CN102382984B - Method for separating magnesium and lithium and enriching lithium from salt lake brine - Google Patents
Method for separating magnesium and lithium and enriching lithium from salt lake brine Download PDFInfo
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- CN102382984B CN102382984B CN2011101851286A CN201110185128A CN102382984B CN 102382984 B CN102382984 B CN 102382984B CN 2011101851286 A CN2011101851286 A CN 2011101851286A CN 201110185128 A CN201110185128 A CN 201110185128A CN 102382984 B CN102382984 B CN 102382984B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 148
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000012267 brine Substances 0.000 title claims abstract description 52
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000011777 magnesium Substances 0.000 title claims abstract description 40
- 229910052749 magnesium Inorganic materials 0.000 title abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 86
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 86
- 150000002500 ions Chemical class 0.000 claims abstract description 79
- 238000000909 electrodialysis Methods 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 53
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 9
- 241001131796 Botaurus stellaris Species 0.000 claims description 116
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 40
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 40
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000012528 membrane Substances 0.000 description 46
- 239000002131 composite material Substances 0.000 description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- 229940085991 phosphate ion Drugs 0.000 description 25
- 239000011780 sodium chloride Substances 0.000 description 16
- 230000000274 adsorptive effect Effects 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 235000014347 soups Nutrition 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明涉及一种盐湖卤水镁锂分离及富集锂的方法和装置。用阴离子交换膜将电渗析装置隔成锂盐室和卤水室两个区域，卤水室内充入盐湖卤水，锂盐室内充入不含Mg2+的支持电解质溶液；将涂覆有离子筛的导电基体置于卤水室中，作为阴极；将涂覆有嵌锂态离子筛的导电基体置于锂盐室中，作为阳极；在外电势的驱动下，使卤水室卤水中的Li+嵌入到离子筛中形成嵌锂态离子筛，锂盐室中的嵌锂态离子筛将Li+释放到导电溶液后，恢复为离子筛；卤水室中的嵌锂后液排出，重新加入盐湖卤水，两室电极交换放置，重复循环操作。高效实现锂与其他离子的分离，同时获得富锂溶液。本方法流程短，操作简单，生产成本低，可连续操作，易于工业化应用。The invention relates to a method and a device for separating magnesium and lithium from salt lake brine and enriching lithium. Anion-exchange membranes are used to separate the electrodialysis device into two areas: a lithium salt chamber and a brine chamber. The brine chamber is filled with salt lake brine, and the lithium salt chamber is filled with a supporting electrolyte solution that does not contain Mg 2+ ; The substrate is placed in the brine chamber as the cathode; the conductive substrate coated with the lithium-intercalated ion sieve is placed in the lithium salt chamber as the anode; driven by the external potential, Li + in the brine of the brine chamber is inserted into the ion sieve The lithium-intercalated ion sieve is formed in the lithium-salt chamber, and the lithium-intercalated ion sieve in the lithium-salt chamber releases Li + into the conductive solution, and then recovers as an ion sieve; the lithium-intercalated liquid in the brine chamber is discharged, and the salt lake brine is added again, and the electrodes in the two chambers Replace and repeat the cycle. Efficiently realize the separation of lithium and other ions, and at the same time obtain a lithium-rich solution. The method has the advantages of short flow, simple operation, low production cost, continuous operation and easy industrial application.
Description
Technical field
The invention belongs to the extraction field of metallurgy, specifically, relate to and a kind ofly make it the magnesium lithium and separate for directly processing salt lake brine, and then the method and apparatus of enriching lithium.
Background technology
Since nineteen ninety, lithium ion battery was by the Sony commercialization, it is more and more important that lithium seems in modern industry, 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.Along with the growth of the market requirement, 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, Mg/Li ratio relatively low (about 6:1) except 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 the coexistence of a large amount of alkaline-earth metal ions.Since diagonal rule, Mg
2+With Li
+Chemical property closely similar, it is very difficult that the magnesium lithium separates, and seriously restricted 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 the technology such as the precipitator method, carborization, ion exchange method, solvent extration to develop 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 object of the invention is to, propose a kind of for directly from salt lake brine the magnesium lithium being separated the method for enriching lithium and supporting device thereof.Efficient realization lithium separates with other ions, obtains simultaneously rich lithium solution.Present method flow process is short, and simple to operate, production cost is low, but operate continuously is easy to industrial applications.
A kind of method of salt lake brine magnesium lithium separation and concentration 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 is filled with of bittern, indoor being filled with of lithium salts do not contain Mg
2+Supporting electrolyte solution, such as 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 finished, can also carry out at least once following operation:
Liquid behind the embedding lithium in the bittern chamber is discharged, again add salt lake brine, then negative electrode and anode exchange are placed, proceed electrodialysis.
After perhaps step (2) is finished, for fear of each exchange negative electrode and anode, can also carry out at least once following operation, further make Li
+With Mg
2+And other cation separation, the Sync enrichment lithium:
Holding anode and negative electrode position are fixed, and liquid behind the embedding lithium in the bittern chamber is discharged, 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 by 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 is filled with of bittern, indoor being filled with 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, take ion(ic)sieve as negative electrode, take noble electrode as electrode is carried out cathodic polarization, 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 arbitrarily Li
+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 method for above-mentioned salt lake brine magnesium lithium separation and concentration lithium, comprise and have the electrodialysis unit that is separated into the electrodialysis cell in two spaces 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, adopt in the aqueous solution steady operation and to Li
+The ion-sieve material that memory effect is arranged by adjusting the 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, by the effective separation of this process implementation lithium and other ions; 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, adjust the electromotive force of system, make 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 is filled with of bittern, indoor being filled with 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, take ion-sieve material as negative electrode, take inert anode as electrode is carried out cathodic polarization, 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 enters the lithium salts chamber from the bittern chamber through exchange membrane and keeps charge balance, and the Li in the bittern chamber
+Transfer in the lithium salts chamber by solid phase;
(3). after step (2) is finished, for further making Li
+With Mg
2+And other cation separation, the Sync enrichment lithium can also proceed 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 by 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 operate as follows: after step (2) is finished, negative electrode and anode position immobilize, 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 be converted to new lithium salts chamber, former lithium salts chamber is converted to new bittern chamber (be about to bittern chamber and lithium salts chamber transition function use), 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 simultaneously rich lithium solution; 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 ion(ic)sieve when carrying out magnesium lithium separation and concentration lithium, can carry out as follows:
(1) iron lithium phosphate is coated on the conducting base, places conductive soln as anode, take noble electrode as negative electrode; Between two electrodes, apply outer electromotive force, make 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 enters the lithium salts chamber from the bittern chamber through exchange membrane and keeps charge balance; Step (1) and (2) total effect are equivalent to the Li in the bittern chamber
+Transfer to first the solid phase ion(ic)sieve, 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 large, good stability, the lithium in the enrichment bittern that can circulate;
1, this method can be processed the bittern of different Mg/Li ratios, particularly can efficiently solve the technical barrier that the magnesium lithium separates in the high Mg/Li ratio bittern;
2, the designed electrodialysis unit of this method can be finished simultaneously the embedding of lithium on two working electrodes 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 finishing one-period, realize continuous circulation work by transposing electrode or electrolyte solution;
3, the designed electrodialysis unit of this method can be finished the enrichment of lithium synchronously when the magnesium lithium separates; And electrodialysis unit is simple in structure, and is easy to operate, energy circular treatment salt lake brine;
4, this method cost is low, is easy to large-scale production.
Description of drawings
Fig. 1 is 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 the variation diagram of electrodialysis time;
Fig. 3 is Li of the present invention
+Concentration is with the variation diagram of recycle ratio.
Embodiment
In order to explain in more detail the present invention, 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 and anode 3 are arranged at respectively in two spaces that are divided into; 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.
Press the weight ratio of 20:1:1 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 membrane after the cooling; The tertiary iron phosphate composite membrane is placed the bittern chamber of electrodialysis unit, and the schematic top plan view of electrodialysis unit as shown in Figure 1; The 2L salt lake brine is added the bittern chamber, and main component and the content of salt lake brine are as shown in the table:
Be that the NaCl solution of 20g/L joins in the lithium salts chamber of electrodialysis unit with 500mL concentration; Take tertiary iron phosphate ion sieve membrane as negative electrode, the inertia graphite in the lithium salts chamber applies the voltage of 0.5V as anode 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 membrane of embedding lithium, and this composite membrane is placed the bittern chamber, adds the 2L salt lake brine, and its main component and content still see the above table; Take the tertiary iron phosphate ion sieve membrane of embedding lithium not as negative electrode, take embedding lithium attitude tertiary iron phosphate ion sieve membrane as anode, between two electrodes, apply the voltage of 0.8V, after pH is to keep 12h under 2,25 ℃, 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.
Press the weight ratio of 90:5:5 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, in 110 ℃ of heat preservation and drynesses 10 hours, obtain tertiary iron phosphate ion(ic)sieve composite membrane after the cooling.
The tertiary iron phosphate composite membrane is placed the bittern chamber, add the 2L salt lake brine, composition and the content of bittern are as shown in the table:
Be that the NaCl solution of 50g/L joins in the lithium salts chamber of electrodialysis unit with 200mL concentration; Take tertiary iron phosphate ion sieve membrane as negative electrode, the Pt electrode in the lithium salts chamber applies the voltage of 1.0V as anode 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 membrane of embedding lithium, and this composite membrane is placed the bittern chamber, adds the 2L salt lake brine, and its main component and content see the above table; Take the tertiary iron phosphate ion sieve membrane of embedding lithium not as negative electrode, take embedding lithium attitude tertiary iron phosphate ion sieve membrane as anode, between two electrodes, apply the voltage of 1.5V, be to carry out electrodialysis under 7,50 ℃ at pH, get liquor analysis Li wherein in the lithium salts chamber every 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.
Press the method for embodiment 2 with 3g Fe
0.98Co
0.02PO
4Make the tertiary iron phosphate composite membrane, the tertiary iron phosphate composite membrane is placed the bittern chamber, add the 500mL salt lake brine, composition and the content of salt lake brine are as shown in the table:
Be that the NaCl solution of 50g/L adds in the lithium salts chamber with 500mL concentration, take the tertiary iron phosphate composite membrane as negative electrode, 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 membrane of embedding lithium.After initial embedding lithium finishes, the tertiary iron phosphate composite membrane 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, and take embedding lithium attitude ion(ic)sieve as anode, the ion(ic)sieve of embedding lithium is not negative electrode, applying the voltage of 2.0V between electrode, 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 mutually conversion of form generation 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 under the same conditions the electrodialysis second time.After for the second time electrodialysis finishes, the Li in the rich lithium solution in lithium salts chamber
+Concentration reaches 229mg/L.
Carry out in this way the embedding lithium of several circulations/take off the electrodialysis process of embedding, 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 continuously under the same conditions 10 electrodialysis, after the 10th electrodialysis finishes, Li in the rich lithium solution
+Concentration reaches 1162mg/L, and its concrete changing conditions as shown in Figure 3;
Embodiment 4
Press the method for embodiment 2 with 10g MnO
2Make the ion(ic)sieve composite membrane, with MnO
2Composite membrane 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 membrane is negative electrode, and Graphite Electrodes is 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 membrane.After initial embedding lithium finishes, the tertiary iron phosphate composite membrane of embedding lithium is not placed the bittern chamber, add the 1L salt lake brine, with 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 anode, not the MnO of embedding lithium
2Ion(ic)sieve is negative electrode, applies the voltage of 1.2V between electrode, keeps 12h under 5 ℃.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 mutually conversion of form generation 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 under the same conditions the electrodialysis second time.After for the second time electrodialysis 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.
Embodiment 5
Press the weight ratio of 8:1:1 with 2gLi
4Ti
5O
12, 0.25g acetylene black and 0.25gPVDF mix, the powder that mixes joined to grind in N-Methyl pyrrolidone (NMP) organic solvent size mixing, 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 membrane; With Li
4Ti
5O
12The ion sieve membrane places the bittern chamber of electrodialysis unit, adds the 1L salt lake brine, and 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; Take Graphite Electrodes as anode, Li
4Ti
5O
12Ion(ic)sieve is negative electrode, applies the voltage of 0.8V between two electrodes, after keeping 10h under 25 ℃, and Li in the bittern chamber
+Concentration be reduced to 157.6mg/L, Mg
2+Concentration there is no variation, Li
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 membrane of embedding lithium.After initial embedding lithium finishes, with the Li of embedding lithium not
4Ti
5O
12Composite membrane 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 anode, not the Li of embedding lithium
4Ti
5O
12Ion(ic)sieve is negative electrode, applies the voltage of 0.8V between electrode, 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.
Press the weight ratio of 8:1:1 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 membrane after the cooling; Take the iron lithium phosphate composite membrane as anode, take nickel foam as negative electrode, 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 membrane 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 membrane, and the iron lithium phosphate composite membrane 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, composition and the content of bittern are as shown in the table:
Take the iron lithium phosphate composite membrane as anode, the tertiary iron phosphate ion(ic)sieve is 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
Press the weight ratio of 8:1:1 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 membrane after the cooling; Take the iron lithium phosphate composite membrane as anode, take nickel foam as negative electrode, 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 membrane 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 membrane, and the iron lithium phosphate composite membrane 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, composition and the content of bittern are as shown in the table:
Take the iron lithium phosphate composite membrane as anode, the tertiary iron phosphate ion(ic)sieve is 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 mutually conversion of form generation 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 membrane 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 under the same conditions electrodialysis; 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 in this way the several circulation, 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 (8)
1. the method for a salt lake brine magnesium lithium separation and concentration lithium 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 is filled with of bittern, indoor being filled with 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;
Described salt lake brine comprises and contains arbitrarily Li
+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.
2. the method for claim 1 is characterized in that,
After step (2) is finished, carry out at least once following operation:
Liquid behind the embedding lithium in the bittern chamber is discharged, again add salt lake brine, then negative electrode and anode exchange are placed, proceed electrodialysis.
3. the method for claim 1 is characterized in that,
After step (2) is finished, carry out at least once following operation:
Holding anode and negative electrode position are fixed, and liquid behind the embedding lithium in the bittern chamber is discharged, 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. 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.
5. such as 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.
6. such as 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.
7. method as claimed in claim 6 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.
8. 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 by 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 is filled with of bittern, indoor being filled with 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, take ion(ic)sieve as negative electrode, take noble electrode as electrode is carried out cathodic polarization, makes the Li in the bittern
+Be embedded into and obtain embedding lithium attitude ion(ic)sieve in the ion(ic)sieve.
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Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1281497C (en) * | 2003-12-20 | 2006-10-25 | 中国科学院青海盐湖研究所 | Method for separating magnesium and concentrating lithium from brine in salt lake |
| CN102049238B (en) * | 2010-11-19 | 2012-08-15 | 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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Application publication date: 20120321 Assignee: Shanghai Hua Dan Technology Development Co. Ltd. Assignor: Central South University Contract record no.: 2017430000029 Denomination of invention: Method and device for separating magnesium and lithium and enriching lithium from salt lake brine Granted publication date: 20130313 License type: Exclusive License Record date: 20171229 |