2g/L.
After lithium adsorbent adds salt, stirring 30～60min, brine temperature is 30～60 DEG C.
The step of solid-liquid separation includes using separation film to carry out the step concentrated；The described material separating film is preferably adopted
Use ceramic membrane；Described separation film preferably employs micro-filtration membrane.
The step of solid-liquid separation preferably uses separation film to concentrate, and obtains adsorbent concentrated solution, then uses plate-and-frame filtration
Adsorbent concentrated solution is dehydrated by device.
The average pore size scope separating film is 50～200nm；Filtration temperature is 30～80 DEG C, operation pressure 0.2～
0.5MPa, crossflow velocity 1～4m/s.
Separating film and carry out needing in concentration process to carry out regular backwash, recoil interval 30～60min, the recoil time is 10
～30s.
According to an embodiment of the invention:
1st step is lithium adsorbent is loaded in absorption cylinder (also referred to as filler cylinder), injects salt and adsorb, then note
Enter eluent and carry out desorbing, obtain stripping liquid.
After 1st step obtains stripping liquid, after being filtered by filter, then will transmit through in liquid feeding the 2nd step
Demagging step.
Eluant is water or phosphoric acid solution, and the pH of phosphoric acid solution is 1～2, desorption temperature 50～100 DEG C.
According to an embodiment of the invention:
In 2nd step, the operating procedure of demagging is that the mode using nanofiltration membrane or ion exchange resin absorption goes demagging
Ion.
NF membrane molecular cut off is 100～300, and nanofiltration operation pressure is 1.0～3.0MPa, and operation temperature is 20～45
℃。
When using NF membrane to carry out demagging, it is to be filtered by least two-stage NF membrane.The cycles of concentration of one-level nanofiltration
Preferably 3～6 times, the cycles of concentration of two grades of nanofiltrations is preferably 8～12 times.
According to an embodiment of the invention:
After using nanofiltration membrane to remove magnesium ion, then carry out demagging with cation exchange resin.
According to an embodiment of the invention:
Concentration step in 3rd step uses in reverse osmosis membrane concentration, the concentration of DTRO membrance concentration, electrodialytic membranes, evaporation and concentration
At least one, obtain containing lithium concentrated brine.
It is furthermore preferred that concentration step is first to concentrate with reverse osmosis membrane, then reverse osmosis membrane concentrated solution is used DTRO membrance concentration
Or at least one in evaporation and concentration concentrates again, obtain containing lithium concentrated brine.
The operating pressure of reverse osmosis concentrated compression process is 3.0～4.0MPa, and temperature is 30～40 DEG C.
According to an embodiment of the invention:
After 3rd step obtains containing lithium concentrated brine, it is added thereto to BaCl2、Na2CO3And NaOH solution is so that salt
In SO4 2-、Ca2+And Mg2+Form precipitation, and remove precipitation.
Addition sequence is to be sequentially added into BaCl2、Na2CO3And NaOH solution.
The BaCl added2Molar concentration rate containing the SO in lithium concentrated brine4 2-Molar concentration big 1%～5%, addition
Na2CO3Molar concentration rate containing the Ca in lithium concentrated brine2+Molar concentration big 1～10%, the molar concentration of the NaOH of addition
Ratio is containing the Mg in lithium concentrated brine2+2 times the biggest 1～5% of molar concentration.
According to an embodiment of the invention:
To eliminate precipitation containing in lithium concentrated brine, add Na2CO3Solution makes Li2CO3Precipitation, by precipitate and separate, baking
After Gan, obtain lithium carbonate.
According to an embodiment of the invention:
The step of precipitation separation is to use ceramic membrane separation, and ceramic membrane pore diameter range is for 20～200nm, preferably membrane aperture
For 50nm, in running, pressure is 0.1～0.5MPa, and temperature is 10～50 DEG C.
According to another aspect of the present invention:
A kind of device being extracted battery grade lithium by salt, includes adsorption-desorption device, demagging device, enrichment facility, inhales
The stripping liquid outlet of attached desorption apparatus is connected with the entrance of demagging device, and the outlet of demagging device connects with the entrance of enrichment facility
Connecing, the concentrated solution outlet of enrichment facility and the first stillpot connect, and are additionally provided with the first sodium carbonate tank on the first stillpot, the
The outlet of one stillpot is also attached to the second solid-liquid separator.
Described adsorption-desorption device is adsorbent packed column.
Being also associated with filter in the outlet of adsorbent packed column, the outlet of filter is connected with demagging device.
Described adsorption-desorption device include be sequentially connected with adsorption tank, the first solid-liquid separator, solve bothrium, solve bothrium
Outlet be connected with demagging device.
The first described solid-liquid separator includes ceramic membrane device and plate filter, ceramic membrane device retain side
Outlet be connected with the entrance of plate filter, the entrance of ceramic membrane device is connected to adsorption tank, plate filter retain side and
Solution bothrium connects.
Described demagging device refers to nano filter membrance device or Di.
Described demagging device refers to NF membrane and the ion exchange resin column being sequentially connected with, and the entrance of NF membrane is connected to
Adsorption-desorption device, the per-meate side of NF membrane is connected to ion exchange resin column, and the outlet of ion exchange resin column is connected to dense
Compression apparatus.
Described enrichment facility is in reverse osmosis membrane apparatus, DTRO film device, electrodialytic membranes device, evaporation concentration device
At least one.
Described enrichment facility refers to reverse osmosis membrane and the DTRO film being sequentially connected with, and the entrance of reverse osmosis membrane is connected to demagging
Device, the side that retains of reverse osmosis membrane is connected to the entrance of DTRO film, and the outlet of DTRO film is connected to the first stillpot.
The outlet of described enrichment facility passes sequentially through the second stillpot and the 3rd solid-liquid separator reconnects and sinks in first
Shallow lake groove；The outlet of enrichment facility is connected to the entrance of the second stillpot, and the outlet of the second stillpot is connected to the 3rd solid-liquid separation
The entrance of device, the outlet retaining side of the 3rd solid-liquid separator is connected to the first stillpot；Second stillpot is respectively provided with
There are barium chloride tank, the second sodium carbonate tank, sodium hydroxide tank.
The second described solid-liquid separator is ceramic membrane filter device.
The 3rd described solid-liquid separator is ceramic membrane filter device.
In described ceramic membrane filter device, ceramic membrane pore diameter range is for 20～200nm, and preferably membrane aperture is 50nm.
In described ceramic membrane device, ceramic membrane pore diameter range is for 20～200nm.
Beneficial effect
The present invention uses adsorbent to adsorb the lithium ion in salt and desorbing, and uses purpose ceramic-film filter to suction
Attached dose retains, and uses reverse osmosis membrane and DTRO film that salt is carried out degree of depth concentration, can be effectively improved the concentration of LiCl
Multiple, is not limited by weather and place of evaporating brine, and significantly improves product yield and product quality that the lithium carbonate sedimentation method obtain.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of device being extracted battery grade lithium by salt that the present invention provides.
Fig. 2 is the structural representation that the another kind that the present invention provides is extracted the device of battery grade lithium by salt.
Wherein, 1, adsorption-desorption device；2, demagging device；3, enrichment facility；4, the first stillpot；5, the first sodium carbonate
Tank；6, the second solid-liquid separator；7, adsorption tank；8, ceramic membrane device；9, plate filter；10, bothrium is solved；11, NF membrane；
12, ion exchange resin column；13, reverse osmosis membrane；14, DTRO film；15, the second stillpot；16, barium chloride tank；17, the second carbonic acid
Sodium tank；18, sodium hydroxide tank；19, the 3rd solid-liquid separator；20, adsorbent packed column；21, filter；22, the first solid-liquid divides
From device；23, adsorbent tank.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail.But those skilled in the art will manage
Solving, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete skill in embodiment
Art or condition person, according to the technology described by the document in this area or condition (such as with reference to Xu Nan equality write " inoranic membrane divides
From technology and application ", Chemical Industry Press, 2003) or carry out according to product description.Agents useful for same or instrument are not noted
Bright production firm person, be can by city available from conventional products.
Approximation language used herein can be used for modifying the statement of any quantity in entire disclosure and claims, and it can
Permit being changed under conditions of its relevant basic function changes being not resulted in.Therefore, such as term " about " repair
The value of decorations is not limited to specified exact value.In at least some cases, approximation language can be with the instrument for measuring this value
Precision corresponding.Unless indicated otherwise in context or statement, otherwise range limit can be combined and/or exchange, and
And this scope is confirmed as and includes all subranges contained herein.Except operation embodiment in or elsewhere
In indicate outside, the numeral of the amount of all expression compositions used in specification and claims, reaction condition etc. or
Express the modification that shall be construed as in all cases by word " about ".
The value expressed using range format should be interpreted as in a flexible way not only including clearly listing as scope
The numerical value of limit value, but also include containing all single numerical value within the range or subinterval, just as each numerical value and Zi Qu
Between be expressly recited out.Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include clearly to list
The concentration of about 0.1% to about 5%, also includes the single concentration (e.g., 1%, 2%, 3% and 4%) in the range of indication and subinterval (example
As, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
The ordinal number used in the claims and specification such as " first ", " second ", " the 3rd " etc., be used for the power of modifying
Profit requirement rather than due to itself containing any preferentially, the order of formerly or one claim is before another claim
Or perform the time sequencing of method step.But, use with difference such as with the right of specific names as just label
The element required and another one, with the element (rather than belonging to for succession) of same names, distinguish claim
Element.
The Main Resources of lithium includes lithium Ore and the salt Han lithium.In the present invention, term " salt " may refer to natural bittern
(such as: salt lake bittern, subsurface brine, geothermal brine or salt manufacturing salt) or the salt of human configuration.Especially, in many feelings
Under condition, compared with other type of salt, salt lake bittern has high lithium concentration, the raw material being suitable as in the present invention.At this
In invention, can be effective from the magnesium containing high concentration and sulphuric acid (they are to be prepared interference component during lithium carbonate by commonsense method)
Lithium carbonate is prepared on ground, and Mg/Li ratio and SO4/ Li ratio more than 10, the salt containing lithium that is difficult to reclaim from which lithium permissible
As the raw material in the present invention.For salt type resource, salt lake bittern is most important source.In orogenic belt (such as Andean
Mountain range) in, the water soluble ingredient (they are from the marine rock dissolution of surrounding) comprising sodium chloride flows into by soon with flowing water
In the lake, mountain top that speed is swelled and formed, and concentrate through long-term, thus separate out salt and pile up formation salt lake.At saturated bittern
Internal salt lake is piled up, and this saturated bittern is referred to as salt lake bittern.Salt lake bittern comprises the sodium chloride being derived from sea water as main one-tenth
Point, and also comprise cation constituent (such as, potassium, lithium, magnesium and calcium) and anion component (such as chlorine, bromine, sulphuric acid and boric acid).
In addition to the impact of seawater component, its composition changes according to the mineral species around salt lake and colcanism.At salt lake halogen
In water, the salt lake bittern that lithium concentration is high becomes the development goal of lithium resource.The method reclaiming lithium in salt mainly included by day
Shine the concentration step of evaporation, by adding the foreign matter removal step of chemicals and by adding the carbonation step of sodium carbonate.
Mainly comprise muriatic salt, for lithium chloride, there is high-dissolvability, and lithium concentration can increase to the highly concentrated of about 60g/L
Degree.But, in the case of salt comprises a large amount of sulfate ion, lithium sulfate can be separated out during evaporation and concentration
(Li2SO4·H2O).Therefore, lithium concentration is only capable of increasing to about 6g/L, and lithium is lost with the form of lithium sulfate.It addition, work as
When salt lake bittern comprises above-mentioned various ion component, magnesium is with the form precipitation of magnesium carbonate and possible by carbonation step
Be blended in as in the lithium carbonate of final products, so that the purity of final products reduces, it is therefore desirable to carbonation step it
Before go demagging.Specifically, the content of magnesium of the salt in Uyuni salt lake (Bolivia), Qinghai Salt Lake (Chinese) etc. is high, and
And the concentration ratio of Mg/Li is 19 to 62.Therefore, not only need a large amount of chemicals (such as calcium hydroxide and sodium carbonate) to go demagging,
But also substantial amounts of magnesium hydroxide and magnesium carbonate mud can be formed, and the salt concentrated is wrapped in mud, and this would interfere with
The recovery of the concentrated brine containing lithium.It addition, the sulfate ion concentration of salt lake bittern is the highest, such as, at Uyuni salt
In lake (Bolivia), SO4The concentration ratio of/Li is 24, in Qinghai Salt Lake (Chinese), and SO4The concentration of/Li than for 138(Ah
In Taka horse salt lake (Chilean), SO4The concentration ratio of/Li is 11), in these salt lakes, present case is, walks in evaporation and concentration
In rapid, lithium concentration is only capable of being increased to 6g/L, it is thus impossible to obtain the concentrated brine being suitable for carbonation step, wherein said carbonic acid
Change step is commonly used to concentration and is about the area with high mercury of more than 60g/L.The most such as magnesium ion, sulfate ion, barium from
The level of the foreign ions such as son is reduced as much as possible, such as, be reduced to ppm level, as less than 20 ppm, is preferably shorter than
0.0005wt%, or lower such as 0.00001wt%, can be adapted for recovery process to reclaim the purest lithium salts containing lithium salt,
Such as lithium chloride and/or lithium carbonate, or lithium metal.
In the present invention in manageable salt, Mg2+And Li+Weight ratio be preferably 1:1～400:1, more preferably 2:1
～200:1, most preferably 2:1～150:1.Li+Mass percent concentration be preferably 0.1～15.0g/L, more preferably 0.3
～10.0g/L, most preferably 0.5～8.0g/L.
Lithium in salt is adsorbed by the present invention initially with lithium adsorbent, the most again by lithium by the way of desorbing
Eluting and obtain stripping liquid.Heretofore described lithium adsorbent has selective absorption to lithium ion known to can using
Solid absorbent, the most this kind of adsorbent is all in granular form, has bigger specific surface area, and its material has generally comprised organic
Adsorbent and inorganic adsorbent.For the adsorbent of organic system, generally refer to macroion exchanger resin, substantially strong acid
Property adsorbent resin, such as IR-120B type cation exchange resin.For inorganic adsorbent, existing aluminium salt can be used to adsorb
Agent is (if formula is LiX 2Al (OH)3·nH2O, wherein X represents anion, it is common that Cl, n represent the number of water of crystallization), nothing
Sizing hydroxide adsorbent (mainly aluminum oxide adsorbent), layered adsorbent (generally arsenate or phosphoric acid salt
Lithium adsorbent, it is also possible to be metatitanic acid salt lithium adsorbent), compound metaantimmonic acid type adsorbent and ion-sieve type adsorbent etc..For from
Sub-sieve-type oxide adsorbent, can enumerate, and includes monoclinic crystal stibate system (such as Li1-xHxSbO3, 0 < x < 1), titanate
System is (such as Li2TiO3), (such as spinel-type Mn oxide, it is by such as MnO for Mn oxide system etc.2、MnCO3Or the manganese such as MnOOH
Compound and such as LiOH, Li2CO3Lithium compound or magnesium compound Mg (OH)2After reaction generates presoma, then through pickling
Prepare), it is also possible to it is to prepare doping type Mn oxide lithium ion doped with other metallic element, especially transition metal
Sieve, such as LiMg0.5Mn1.5O4、LiZn0.5Mn1.5O4、LiTi0.5Mn1.5O4、LiFe0.5Mn1.5O4、Li1.33-x/3CoxMn1.67-2x/ 3O4、LiFeMnO4、LiAlMnO4、LiCu0.5Mn1.5O4Deng.Can also be compound-type adsorbent, such as, hand at weakly-basic anion
Change and the space of resin is attached with substantial amounts of LiX 2Al (OH)3·nH2The compound-type adsorbent of O, wherein X is halogen.At this
Some bright embodiments have employed aluminium containing salt type adsorbent, other embodiment use iron phosphate ion sieve,
It is FeSO4、MexFeyPO4In the mixture of one or more.Me is the one in Mg, Al, Ti, Ni, Co, Mn, Mo, Nb
Or several mixing.0 < x < 1,0 < y < 1.Its preparation method can refer to patent documentation CN102049237.
For above-mentioned adsorption operations, can use and adsorbent is filled in adsorption column, make salt flow through absorption
Adsorbent bed in post, thus complete lithium ion absorption on the sorbent, the most again by adding eluent so that lithium
Ion is eluted, and after obtaining stripping liquid, after further preferably being filtered by filter, then will transmit through liquid and is sent to follow-up
Demagging process in step, filter can use coarse filter, and effect is to remove absorbent particles therein and silt, such as
Use the filter elements such as the sand filtration of routine, filter cloth.
Owing to when carrying out Adsorption and desorption operation, still suffering from some magnesium ions and other diatomic base metal ion deposited
It is in stripping liquid, when the stripping liquid afforded is carried out demagging ion, the magnesium in stripping liquid/lithium ratio can be reduced, here
Remove magnesium ion operation can use the methods such as the sedimentation method, nanofiltration or ion exchange resin demagging, but in the present invention
A preferred implementation in, use nanofiltration or the method for ion exchange resin demagging.
During when employing, in the adsorption column be filled with adsorbent, infeed eluent carries out eluting to lithium adsorbent, with
The carrying out of elution process, the Mg in stripping liquid2+Content can decline, and finds through overtesting, reduces the Mg in stripping liquid2+
Content, advantageously reduces the technical load of nanofiltration, improves nanofiltration cycles of concentration, the Mg of reduction nanofiltration permeate2+Content, but from
For Ling Yifangmian, find Mg2+In the presence of ion, NF membrane has Li in negative interception effect, i.e. nanofiltration permeate to lithium ion+
The phenomenon that concentration increases, therefore Mg2+Content can not be too low, otherwise in nanofiltration process, lithium ion during nanofiltration
Negative retain phenomenon and weaken, it may appear that the situation that a part of lithium ion is trapped occurs, and has influence on product yield.When in stripping liquid
Mg2+Desorbing is stopped when content is 2～3g/L.Under this optimum condition, Li in NF membrane permeate+Concentration compares material liquid can
Improve 10～20%.But, this mode of operation has yet suffered from operating time length, inefficient problem.
Lithium adsorbent is carried out to the process of adsorption operations, in an improvement embodiment of the present invention, be by inciting somebody to action
Lithium adsorbent is mixed in salt, makes it be scattered in salt after stirring, and this mode of operation can have higher work efficiency,
Reaching to adsorb the saturated time is shorter than the mode using adsorbent to fill.The operation being mixed in salt by adsorbent, can adopt
With being placed on agitator tank, then adding adsorbent continuous stirring in agitator tank, lithium ion is adsorbed onto on adsorbent, is inhaled
Attached dose and salt mixed liquor；Stirring 30～60min, brine temperature is 30～60 DEG C.The addition in salt of lithium adsorbent
Preferably 0.05～5g/L, more excellent 0.2g/L.
After above-mentioned adsorption process completes, then the mixed liquor of lithium adsorbent and salt is carried out solid-liquid separation process, with
Make adsorbent be separated, so preferably it can be carried out desorption operations, solid-liquid separation described here, limit the most especially
Fixed.The method processed as concrete solid-liquid separation, can enumerate centrifugation mode, expression separation mode, filter type, floating
Separate mode, settlement separate mode.Wherein in a kind of preferred implementation, it is to need to send into separate in film by mixed liquor to carry out
Concentrate, other ions such as Mg in salt lake2+、Ca2+Discharge Deng as permeate.Separation film described here preferably employs micro-
Filter membrane, after obtaining concentrated solution, then makes concentrated solution be dehydrated further, such as by the method for conventional dehydration: evaporation, from
The hearts etc., more excellent is that the mode using plate-and-frame filtration is dehydrated, and obtains adsorbent filter cake.Micro-filtration membrane for this step is average
Aperture is the film of 0.01 μm～5mm.As the material of these micro-filtration membrane, send out as long as being capable of that adsorbent is concentrated such
Improving eyesight, be not particularly limited, can enumerate: cellulose, cellulose esters, polysulfones, polyether sulfone, polrvinyl chloride, chloropropene,
The organic materials such as polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, politef, or rustless steel
Deng the inorganic material such as metal or pottery.The material of micro-filtration membrane can consider that the character of mixed liquor or operating cost are come suitably
Select, from inorganic material such as handling easiness consideration, preferably ceramics.Ceramic membrane filter temperature is 30～80 DEG C, operates pressure 0.2
～0.5MPa, crossflow velocity 1～4m/s.In another embodiment, by the average pore size of micro-filtration membrane being controlled 50～
Time between 200nm, the yield of the lithium finally given can be improved further.
Improving in embodiment at one, preferably ceramic membrane filter is carried out recoil process, recoiling device is adopted automatically
Recoiling ceramic membrane filter equipment with ceramic membrane infiltration clear liquid, the adsorbent filter cake recoil that will be attached to membrane channels surface is de-
Fall, effectively alleviate fouling membrane, improve membrane flux, contribute to system and run steadily in the long term.Recoil interval is too short, extends filtration
Time, add cost；Recoil interval is long, and the filter cake on film surface is blocked up, and ceramic membrane can be in a long time under small throughput
Run, also extend filtration time.The recoil time is too short, it is impossible to being recoiled completely by the adsorbent on film surface comes off, filtration flux
Can not there is efficient recovery；Recoil overlong time, recoil needs more amount of seepage, also needs to continue ceramic membrane and processes, increases and filter
Negative volume, so selecting recoil interval 30～60min, the recoil time is 10～30s.
After separation membrance concentration liquid being dehydrated further and obtain adsorbent filter cake, in order to improve further
Product purity, it is also desirable to wash it, in order to remove the foreign ion carried secretly in filter cake, solves with stripping liquid the most again
Inhale operation.The preferred water of detergent or the aqueous solution of LiCl, wherein electrical conductivity of water is preferably 2～10 μ s/cm, the aqueous solution of LiCl
The concentration of LiCl be preferably 0.02～5g/L；Lithium ion stripping liquid is water (preferably deionized water) or phosphoric acid solution, phosphoric acid
The pH of solution is preferably controlled in 1～2, desorption temperature preferably 50～100 DEG C.
After obtaining stripping liquid, wherein there are Li ion, also can be with a certain amount of such as Mg2+、Ca2+Deng impurity
Ion, it follows that need to remove further Mg2+、Ca2+Deng foreign ion.As stated above, can use nanofiltration or
The method of ion exchange resin is removed foreign ion, and the lithium adsorbent in previous step plays the effect of preliminary de-magging, this step
Suddenly Mg/Li ratio can be reduced, it is often more important that separate to subsequent nano-filtration and lighten the load, make the transmitance of magnesium in nanofiltration technique also
Reducing, more importantly this step can reduce the intensity of the magnesium ion in filtration system, makes the cycles of concentration in nanofiltration technique
Improving so that in nanofiltration process, cycles of concentration improves, improve the extract yield of lithium, equipment automatization easily realizes.
NF membrane is defined as " stoping the pressure drive membrane of the macromole of the particle less than 2nm and dissolving " herein
Film.The effective NF membrane being applicable to the present invention is preferably such film: have electric charge on this film surface, separates thereby through pore
(particle size separation) and the combination of the electrostatic separation of electric charge that has benefited from this film surface and show the separation efficiency of raising.Cause
This, it is necessary to use such NF membrane, this NF membrane can using as reclaim target alkali metal ion from there is different electricity
Macromolecule class material is removed by electric charge while other ions of lotus characteristic separate, by particle size separation.As this
The material of NF membrane used in invention, it is possible to use cellulose acetate based polymer, polyamide, SPSF, polyacrylonitrile,
The macromolecular materials such as polyester, polyimides and polyvinyl.The described film being not limited to only be made up of a kind of material, Ke Yishi
Comprise the film of multiple described material.About membrane structure, described film can be anisotropic membrane, and it has cause at least one side of film
Close layer, and there is the micropore become larger to film inside or another side aperture from compacted zone；Or composite membrane, it is non-
There is on the compacted zone of symmetric membrane the thinnest functional layer formed by other material.
Advantageously, described NF membrane can be one-level nanofiltration or two-stage nanofiltration, preferably two-stage nanofiltration, uses two-stage to receive
Filter magnesium and can improve the clearance of magnesium further, other divalent ion can also be removed simultaneously further, make product
Purity higher.This can improve the rejection of divalent salts mainly due to multistage nanofiltration, but the filtration progression of nanofiltration is the most not
Can too much otherwise can cause after multistage filtering, in system, some lithium ion is also trapped, and has influence on yield.Receive
Membrane retention molecular weight is 100～300, and nanofiltration operation pressure is 1.0～3.0MPa, it is preferable that nanofiltration operation pressure can be
2.5MPa, operation temperature is 20～45 DEG C, and further, operation temperature can be 25～40 DEG C.Temperature is too low, can cause nanofiltration
The flux of film is low, directly affects treating capacity and the treatment effeciency of whole technique, and temperature is too high, can make organic nanofiltration membrane element
Become certain burden, long hot operation, NF membrane reduced lifetime can be caused, the most non-renewable.Hypotony, equally
The flux that can cause NF membrane is low, furthermore also results in NF membrane element to Mg2+Rejection reduce, hypertonia, can directly
Causing operation energy consumption to increase, Financial cost strengthens, and next also results in system temperature in running and raises too fast, affects membrane element
The life-span of part.The cycles of concentration of one-level nanofiltration is preferably 3～6 times, if cycles of concentration is too high, flux can be caused less, system
Energy consumption is excessive, if cycles of concentration hour, then subsequent technique burden can not be made higher, two grades of nanofiltrations dense penetrating fluid concentration
Demagnification number is preferably 8～12 times.In a preferred embodiment, have employed two-stage nanofiltration, the operation temperature 30 of one-level nanofiltration
DEG C, pressure 3.0 MPa, the operation temperature of two grades of nanofiltrations is 40 DEG C, and pressure is 3.0 MPa；Reverse osmosis operating pressure 3.5 MPa,
Temperature is 35 DEG C.In a preferred embodiment, NF membrane is for rejection >=98% of magnesium sulfate.
Lithium therein i.e. can be entered by ion exchange resin permeate or NF membrane permeate by carbonate precipitation method
Row precipitation purification, but it is preferably it is carried out concentration, after the concentration of lithium ion is further improved, Ke Yiti
Its yield high, the consumption of reduction medicament.According to an embodiment of the invention, obtain ion exchange resin permeate it
After, need to will transmit through liquid and concentrate, to improve its concentration.The mode concentrated can use reverse osmosis membrane to concentrate, evaporation and concentration
Deng.More excellent using first uses reverse osmosis membrane to concentrate ion exchange resin permeate, the most again by DTRO film (dish
Tubular type reverse osmosis membrane) or electrodialytic membranes carry out concentration concentration, make the concentration of LiCl can promote 20～30 times, then will concentrate
The mode of liquid evaporation concentrates further.Vaporizer can be multi-effect evaporator.
As the material of reverse osmosis membrane, generally use cellulose acetate base polymer, polyamide, polyester, polyimides, second
The macromolecular materials such as alkenyl polymer.It addition, construct as it, at least side at film is had to have compacted zone, from this compacted zone
Internal to film or opposite side surface has the anisotropic membrane of the minute aperture in the aperture slowly becoming big and at this anisotropic membrane
Compacted zone on there is the composite membrane etc. of the thinnest active layer formed by other materials.Wherein, as the shape of reverse osmosis membrane
Formula, has macaroni yarn, flat film etc. generally, it is preferred to the thickness of macaroni yarn peace film is 10 μm～1mm, the external diameter of macaroni yarn is 50 μm
～4mm.It addition, as flat film, preferably anisotropic membrane, as composite membrane preferably by substrate support such as fabric, fabric, non-woven fabrics
But film., the method for the present invention can not to be used with relying on the material of reverse osmosis membrane, membrane structure or form, for
Any one situation is the most effective.The concentrated solution of reverse osmosis membrane apparatus typically has pressure energy, in order to reduce operating cost, preferably
Reclaim this energy.As the method recovered energy, can return with the energy recycle device on the high-pressure pump being installed to arbitrary portion
Receive, preferably use the special Scroll-type energy recovery pump before and after being arranged on high-pressure pump or between assembly to reclaim.
The operating pressure of reverse osmosis concentrated compression process is 3.0～4.0MPa, and temperature is 30～40 DEG C.Temperature is too low, can cause
The flux of reverse osmosis membrane is low, directly affects treating capacity and the treatment effeciency of whole technique, and temperature is too high, to organic nanofiltration membrane unit
Part can cause certain burden, long hot operation, can cause NF membrane reduced lifetime, the most non-renewable.Pressure mistake
Low, the flux also resulting in NF membrane is low, furthermore also results in NF membrane element to Mg2+Rejection reduce, hypertonia,
Can directly result in operation energy consumption to increase, Financial cost strengthens, and compared to traditional magnesium ion exchanger resin demagging, then uses reverse osmosis
The technique carrying out concentrating, in the method for the present invention, can improve the cycles of concentration of reverse osmosis to 5～8 times, and traditional method
The cycles of concentration of reverse osmosis only has 2～3 times, even lower.
In an embodiment of the invention, when the mode of above-mentioned concentration can use reverse osmosis membrane to concentrate, remove
The operation of magnesium step be use NF membrane concentrate, if this is because use ion exchange resin carry out demagging operation time,
Introducing sodium ion in system, this makes the content of the sodium ion in system be greatly improved, and result in the mistake of reverse osmosis process
In journey, cycles of concentration is the highest, shows that flux when reverse osmosis runs is too low, it is impossible to needed for reaching engineering, and also result in right
Time-consuming, problem that energy consumption is big when the concentrated solution of reverse osmosis concentrates further.And when have employed absorption and nanofiltration separation technique, just
Removing magnesium ion efficiently, do not introduce sodium ion, can make the cycles of concentration that reverse osmosis process holding is higher, this is just to follow-up
Evaporating brine, concentrate or evaporate advantageously, when needs carry out precipitation extraction to lithium ion, spent medicament is the most little.Logical
In the case of Chang, when using nanofiltration to remove magnesium ion, reverse osmosis can be made for using ion exchange resin demagging
The cycles of concentration of permeable membrane is improved to more than 6 times by 3 times.
Term " cycles of concentration " refer in the present invention the volume of feed liquid to be filtered terminate with thickening filtration after dense
The ratio of the system of contracting liquid.
In the embodiment of one improvement of the present invention, it is also possible to the NF membrane permeate during demagging is sent into ion
Exchanger resin adsorption tower carries out degree of depth removing calcium and magnesium ion, it is preferred to use weak-type cation exchange resin, cation exchange resin
The selective cation exchange resin that has alkaline earth metal cation of dawn known to those skilled in the art may be used to
The present invention.Ground can be enumerated, such as: the commercial goods Lewatit MonoPlus TP208 of Germany Lanxess Europe GmbH
Deng.The flowing velocity of stripping liquid is preferably 3～10BV/h.Salt after degree of depth demagging calcium is re-fed in follow-up concentration step.
According to an embodiment of the invention, the salt after concentration then enters after vaporizer is evaporated, and adds wherein
Enter BaCl2、Na2CO3And NaOH solution so that the SO in salt4 2-、Ca2+And Mg2+Precipitate Deng being formed, the BaSO of generation4、
CaCO3、Mg(OH)2, and carry out solid-liquid separation by purpose ceramic-film filter, remove foreign ion therein.As improvement, add
BaCl2Molar concentration rate containing the SO in lithium concentrated brine4 2-Molar concentration big 1%～5%, the Na of addition2CO3Molar concentration
Ratio is containing the Ca in lithium concentrated brine2+Molar concentration big 1～10%, the molar concentration rate of the NaOH of addition is containing in lithium concentrated brine
Mg2+2 times the biggest 1～5% of molar concentration.As the improvement of said method, add BaCl2、Na2CO3And NaOH precipitation
Being both needed to stirring during agent, mixing time is 20～40min, the preferred 30min of mixing time.
Na is added in the concentrated solution eliminate precipitation2CO3Solution carries out precipitation, can form Li2CO3Precipitation,
Precipitation uses purpose ceramic-film filter to carry out powder body washing, removes ion therein, then obtains Li with after drying by centrifugation2CO3Become
Product.Na2CO3Solution through film filter, accurate filter etc. process after, Na2CO3Purity more than 99.5%.Li2CO3Wash
Washing employing " on a small quantity, repeatedly " mode of washing, cycles of concentration is 5～8 times, and amount of water is 3～5 times of concentrated solution volume, to pottery
Membrane permeation liquid electrical conductivity is less than 100 μ s/cm.
By ceramic membrane to precipitation (BaSO described above4、CaCO3、Mg(OH)2、Li2CO3) carry out filtration and go to a good appetite suddenly appearing in a serious disease, aperture
If scope is too small, then filtration flux can be caused low, it is impossible to needed for meeting engineering, if aperture is excessive, then can cause a part
Precipitation cannot be retained, and enters to per-meate side, has influence on the quality of product.Pressure is too small, and filtration flux can be caused little, pressure
Power is excessive, some less granule particles can be caused to be forced through film layer, enter to per-meate side.Temperature is too low, can cause filtering and lead to
Measure low, and when temperature is too high, influence whether the dissolubility of granule, make part precipitation granule again dissolve, enter to per-meate side.
It is furthermore preferred that ceramic membrane pore diameter range is for 20～200nm, preferably membrane aperture is 50nm, in running pressure be 0.1～
0.5MPa, temperature is 10～50 DEG C.
The ion concentration of the salt lake bittern used in the examples below is as shown in table 1:
Table 1
Based on above-mentioned method, the extraction segregation apparatus that can use as depicted in figs. 1 and 2, in FIG, this device master
If being sequentially connected with by adsorption-desorption device 1, demagging device 2, enrichment facility the 3, first stillpot the 4, second solid-liquid separator 6
Constitute.The effect of adsorption-desorption device 1 is to adsorb the lithium in salt and desorbing, obtains stripping liquid.
Adsorption-desorption device 1 can be individually only with structure as shown in Figure 2, it is simply that by adsorbent packed column 20
Salt carries out adsorption-desorption, and in adsorbent packed column 20, filling is lithium adsorbent, first salt feeds adsorbent and fills
In post 20, carry out the operation adsorbed, discharge salt, feed stripping liquid the most again, stripping liquid is fed in demagging device 2, one
In individual embodiment, may reconnect a filter 21 in the exit of adsorbent packed column 20, its effect is for removing
Fall some solid impurities in stripping liquid.
In an other embodiment, as shown in fig. 1, it includes an adsorption tank 7 to adsorption-desorption device 1,
The effect of adsorption tank 7 is to deposit salt, then adds lithium adsorbent wherein, therefore, is also associated with one above adsorption tank 7
Adsorbent tank 23, for adding lithium adsorbent in adsorption tank 7.The outlet of adsorption tank 7 is connected to the first solid-liquid separator 22, by
The mixed liquor of salt and lithium adsorbent it is mainly in adsorption tank 7, after it being sent in the first solid-liquid separator 22, can be by
Isolating through adsorbing saturated lithium adsorbent, the first solid-liquid separator 22 can use the equipment for separating liquid from solid of routine, at one
In embodiment, preferably use ceramic membrane device 8 and plate filter 9, the most so, ceramic membrane device 8
Entrance is connected to the outlet of adsorption tank 7, and the concentration side of ceramic membrane device 8 is connected with the entrance of plate filter 9, to lithium adsorbent
After carrying out concentration operation with the mixed liquor of salt, then concentrated solution is fed through plate filter 9 carries out filter pressing, lithium can be obtained
Adsorbent filter cake, then the outlet retaining side of plate filter 9 reconnects in solving bothrium 10, can be discharged by filter cake, so
After bothrium 10 adds stripping liquid solving again, lithium adsorbent can be carried out desorption operations, after having obtained stripping liquid, then pass through
Solve the outlet of the stripping liquid on bothrium 10 to be connected on the entrance of demagging device 2.
Demagging device 2 can use ion interchange unit or nanofiltration device, in one embodiment, demagging device
2 include NF membrane 11 and the ion exchange resin column 12 being sequentially connected with, and the per-meate side of NF membrane 11 is connected to ion exchange resin
The entrance of post 12, the outlet of ion exchange resin column 12 reconnects in enrichment facility 3.
Enrichment facility 3 can use in reverse osmosis membrane apparatus, DTRO film device, electrodialytic membranes device, evaporation concentration device
Any one.In one embodiment, the reverse osmosis membrane 13 and DTRO film being sequentially connected with as shown in Figure 1 can be used
14, the outlet retaining side of reverse osmosis membrane 13 is connected to DTRO film 14, and reverse osmosis membrane 13 concentrates it to the salt after demagging
After, DTRO film 14 it is concentrated further.
The outlet of DTRO film 14 can be directly connected to the first stillpot 4, and the first stillpot 4 is in concentrated solution
Lithium ion precipitates, it is thus achieved that lithium carbonate, and the first stillpot 4 connects the first sodium carbonate tank 5, and its effect is in stillpot
Add sodium carbonate.The outlet of the first stillpot 4 is connected to the entrance of the second solid-liquid separator 6, for being sunk by the lithium carbonate of acquisition
Shallow lake separates, and the second solid-liquid separator 6 can use ceramic membrane.
In an other embodiment, the outlet of DTRO film 14 can also be first to be connected on the second stillpot 15,
The outlet of the second stillpot 15 reconnect be provided with on the 3rd solid-liquid separator 19, the second stillpot 15 barium chloride tank 16,
Two sodium carbonate tanks 17, sodium hydroxide tank 18, namely for adding precipitant in the second stillpot 15.3rd solid-liquid separator
19 can use ceramic membrane.
Embodiment 1
By 100gFeSO4Ion sieve lithium adsorbent loads packed column, and with the speed of 3 BV/h, salt lake bittern is sent into absorption
In agent bed, reach to adsorb saturated after 2h, Li+Concentration no longer reduce；Desorbing is carried out, the pH control of phosphoric acid solution with phosphoric acid solution
System is about 1, and the flow velocity of strippant is to complete desorbing after 2 BV/h, about 3h, and lithium stripping workshop is again through weak-type cation
Exchanger resin D113 removes a small amount of magnesium in stripping liquid, and the flow-control of stripping liquid is at 5 BV/h, then will process with reverse osmosis membrane
After stripping liquid in lithium concentration be concentrated into about 20g/L, reverse osmosis concentration temperature controls at 30 DEG C, operate pressure
0.15Mpa, i.e. can make lithium ion be changed into lithium carbonate by the way of adding sodium carbonate and precipitate, obtain lithium carbonate 8.56g altogether,
Purity about 93%.
Embodiment 2
Difference with embodiment 1 is: the process of Adsorption and desorption uses and is mixed in salt by adsorbent, then leads to
Cross ceramic membrane filter, the mode of plate-and-frame filtration carries out desorbing after being dehydrated by adsorbent again.Concrete step is:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 40
DEG C, stir 60min, the Li in salt+Enter in adsorbent, now Li in solution+Concentration be reduced to 1.07g/L, FeSO4From
Sub-sieve adsorbant is about 40mg/g to the adsorbance of Li, then with ceramic membrane, mixed liquor is carried out thickening filtration, putting down of ceramic membrane
All apertures are respectively adopted 5,20,50,200,500 nm, filter pressure 0.2 MPa, crossflow velocity 3 m/s, filtration temperature 50 DEG C,
Recoil interval 40min, the recoil time is 10s；Ceramic membrane filter concentrated solution, through filter press, removes the major part in concentrated solution
Impurity and water, adsorbed the adsorbent filter cake of lithium, by the adsorbent filter cake of filter pressing gained first with the water pair of electrical conductivity 6s/cm
Adsorbent filter cake washs, remove in filter cake carry secretly magnesium, sodium, the foreign ion such as calcium, then be placed in 1L phosphoric acid solution and carry out
Stirring, the pH of phosphoric acid solution controls about 1, and mixing time is 60min, and controlling solution temperature is 50 DEG C, Li+Entrance phosphoric acid is molten
In liquid, obtaining lithium stripping workshop, lithium stripping workshop removes lacking in stripping liquid through weak-type cation exchange resin D113 again
Amount magnesium, the flow-control of stripping liquid, at 5 BV/h, finally uses reverse osmosis membrane to concentrate, and reverse osmosis concentration temperature controls 30
DEG C, operate pressure 0.15Mpa, can be by adding when the lithium concentration in lithium stripping liquid is concentrated into about about 20g/L
The mode of sodium carbonate makes lithium ion be changed into lithium carbonate precipitation, precipitates after solid-liquid separation, washing, obtains lithium carbonate.Examination
Test result such as table 2.
Table 2
Adsorbent is suspended in salt and adsorbs by employing, then carries out the mode of filtering and concentrating adsorbent with ceramic membrane, can
To be effectively improved process efficiency, it is possible to save the adsorption time of resin；It addition, as can be seen from the table, due at microfiltration
During, adsorbent is in the dual function effect of the cross-flow of microfiltration, separation, and colloid, macromole impurity in salt are difficult to
In Surface coating, the deposition of adsorbent, it is possible to prevent adsorbent to be contaminated, and in microfiltration process, these macromole impurity are
Per-meate side can be entered to through micro-filtration membrane, prevent impurity effect to the service life of adsorbent the most further so that inhale
Attached dose can adsorb lithium ion as much as possible, improve the yield of lithium, it also avoid depositing contaminants on adsorbent, improve product
The purity of product.Compared with Example 1 it can be seen that under the conditions of the consumption of identical adsorbent, in the present embodiment obtained by
Lithium carbonate yield is high, purity is good.
Embodiment 3
Difference with embodiment 2 is: after obtaining stripping liquid, carries out demagging, calcium ion by one-level NF membrane.Tool
The step of body is:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 40
DEG C, stir 60min, the Li in salt+Enter in adsorbent, now Li in solution+Concentration be reduced to 1.07g/L, FeSO4From
Sub-sieve adsorbant is about 40mg/g to the adsorbance of Li, then with ceramic membrane, mixed liquor is carried out thickening filtration, putting down of ceramic membrane
All aperture 50 nm respectively, filter pressure 0.2 MPa, crossflow velocity 3 m/s, filtration temperature 50 DEG C, recoil interval 40min, recoil
Time is 10s；Ceramic membrane filter concentrated solution, through filter press, is removed the most of impurity in concentrated solution and water, is inhaled
The adsorbent filter cake of attached lithium, first washes the adsorbent filter cake of filter pressing gained adsorbent filter cake with the water of electrical conductivity 6s/cm
Wash, remove in filter cake carry secretly magnesium, sodium, the foreign ion such as calcium, then be placed in 1L phosphoric acid solution and be stirred, the pH of phosphoric acid solution
Controlling about 1, mixing time is 60min, and controlling solution temperature is 50 DEG C, Li+Enter in phosphoric acid solution, obtain lithium desorbing molten
Liquid, a small amount of magnesium in lithium stripping workshop another level NF membrane removal stripping liquid, NF membrane molecular cut off 300Da, material is poly-
Ether sulfone, operates pressure 2.0 MPa, operates temperature 30 DEG C, and cycles of concentration is 5 times, uses reverse osmosis membrane to enter the permeate of nanofiltration
Row concentrates, and reverse osmosis concentration temperature controls at 30 DEG C, operates pressure 0.15Mpa, and cycles of concentration has reached 5 times, then by adding
The mode of sodium carbonate makes lithium ion be changed into lithium carbonate precipitation, precipitates after solid-liquid separation, washing, obtains lithium carbonate, altogether
Obtain lithium carbonate 14.01g, purity 96%.By embodiment 2 and embodiment 3 it can be seen that work as and use nanofiltration as demagging means
Time relative to use magnesium ion exchanger resin carry out demagging, the cycles of concentration in reverse osmosis concentration step can be effectively improved.
Reference examples 1
Reference examples 1 is with the difference of embodiment 3: be provided without lithium adsorbent and salt is carried out adsorption operations, but by halogen
The penetrating fluid of ceramic membrane, after the alumina ceramic membrane of average pore size 200 nm carries out pre-filtering, is sent into follow-up receiving by water
Filter in the step of magnesium, reverse osmosis concentration, sodium carbonate precipitation.The cycles of concentration of the NF membrane in this reference examples is 3 times, is less than
Cycles of concentration in embodiment 3 is 5 times.It can thus be seen that NF membrane can be significantly increased by the pre-demagging of absorption method
Cycles of concentration.
Embodiment 4
Embodiment 4 is with the difference of embodiment 3: after the demagging, concentration of one-level NF membrane, nanofiltration passed through
Liquid spent ion exchange resin carries out degree of depth demagging, then the permeate of ion exchange resin is sent to follow-up reverse osmosis concentration,
During sodium carbonate precipitation.Concrete step is:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 40
DEG C, stir 60min, the Li in salt+Enter in adsorbent, now Li in solution+Concentration be reduced to 1.07g/L, FeSO4From
Sub-sieve adsorbant is about 40mg/g to the adsorbance of Li, then with ceramic membrane, mixed liquor is carried out thickening filtration, putting down of ceramic membrane
All aperture 50 nm respectively, filter pressure 0.2 MPa, crossflow velocity 3 m/s, filtration temperature 50 DEG C, recoil interval 40min, recoil
Time is 10s；Ceramic membrane filter concentrated solution, through filter press, is removed the most of impurity in concentrated solution and water, is inhaled
The adsorbent filter cake of attached lithium, first washes the adsorbent filter cake of filter pressing gained adsorbent filter cake with the water of electrical conductivity 6s/cm
Wash, remove in filter cake carry secretly magnesium, sodium, the foreign ion such as calcium, then be placed in 1L phosphoric acid solution and be stirred, the pH of phosphoric acid solution
Controlling about 1, mixing time is 60min, and controlling solution temperature is 50 DEG C, Li+Enter in phosphoric acid solution, obtain lithium desorbing molten
Liquid, a small amount of magnesium in lithium stripping workshop another level NF membrane removal stripping liquid, NF membrane molecular cut off 300Da, material is poly-
Ether sulfone, operates pressure 2.0 MPa, operates temperature 30 DEG C, and cycles of concentration is 5 times, is exchanged by cation by the permeate of nanofiltration
After resin Lewatit MonoPlus TP208 carries out degree of depth demagging, the permeate of ion exchange resin uses reverse osmosis membrane to enter
Row concentrates, and reverse osmosis concentration temperature controls at 30 DEG C, operates pressure 0.15Mpa, and cycles of concentration is 5 times, then by adding carbonic acid
The mode of sodium makes lithium ion be changed into lithium carbonate precipitation, precipitates after solid-liquid separation, washing, obtains lithium carbonate, obtains altogether
Lithium carbonate 13.95g, purity 96.5%.By embodiment 3 and embodiment 4 it can be seen that can use and further sodium filter be passed through
Liquid cation exchange resin carries out degree of depth demagging, may finally improve the purity of lithium carbonate.
Embodiment 5
Difference with embodiment 1 is: the process of Adsorption and desorption uses and is mixed in salt by adsorbent, then leads to
Cross ceramic membrane filter, the mode of plate-and-frame filtration carries out desorbing after being dehydrated by adsorbent again.Concrete step is:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 50
DEG C, stir 50min, the Li in salt+Enter in adsorbent, now Li in solution+Concentration be reduced to 1.02g/L, FeSO4From
Sub-sieve adsorbant is about 40mg/g to the adsorbance of Li, then with ceramic membrane, mixed liquor is carried out thickening filtration, putting down of ceramic membrane
All aperture 200 nm, filter pressure 0.4 MPa, crossflow velocity is respectively adopted 0.5 m/s, 1 m/s, 2 m/s, 3 m/s, 4 m/s,
Filtration temperature 60 DEG C, recoil interval 30min, the recoil time is 30s；Ceramic membrane filter concentrated solution, through filter press, is removed dense
Contracting liquid in most of impurity and, adsorbed the adsorbent filter cake of lithium, the adsorbent filter cake of filter pressing gained first used
Adsorbent filter cake is washed by the aqueous solution (concentration of LiCl is 0.2g/L) of LiCl, remove in filter cake carry secretly magnesium, sodium, calcium
Deng foreign ion, then being placed in 1L phosphoric acid solution and be stirred, the pH of phosphoric acid solution controls about 1, and mixing time is
50min, controlling solution temperature is 45 DEG C, Li+Entering in phosphoric acid solution, obtain lithium stripping workshop, lithium stripping workshop is again through weak
Acid type cation exchange resin D113 removes a small amount of magnesium in stripping liquid, and the flow-control of stripping liquid, at 5 BV/h, finally uses
Reverse osmosis membrane concentrates, and reverse osmosis concentration temperature controls at 30 DEG C, operate pressure 0.15Mpa, by the lithium in lithium stripping liquid from
Lithium ion can be made when sub-concentration is concentrated into about about 20g/L by the way of adding sodium carbonate to be changed into lithium carbonate precipitate,
Precipitate after solid-liquid separation, washing, obtain lithium carbonate.Result of the test such as table 3.
Table 3
When crossflow velocity is 0m/s, i.e. the mode of dead-end filtration, by contrast it can be seen that use the dense of cross flow filter
Compressed mode, for dead-end filtration, is conducive to not making impurity gathering in filter cake, can be effectively prevented from adsorbent
Polluting, it is favourable for the final raising absorption of lithium, elution amount, can improve the extract yield of lithium.It addition, use difference
Crossflow velocity time, can cause the different pollution form of adsorbent filter cake, wherein when using 4m/s crossflow velocity, can be effective
Ground solves lithium ion extraction yield and the technical problem of purity.
Embodiment 6
The present embodiment use aluminum salt adsorbent fill in adsorption column the Li in salt+Absorption, and stripping liquid is adopted
Concentrate with two grades of nanofiltrations, then the permeate of nanofiltration is carried out the sedimentation method remove removal of impurity alkali metal ion.Concrete step is:
Salt lake bittern through aluminum salt adsorbent to Li+After absorption, feed deionized water the most again and carry out eluting, obtain desorbing
Liquid, along with the process of desorbing, the Mg in stripping liquid2+Content can decline, as the Mg detected in stripping liquid2+Content is respectively
Be about 0.5,2,3,4 g/L time, stripping liquid is sent into coarse filter and removes absorbent particles therein and silt, permeate enters
One-level NF membrane element filters, and stripping liquid, after one-level NF membrane element, obtains one-level nanofiltration permeate, one-level nanofiltration
Membranous system operation temperature is 45 DEG C, and pressure is 1.5 MPa, and cycles of concentration is 4 times.One-level NF membrane permeate enters two grades of nanofiltrations
Membrane component, obtains two grades of nanofiltration permeate, and two grades of nanofiltration membrane system operation temperature are 20 DEG C, and pressure is 3.5 MPa, cycles of concentration
It it is 8 times.Two grades of NF membrane permeate enter counter-infiltration system and concentrate, operating pressure 3.0 MPa of reverse osmosis, and temperature is 30 DEG C,
After concentrating 6 times, reverse osmosis concentrated liquid carries out evaporating brine and after multiple-effect evaporation, obtains the dope of multiple-effect evaporation.To multiple-effect evaporation
Dope is sequentially added into precipitant BaCl2、Na2CO3And NaOH, the BaCl of addition2Molar concentration rate salt brine in SO4 2-'s
Molar concentration big 1%, Na2CO3Molar concentration rate salt brine in Ca2+Molar concentration big 1%, the molar concentration rate salt brine of NaOH
In Mg2+The amount the biggest 1% of molar concentration 2 times, be all stirred 30min after adding precipitant every time, after precipitation, enter
Entering purpose ceramic-film filter and carry out filtering and impurity removing, ceramic membrane aperture is 200nm, and pressure is 0.5MPa, opens recoil in filter process
Device, recoil is spaced apart 15min, and the recoil time is 10s, after ceramic membrane filter, obtains ceramic membrane permeate, and turbidity is little
In 0.5NTU.Ion concentration data in each group of test are as shown in the table.
Table 4
By the 4 of the present embodiment groups of tests, it can be seen that as the Mg in stripping liquid2+When the concentration of ion is 0.5 g/L,
The yield causing final lithium is the highest, less than Mg in stripping liquid2+Ion is the situation of 2～3 g/L.Work as Mg2+Ion is that 4g/L is dense
Degree, influences whether cycles of concentration and the separation efficiency of reverse osmosis, result in final lithium yield and also occurs declining.And use tradition
Magnesium ion exchanger resin-hyperfiltration, the cycles of concentration of reverse osmosis membrane can only achieve about 3 times.
Embodiment 7
The present embodiment is to have adjusted relevant technological parameter to the difference of embodiment 6.Make the Li in ceramic membrane clear liquid+Contain
Amount improves further, and reduces the content of impurity alkali metal ion.
Salt lake bittern through aluminum salt adsorbent to Li+After absorption, feed deionized water the most again and carry out eluting, obtain desorbing
Liquid, as the Mg detected in stripping liquid2+When content is about 3 g/L, stripping liquid is sent into coarse filter and removes adsorbent therein
Granule and silt, permeate enters one-level NF membrane element and filters, the Ca in stripping liquid2+Content is 48.59mg/L, Mg2+
Content is 3g/L, Li+Content is 411mg/L.Stripping liquid after one-level NF membrane element, Ca in permeate2+、Mg2+And Li+'s
Content is 29mg/L, 370 mg/L and 575 mg/L.One-level nanofiltration membrane system operation temperature is 25 DEG C, and pressure is 3.5 MPa, dense
Demagnification number is 5 times.One-level NF membrane permeate enters two grades of NF membrane elements, Ca in two grades of nanofiltration permeate2+、Mg2+And Li+'s
Content is 12.54 mg/L, 137.5 mg/L, 680 mg/L.Two grades of nanofiltration membrane system operation temperature are 40 DEG C, and pressure is 1.5
MPa, cycles of concentration is 10 times.Two grades of NF membrane permeate enter counter-infiltration system and concentrate, the operating pressure 4.0 of reverse osmosis
MPa, temperature is 40 DEG C, and after concentrating 6 times, reverse osmosis concentrated liquid carries out evaporating brine and after multiple-effect evaporation, Ca2+、Mg2+And Li+Contain
Amount is 0.17g/L, 1.21 g/L, 17.1g/L.Precipitant BaCl it is sequentially added in the dope of multiple-effect evaporation2、Na2CO3And
NaOH, the BaCl of addition2Molar concentration rate salt brine in SO4 2-Molar concentration big 5%, Na2CO3Molar concentration rate salt brine
In Ca2+Molar concentration big 10%, the Mg in the molar concentration rate salt brine of NaOH2+The amount the biggest 5% of molar concentration 2 times, often
All it is stirred 30min after secondary addition precipitant, after precipitation, enters purpose ceramic-film filter and carry out filtering and impurity removing, ceramic membrane
Aperture is 20nm, and pressure is 0.1MPa, opens recoiling device in filter process, and recoil is spaced apart 15min, and the recoil time is 10s.
Ceramic membrane clear liquid turbidity is less than 0.5NTU, Mg2++ Ca2+Content is 7.5mg/L, SO4 2- Content is 17 mg/L, Li+Content is
18.8g/L.And using traditional magnesium ion exchanger resin-hyperfiltration, the cycles of concentration of reverse osmosis membrane can only achieve 2.5 times of left sides
Right.
Embodiment 8
The present embodiment is to have adjusted relevant technological parameter to the difference of embodiment 7.Make the Li in ceramic membrane clear liquid+Contain
Amount improves further, and reduces the content of impurity alkali metal ion.
Salt lake bittern through aluminum salt adsorbent to Li+After absorption, feed deionized water the most again and carry out eluting, obtain desorbing
Liquid, as the Mg detected in stripping liquid2+When content is about 3 g/L, stripping liquid is sent into coarse filter and removes adsorbent therein
Granule and silt, permeate enters one-level NF membrane element and filters, the Ca in stripping liquid2+Content is 47.65mg/L, Mg2+
Content is 3g/L, Li+Content is 421mg/L.Stripping liquid after one-level NF membrane element, Ca in permeate2+、Mg2+And Li+'s
Content is 24mg/L, 370 mg/L and 615 mg/L.One-level nanofiltration membrane system operation temperature is 30 DEG C, and pressure is 3.0 MPa, dense
Demagnification number is 5 times.One-level NF membrane permeate enters two grades of NF membrane elements, Ca in two grades of nanofiltration permeate2+、Mg2+And Li+'s
Content is 12.24 mg/L, 137.5 mg/L, 730 mg/L.Two grades of nanofiltration membrane system operation temperature are 40 DEG C, and pressure is 3.0
MPa, cycles of concentration is 11 times.Two grades of NF membrane permeate enter counter-infiltration system and concentrate, the operating pressure 3.5 of reverse osmosis
MPa, temperature is 35 DEG C, and after concentrating 8 times, reverse osmosis concentrated liquid carries out evaporating brine and after multiple-effect evaporation, Ca2+、Mg2+And Li+Contain
Amount is 0.14g/L, 1.01 g/L, 19.1g/L.Precipitant BaCl it is sequentially added in the dope of multiple-effect evaporation2、Na2CO3And
NaOH, the BaCl of addition2Molar concentration rate salt brine in SO4 2-Molar concentration big 2%, Na2CO3Molar concentration rate salt brine
In Ca2+Molar concentration big 2%, the Mg in the molar concentration rate salt brine of NaOH2+The amount the biggest 2% of molar concentration 2 times, often
All it is stirred 30min after secondary addition precipitant, after precipitation, enters purpose ceramic-film filter and carry out filtering and impurity removing, ceramic membrane
Aperture is 50nm, and pressure is 0.3MPa, opens recoiling device in filter process, and recoil is spaced apart 15min, and the recoil time is 10s.
Ceramic membrane clear liquid turbidity is less than 0.5NTU, Mg2++ Ca2+Content is 7.3mg/L, SO4 2- Content is 14 mg/L, Li+Content is
21.8g/L.And using traditional magnesium ion exchanger resin-hyperfiltration, the cycles of concentration of reverse osmosis membrane can only achieve 3.5 times of left sides
Right.
Embodiment 9
In the present embodiment, use and first adsorbent be mixed in salt, upon adsorption completely after, by ceramic membrane cross flow filter
Mixed liquor, obtains the concentrated solution containing adsorbent, then after being dehydrated further by concentrated solution filter press, will the lithium of dehydration
Adsorbent filter cake fills in adsorbent, adds eluting water and carries out desorbing, obtains stripping liquid.Again by stripping liquid nanofiltration, ion
The method of exchanger resin carries out demagging, then after concentrating with reverse osmosis membrane, adds precipitant BaCl2、Na2CO3And NaOH
Make Ca2+、Mg2+Foreign ion precipitates, and after being separated by precipitate, then precipitates Li with sodium carbonate+, obtain lithium carbonate precipitation.Specifically
Step be:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 40
DEG C, stir 60min, the Li in salt+Enter in adsorbent, FeSO4Ion sieve adsorbent is about 40mg/g to the adsorbance of Li,
With ceramic membrane, mixed liquor is carried out thickening filtration again, the average pore size of ceramic membrane 50 nm, filter pressure 0.2 MPa, film respectively
Surface current speed 3 m/s, filtration temperature 50 DEG C, recoil interval 40min, the recoil time is 10s；Ceramic membrane filter concentrated solution is through sheet frame
Filter pressing, removes the most of impurity in concentrated solution and water, has been adsorbed the adsorbent filter cake of lithium, by the adsorbent of filter pressing gained
Adsorbent filter cake is first washed by filter cake with the water of electrical conductivity 6s/cm, remove in filter cake carry secretly magnesium, sodium, the impurity such as calcium from
Son, then adsorbent is filtered even being filled in adsorption column, adding deionized water and carry out eluting, the flow velocity of eluant is 2 BV/h, when
As the Mg detected in stripping liquid2+When content is about 2 g/L, permeate enters one-level NF membrane element and filters, stripping liquid
In Ca2+Content is 42.65mg/L, Mg2+Content is 2g/L, Li+Content is 450mg/L.Stripping liquid is through one-level nanofiltration membrane element
After part, Ca in permeate2+、Mg2+And Li+Content be 20mg/L, 450 mg/L and 556 mg/L.One-level nanofiltration membrane system operates
Temperature is 45 DEG C, and pressure is 1.5 MPa, and cycles of concentration is 5 times, NF membrane molecular cut off 300Da, and material is polyether sulfone.One
Level NF membrane permeate enters ion exchange resin adsorption tower and carries out degree of depth demagging, in ion exchange resin adsorption tower permeate,
Ca2+、Mg2+And Li+Content be 10mg/L, 7 mg/L and 7 50mg/L.Ion exchange resin permeate enters counter-infiltration system
Concentrating, operating pressure 3.0 MPa of reverse osmosis, temperature is 30 DEG C, after concentrating 6 times, is sequentially added into precipitant in concentrated solution
BaCl2、Na2CO3And NaOH, the BaCl of addition2Molar concentration rate salt brine concentrated solution in SO4 2-Molar concentration big 2%,
Na2CO3Molar concentration rate salt brine concentrated solution in Ca2+Molar concentration big 2%, the molar concentration rate salt brine concentrated solution of NaOH
In Mg2+The amount the biggest 2% of molar concentration 2 times, be all stirred 30min after adding precipitant every time, after precipitation, enter
Entering purpose ceramic-film filter and carry out filtering and impurity removing, ceramic membrane aperture is 200nm, and pressure is 0.5MPa.Ceramic membrane clear liquid turbidity is less than
0.5NTU, is added thereto to the Na refined2CO3Solution, after being stirred, enters purpose ceramic-film filter and concentrates and wash, right
After it is centrifuged and dries, obtain Li2CO3Finished product, after testing, it is thus achieved that Li2CO3 16.44g, purity is 99.5%, reaches battery
Level Li2CO3Standard.
Embodiment 10
Difference with embodiment 9 is: after concentrating stripping liquid reverse osmosis membrane, in addition it is also necessary to it is used DTRO
Film, MVR vaporizer carry out degree of depth concentration, then to evaporation and concentration liquid adds precipitant BaCl2、Na2CO3And NaOH makes Ca2+、
Mg2+Foreign ion precipitates.Concrete step is:
By 100gFeSO4Heated and stirred in the salt lake bittern of ion sieve adsorbent addition 50L, controlling solution temperature is 40
DEG C, stir 60min, the Li in salt+Enter in adsorbent, FeSO4Ion sieve adsorbent is about 40mg/g to the adsorbance of Li,
With ceramic membrane, mixed liquor is carried out thickening filtration again, the average pore size of ceramic membrane 50 nm, filter pressure 0.2 MPa, film respectively
Surface current speed 3 m/s, filtration temperature 50 DEG C, recoil interval 40min, the recoil time is 10s；Ceramic membrane filter concentrated solution is through sheet frame
Filter pressing, removes the most of impurity in concentrated solution and water, has been adsorbed the adsorbent filter cake of lithium, by the adsorbent of filter pressing gained
Adsorbent filter cake is first washed by filter cake with the water of electrical conductivity 6s/cm, remove in filter cake carry secretly magnesium, sodium, the impurity such as calcium from
Son, then adsorbent is filtered even being filled in adsorption column, adding deionized water and carry out eluting, the flow velocity of eluant is 2 BV/h, when
As the Mg detected in stripping liquid2+When content is about 2 g/L, permeate enters one-level NF membrane element and filters, stripping liquid
In Ca2+Content is 42.65mg/L, Mg2+Content is 2g/L, Li+Content is 450mg/L.Stripping liquid is through one-level nanofiltration membrane element
After part, Ca in permeate2+、Mg2+And Li+Content be 20mg/L, 450 mg/L and 556 mg/L.One-level nanofiltration membrane system operates
Temperature is 45 DEG C, and pressure is 1.5 MPa, and cycles of concentration is 5 times, NF membrane molecular cut off 300Da, and material is polyether sulfone.One
Level NF membrane permeate enters ion exchange resin adsorption tower and carries out degree of depth demagging, in ion exchange resin adsorption tower permeate,
Ca2+、Mg2+And Li+Content be 10mg/L, 7 mg/L and 7 50mg/L.Ion exchange resin permeate enters counter-infiltration system
Concentrating, operating pressure 3.0 MPa of reverse osmosis, temperature is 30 DEG C, and after concentrating 6 times, reverse osmosis concentrated liquid enters DTRO film to be carried out
The degree of depth concentrates, and enters MVR vaporizer and be evaporated after concentrating 4 times, the Ca after evaporation2+、Mg2+And Li+Content be 0.23g/L,
0.17g/L、18g/L.Precipitant BaCl it is sequentially added in the dope of multiple-effect evaporation2、Na2CO3And NaOH, the BaCl of addition2
Molar concentration rate salt brine concentrated solution in SO4 2-Molar concentration big 2%, Na2CO3Molar concentration rate salt brine concentrated solution in
Ca2+Molar concentration big 2%, the Mg in the molar concentration rate salt brine concentrated solution of NaOH2+The amount the biggest 2% of molar concentration 2 times,
All it is stirred 30min after adding precipitant every time, after precipitation, enters purpose ceramic-film filter and carry out filtering and impurity removing, pottery
Membrane aperture is 200nm, and pressure is 0.5MPa.Ceramic membrane clear liquid turbidity is less than 0.5NTU, is added thereto to the Na refined2CO3Molten
Liquid, after being stirred, enters purpose ceramic-film filter and concentrates and wash, after it is centrifuged and is dried, obtain Li2CO3Become
Product, after testing, it is thus achieved that Li2CO3 21.54g, purity is 99.8%, reaches LITHIUM BATTERY Li2CO3Standard.
Embodiment 11
Difference with embodiment 9 is: after having obtained the dope of multiple-effect evaporation, and the order adding precipitant is to add successively
Enter NaOH, BaCl2And Na2CO3, then carried out filtering precipitation, lithium carbonate precipitation, centrifugation, the operation of drying, obtain
Li2CO3 19.02g, purity is 99.1%.
Embodiment 12
By 100gFeSO4Ion sieve adsorbent adds in the salt lake bittern of 50L, after adding activated carbon (concentration about 3g/L)
Heated and stirred, controlling solution temperature is 50 DEG C, stirs 50min, the Li in salt+Enter in adsorbent, now Li in solution+'s
Concentration is reduced to 1.02g/L, FeSO4Ion sieve adsorbent is about 40mg/g to the absorption of Li, through ceramic membrane filter thickening filtration,
The average pore size of ceramic membrane is 200 nm, filter pressure 0.4 MPa, crossflow velocity 4 m/s, filtration temperature 60 DEG C, recoil interval
40min, the recoil time is 30s, cycles of concentration about 52 times；Clear liquid can enter and carry magnesium operation recovery magnesium, ceramic membrane filter concentrated solution
Through filter press, remove the most of impurity in concentrated solution and water, adsorbed the absorption filter cake of lithium, the filter of filter press
Liquid reclaims magnesium also into putting forward magnesium technique, and by the adsorbent filter cake of filter pressing gained, first with the aqueous solution of LiCl, (concentration of LiCl is
0.2g/L) adsorbent filter cake is washed, remove in filter cake carry secretly magnesium, sodium, the foreign ion such as calcium, then it is molten to be placed in 1L phosphoric acid
Being stirred in liquid, mixing time is 50min, and controlling solution temperature is 45 DEG C, Li+Enter in phosphoric acid solution, obtain lithium desorbing
Solution, lithium the stripping workshop a small amount of magnesium in weak-type cation exchange resin D113 removes stripping liquid, the stream of stripping liquid again
Amount controls at 5 BV/h, finally uses reverse osmosis membrane to concentrate, and reverse osmosis concentration temperature controls at 30 DEG C, operates pressure
0.15Mpa, can be by the way of adding sodium carbonate when the lithium concentration in lithium stripping liquid is concentrated into about about 20g/L
Make lithium ion be changed into lithium carbonate precipitation, obtain lithium carbonate 22.16g, purity about 99% altogether.It can be seen that by adsorbent
System adds activated carbon, can effectively make adsorbent disperse more uniform, and activated carbon can adsorb a part and have
Machine thing impurity, it is to avoid these impurity effects service lifes to adsorbent, yield and the purity of the lithium carbonate obtained is more preferable.
Claims (38)
1. the technique being extracted battery grade lithium by salt, it is characterised in that comprise the steps: the 1st step, with lithium adsorbent pair
Salt adsorbs, then with eluant, lithium adsorbent is carried out desorbing, obtains stripping liquid；2nd step, by stripping liquid demagging, obtain
The stripping liquid of demagging；3rd step, concentrates the stripping liquid of demagging, obtains containing lithium concentrated brine；In 1st step, it is that lithium is adsorbed
Agent is dispersed in salt, obtains mixed liquor, then mixed liquor is carried out solid-liquid separation, and the lithium adsorbent after separating is carried out desorbing.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Mg in described salt2+
And Li+Weight ratio be 1:1～400:1.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Mg in described salt2+
And Li+Weight ratio be 2:1～200:1.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Mg in described salt2+
And Li+Weight ratio be 2:1～150:1.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Li in described salt+'s
Mass percent concentration is 0.1～15.0g/L.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Li in described salt+'s
Mass percent concentration is 0.3～10.0g/L.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: Li in described salt+'s
Mass percent concentration is 0.5～8.0g/L.
The technique being extracted battery grade lithium by salt the most according to claim 1, it is characterised in that: lithium adsorbent refers to aluminium salt
The mixture of one or more in lithium adsorbent, hydroxide adsorbent, metaantimmonic acid type adsorbent, ion-sieve type adsorbent.
The most according to claim 1 by salt extract battery grade lithium technique, it is characterised in that: lithium adsorbent at salt
In addition 0.05～5g/L.
The most according to claim 1 by salt extract battery grade lithium technique, it is characterised in that: lithium adsorbent at halogen
Addition 0.2g/L in water.
11. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: lithium adsorbent adds halogen
After water, stirring 30～60min, brine temperature is 30～60 DEG C.
12. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: described solid-liquid separation
Step include using and separate film and carry out the step that concentrates.
13. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: the step of solid-liquid separation
It is to use separation film to concentrate, obtains adsorbent concentrated solution, then with plate filter, adsorbent concentrated solution is dehydrated.
14. according to the technique being extracted battery grade lithium by salt described in claim 12 or 13, it is characterised in that: described separation
The material of film uses ceramic membrane.
15. according to the technique being extracted battery grade lithium by salt described in claim 12 or 13, it is characterised in that: described separation
Film uses micro-filtration membrane；The average pore size scope separating film is 50～200nm；Filtration temperature is 30～80 DEG C, operation pressure 0.2～
0.5MPa, crossflow velocity 1～4m/s.
16. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: the eluant in the 1st step
Being water or phosphoric acid solution, the pH of phosphoric acid solution is 1～2, desorption temperature 50～100 DEG C.
17. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: the behaviour of demagging in the 2nd step
It is that the mode using nanofiltration membrane or ion exchange resin absorption removes magnesium ion as step.
18. techniques being extracted battery grade lithium by salt according to claim 17, it is characterised in that: NF membrane retains molecule
Amount is 100～300, and nanofiltration operation pressure is 1.0～3.0MPa, and operation temperature is 20～45 DEG C.
19. techniques being extracted battery grade lithium by salt according to claim 17, it is characterised in that: use NF membrane to carry out
During demagging, being to be filtered by least two-stage NF membrane, the cycles of concentration of one-level nanofiltration is 3～6 times, the concentration of two grades of nanofiltrations
Multiple is 8～12 times.
20. techniques being extracted battery grade lithium by salt according to claim 19, it is characterised in that: use nanofiltration membrane
After removing magnesium ion, then carry out demagging with cation exchange resin.
21. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: the concentration step in the 3rd step
At least one used in reverse osmosis membrane concentration, the concentration of DTRO membrance concentration, electrodialytic membranes, evaporation and concentration rapid, obtains concentrating containing lithium
Salt.
22. techniques being extracted battery grade lithium by salt according to claim 21, it is characterised in that: concentration step is first to use
Reverse osmosis membrane concentrates, then uses at least one in DTRO membrance concentration or evaporation and concentration to carry out dense again reverse osmosis membrane concentrated solution
Contracting, obtains containing lithium concentrated brine.
23. techniques being extracted battery grade lithium by salt according to claim 21, it is characterised in that: reverse osmosis concentrated compression process
Operating pressure be 3.0～4.0MPa, temperature is 30～40 DEG C.
24. techniques being extracted battery grade lithium by salt according to claim 1, it is characterised in that: the 3rd step obtains containing lithium
After concentrated brine, it is added thereto to BaCl2、Na2CO3And NaOH solution is so that the SO in salt4 2-、Ca2+And Mg2+Shape
Become precipitation, and remove precipitation.
25. techniques being extracted battery grade lithium by salt according to claim 24, it is characterised in that: addition sequence is successively
Add BaCl2、Na2CO3And NaOH solution.
26. techniques being extracted battery grade lithium by salt according to claim 24, it is characterised in that: the BaCl of addition2Rub
That concentration ratio is containing the SO in lithium concentrated brine4 2-Molar concentration big 1%～5%, the Na of addition2CO3Molar concentration rate containing lithium concentrate
Ca in salt2+Molar concentration big 1～10%, the molar concentration rate of the NaOH of addition is containing the Mg in lithium concentrated brine2+Rub
2 times the biggest 1～5% of that concentration.
27. techniques being extracted battery grade lithium by salt according to claim 24, it is characterised in that: to eliminating precipitation
Containing in lithium concentrated brine, add Na2CO3Solution makes Li2CO3Precipitation, after precipitate and separate, drying, obtains lithium carbonate.
28. according to the technique being extracted battery grade lithium by salt described in claim 24 or 27, it is characterised in that: precipitation separation
Step is to use ceramic membrane separation, and ceramic membrane pore diameter range is that membrane aperture is 50nm for 20～200nm, pressure in running
Being 0.1～0.5MPa, temperature is 10～50 DEG C.
29. 1 kinds of devices being extracted battery grade lithium by salt, include adsorption-desorption device (1), demagging device (2), concentrate dress
Put (3), it is characterised in that: the stripping liquid outlet of adsorption-desorption device (1) is connected with the entrance of demagging device (2), demagging device
(2) outlet is connected with the entrance of enrichment facility (3), and the concentrated solution outlet of enrichment facility (3) and the first stillpot (4) connect,
Being additionally provided with the first sodium carbonate tank (5) on the first stillpot (4), the outlet of the first stillpot (4) is also attached to the second solid-liquid
Separator (6)；Described adsorption-desorption device (1) include be sequentially connected with adsorption tank (7), the first solid-liquid separator (22),
Solving bothrium (10), the outlet solving bothrium (10) is connected with demagging device (2).
30. devices being extracted battery grade lithium by salt according to claim 29, it is characterised in that: the first described solid-liquid
Separator (22) includes ceramic membrane device (8) and plate filter (9), the outlet retaining side of ceramic membrane device (8) and plate
The entrance of frame filter (9) connects, and the entrance of ceramic membrane device (8) is connected to adsorption tank (7), retaining of plate filter (9)
Side is connected with solving bothrium (10).
31. devices being extracted battery grade lithium by salt according to claim 29, it is characterised in that: described demagging device
(2) nano filter membrance device or Di are referred to.
32. devices being extracted battery grade lithium by salt according to claim 29, it is characterised in that: described demagging device
(2) referring to NF membrane (11) and the ion exchange resin column (12) being sequentially connected with, the entrance of NF membrane (11) is connected to absorption and solves
Inhaling device (1), the per-meate side of NF membrane (11) is connected to ion exchange resin column (12), the outlet of ion exchange resin column (12)
It is connected to enrichment facility (3).
33. devices being extracted battery grade lithium by salt according to claim 29, it is characterised in that: described enrichment facility
(3) at least one in reverse osmosis membrane apparatus, DTRO film device, electrodialytic membranes device, evaporation concentration device.
34. devices being extracted battery grade lithium by salt according to claim 33, it is characterised in that: described enrichment facility
(3) referring to reverse osmosis membrane (13) and the DTRO film (14) being sequentially connected with, the entrance of reverse osmosis membrane (13) is connected to demagging device
(2), the side that retains of reverse osmosis membrane (13) is connected to the entrance of DTRO film (14), and the outlet of DTRO film (14) is connected to the first precipitation
Groove (4).
35. devices being extracted battery grade lithium by salt according to claim 29, it is characterised in that: described enrichment facility
(3) outlet passes sequentially through the second stillpot (15) and the 3rd solid-liquid separator (19) reconnects in the first stillpot (4)；Concentrate
The outlet of device (3) is connected to the entrance of the second stillpot (15), and the outlet of the second stillpot (15) is connected to the 3rd solid-liquid and divides
From the entrance of device (19), the outlet retaining side of the 3rd solid-liquid separator (19) is connected to the first stillpot (4).
36. devices being extracted battery grade lithium by salt according to claim 35, it is characterised in that: at the second stillpot
(15) barium chloride tank (16), the second sodium carbonate tank (17), sodium hydroxide tank (18) it are respectively arranged with on.
37. devices being extracted battery grade lithium by salt according to claim 35, it is characterised in that: the second described solid-liquid
Separator (6) is ceramic membrane filter device.
38. devices being extracted battery grade lithium by salt according to claim 35, it is characterised in that: the 3rd described solid-liquid
Separator (19) is ceramic membrane filter device.
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