CN207375760U - A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio - Google Patents
A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio Download PDFInfo
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Abstract
The utility model provides a kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio, includes：Sulfuric acid adds in tank, for adding in sulfuric acid into precipitation tank；Precipitation tank carries out sedimentation separation for the boric acid in bittern containing lithium；Monovalent ion selectivity electric dialyzator, is connected to precipitation tank, for carrying out electrodialysis process to removing boron bittern；NF membrane is connected to the dope room of monovalent ion selectivity electric dialyzator, for being filtered processing to electrodialysis dope；Exchange resin tower, be connected to NF membrane penetrates side, was used for nanofiltration permeate liquid and carries out except impurity ion processing；Reverse osmosis membrane is connected to the material liquid outlet of exchange resin tower, for carrying out concentration to feed liquid；High pressure reverse osmosis membrane is connected to the concentration side of reverse osmosis membrane, is concentrated for the dope to reverse osmosis membrane.The utility model has good operability, reduces whole energy consumption, improves the efficiency of lithium.
Description
Technical field
The utility model belongs to chemical industry of inorganic salt field, and specifically, the utility model is related to one kind from high Mg/Li ratio salt lake
The device of lithium is carried in bittern.
Background technology
The lithium metal most light as nature is very important energy metal, lithium and its compound because with many heavy
The characteristic wanted and be widely used in the fields such as glass, ceramics, battery and nuclear industry.In recent years, information technology is grown rapidly,
Lithium ion lithium battery becomes one of field with the fastest developing speed.And since countries in the world are to the pass of fossil energy shortage problem
Note is proposed detailed clean energy resource, especially Development of Electric Vehicles strategy both at home and abroad.Therefore, lithium has become 21 century
Energy and material, be referred to as promote the world advance important element.
And the lithium production capacity 80% in the whole world has all fully been exploited, soon from salt lake for the low magnesium lithium salts lake for being easy to exploitation
The lithium that speed increases is in urgent need needs and extracts lithium resource from high Mg/Li ratio salt lake, to meet battery industry demand.
China's bittern lithium resource is very abundant, based on Qinghai Salt Lake lithium resource reserves.Qinghai Salt Lake Bittern belongs to multigroup
Subsystem, composition is complicated, and wherein inorganic salts exist mostly in the form of monovalence or divalent ion, wherein lithium magnesium ion radius it is close,
Chemical property is similar, and high Mg/Li ratio is the main feature of Qinghai Salt Lake resource, lithium concentration in 0.3g/L ~ 6g/L, magnesium from
Between 100 ~ 125g/L, magnesium lithium mass ratio exists sub- concentration（20~100）：Between 1 so that separating magnesium and lithium becomes difficult, while
It is the emphasis and key point that salt lake puies forward lithium technology.
The method for proposing lithium and industrialization for high Mg/Li ratio salt lake has calcining leaching method, absorption method and UF membrane
Method.Though wherein calcining leaching method can solve the problems, such as the separating magnesium and lithium in salt lake brine with high magnesium-lithium ratio, energy consumption is larger, economy effect
Benefit is unsatisfactory.Absorption method can be respectively applied to the salt lake bittern of low Mg/Li ratio and high Mg/Li ratio, but there are adsorbents for absorption method
Molten damage is big, consumes a large amount of fresh water, produces the problems such as obtained lithium carbonate product quality is not high.Nano filtering process can be directly from salt lake bittern
Middle extraction lithium, but due in bittern total ion concentration it is excessively high, old halogen is directly excessive into the pressure applied needed for nanofiltration, more than nanofiltration
The carrying scope of film, therefore need to be diluted old halogen using a large amount of fresh water before membranous system is entered, consume a large amount of fresh water.
Utility model content
The utility model provides that the utility model is related to a kind of devices that lithium is carried from salt lake brine with high magnesium-lithium ratio.According to
Contained complicated components in bittern, are integrated with selective electrodialysis, NF membrane, anion-cation exchange resin, reverse osmosis membrane and height
Reverse osmosis membrane to be pressed, makes full use of selective electrodialysis and Nanofiltration Membrane Separation Technology so that the monovalent ions such as lithium chloride penetrate, and 98%
Above divalent ion is intercepted, and so as to fulfill magnesium ion, chemical agent addition cost can be greatly reduced.
Technical solution is：
A kind of method that lithium is carried from salt lake brine with high magnesium-lithium ratio, includes the following steps：
1st step carries out the bittern containing lithium after natural evaporation to handle except boron；
2nd step, to the 1st step except the bittern after boron is by monovalent ion selectivity electrodialysis process, make lithium ion penetrate from
Sub- selective membrane obtains the electrodialysis concentrate of rich lithium；
3rd step, the electrodialysis concentrate for the rich lithium that the 2nd step is obtained are sent into NF membrane and are filtered, and penetrate lithium ion
NF membrane obtains nanofiltration permeate liquid；
4th step, the nanofiltration permeate liquid that the 3rd step is obtained are sent into ion exchange resin treatment, imurity-removal ion；
The ion exchange resin permeate that 4th step obtains is sent into reverse osmosis membrane and is concentrated, obtains reverse osmosis by the 5th step
Saturating concentrate；
The reverse osmosis concentrated liquid that 5th step obtains is sent into high pressure reverse osmosis membrane and is concentrated by the 6th step, obtains lithium concentration
Liquid.
In 1st step, the Mg in bittern containing lithium2+With Li+Weight ratio for 280~1: 1, bittern contains Li+Concentration
0.01~15g/L.
In 1st step, sink except the method for boron is selected from sulfuric acid precipitation method, boron selective ion exchanger resin method, lime
Shallow lake method, active carbon adsorption, electrolytic coagulation either aluminium hydroxide absorption method；It preferably adds in sulfuric acid and forms boric acid precipitation, and
Boric acid is removed by way of separation of solid and liquid.
In 2nd step, the selectively electrodialytic current density of monovalent ion is 40A/m2~500A/m2；The electricity of rich lithium
Mg in dialysis concentrate2+With Li+Weight ratio be 2~3: 1.
In 2nd step, it is necessary in selective electrodialysis anode chamber during monovalent ion selectivity electrodialysis process
While adding a blocking liquid bath, prevent the chlorion in bittern from entering anode chamber's oxidation reaction generation chlorine.
In 3rd step, the dope of NF membrane returns to monovalent ion selectivity electrodialysis process；In nanofiltration permeate liquid
Mg2+Concentration be less than 200mg/L；For nanofiltration filtration temperature at 30~60 DEG C, 1.5~4.0Mpa of operating pressure, nanofiltration concentrates 2~4
Times.
In 4th step, ion exchange resin refers to cation exchange resin, anion exchange resin either the two
Mixing.
In 5th step, the clear liquid of reverse osmosis membrane returns again to monovalent ion selectivity electrodialysis process；Osmosis filtration
Temperature is at 30~50 DEG C, 2.0~4.0 Mpa of operating pressure, 2~4 times of reverse osmosis concentration.
In 6th step, the clear liquid of high pressure reverse osmosis membrane returns again to monovalent ion selectivity electrodialysis process；High pressure is anti-
Permeation filtration temperature is at 30~50 DEG C, 8.0~10.0 Mpa of operating pressure, 2 times of high pressure reverse osmosis concentration.
In 1st step, what is obtained needs after Fenton oxidation is handled except boron bittern, enter back into the 2nd step monovalence from
Sub- selectivity electrodialysis is taken care of oneself；In Fenton oxidation processing, Fe2+And H2O2Concentration is respectively 40~250mg/L and 100~600mg/
L, system pH are 3~4, and reaction temperature is 10~60 DEG C, and the reaction time is 15~120min.
A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio, includes：
Sulfuric acid adds in tank, for adding in sulfuric acid into precipitation tank；
Precipitation tank carries out sedimentation separation for the boric acid in bittern containing lithium；
Monovalent ion selectivity electric dialyzator, is connected to precipitation tank, for carrying out electrodialysis process to removing boron bittern；
NF membrane is connected to the dope room of monovalent ion selectivity electric dialyzator, for being filtered to electrodialysis dope
Processing；
Exchange resin tower, be connected to NF membrane penetrates side, was used for nanofiltration permeate liquid and carries out except at foreign ion
Reason；
Reverse osmosis membrane is connected to the material liquid outlet of exchange resin tower, for carrying out concentration to feed liquid；
High pressure reverse osmosis membrane is connected to the concentration side of reverse osmosis membrane, is concentrated for the dope to reverse osmosis membrane.
The concentration side of the NF membrane is connected to the liquor inlet of monovalent ion selectivity electric dialyzator.
What is loaded in the exchange resin tower is cation exchange resin, anion exchange resin either negative and positive
The mixing of ion exchange resin.
The per-meate side of reverse osmosis membrane is connected to the liquor inlet of monovalent ion selectivity electric dialyzator.
The per-meate side of high pressure reverse osmosis membrane is connected to the liquor inlet of monovalent ion selectivity electric dialyzator.
Precipitation tank is to be connected to monovalent ion selectivity electric dialyzator by Fenton oxidation device.
Advantageous effect
（1）The separating magnesium and lithium technology of the utility model is a kind of method that lithium is carried from salt lake brine with high magnesium-lithium ratio, finally
Realize the purpose of extraction lithium.（2）It in production technology, is concentrated using reverse osmosis membrane and high pressure reverse osmosis membrane, not using steaming
Concentration technology is sent out, has saved energy consumption.（3）The dope of nanofiltration, reverse osmosis and clear liquid reverse osmosis high pressure are returned into selective electric osmose
Analysis system not only realizes the recycling of lithium resource, has also recycled freshwater resources.
Description of the drawings
Fig. 1 is the flow chart of recovery process provided by the utility model.
Fig. 2 is installation drawing provided by the utility model.
1st, sulfuric acid adds in tank；2nd, precipitation tank；3rd, monovalent ion selectivity electric dialyzator；4th, NF membrane；5th, amberlite
Fat tower；6th, reverse osmosis membrane；7th, high pressure reverse osmosis membrane.
Specific embodiment
The utility model is integrated with selective electrodialysis, NF membrane, zwitterion friendship according to contained complicated components in bittern
Resin, reverse osmosis membrane and high pressure reverse osmosis membrane are changed, makes full use of selective electrodialysis and Nanofiltration Membrane Separation Technology so that chlorination
The monovalent ions such as lithium penetrate, and more than 98% divalent ion is intercepted, and so as to fulfill magnesium ion, chemical drugs can be greatly reduced
Cost is added in agent.
Main process route is as shown in Figure 1.
（1）The bittern concentrated through natural evaporation is carried into boron through sulfuric acid process, obtains boron removal bittern；The purpose of this step is to remove water
In boron, improve the quality of bittern, sink except the method for boron is selected from sulfuric acid precipitation method, boron selective ion exchanger resin method, lime
Shallow lake method, active carbon adsorption, electrolytic coagulation either aluminium hydroxide absorption method；Preferred method is to add in sulfuric acid formation boric acid to sink
It forms sediment, and boric acid is removed by way of separation of solid and liquid, bittern can so be made to make electrodialytic raising one in the process in acidity
Valency ion selectivity penetrates the separating magnesium and lithium effect of film；Mg in bittern containing lithium2+With Li+Weight ratio for 280~1: 1, bittern
Containing Li+0.01~15g/L of concentration.
（2）Boron removal bittern passes through the electrodialysis plant with monovalent ion selective membrane, and divalent ion is trapped in bittern, and one
Valency ion permeable ion-selective membrane realizes separating magnesium and lithium, obtains the bittern of low Mg/Li ratio, wherein Mg/Li ratio exists（2~3）：1, one
The electrodialytic current density of valency ion selectivity is 40A/m2~500A/m2, the boron removal bittern handled can return to salt pan,
After can further the magnesium ion of concentration be removed, continue reuse, to improve the yield of lithium；One used in electrodialysis plant
Valency ion selectivity anode membrane is the CIMS types or K192 type films of Japanese ASTOM companies production；Monovalent ion selectivity cavity block is
The ACS types or A192 type films of ASTOM companies production.
（3）The bittern of low Mg/Li ratio passes through nanofiltration membrane, and more than 90% magnesium ion and sulfate radical are trapped, obtain low
Lithium magnesium than bittern, wherein magnesium ion concentration be less than 200mg/L, concentrated water return step（2）Recycling lithium ion is mixed with boron removal bittern；
Selection has divalent ion the NF membrane of retention, and representative NF membrane includes IP100 films, DK films and the life of other companies
The NF membrane with similar performance of production.
（4）Low lithium magnesium than bittern by anion-cation exchange resin, depth sulfate radical and calcium and magnesium boron ion, obtain lithium
Bittern, ion exchange resin refer to the mixing of cation exchange resin, anion exchange resin either the two, amberlite
The species of fat is not particularly limited, as long as the foreign ions such as the calcium in bittern, magnesium, sulfate radical, carbonate can be removed i.e.
It can；
（5）Lithium bittern is concentrated by reverse osmosis membrane, and dope is lithium primary concentrate, and clear liquid goes back to selective electrodialysis system
System is as concentrated water starting liquid；Osmosis filtration temperature is at 30~50 DEG C, 2.0~4.0 Mpa of operating pressure, reverse osmosis concentration 2~4
Times；
（6）Lithium primary concentrate is concentrated by high pressure reverse osmosis membrane, and dope is final lithium concentrate, in lithium concentrate lithium from
Sub- concentration reaches more than 10g/L, and clear liquid returns selective electrodialysis system as concentrated water starting liquid.High pressure osmosis filtration temperature exists
30~50 DEG C, 8.0~10.0 Mpa of operating pressure, 2 times of high pressure reverse osmosis concentration.
Due to, also containing certain COD, can be had an impact in the bittern after concentration to ion selectivity through film.
In one improved embodiment, the bittern that boron is removed after natural evaporation can also be handled using Fenton oxidation, due to using sulphur
When acid system removes boron, bittern can be acidified, on the one hand sulfuric acid plays the role of, except boron, on the other hand, playing in Fenton oxidation
The effect of acid adding, has a dual effect.On the other hand, due to introducing ferrous ion during Fenton oxidation, ferrous iron from
For son during monovalence is selectively electrodialytic, monovalence selectively still has the transmission of certain ferrous ion through film
Property, therefore ferrous ion can be stayed in dope side, this part ferrous ion can pass through nanofiltration in subsequent nanofiltration process
Electrical charge rejection effect improves permeability of the monovalent ion in NF membrane.
Device is as shown in Figure 2 used by the utility model.
Include：
Sulfuric acid adds in tank 1, for adding in sulfuric acid into precipitation tank 2；
Precipitation tank 2 carries out sedimentation separation for the boric acid in bittern containing lithium；
Monovalent ion selectivity electric dialyzator 3, is connected to precipitation tank 2, for carrying out electrodialysis process to removing boron bittern；
NF membrane 4 is connected to the dope room of monovalent ion selectivity electric dialyzator 3, for being carried out to electrodialysis dope
Filter is handled；
Exchange resin tower 5, be connected to NF membrane 4 penetrates side, was used for nanofiltration permeate liquid and carries out except foreign ion
Processing；
Reverse osmosis membrane 6 is connected to the material liquid outlet of exchange resin tower 5, for carrying out concentration to feed liquid；
High pressure reverse osmosis membrane 7 is connected to the concentration side of reverse osmosis membrane 6, is concentrated for the dope to reverse osmosis membrane 6.
The concentration side of the NF membrane 4 is connected to the liquor inlet of monovalent ion selectivity electric dialyzator 3.
What is loaded in the exchange resin tower 5 is cation exchange resin, anion exchange resin either the moon
The mixing of cation exchange resin.
The per-meate side of reverse osmosis membrane 6 is connected to the liquor inlet of monovalent ion selectivity electric dialyzator 3.
The per-meate side of high pressure reverse osmosis membrane 7 is connected to the liquor inlet of monovalent ion selectivity electric dialyzator 3.
The water quality of the bittern after natural evaporation employed in following embodiment is as follows：
Embodiment 1
（1）Bittern is after natural evaporation concentrates, wherein Mg2+Concentration is 123.4g/L, Li+Concentration is 2.40g/L, Na+It is dense
It spends for 2.20g/L, B+Concentration is 1.60g/L, SO4 2-Concentration is 32.6g/L, COD 187.7mg/L, and sulfuric acid is added to be carried after being acidified
Boron is obtained except boron bittern, B in bittern+Concentration is 50mg/L；
（2）It will be mixed except boron bittern with concentrated water caused by back segment nanofiltration process, subsequently into the electricity of ion selection function
The dilute side of electrodialysis equipment mixes the starting as concentrated water using pure water with clear liquid caused by reverse osmosis and high pressure reverse osmosis process
Liquid, under the action of electric field force, monovalent ion enters concentrated water side by dilute side through ion-selective membrane, and divalent ion is most of
It is trapped, so as to form the bittern of low Mg/Li ratio, wherein Mg in concentrated water side2+Concentration is 4.90g/L, Li+Concentration for 1.70g/L,
Na+Concentration is 3.0g/L, SO4 2-Concentration is 0.062g/L, and the boron removal bittern handled returns to salt pan；
（3）Low Mg/Li ratio bittern is by being pumped into nanofiltration system, and by valve control operation flow and pressure, pressure control exists
2.0Mpa, filtration temperature are 35 DEG C, concentrate 3 times, the clear liquid of nanofiltration for low lithium magnesium than bittern, wherein Mg2+Concentration is 0.085g/
L、Li+Concentration is 1.80g/L, Na+Concentration is 3.10g/L, SO4 2-Concentration is 0.01g/L, and the dope of nanofiltration returns selective electrodialysis
System is mixed with boron removal bittern, Mg2+Concentration is 14.5g/L, Li+Concentration is 1.50g/L, Na+Concentration is 2.80g/L, SO4 2-It is dense
It spends for 0.17g/L；
（4）Low lithium magnesium than bittern by anion-cation exchange resin, depth sulfate radical and calcium and magnesium boron ion, obtain lithium
Bittern, wherein Mg2+Concentration is 2mg/L；
（5）Lithium bittern is by being pumped into counter-infiltration system, and by valve control operation flow and pressure, pressure control exists
3.0Mpa, filtration temperature be 35 DEG C, concentrate 3.5 times, reverse osmosis dope be lithium primary concentrate, wherein Li+Concentration is
5.16g/L, reverse osmosis clear liquid return selective electrodialysis system as concentrated water starting liquid；
（6）Lithium primary concentrate is handled by high pressure counter-infiltration system, concentrates 2 times, pressure control is in 9.0Mpa, filtering temperature
Spend for 35 DEG C, concentrate 2 times, the reverse osmosis dope of high pressure be final lithium concentrate, wherein Li+Concentration is 10.25g/L, and high pressure is anti-
The clear liquid of infiltration returns selective electrodialysis system as concentrated water starting liquid.
Embodiment 2
（1）Bittern is after natural evaporation concentrates, wherein Mg2+Concentration is 112.5g/L, Li+Concentration is 3.0g/L, Na+Concentration
For 2.8g/L, B+Concentration is 2.0g/L, SO4 2-Concentration is 28.4g/L, COD 189.9mg/L, and sulfuric acid is added to carry boron after being acidified, is obtained
Except boron bittern, B in bittern+Concentration is 48mg/L；
（2）It will be mixed except boron bittern with concentrated water caused by back segment nanofiltration process, subsequently into the electricity of ion selection function
The dilute side of electrodialysis equipment mixes the starting as concentrated water using pure water with clear liquid caused by reverse osmosis and high pressure reverse osmosis process
Liquid, under the action of electric field force, monovalent ion enters concentrated water side by dilute side through ion-selective membrane, and divalent ion is most of
It is trapped, so as to form the bittern of low Mg/Li ratio, wherein Mg in concentrated water side2+Concentration is 4.50g/L, Li+Concentration for 2.10g/L,
Na+Concentration is 3.50g/L, SO4 2-Concentration is 0.060g/L, and the boron removal bittern handled returns to salt pan；
（3）Low Mg/Li ratio bittern is by being pumped into nanofiltration system, and by valve control operation flow and pressure, pressure control exists
2.5Mpa, filtration temperature are 38 DEG C, concentrate 3.5 times, the clear liquid of nanofiltration for low lithium magnesium than bittern, wherein Mg2+Concentration is
0.080g/L、Li+Concentration is 2.20g/L, Na+Concentration is 3.6g/L, SO4 2-Concentration is 0.01g/L, and the dope of nanofiltration returns selectivity
Electrodialysis system is mixed with boron removal bittern, Mg2+Concentration is 15.6g/L, Li+Concentration is 1.85g/L, Na+Concentration for 3.25g/L,
SO4 2-Concentration is 0.18g/L；
（4）Low lithium magnesium than bittern by anion-cation exchange resin, depth sulfate radical and calcium and magnesium boron ion, obtain lithium
Bittern, wherein Mg2+Concentration is 1mg/L；
（5）Lithium bittern is by being pumped into counter-infiltration system, and by valve control operation flow and pressure, pressure control exists
3.0Mpa, filtration temperature be 33 DEG C, concentrate 3 times, reverse osmosis dope be lithium primary concentrate, wherein Li+Concentration is 6.50g/
L, reverse osmosis clear liquid return selective electrodialysis system as concentrated water starting liquid；
（6）Lithium primary concentrate is handled by high pressure counter-infiltration system, concentrates 2 times, pressure control is in 10.0Mpa, filtering
Temperature be 35 DEG C, concentrate 2 times, the reverse osmosis dope of high pressure be final lithium concentrate, wherein Li+Concentration is 12.8g/L, and high pressure is anti-
The clear liquid of infiltration returns selective electrodialysis system as concentrated water starting liquid.
Embodiment 3
（1）Bittern is after natural evaporation concentrates, wherein Mg2+Concentration is 132.1g/L, Li+Concentration is 2.3g/L, Na+Concentration
For 2.2g/L, B+Concentration is 2.3g/L, SO4 2-Concentration is 33.1g/L, COD 190.9mg/L, and sulfuric acid is added to carry boron after being acidified, is obtained
Except boron bittern, B in bittern+Concentration is 48mg/L；
（2）It will be mixed except boron bittern with concentrated water caused by back segment nanofiltration process, subsequently into the electricity of ion selection function
The dilute side of electrodialysis equipment mixes the starting as concentrated water using pure water with clear liquid caused by reverse osmosis and high pressure reverse osmosis process
Liquid, under the action of electric field force, monovalent ion enters concentrated water side by dilute side through ion-selective membrane, and divalent ion is most of
It is trapped, so as to form the bittern of low Mg/Li ratio, wherein Mg in concentrated water side2+Concentration is 6.40g/L, Li+Concentration for 2.30g/L,
Na+Concentration is 3.20g/L, SO4 2-Concentration is 0.072g/L, and the boron removal bittern handled returns to salt pan；
（3）Low Mg/Li ratio bittern is by being pumped into nanofiltration system, and by valve control operation flow and pressure, pressure control exists
2.8Mpa, filtration temperature are 35 DEG C, concentrate 3.0 times, the clear liquid of nanofiltration for low lithium magnesium than bittern, wherein Mg2+Concentration is
0.092g/L、Li+Concentration is 2.11g/L, Na+Concentration is 3.3g/L, SO4 2-Concentration is 0.01g/L, and NF membrane is to Li+Transmission
Rate is 91.7%, and the dope of nanofiltration returns selective electrodialysis system and mixed with boron removal bittern, Mg2+Concentration is 13.3g/L, Li+Concentration
For 1.90g/L, Na+Concentration is 3.12g/L, SO4 2-Concentration is 0.15g/L；
（4）Low lithium magnesium than bittern by anion-cation exchange resin, depth sulfate radical and calcium and magnesium boron ion, obtain lithium
Bittern, wherein Mg2+Concentration is 1mg/L；
（5）Lithium bittern is by being pumped into counter-infiltration system, and by valve control operation flow and pressure, pressure control exists
3.5Mpa, filtration temperature be 30 DEG C, concentrate 3 times, reverse osmosis dope be lithium primary concentrate, wherein Li+Concentration is 6.80g/
L, reverse osmosis clear liquid return selective electrodialysis system as concentrated water starting liquid；
（6）Lithium primary concentrate is handled by high pressure counter-infiltration system, concentrates 2 times, pressure control is in 9.5Mpa, filtering temperature
Spend for 38 DEG C, concentrate 2 times, the reverse osmosis dope of high pressure be final lithium concentrate, wherein Li+Concentration is 11.9g/L, high pressure reverse osmosis
Saturating clear liquid returns selective electrodialysis system as concentrated water starting liquid.
Embodiment 4
（1）Bittern is after natural evaporation concentrates, wherein Mg2+Concentration is 132.1g/L, Li+Concentration is 2.3g/L, Na+Concentration
For 2.2g/L, B+Concentration is 2.3g/L, SO4 2-Concentration is 33.1g/L, COD 192.5ppm, and sulfuric acid is added to carry boron after being acidified, must be removed
Boron bittern, B in bittern+Concentration is 48mg/L；
（2）Difference with embodiment 3 is：It will remove and oxidation is carried out in boron bittern feeding Fenton oxidation device except COD processing, lead to
After crossing addition reagent, make Fe2+And H2O2Concentration is respectively 150mg/L and 200mg/L, and system pH is 3~4, and reaction temperature is
40 DEG C, reaction time 40min；Treated bittern again with back segment nanofiltration process caused by concentrated water mix, subsequently into
The dilute side of the electrodialysis plant of ion selection function mixes pure water and clear liquid caused by reverse osmosis and high pressure reverse osmosis process
Cooperate the starting liquid for concentrated water, under the action of electric field force, monovalent ion enters concentrated water side by dilute side through ion-selective membrane,
And divalent ion is largely trapped, so as to form the bittern of low Mg/Li ratio, wherein Mg in concentrated water side2+Concentration is 4.20g/L, Li+Concentration is 2.56g/L, Na+Concentration is 3.10g/L, SO4 2-Concentration is 0.054g/L；
（3）Low Mg/Li ratio bittern is by being pumped into nanofiltration system, and by valve control operation flow and pressure, pressure control exists
2.8Mpa, filtration temperature are 35 DEG C, concentrate 3.0 times, the clear liquid of nanofiltration for low lithium magnesium than bittern, wherein Mg2+Concentration is
0.065g/L、Li+Concentration is 2.48g/L, Na+Concentration is 3.1g/L, SO4 2-Concentration is 0.01g/L, and NF membrane is to Li+Transmission
Rate is 96.9%, compared with embodiment 3, make NF membrane to Li+The transmitance of transmitance be improved, the dope of nanofiltration
It returns selective electrodialysis system to mix with boron removal bittern, Mg2+Concentration is 15.5g/L, Li+Concentration is 1.30g/L, Na+Concentration is
3.02g/L、SO4 2-Concentration is 0.11g/L；
（4）Low lithium magnesium than bittern by anion-cation exchange resin, depth sulfate radical and calcium and magnesium boron ion, obtain lithium
Bittern, wherein Mg2+Concentration is 1mg/L；
（5）Lithium bittern is by being pumped into counter-infiltration system, and by valve control operation flow and pressure, pressure control exists
3.5Mpa, filtration temperature be 30 DEG C, concentrate 3 times, reverse osmosis dope be lithium primary concentrate, wherein Li+Concentration is 7.87g/
L, reverse osmosis clear liquid return selective electrodialysis system as concentrated water starting liquid；
（6）Lithium primary concentrate is handled by high pressure counter-infiltration system, concentrates 2 times, pressure control is in 9.5Mpa, filtering temperature
Spend for 38 DEG C, concentrate 2 times, the reverse osmosis dope of high pressure be final lithium concentrate, wherein Li+Concentration is 14.9g/L, high pressure reverse osmosis
Saturating clear liquid returns selective electrodialysis system as concentrated water starting liquid.
Claims (5)
1. a kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio, which is characterized in that include：
Sulfuric acid adds in tank（1）, for precipitation tank（2）Middle addition sulfuric acid；
Precipitation tank（2）, sedimentation separation is carried out for the boric acid in bittern containing lithium；
Monovalent ion selectivity electric dialyzator（3）, it is connected to precipitation tank（2）, for carrying out electrodialysis process to removing boron bittern；
NF membrane（4）, it is connected to monovalent ion selectivity electric dialyzator（3）Dope room, for being carried out to electrodialysis dope
Filter is handled；
Exchange resin tower（5）, it is connected to NF membrane（4）Penetrate side, be used for nanofiltration permeate liquid and carried out except foreign ion
Processing；
Reverse osmosis membrane（6）, it is connected to exchange resin tower（5）Material liquid outlet, for feed liquid carry out concentration；
High pressure reverse osmosis membrane（7）, it is connected to reverse osmosis membrane（6）Concentration side, for reverse osmosis membrane（6）Dope carry out it is dense
Contracting.
2. the device according to claim 1 that lithium is carried from salt lake brine with high magnesium-lithium ratio, which is characterized in that the nanofiltration
Film（4）Concentration side be connected to monovalent ion selectivity electric dialyzator（3）Liquor inlet.
3. the device according to claim 1 that lithium is carried from salt lake brine with high magnesium-lithium ratio, which is characterized in that the ion
Exchange resin tower（5）Middle filling is cation exchange resin, anion exchange resin either anion-cation exchange resin
Mixing.
4. the device according to claim 1 that lithium is carried from salt lake brine with high magnesium-lithium ratio, which is characterized in that reverse osmosis membrane
（6）Per-meate side be connected to monovalent ion selectivity electric dialyzator（3）Liquor inlet.
5. the device according to claim 1 that lithium is carried from salt lake brine with high magnesium-lithium ratio, which is characterized in that high pressure is reverse osmosis
Film（7）Per-meate side be connected to monovalent ion selectivity electric dialyzator（3）Liquor inlet.
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| CN107399747A (en) * | 2017-08-17 | 2017-11-28 | 江苏久吾高科技股份有限公司 | A kind of method and device that lithium is carried from salt lake brine with high magnesium-lithium ratio |
| CN109824065A (en) * | 2019-03-06 | 2019-05-31 | 中国科学院青海盐湖研究所 | A kind of method of separating magnesium and lithium and enriching lithium |
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