CN102382984A - Method and device for separating magnesium and lithium and enriching lithium from salt lake brine - Google Patents
Method and device for separating magnesium and lithium and enriching lithium from salt lake brine Download PDFInfo
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- CN102382984A CN102382984A CN2011101851286A CN201110185128A CN102382984A CN 102382984 A CN102382984 A CN 102382984A CN 2011101851286 A CN2011101851286 A CN 2011101851286A CN 201110185128 A CN201110185128 A CN 201110185128A CN 102382984 A CN102382984 A CN 102382984A
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Abstract
The invention relates to a method and a device for separating magnesium and lithium and enriching the lithium from salt lake brine. The method comprises the following steps of: separating an electrodialyzing device into two areas by using an anion exchange membrane, namely a lithium salt chamber and a brine chamber, filling the salt lake brine in the brine chamber, and filling a supporting electrolyte solution which does not contain Mg<2+> in the lithium salt chamber; placing a conducting matrix coated by an ionic sieve in the brine chamber as a cathode; placing the conducting matrix coated by a lithium-embedded ionic sieve in the lithium salt chamber as an anode; under the driving of an external electric potential, embedding Li <1+> in the brine in the brine chamber into the ionic sieve to form the lithium-embedded ionic sieve, and recovering the lithium-embedded ionic sieve into the ionic sieve after the lithium-embedded ionic sieve in the lithium salt chamber releases the Li <1+> into a conducting solution; and discharging a liquid in the brine chamber after the lithium is embedded, adding the salt lake brine again, alternatively placing electrodes in the two chambers, and repeating and circulating operations. Through the method and the device for separating magnesium and lithium and enriching lithium in the salt lake brine, the separation of the lithium and other ions is effectively realized, and a lithium-enriched solution is synchronously obtained. The method has a short flow and low production cost, is simple to operate, can be operated continuously, and is easy to industrially apply.
Description
Technical field
The invention belongs to the extraction field of metallurgy, specifically, relate to a kind of salt lake brine that is used for directly handling, make it the magnesium lithium and separate, and then the method and apparatus of enriching lithium.
Background technology
Since nineteen ninety, lithium ion battery was by the Sony commercialization; Lithium seems more and more important in the industry in modern times; Be described as " the new forms of energy metal of 21 century ", because its high-energy-density and very long cycle life, lithium ion battery is widely used in the electronics; The market requirement of lithium sharply enlarges, and the exploitation of lithium resource seems more important.
At nature, lithium mainly exists with ore and two kinds of forms of bittern, and most of lithium resource is present in bittern especially in the salt lake brine, and its reserves account for more than 80% of whole lithium resource reserves.The growth of As market, the mineral lithium resource seems, and supply falls short of demand, and cost of winning is high, and people begin to develop the lithium resource in the salt lake brine.Usually the muriate, vitriol and the carbonate that contain sodium, potassium, magnesium, calcium, boron, lithium in the bittern; Remove the Mg/Li ratio relatively low (about 6: 1) of minority salt lake such as Chilean Atacama salt lake brine; Mg/Li ratio in other most of salt lake brines is all more than 40; The highest reaches 1837, lithium and a large amount of alkaline earth metal ion coexistences.Since diagonal rule, Mg
2+With Li
+Chemical property closely similar, the magnesium lithium separates very difficulty, has seriously restricted the extraction and the application of lithium.All the time, from the high Mg/Li ratio salt lake brine, extract lithium and become a global problem.Investigators adopt technology such as the precipitator method, carborization, ion exchange method, solvent extration to develop the lithium resource in the bittern, but the most process of these methods is complicated, and cost is high, and is serious to equipment corrosion, and product purity is not high, is unfavorable for scale operation.
Summary of the invention
The objective of the invention is to, proposing a kind of be used for directly separates the magnesium lithium from salt lake brine the method for enriching lithium and supporting device thereof.Efficient realization lithium separates with other ionic, obtains rich lithium solution simultaneously.Present method flow process is short, and simple to operate, production cost is low, but operate continuously is easy to industrial applications.
The method of a kind of salt lake brine magnesium lithium separation and enriching lithium in turn includes the following steps:
(1) with anion-exchange membrane the electrodialysis cell of electrodialysis unit vertically is divided into two zones in lithium salts chamber and bittern chamber, the indoor salt lake brine that charges into of bittern, indoor the charging into of lithium salts do not contain Mg
2+Supporting electrolyte solution, like NaCl, KCl, NH
4Cl, Na
2SO
4, K
2SO
4, NaNO
3, KNO
3Solution.
The conducting base that (2) will be coated with ion(ic)sieve places the bittern chamber as negative electrode; Place the lithium salts chamber as anode the conducting base that is coated with embedding lithium attitude ion(ic)sieve, under the driving of electromotive force, make the Li in the bittern of bittern chamber outside
+Be embedded into formation embedding lithium attitude ion(ic)sieve in the ion(ic)sieve, the embedding lithium attitude ion(ic)sieve in the lithium salts chamber is with Li simultaneously
+After being discharged into conductive soln, revert to ion(ic)sieve; Realize the Li in the bittern chamber
+With Mg
2+And other cationic separation, lithium enrichment in the lithium salts chamber obtains rich lithium solution simultaneously.
Through the operation of above-mentioned steps (2), the Li in the bittern of bittern chamber
+Be embedded into formation embedding lithium attitude ion(ic)sieve in the ion(ic)sieve, the embedding lithium attitude ion(ic)sieve in the lithium salts chamber is with Li simultaneously
+After being discharged into conductive soln, revert to ion(ic)sieve; So two electrodes can be reused by switch.
Therefore, after step (2) is accomplished, can also carry out once following operation at least:
Liquid behind the embedding lithium in the bittern chamber is discharged, add salt lake brine again, then negative electrode and anode exchange are placed, proceed electrodialysis.
After perhaps step (2) is accomplished,, can also carry out once following operation at least, further make Li for fear of each exchange negative electrode and anode
+With Mg
2+And other cation separation, enriching lithium simultaneously:
Holding anode and negative electrode stationkeeping are discharged liquid behind the embedding lithium in the bittern chamber, and the lithium-containing solution in the lithium salts chamber is transferred in the bittern chamber, and new salt lake brine is joined in the lithium salts chamber; Be about to bittern chamber and lithium salts chamber transition function and use, proceed electrodialysis.(be aforesaid operations of every repetition, use once with regard to transition function bittern chamber and lithium salts chamber)
Described embedding lithium attitude ion(ic)sieve directly adopts iron lithium phosphate or LiMn
2O
4In a kind of; Described iron lithium phosphate is LiFePO
4, Li
xMe
yFePO
4, LiFe
xMe
yPO
4, LiFePO
4/ C, Li
xMe
yFePO
4/ C, LiFe
xMe
yPO
4The mixture of one or more the among/C, wherein Me is one or more the mixing among Mn, Co, Mo, Ti, Al, Ni, the Nb, 0＜x＜1,0＜y＜1;
Perhaps obtain through following process: with anion-exchange membrane electrodialysis unit is divided into two zones in lithium salts chamber and bittern chamber, the indoor salt lake brine that charges into of bittern, indoor the charging into of lithium salts do not contain Mg
2+Supporting electrolyte solution; Will be to Li
+Selective adsorbing ion(ic)sieve is coated on the conducting base, places the bittern chamber of electrodialysis unit, is negative electrode with the ion(ic)sieve, is that counter electrode carries out cathodic polarization with the noble electrode, makes the Li in the bittern
+Be embedded into and obtain embedding lithium attitude ion(ic)sieve in the ion(ic)sieve.
Described salt lake brine comprises and contains Li arbitrarily
+Solution, arbitrarily original bittern and the bittern after the evaporation concentration thereof in the salt lake and carry potassium after the old halogen of evaporation in one or more.
Described conducting base is to be coated with a kind of in ruthenium titanium net, graphite cake, Pt family metal and Alloy Foil thereof, carbon cloth, the graphite paper.
The temperature of solution is 0～80 ℃ in the described electrodialysis unit, and the pH value is 2～12; Two interelectrode voltage ranges are 0.5～2.0V in the electrodialysis unit.
Described ion(ic)sieve is tertiary iron phosphate, lithium titanate, MnO
2In one or more mixture.
Described tertiary iron phosphate is Fe
1-xMe
xPO
4, wherein Me is one or more the mixing among Mn, Co, Mo, Ti, Al, Ni, the Nb, the scope of x is: 0≤x≤0.1; Lithium titanate is Li
4Ti
5O
12, Li
xMe
yTi
5O
12, Li
4Me
mTi
nO
12In one or more mixture; Me is one or more the mixing among V, Fe, Co, Mn, Al, Ba, Ag, Zr, Sr, Nb, the F; 0＜x＜4,0＜y＜4,0＜m＜5,0＜n＜5.
The corollary apparatus of the above-mentioned salt lake brine magnesium lithium separation and the method for enriching lithium; Comprise and have the electrodialysis unit that is separated into two spatial electrodialysis cells by anion-exchange membrane; And negative electrode and anode, described negative electrode and anode are arranged at respectively in two spaces that are divided into; Described negative electrode is the conducting base that is coated with ion(ic)sieve, and anode is the conducting base that is coated with embedding lithium attitude ion(ic)sieve.
Technical measures of the present invention are: a kind of electrodialysis unit of autonomous design is employed in the aqueous solution steady operation and to Li
+The ion(ic)sieve material that memory effect is arranged through adjustment system electromotive force, makes the Li in the solution
+Be embedded in the lattice of ion(ic)sieve, other ions are stayed in the solution, realize that through this process lithium effectively separates with other ionic; Again the ion(ic)sieve of embedding lithium attitude is placed and do not contain Mg
2+Supporting electrolyte solution such as NaCl solution in, the electromotive force of adjustment system makes the Li in the embedding lithium attitude ion(ic)sieve
+Be discharged in the solution, obtain rich lithium solution, realize the high efficiency separation of magnesium lithium and the enrichment of lithium; Its advantage is: in the electrodialysis unit operational process, when the lithium in the bittern was embedded into ion(ic)sieve, embedding lithium attitude ion(ic)sieve took off lithium to the lithium salts chamber, and this process effectively reduces energy consumption, has improved the extraction efficiency of lithium.
Concrete step is:
(1). the initial embedding lithium of ion(ic)sieve: with anion-exchange membrane electrodialysis unit is divided into two zones in lithium salts chamber and bittern chamber, the indoor salt lake brine that charges into of bittern, indoor the charging into of lithium salts do not contain Mg
2+Supporting electrolyte solution; Will be to Li
+Selective adsorbing ion(ic)sieve is coated on the conducting base, places the bittern chamber of electrodialysis unit, and it is fully contacted with salt lake brine, is negative electrode with the ion(ic)sieve material, is that counter electrode carries out cathodic polarization with the inert anode, makes the Li in the bittern
+Be embedded into and obtain embedding lithium attitude ion(ic)sieve in the ion(ic)sieve;
(2). the magnesium lithium separates: ion(ic)sieve is coated on the conducting base, places the bittern chamber that bittern is housed, as negative electrode; Embedding lithium attitude ion(ic)sieve is coated in places adding not contain Mg on the conducting base
2+The lithium salts chamber of supporting electrolyte solution in, as anode, under the driving of electromotive force, make the Li in the bittern of bittern chamber outside
+Be embedded into formation embedding lithium attitude ion(ic)sieve in the ion(ic)sieve, and the embedding lithium attitude ion(ic)sieve in the lithium salts chamber is with Li
+Be discharged in the conductive soln, because anion-exchange membrane stops cationic mutual migration between bittern chamber and two zones, lithium salts chamber, negatively charged ion sees through exchange membrane entering lithium salts chamber and keeps charge balance from the bittern chamber, and the Li in the bittern chamber
+Transfer in the lithium salts chamber through solid phase;
(3). after step (2) is accomplished, for further making Li
+With Mg
2+And other cation separation, the while enriching lithium, can also operate as follows:
Liquid behind the embedding lithium in the bittern chamber is discharged; Again add salt lake brine; Place the bittern chamber as negative electrode the ion(ic)sieve conducting base of gained in step (2) the lithium salts chamber; Place the lithium salts chamber as anode the embedding lithium attitude ion(ic)sieve conducting base of gained in the bittern chamber, carry out electrodialysis, make the Li in the bittern
+Be embedded in the ion(ic)sieve, and the Li in the embedding lithium attitude ion(ic)sieve
+Be discharged in the solution of lithium salts chamber, make the Li in the bittern chamber
+Transfer in the solution in the lithium salts chamber through solid phase, further realized the Li in the bittern chamber
+With Mg
2+And other cationic separation, lithium enrichment in the lithium salts chamber obtains rich lithium solution simultaneously; Operate the enrichment that can realize lithium, the Li in rich lithium solution by above-mentioned electrodialysis process recirculation
+Can be used for directly extracting lithium when reaching finite concentration.
For simplifying aforesaid operations; Avoid electrode constantly transposing between bittern chamber and lithium salts chamber; Above-mentioned step (3) can also be operated as follows: after step (2) was accomplished, negative electrode and anode position immobilized, and liquid behind the embedding lithium in the bittern chamber is discharged respectively; Lithium-containing solution in the lithium salts chamber is transferred in the half dialysis groove (being the bittern chamber) at embedding lithium attitude ion(ic)sieve place, salt lake brine is joined in the half dialysis groove (being the lithium salts chamber) at ion(ic)sieve place; Make former bittern chamber convert new lithium salts chamber into, former lithium salts chamber converts new bittern chamber (be about to bittern chamber with lithium salts chamber transition function use) into, proceeds electrodialysis, repeats the operation of above-mentioned this new step (3), has realized the Li in the bittern
+With Mg
2+And other cationic separation, obtain rich lithium solution simultaneously; Can realize the enrichment of lithium, the Li in rich lithium solution by above-mentioned electrodialysis process repetitive operation
+Can be used for directly extracting lithium when reaching finite concentration.
Use the inventive method, and to adopt tertiary iron phosphate be that ion(ic)sieve carries out that the magnesium lithium separates and during enriching lithium, can carry out as follows:
(1). iron lithium phosphate being coated on the conducting base, placing conductive soln as anode, is negative electrode with the noble electrode; Electromotive force outside between two electrodes, applying makes the Li in the iron lithium phosphate
+Take off and be embedded in the solution, iron lithium phosphate is converted into the tertiary iron phosphate ion(ic)sieve;
(2). the magnesium lithium separates: the tertiary iron phosphate ion(ic)sieve of step (1) gained is coated on the conducting base, places the bittern chamber that bittern is housed, as negative electrode; Iron lithium phosphate is coated on the conducting base, places to be equipped with not contain Mg
2+The lithium salts chamber of supporting electrolyte solution in, as anode, under the driving of electromotive force, make the Li in the bittern of bittern chamber outside
+Be embedded into formation embedding lithium attitude ion(ic)sieve in the tertiary iron phosphate ion(ic)sieve, and the iron lithium phosphate in the while lithium salts chamber is with Li
+Be discharged in the conductive soln; Because anion-exchange membrane stops cationic mutual migration between bittern chamber and two zones, lithium salts chamber, negatively charged ion sees through exchange membrane entering lithium salts chamber and keeps charge balance from the bittern chamber; Step (1) and (2) total effect are equivalent to the Li in the bittern chamber
+Transfer to the solid phase ion(ic)sieve earlier, and then transfer in the lithium salts chamber, thereby lithium is separated with magnesium;
Iron lithium phosphate is LiFePO
4, Li
xMe
yFePO
4, LiFe
xMe
yPO
4, LiFePO
4/ C, Li
xMe
yFePO
4/ C, LiFe
xMe
yPO
4The mixture of one or more in the mixture of one or more the among/C; Me is one or more the mixing among Mg, Al, Ti, Ni, Co, Mn, Mo, the Nb; 0＜x＜1,0＜y＜1.
The present invention has following advantage:
Ion(ic)sieve of the present invention is to Li
+Have good selectivity, and adsorptive capacity is big, good stability, the lithium in the enrichment bittern that can circulate;
1, this method can be handled the bittern of different Mg/Li ratios, particularly can efficiently solve the isolating technical barrier of magnesium lithium in the high Mg/Li ratio bittern;
2, the electrodialysis unit that this method designed can be accomplished the embedding of lithium on two working electrodes simultaneously and deviate from, and realize that the efficient selective of lithium extracts, and bath voltage is low, and energy consumption is low; After the operation of accomplishing one-period, realize continuous cycle operation through transposing electrode or electrolyte solution;
3, the electrodialysis unit that this method designed can be accomplished the enrichment of lithium synchronously in the isolating while of magnesium lithium; And electrodialysis unit is simple in structure, and is easy to operate, ability circular treatment salt lake brine;
4, this method cost is low, is easy to large-scale production.
Description of drawings
Fig. 1 is an electrodialysis cell schematic top plan view of the present invention;
1 is anion-exchange membrane among the figure, and 2 is negative electrode, and 3 is anode, and 4 is the bittern chamber, and 5 is the lithium salts chamber
Fig. 2 is Li of the present invention
+Concentration is with electrodialysis change of time figure;
Fig. 3 is Li of the present invention
+Concentration is with the variation diagram of recycle ratio.
Embodiment
In order to explain the present invention in more detail, enumerate following examples and describe, but the present invention is not limited to these embodiment.
Apparatus of the present invention are referring to Fig. 1, and the electrodialysis cell of electrodialysis unit becomes two spaces with anion-exchange membrane 1 vertical isolation, i.e. bittern chamber 4 and lithium salts chamber 5, and negative electrode 2 is arranged at respectively in two spaces that are divided into anode 3; Negative electrode 2 is for being coated with the conducting base of ion(ic)sieve, and anode 3 is for being coated with the conducting base of embedding lithium attitude ion(ic)sieve.
The weight ratios of pressing 20: 1: 1 are with 10gFePO
4Ion(ic)sieve, 0.5g high purity graphite and 0.5gPVDF mix; N-Methyl pyrrolidone (NMP) organic solvent joined in the powder that mixes to grind size mixing; Soup compound is coated on the graphite cake; Heat preservation and dryness is 12 hours in 110 ℃ vacuum chamber, obtains tertiary iron phosphate ion(ic)sieve composite package after the cooling; The tertiary iron phosphate composite package is placed the bittern chamber of electrodialysis unit, and the schematic top plan view of electrodialysis unit is as shown in Figure 1; The 2L salt lake brine is added the bittern chamber, and the staple and the content of salt lake brine are as shown in the table:
With 500mL concentration is that the NaCl solution of 20g/L joins in the lithium salts chamber of electrodialysis unit; With tertiary iron phosphate ion sieve membrane is negative electrode, is anode with the inertia graphite in the lithium salts chamber, applies the voltage of 0.5V at the electrode two ends, after keeping 15h under 25 ℃, and the Li in the bittern chamber
+Concentration is reduced to 358mg/L, Mg
2+Concentration be about 17994mg/L, the tertiary iron phosphate ion(ic)sieve is to Li
+Adsorptive capacity be about 28.4mg/g, to Mg
2+Adsorptive capacity be about 1.2mg/g;
After initial embedding lithium finishes, the solution in bittern chamber and the lithium salts chamber is discharged respectively, embedding lithium attitude tertiary iron phosphate ion sieve membrane is placed the lithium salts chamber, adding 500mL concentration is the NaCl solution of 20g/L; According to method identical among this embodiment, with 10gFePO
4Ion(ic)sieve is made into the not tertiary iron phosphate composite package of embedding lithium, and this composite package is placed the bittern chamber, adds the 2L salt lake brine, and its staple and content are still seen upward table; With the tertiary iron phosphate ion sieve membrane of embedding lithium not is negative electrode, is anode with embedding lithium attitude tertiary iron phosphate ion sieve membrane, between two electrodes, applies the voltage of 0.8V, after pH is to keep 12h under 2,25 ℃, and the Li in the bittern chamber
+Concentration is reduced to 345mg/L, Mg
2+Concentration be about 17995mg/L, the tertiary iron phosphate ion(ic)sieve is to Li
+Adsorptive capacity be 31mg/g, to Mg
2+Adsorptive capacity be about 1mg/g; Obtain Li in the lithium salts chamber simultaneously
+Concentration is the rich lithium solution of 561mg/L.
The weight ratios of pressing 90: 5: 5 are with 9gFe
0.99Mn
0.01PO
4, 0.5g high purity graphite and 0.5gPVDF mix; The powder that mixes joined to grind in N-Methyl pyrrolidone (NMP) organic solvent size mixing; With soup compound spraying or brush in that to be coated with the ruthenium titanium online; Under vacuum condition,, obtain tertiary iron phosphate ion(ic)sieve composite package after the cooling in 110 ℃ of heat preservation and drynesses 10 hours.
The tertiary iron phosphate composite package is placed the bittern chamber, add the 2L salt lake brine, the composition and the content of bittern are as shown in the table:
With 200mL concentration is that the NaCl solution of 50g/L joins in the lithium salts chamber of electrodialysis unit; With tertiary iron phosphate ion sieve membrane is negative electrode, is anode with the Pt electrode in the lithium salts chamber, applies the voltage of 1.0V at the electrode two ends, after keeping 10h under 50 ℃, and Li in the bittern chamber
+Concentration be reduced to 55.1mg/L, Mg
2+Concentration be 1254mg/L, the tertiary iron phosphate ion(ic)sieve is to Li
+Adsorptive capacity be 32.2mg/g, to Mg
2+Adsorptive capacity be 1.33mg/g.
After initial embedding lithium finishes, the solution in bittern chamber and the lithium salts chamber is discharged respectively, embedding lithium attitude tertiary iron phosphate ion sieve membrane is placed the lithium salts chamber, adding 500mL concentration is the NaCl solution of 50g/L; According to method identical among this embodiment, with 9gFePO
4Ion(ic)sieve is made into the not tertiary iron phosphate composite package of embedding lithium, and this composite package is placed the bittern chamber, adds the 2L salt lake brine, and its staple and content are seen upward table; With the tertiary iron phosphate ion sieve membrane of embedding lithium not is negative electrode, is anode with embedding lithium attitude tertiary iron phosphate ion sieve membrane, between two electrodes, applies the voltage of 1.5V, is to carry out electrodialysis under 7,50 ℃ at pH, whenever gets the liquor analysis Li wherein in the lithium salts chamber at a distance from 1h
+Concentration, concrete outcome is as shown in Figure 2; After keeping 10h, the Li in the bittern chamber
+Concentration is reduced to 55mg/L, Mg
2+Concentration be about 1254mg/L, the tertiary iron phosphate ion(ic)sieve is to Li
+Adsorptive capacity be about 32.2mg/g, to Mg
2+Adsorptive capacity be about 1.33mg/g; Obtain Li in the lithium salts chamber simultaneously
+Concentration is the rich lithium solution of 576mg/L.
The method of pressing embodiment 2 is with 3gFe
0.98Co
0.02PO
4Process the tertiary iron phosphate composite package, the tertiary iron phosphate composite package is placed the bittern chamber, add the 500mL salt lake brine, the composition and the content of salt lake brine are as shown in the table:
With 500mL concentration is in the NaCl solution adding lithium salts chamber of 50g/L, is negative electrode with the tertiary iron phosphate composite package, and inertia graphite is anode, applies the voltage of 2.0V, after keeping 10h under 80 ℃, and Li in the bittern chamber
+Concentration be reduced to 268.4mg/L, Mg
2+Concentration be 17991mg/L, Fe
0.98Co
0.02PO
4Ion(ic)sieve is to Li
+Adsorptive capacity be 38.6mg/g, to Mg
2+Adsorptive capacity be 1.5mg/g.
According to method identical among this embodiment, with 3g Fe
0.98Co
0.02PO
4Ion(ic)sieve is made into the not tertiary iron phosphate composite package of embedding lithium.After initial embedding lithium finishes, the tertiary iron phosphate composite package of embedding lithium is not placed the bittern chamber, add the 500mL salt lake brine; Embedding lithium attitude ion(ic)sieve is placed the lithium salts chamber; Adding 500mL concentration is the NaCl solution of 50g/L, is anode with embedding lithium attitude ion(ic)sieve, and the ion(ic)sieve of embedding lithium is not a negative electrode; Between electrode, applying the voltage of 2.0V, is to keep 10h under 12,80 ℃ at pH.After electrodialysis finishes, Li in the bittern chamber
+Concentration be reduced to 269.1mg/L, the lithium salts chamber obtains Li in the rich lithium solution
+Concentration be 115mg/L.After this electrodialysis process finishes, embedding lithium attitude ion(ic)sieve and the not form generation conversion each other of the ion(ic)sieve of embedding lithium; Keep two electrode positions constant; Liquid behind the embedding lithium in the electrodialysis unit is discharged; Again join in the former bittern chamber after rich lithium solution is transferred to storage tank, the 500mL salt lake brine is joined new bittern chamber (former lithium salts chamber), carry out the electrodialysis second time under the same conditions.After electrodialysis for the second time finishes, the Li in the rich lithium solution in lithium salts chamber
+Concentration reaches 229mg/L.
Carry out several round-robin embedding lithiums/take off the electrodialysis process of embedding in this way, after the 3rd electrodialysis, the Li of rich lithium solution in the lithium salts chamber
+Concentration is 351mg/L, rich lithium solution Li after the 4th electrodialysis
+Concentration increases to 465mg/L; Carried out 10 electrodialysis under the same conditions continuously, after the 10th electrodialysis finishes, Li in the rich lithium solution
+Concentration reaches 1162mg/L, and its concrete changing conditions is as shown in Figure 3;
The method of pressing embodiment 2 is with 10g MnO
2Process the ion(ic)sieve composite package, with MnO
2Composite package places the bittern chamber, adds the 1L salt lake brine, and the composition of salt lake brine and content are consistent with embodiment 3; Graphite Electrodes is placed the lithium salts chamber, and adding 500mL concentration is the NaCl solution of 20g/L.With MnO
2Composite package is a negative electrode, and Graphite Electrodes is an anode, applies the voltage of 1.2V, after keeping 12h under 5 ℃, and Li in the bittern chamber
+Concentration be reduced to 286mg/L, Mg
2+Concentration be 17982mg/L, MnO
2Ion(ic)sieve is to Li
+Adsorptive capacity be 21.4mg/g, to Mg
2+Adsorptive capacity be 1.8mg/g.
According to method identical among this embodiment, with 10g MnO
2Ion(ic)sieve is made into the not MnO of embedding lithium
2Composite package.After initial embedding lithium finishes, the tertiary iron phosphate composite package of embedding lithium is not placed the bittern chamber, add the 1L salt lake brine, embedding lithium attitude MnO
2Ion(ic)sieve places the lithium salts chamber, and adding 500mL concentration is the NaCl solution of 20g/L, with embedding lithium attitude MnO
2Ion(ic)sieve is an anode, not the MnO of embedding lithium
2Ion(ic)sieve is a negative electrode, between electrode, applies the voltage of 1.2V, under 5 ℃, keeps 12h.After electrodialysis finishes, Li in the bittern chamber
+Concentration be reduced to 284.2mg/L, the lithium salts chamber obtains Li in the rich lithium solution
+Concentration be 428.3mg/L.
After electrodialysis finishes, embedding lithium attitude ion(ic)sieve and the not form generation conversion each other of embedding lithium ion sieve; Keep two electrode positions constant; Liquid behind the embedding lithium in the electrodialysis unit is discharged; Again join in the former bittern chamber after the rich lithium solution of 500mL is transferred to storage tank, the 1L salt lake brine is joined new bittern chamber (former lithium salts chamber), carry out the electrodialysis second time under the same conditions.After electrodialysis for the second time finishes, Li in the bittern chamber
+Concentration be reduced to 286.3mg/L, Li in the rich lithium solution of secondary that the lithium salts chamber obtains
+Concentration be 855.1mg/L.
The weight ratios of pressing 8: 1: 1 are with 2gLi
4Ti
5O
12, 0.25g acetylene black and 0.25gPVDF mix, and the powder that mixes joined to grind in N-Methyl pyrrolidone (NMP) organic solvent size mixing, and soup compound is coated on the graphite paper, under vacuum condition, in 120 ℃ of heat preservation and drynesses 12 hours, obtains Li after the cooling
4Ti
5O
12The ion(ic)sieve composite package; With Li
4Ti
5O
12The ion sieve membrane places the bittern chamber of electrodialysis unit, adds the 1L salt lake brine, and the composition and the content of bittern are as shown in the table:
Graphite Electrodes is placed the lithium salts chamber of electrodialysis unit, add the NaCl solution 500ml of 20g/L; With the Graphite Electrodes is anode, Li
4Ti
5O
12Ion(ic)sieve is a negative electrode, between two electrodes, applies the voltage of 0.8V, after keeping 10h under 25 ℃, and Li in the bittern chamber
+Concentration be reduced to 157.6mg/L, Mg
2+Concentration do not change Li basically
4Ti
5O
12Ion(ic)sieve is to Li
+Adsorptive capacity be 21.2mg/g.
According to method identical among this embodiment, with 2g Li
4Ti
5O
12Ion(ic)sieve is made into the not ion(ic)sieve composite package of embedding lithium.After initial embedding lithium finishes, with the Li of embedding lithium not
4Ti
5O
12Composite package places the bittern chamber, adds the 1L salt lake brine, and embedding lithium attitude ion sieve membrane is placed the lithium salts chamber, and adding 500mL concentration is the NaCl solution of 20g/L, with embedding lithium attitude Li
4Ti
5O
12Ion(ic)sieve is an anode, not the Li of embedding lithium
4Ti
5O
12Ion(ic)sieve is a negative electrode, between electrode, applies the voltage of 0.8V, is to keep 10h under 5,5 ℃ at pH.After electrodialysis finishes, Li in the bittern chamber
+Concentration be reduced to 155.4mg/L, the lithium salts chamber obtains Li in the rich lithium solution
+Concentration be 88.7mg/L.
The weight ratios of pressing 8: 1: 1 are with 4gLiFe
0.99Mn
0.01PO
4/ C, 0.5g high purity graphite and 0.5gPVDF mix; Add N-Methyl pyrrolidone (NMP) organic solvent and grind furnishing pulpous state fluid, soup compound is coated on the graphite paper, under vacuum condition; Be warming up to 110 ℃ of insulations 12 hours, obtain the iron lithium phosphate composite package after the cooling; With the iron lithium phosphate composite package is anode, is negative electrode with the nickel foam, and placing 1L concentration is the NaCl solution of 30g/L, applies the voltage 10h of 1.1V at the electrode two ends, and the iron lithium phosphate composite package is converted into the tertiary iron phosphate ion(ic)sieve;
Press method identical among this embodiment with 4gLiFe
0.99Mn
0.01PO
4/ C is made into the iron lithium phosphate composite package, and the iron lithium phosphate composite package is placed the lithium salts chamber of electrodialysis unit, adds the NaCl solution 500ml of 30g/L; The tertiary iron phosphate ion(ic)sieve of gained is placed the bittern chamber, add the 1L salt lake brine, the composition and the content of bittern are as shown in the table:
With the iron lithium phosphate composite package is anode, and the tertiary iron phosphate ion(ic)sieve is a negative electrode, after pH is the voltage that applies 1.0V under 8,25 ℃, keeps 15h, and Li in the bittern chamber
+Concentration be reduced to 66.5mg/L, Mg
2+Concentration be 1257mg/L, Li in the lithium salts chamber
+Concentration be 267.4mg/L.
Embodiment 7
The weight ratios of pressing 8: 1: 1 are with 2gLiFePO
4/ C, 0.25g high purity graphite and 0.25gPVDF mix; Add N-Methyl pyrrolidone (NMP) organic solvent and grind furnishing pulpous state fluid; Soup compound is coated on the carbon cloth; After placing vacuum drying oven to vacuumize, be warming up to 110 ℃ of insulations 12 hours, obtain the iron lithium phosphate composite package after the cooling; With the iron lithium phosphate composite package is anode, is negative electrode with the nickel foam, and placing 1L concentration is the NaCl solution of 20g/L, applies the voltage 12h of 1.0V at the electrode two ends, and the iron lithium phosphate composite package is converted into the tertiary iron phosphate ion(ic)sieve;
Press method identical among this embodiment with 2gLiFePO
4/ C is made into the iron lithium phosphate composite package, and the iron lithium phosphate composite package is placed the lithium salts chamber of electrodialysis unit, adds the NaCl solution 1L of 50g/L; The tertiary iron phosphate ion(ic)sieve of gained is placed the bittern chamber, add the 1L salt lake brine, the composition and the content of bittern are as shown in the table:
With the iron lithium phosphate composite package is anode, and the tertiary iron phosphate ion(ic)sieve is a negative electrode, after pH is the voltage that applies 1.0V under 10,30 ℃, keeps 12h, and Li in the bittern chamber
+Concentration be reduced to 442.3mg/L, Li in the lithium salts chamber
+Concentration be 57.8mg/L.After electrodialysis finishes, after electrodialysis finishes, embedding lithium attitude ion(ic)sieve and the not form generation conversion each other of embedding lithium ion sieve; Position transposing with above-mentioned two electrodes; The tertiary iron phosphate ion(ic)sieve that is about to the iron lithium phosphate composite package conversion gained in the lithium salts chamber places the bittern chamber as negative electrode; The embedding lithium attitude ion(ic)sieve that tertiary iron phosphate ion(ic)sieve in the bittern chamber is transformed gained places the lithium salts chamber as anode, carries out electrodialysis under the same conditions; After electrodialysis finishes, Li in the bittern chamber
+Concentration become 384.6mg/L, Li in the lithium salts chamber
+Concentration be increased to 115.7mg/L.
Carry out the several circulation in this way, after the 6th electrodialysis finishes, Li in the bittern chamber
+Concentration become 153.5mg/L, Li in the lithium salts chamber
+Concentration be increased to 346.8mg/L.
Claims (10)
1. a salt lake brine magnesium lithium separates and the method for enriching lithium, it is characterized in that, in turn includes the following steps:
(1) with anion-exchange membrane the electrodialysis cell of electrodialysis unit vertically is separated into two zones in lithium salts chamber and bittern chamber, the indoor salt lake brine that charges into of bittern, indoor the charging into of lithium salts do not contain Mg
2+Supporting electrolyte solution;
The conducting base that (2) will be coated with ion(ic)sieve places the bittern chamber as negative electrode; Place the lithium salts chamber as anode the conducting base that is coated with embedding lithium attitude ion(ic)sieve, under the driving of electromotive force, make the Li in the bittern of bittern chamber outside
+Be embedded into formation embedding lithium attitude ion(ic)sieve in the ion(ic)sieve, the embedding lithium attitude ion(ic)sieve in the lithium salts chamber is with Li simultaneously
+After being discharged into conductive soln, revert to ion(ic)sieve; Realize the Li in the bittern chamber
+With Mg
2+And other cationic separation, lithium enrichment in the lithium salts chamber obtains rich lithium solution simultaneously.
2. the method for claim 1 is characterized in that,
After step (2) is accomplished, carry out once following operation at least:
Liquid behind the embedding lithium in the bittern chamber is discharged, add salt lake brine again, then negative electrode and anode exchange are placed, proceed electrodialysis.
3. the method for claim 1 is characterized in that,
After step (2) is accomplished, carry out once following operation at least:
Holding anode and negative electrode stationkeeping are discharged liquid behind the embedding lithium in the bittern chamber, and the lithium-containing solution in the lithium salts chamber is transferred in the bittern chamber, and new salt lake brine is joined in the lithium salts chamber; Be about to bittern chamber and lithium salts chamber transition function and use, proceed electrodialysis.
4. like claim 1 or 2 or 3 described methods, it is characterized in that described salt lake brine comprises and contains Li arbitrarily
+Solution, arbitrarily original bittern and the bittern after the evaporation concentration thereof in the salt lake and carry potassium after the old halogen of evaporation in one or more.
5. the method for claim 1 is characterized in that, the described conducting base of step (2) is to be coated with a kind of in ruthenium titanium net, graphite cake, Pt family metal and Alloy Foil thereof, carbon cloth, the graphite paper.
6. like claim 1 or 2 or 3 described methods, it is characterized in that the temperature of solution is 0～80 ℃ in the electrodialysis unit, the pH value is 2～12; Two interelectrode voltage ranges are 0.5～2.0V in the electrodialysis unit.
7. like claim 1 or 2 or 3 described methods, it is characterized in that described ion(ic)sieve is tertiary iron phosphate, lithium titanate, MnO
2In one or more mixture.
8. method as claimed in claim 7 is characterized in that, described tertiary iron phosphate is Fe
1-xMe
xPO
4, wherein Me is one or more the mixing among Mn, Co, Mo, Ti, Al, Ni, the Nb, the scope of x is: 0≤x≤0.1; Lithium titanate is Li
4Ti
5O
12, Li
xMe
yTi
5O
12, Li
4Me
mTi
nO
12In one or more mixture; Me is one or more the mixing among V, Fe, Co, Mn, Al, Ba, Ag, Zr, Sr, Nb, the F; 0＜x＜4,0＜y＜4,0＜m＜5,0＜n＜5.
9. the method for claim 1 is characterized in that, described embedding lithium attitude ion(ic)sieve directly adopts iron lithium phosphate or LiMn
2O
4In a kind of; Described iron lithium phosphate is LiFePO
4, Li
xMe
yFePO
4, LiFe
xMe
yPO
4, LiFePO
4/ C, Li
xMe
yFePO
4/ C, LiFe
xMe
yPO
4The mixture of one or more the among/C, wherein Me is one or more the mixing among Mn, Co, Mo, Ti, Al, Ni, the Nb, 0＜x＜1,0＜y＜1;
Perhaps obtain through following process: with anion-exchange membrane electrodialysis unit is divided into two zones in lithium salts chamber and bittern chamber, the indoor salt lake brine that charges into of bittern, indoor the charging into of lithium salts do not contain Mg
2+Supporting electrolyte solution; Will be to Li
+Selective adsorbing ion(ic)sieve is coated on the conducting base, places the bittern chamber of electrodialysis unit, is negative electrode with the ion(ic)sieve, is that counter electrode carries out cathodic polarization with the noble electrode, makes the Li in the bittern
+Be embedded into and obtain embedding lithium attitude ion(ic)sieve in the ion(ic)sieve.
10. the described salt lake brine magnesium of claim 1 lithium separates and the corollary apparatus of the method for enriching lithium; It is characterized in that; Comprise and have the electrodialysis unit that is separated into two spatial electrodialysis cells by anion-exchange membrane; And negative electrode and anode, described negative electrode and anode are arranged at respectively in two spaces that are divided into; Described negative electrode is the conducting base that is coated with ion(ic)sieve, and anode is the conducting base that is coated with embedding lithium attitude ion(ic)sieve.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57105206A (en) * | 1980-12-22 | 1982-06-30 | Ishikawajima Harima Heavy Ind Co Ltd | Method for removing silicon content from digested liquid of pulp |
| CN1626443A (en) * | 2003-12-20 | 2005-06-15 | 中国科学院青海盐湖研究所 | Method for separating magnesium and concentrating lithium from brine in salt lake |
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN202181336U (en) * | 2011-07-04 | 2012-04-04 | 中南大学 | Device for separating magnesium and lithium from salt lake brine and enriching lithium |
-
2011
- 2011-07-04 CN CN2011101851286A patent/CN102382984B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57105206A (en) * | 1980-12-22 | 1982-06-30 | Ishikawajima Harima Heavy Ind Co Ltd | Method for removing silicon content from digested liquid of pulp |
| CN1626443A (en) * | 2003-12-20 | 2005-06-15 | 中国科学院青海盐湖研究所 | Method for separating magnesium and concentrating lithium from brine in salt lake |
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN202181336U (en) * | 2011-07-04 | 2012-04-04 | 中南大学 | Device for separating magnesium and lithium from salt lake brine and enriching lithium |
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