CN107720786A - A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method - Google Patents
A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method Download PDFInfo
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 228
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 101
- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 88
- 239000011777 magnesium Substances 0.000 claims abstract description 77
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000909 electrodialysis Methods 0.000 claims abstract description 34
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 238000001728 nano-filtration Methods 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 32
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 27
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 238000010612 desalination reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000001764 infiltration Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 7
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 51
- 229910001416 lithium ion Inorganic materials 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000009993 causticizing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009298 carbon filtering Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- -1 lithium sulfates Lithium hydroxide Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 229940061584 phosphoramidic acid Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method, it includes step：It is prepared by separating magnesium and lithium, depth demagging, acidity adjustment, enrichment concentration, bipolar membrane electrodialysis and lithium hydroxide；In the preparation method, the divalent ions such as magnesium calcium are realized with lithium by separating magnesium and lithium and depth demagging and are kept completely separate, the depth of acquisition obtains rich lithium concentrate except magnesium liquid after acidity adjustment and enrichment concentration, again through bipolar membrane electrodialysis, realize the separation of lithium and boron, so as to obtain lithium hydroxide pregnant solution and boron-rich feed liquid, hydrochloric acid pregnant solution, lithium hydroxide pregnant solution can be used to prepare high-purity LITHIUM BATTERY lithium hydroxide, and boron-rich feed liquid also can be through preparing boric acid, hydrochloric acid pregnant solution can carry out reuse.Preparation in accordance with the present invention reduces the energy consumption and cost for preparing lithium hydroxide product for raw material by salt lake bittern, and have very prominent environment-friendly advantage by using the method for a variety of membrane separation process efficient couplings.
Description
Technical field
The invention belongs to salt lake resources technical field of comprehensive utilization, it relates in particular to which a kind of be based on UF membrane coupled method
LITHIUM BATTERY lithium hydroxide preparation method.
Background technology
Lithium ore and bittern are the main production raw material of lithium hydroxide, in addition also can be by lithium salts such as lithium carbonate, lithium sulfates
Lithium hydroxide product is made by being processed further in product.Wherein, the main method bag of lithium hydroxide is produced using bittern as raw material
Include：Calcination method, ion-exchange membrane electrolysis, aluminate lithium precipitation method etc..According to processing method, chemical method and electrolysis two are broadly divided into
Kind method；Lithium carbonate is mainly carried out causticization by chemical method, and the LiOH solution of concentration about 3% can be obtained in causticization process, with
Afterwards by further concentration and crystallization, the higher lithium hydroxide product of purity is obtained.Lithium battery generally requires very high purity
The impurity element such as lithium hydroxide, calcium, sodium, chlorine need to remove as far as possible, but in passing through the lithium hydroxide product that causticizing reaction obtains
Concentration impurity ion is difficult further reduces, it is necessary to be adsorbed by complicated technique, such as using the ion exchange resin of calcium base
Method purified, so can largely increase the cost of production process, and also need to largely post-process work
Skill, such as purification and concentration, also can largely increase operating time and running cost.Compared with chemical causticizing process, electrolysis
Voltage and energy consumption needed for method is higher, largely have impact on the security and economy of operation, and can produce a large amount of
Cl2Gas, on the one hand there is very big corrosion to electrode, on the other hand it can not be directly discharged, it is necessary to catch as pernicious gas
Catch or recovery process, its production cost can also improve therewith.Therefore, at present causticizing process and electrolysis both prepare lithium hydroxide
The common technology of product, due to it is above-mentioned the defects of large-scale industrialization application relatively difficult to achieve, and due to production technology cost
It is higher, it is unfavorable for the lifting of salt lake lithium hydroxide product core competitiveness.Therefore, it is a kind of with prominent technical advantage to need exploitation badly
With cost advantage, by the method for the LITHIUM BATTERY lithium hydroxide of salt lake richness lithium bittern direct preparation of high-purity.
Electrodialytic technique is a kind of electrically driven (operated) membrane separating process, the effect of electric field can be utilized to realize target in solution
Mass transport process of the charged ion in single-phase, its process have that current utilization efficiency is high, process energy consumption is low, ion exchange membrane module
The advantages that being easily changed.Wherein, bipolar membrane electrodialysis process the preparation field of lithium hydroxide have very prominent advantage and
Development potentiality, but this method is not yet applied to directly prepare LITHIUM BATTERY hydroxide as raw material using salt lake richness lithium bittern at present
Lithium, still there are substantial amounts of matter of science and technology and industrialization bottleneck to need to solve.As a kind of Bipolar Membrane method reclaims hydrogen-oxygen from solution
Change the method for lithium, it is handled with bipolar membranous system the solution containing lithium sulfate, is obtained after the processing of bipolar membranous system
Sulfuric acid and lithium hydroxide, solve the environmental issue of traditional lithium hydroxide preparation method, realize preparation process energy-conserving and environment-protective,
Reduce operating cost；But the raw material of this method are the battery production accessory substances of main sulfur acid lithium, and calcium therein,
The impurity ion contents such as magnesium, sodium are very low, therefore this method can not be by the LITHIUM BATTERY hydrogen-oxygen of salt lake richness lithium bittern direct preparation of high-purity
Change lithium.A kind of and for example method that lithium hydroxide is extracted by salt lake bittern, it is removed in salt lake bittern by adding sodium carbonate first
Calcium ions and magnesium ions obtain low Mg/Li ratio bittern, carrying out enrichment to low Mg/Li ratio bittern using common electrodialysis is concentrated to give concentration halogen
Water, add proper amount of sodium carbonate again afterwards and carry out depth demagging, add sodium carbonate and obtain lithium carbonate；Obtained lithium carbonate is molten
Lithium hydroxide product is prepared by electrolysis-bipolar membrane electrodialysis system after solution；But this method is dropped by adding sodium carbonate
Mg/Li ratio in low bittern is, it is necessary to consume substantial amounts of soda ash, increase process costs, and caused a large amount of carbonate by-products are difficult
It is utilized effectively, in addition, intermediate products-lithium carbonate must be prepared by salt lake bittern first in this method, recycle
Electrolysis-bipolar membrane electrodialysis system carries out the preparation of lithium hydroxide, therefore lithium ion will at least pass through twice evaporation knot in bittern
Brilliant process (being the crystallization of lithium carbonate for the first time, be the crystallization of lithium hydroxide for the second time), causes the flow of the technique longer, and
And it is difficult to ensure that lithium ion yield in Lithium hydroxide preparation process, while add the preparation technology energy consumption of product.
The content of the invention
To solve the above-mentioned problems of the prior art, the invention provides a kind of LITHIUM BATTERY based on UF membrane coupled method
Lithium hydroxide preparation method, the LITHIUM BATTERY lithium hydroxide preparation method by rationally coupling a variety of membrane separation processes, so as to efficiently,
Inexpensively magnesium lithium and lithium boron are efficiently separated.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method, including step：
Separating magnesium and lithium：Using lithium-containing solution as nanofiltration raw water, and separating magnesium and lithium is carried out by nano filtering process, obtain nanofiltration production water
With nanofiltration concentrated water；Wherein, in the lithium-containing solution, Li+Concentration be 0.05g/L~2.0g/L, Mg2+Concentration be 0.25g/
L~20.0g/L, Mg/Li ratio are no more than 200；In water is produced in the nanofiltration, Li+Concentration be 0.10g/L~2.50g/L, Mg2+'s
Concentration is 0.01g/L~2.4g/L, and Mg/Li ratio is 0.01~3.0；
Depth demagging：Water is produced into the nanofiltration depth demagging, institute are carried out by ion-exchange or the precipitation method or ultrafiltration
State the magnesium ion in nanofiltration production water and calcium ion is removed, obtain depth and remove magnesium liquid；Wherein, in the depth removes magnesium liquid, Li+
Concentration be 0.05g/L~2.0g/L, Mg2+Concentration be 0.1mg/L~20.0mg/L；
Acidity adjustment：By the depth except the pH of magnesium liquid is adjusted to 3.0~7.0, obtain acidifying depth and remove magnesium liquid；
Enrichment concentration：By the acidifying depth except magnesium liquid carries out enrichment concentration by film concentration systems, rich lithium concentration is obtained
Liquid and desalination production water；Wherein, in the rich lithium concentrate, Li+Concentration be 2.0g/L~20.0g/L；In the desalination production
In water, Li+Concentration be 0.01g/L~0.10g/L；
Bipolar membrane electrodialysis：The rich lithium concentrate is handled by bipolar membrane electrodialysis system, the Bipolar Membrane electric osmose
Analysis system includes the anode chamber that is oppositely arranged and cathode chamber, be folded between the anode chamber and the cathode chamber by Bipolar Membrane,
Cavity block and anode membrane are alternately arranged the membrane stack of composition, and the Bipolar Membrane includes the anode film and cathodic coating mutually attached, the Bipolar Membrane
Cathodic coating and the anode membrane is relative forms alkali room, the anode film of the Bipolar Membrane and cavity block is relative forms sour room, it is described
Anode membrane and the relative formation feed liquid room of the cavity block；Pole liquid is passed through into the anode chamber and the cathode chamber, into the alkali room
Lithium hydroxide solution is passed through, hydrochloric acid solution is passed through in the sour room, while the rich lithium concentrate is passed through into the feed liquid room,
In the presence of DC electric field, the Li in the rich lithium concentrate+Enter the alkali room through the anode membrane, and in the alkali room shape
Into lithium hydroxide pregnant solution；Cl in the rich lithium concentrate-Enter the sour room through the cavity block, and formed in the sour room
Hydrochloric acid pregnant solution；Boron-rich feed liquid is formed in the feed liquid room；
It is prepared by lithium hydroxide：The lithium hydroxide pregnant solution is through evaporating, crystallizing acquisition coarse lithium hydroxide monohydrate；Described one
Water lithium hydroxide crude product is through recrystallizing, dry acquisition LITHIUM BATTERY lithium hydroxide.
Further, the boron-rich feed liquid is through evaporative crystallization, and separation of solid and liquid, obtains boric acid.
Further, by the way that salt lake bittern is diluted, filtering and impurity removing, obtain the lithium-containing solution.
Further, the desalination production water is back in the separating magnesium and lithium step, for diluting the salt lake bittern.
Further, in the lithium-containing solution, Li+Concentration be 0.10g/L~0.40g/L, Mg2+Concentration be
0.5g/L~10.0g/L, Mg/Li ratio are 20~50；In water is produced in the nanofiltration, Li+Concentration be 0.30g/L~0.60g/L,
Mg2+Concentration be 0.01g/L~0.6g/L, Mg/Li ratio is 0.02~1.0.
Further, in the depth removes magnesium liquid, Li+Concentration be 0.30g/L~0.60g/L, Mg2+Concentration be
0.1mg/L~5.0mg/L.
Further, in the acidity adjustment step, by the depth except the pH of magnesium liquid is adjusted to 4.5~5.5, obtain
The acidifying depth removes magnesium liquid.
Further, in the rich lithium concentrate, Li+Concentration be 3.0g/L~6.0g/L；In the desalination production water
In, Li+Concentration be 0.04g/L~0.08g/L.
Further, the pole liquid is sodium chloride solution or metabisulfite solution.
Further, it is described desalination production water be back in the bipolar membrane electrodialysis step, for prepare the pole liquid and/
Or the lithium hydroxide solution.
Further, the hydrochloric acid pregnant solution is back in the acidity adjustment step, for adjusting the depth demagging
The pH of liquid, magnesium liquid is removed to obtain the acidifying depth.
Further, the film concentration systems are selected from counter-infiltration system, common electrodialysis system or the reverse osmosis being sequentially connected
Permeable system and electrodialysis system.
Further, in the lithium-containing solution, Mg/Li ratio is 20~200.
The present invention is special by using the technique of a variety of membrane separating method-nanofiltrations, ion exchange and bipolar membrane electrodialysis
Point, it is proposed that a variety of membrane separating method couplings of multistage nanofiltration-ion exchange-counter-infiltration/common electrodialysis-bipolar membrane electrodialysis
Salt lake puies forward lithium method.Substantially shorten preparation technology flow compared with conventional method, effectively increase salt lake brine with high magnesium-lithium ratio
The efficiency of lithium hydroxide product is prepared, while realizes effective concentration of lithium and the separation of boron, it is original to reduce by salt lake bittern
Material prepares the energy consumption and cost of lithium hydroxide product, realizes the high-recovery of lithium and the high reclamation rate of fresh water；Processing procedure
Any organic reagent is not introduced, and will not produce discarded object and sewage, and there is very prominent environment-friendly advantage.
Brief description of the drawings
The following description carried out in conjunction with the accompanying drawings, above and other aspect, feature and the advantage of embodiments of the invention
It will become clearer, in accompanying drawing：
Fig. 1 is the technological process according to the LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method of the present invention
Figure；
Fig. 2 is the schematic diagram according to the three Room bipolar membrane electrodialysis systems of the present invention；
Fig. 3 is film stacking structure schematic diagram in the three Room bipolar membrane electrodialysis systems according to the present invention.
Embodiment
Hereinafter, with reference to the accompanying drawings to embodiments of the invention are described in detail.However, it is possible to come in many different forms real
Apply the present invention, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these implementations
Example is in order to explain the principle and its practical application of the present invention, so that others skilled in the art are it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.In the accompanying drawings, for the sake of clarity, element can be exaggerated
Shape and size, and identical label will be used to indicate same or analogous element all the time.
The invention provides a kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method, referring particularly to Fig. 1,
The LITHIUM BATTERY lithium hydroxide preparation method comprises the steps：
Step S1, separating magnesium and lithium.
Specifically, using lithium-containing solution as nanofiltration raw water, separating magnesium and lithium is carried out by nano filtering process, obtains low Mg/Li ratio
The nanofiltration concentrated water of water and high Mg/Li ratio is produced in nanofiltration.
More specifically, in the lithium-containing solution, Li+Concentration be 0.05g/L~2.0g/L, Mg2+Concentration be
0.25g/L~20.0g/L, Mg/Li ratio are no more than 200.
Usually, the lithium-containing solution with above-mentioned composition is obtained by salt lake bittern after dilution, filtering and impurity removing, described
Salt lake bittern is preferably salt lake original halogen caused old halogen or nearly old halogen, such as wherein Li after potassium is carried+Concentration for 0.1g/L~
10.0g/L、Mg2+Concentration be 5.0g/L~120g/L；It can wherein be diluted doped with partial organic substances and/or suspension
After filtered, remove these organic matters and/or suspension, you can obtain as nanofiltration raw water lithium-containing solution.
It is preferred that the multi-medium filtering by media such as manganese sand filter, ceramic filter, activated carbon filtering, PP cotton melt-blown filters
Device carrys out filtering and impurity removing.
Preferably, in the lithium-containing solution as nanofiltration raw water, Li+Concentration be preferably 0.10g/L~0.40g/L, Mg2+
Concentration be preferably 0.5g/L~10.0g/L, Mg/Li ratio is 20~50.
What deserves to be explained is in the comprehensive utilization of salt lake bittern, (i.e. Mg/Li ratio is in 20~200 scopes for high Mg/Li ratio
It is interior) salt lake bittern is more difficult, it is necessary to coupling between considering kinds of processes during magnesium lithium therein is separated
And the factors such as separation costs, technology difficulty, and the handling process of low Mg/Li ratio salt lake bittern is relatively simple；Therefore, originally
The method of invention is more suitable for the salt lake bittern that processing wherein Mg/Li ratio is 20~200, and it can having by a variety of separation means
Effect coupling, it is final simple, efficiently, inexpensively separate lithium therein.
In the nanofiltration production water of acquisition, Li+Concentration be 0.10g/L~2.50g/L, Mg2+Concentration for 0.01g/L~
2.4g/L, Mg/Li ratio are 0.01~3.0；Preferably, Li+Concentration be 0.30g/L~0.60g/L, Mg2+Concentration be 0.01g/
L~0.6g/L, Mg/Li ratio are 0.02~1.0.
Nanofiltration concentrated water can typically be discharged into salt Tanaka and be tedded to use it for anything else.
Step S2, depth demagging.
Specifically, water is produced into nanofiltration and carries out depth demagging, nanofiltration production by ion-exchange or the precipitation method or ultrafiltration
Magnesium ion and calcium ion in water are removed substantially, are obtained depth and are removed magnesium liquid.
More specifically, in the depth removes magnesium liquid, Li+Concentration be 0.05g/L~2.0g/L, Mg2+Concentration be
0.1mg/L~20.0mg/L；Preferably, Li+Concentration be 0.30g/L~0.60g/L, Mg2+Concentration for 0.1mg/L~
5.0mg/L。
According to ion-exchange, then using the nanofiltration of amberplex (resin cation) primary attachment produce magnesium in water from
Son and calcium ion；According to the precipitation method, then carry out precipitation using sodium hydroxide, sodium carbonate and other magnesium calcium ions precipitate agent and go
Remove；According to ultrafiltration, then ultrafiltration removal is carried out using magnesium calcium ion complexing agent.
In this way, by depth demagging, the divalent ions such as the magnesium calcium in system and lithium boron can be separated substantially.
Step S3, acidity adjustment.
Its pH is adjusted to 3.0~7.0, preferably 4.5~5.5 by removing acid adding in magnesium liquid to depth, it is deep to obtain acidifying
Degree removes magnesium liquid.
Step S4, enrichment concentration.
Specifically, acidifying depth is subjected to enrichment concentration except magnesium liquid by film concentration systems, obtain rich lithium concentrate with
Desalination production water.
More specifically, in the rich lithium concentrate, Li+Concentration be 2.0g/L~20.0g/L, preferably 3.0g/L~
6.0g/L；And in water is produced in the desalination, Li+Concentration be 0.01g/L~0.10g/L, preferably 0.04g/L~0.08g/L.
Usually, the film concentration systems may be selected from any one in counter-infiltration system, common electrodialysis system, or according to
The counter-infiltration system and electrodialysis system of secondary connected coupling.
Preferably, it can will be used as thinned water in desalination production water return to step S1, to realize recycling for resource, reduce
Separation costs.
Step S5, bipolar membrane electrodialysis.
Specifically, the step is carried out based on a three Room bipolar membrane electrodialysis systems；With reference to shown in Fig. 2 and Fig. 3,
The bipolar membrane electrodialysis system includes the anode chamber that is oppositely arranged and cathode chamber, and wherein anode chamber switches on power positive pole, and negative electrode
Room switches on power negative pole；One group of membrane stack is folded between anode chamber and cathode chamber, the membrane stack includes Bipolar Membrane, the moon being alternately arranged
Film A and anode membrane C, wherein Bipolar Membrane include the catalysis of the anode film C1 and cathodic coating A1 and sandwiched that mutually attach between
Layer (not shown)；Cathodic coating A1 and anode membrane C in Bipolar Membrane be relative to form alkali room, anode film C1 and cavity block in Bipolar Membrane
A is relative to form sour room, cavity block A and the relative formation feed liquid rooms of anode membrane C.The bipolar membrane electrodialysis system also by pipeline (in figure not
Show) pole flow container, alkali liquid tank, acid solution tank and material liquid tank are circumscribed with, specifically, pole flow container is used to store pole liquid, and pole liquid is in pole liquid
Circulated between tank and cathode chamber, anode chamber；Lithium hydroxide solution is passed through into alkali room, hydrochloric acid solution is passed through into sour room, to material
Rich lithium concentrate is passed through in liquid room, while pole liquid is passed through into anode chamber and cathode chamber, in the presence of DC electric field, rich lithium is dense
Li in contracting liquid+Enter alkali room through anode membrane C, the Cl in rich lithium concentrate-Enter sour room through cavity block A, and be located at Bipolar Membrane surface
Hydrone Catalytic Layer in Bipolar Membrane catalytic action electrolysis produce H+And OH-, under electrostatic field, OH-Into alkali room,
So as to the Li with entering alkali room through anode membrane C+LiOH solution is formed, and is back in alkali liquid tank and circulates, that is, it is rich to obtain lithium hydroxide
Liquid collecting, while under electrostatic field, H+Into sour room, so as to the Cl with entering sour room through cavity block A-HCl solution is formed, and is returned
It is back in acid solution tank and circulates, that is, obtains hydrochloric acid pregnant solution, and uncharged boric acid is retained in feed liquid room, and finally it flow to feed liquid
Tank, that is, obtain boron-rich feed liquid.
What deserves to be explained is in fig. 2, the structure in membrane stack does not represent sour room in the present invention, alkali room and feed liquid room
Exact arrangement mode, only represent inside membrane stack by some amberplexes (i.e. above-mentioned anode membrane C, cavity block A and Bipolar Membrane) hand over
For the sour room of arrangement form, alkali room and feed liquid room, and the feed solution flow direction related to these sour rooms, alkali room and feed liquid room.
In addition, it is necessary to explanation, alternative saturating because the fixed group in anode film C1 material carries negative electrical charge
Cation is crossed, so as to represent anode film C1 using "-" in figure 3；Ground is corresponded, due to consolidating in cathodic coating A1 material
Determine group and carry positive charge, selectively permeable anion, so as to represent cathodic coating A1 with "+" in figure 3.
Usually, pole liquid is sodium chloride solution or metabisulfite solution.
Preferably, obtained in step S4 desalination production water also it is negotiable be used as into this step prepare pole liquid, lithium hydroxide
The reagents such as solution.
Thus, by the effect of bipolar membrane electrodialysis, i.e., lithium boron is separated.
Preferably, the boron-rich feed liquid of acquisition is through evaporative crystallization, and separation of solid and liquid, you can obtains boric acid.
Step S6, prepared by lithium hydroxide.
Specifically, lithium hydroxide pregnant solution is through evaporating, crystallizing acquisition coarse lithium hydroxide monohydrate, the Lithium hydroxide monohydrate
Crude product again through recrystallizing, dry obtain LITHIUM BATTERY lithium hydroxide.
During above-mentioned steps S5 carries out bipolar membrane electrodialysis, also have part sodium ion and enter alkali room through anode membrane,
So as to be mixed into the form of sodium hydroxide in lithium hydroxide pregnant solution；Based on lithium hydroxide and the huge poor solubility of sodium hydroxide
It is different, you can to separate the two the step of by evaporating, crystallizing.
What deserves to be explained is during above-mentioned nanofiltration and other UF membranes, it is not particularly limited for series, this
Art personnel can be according to the concentration relative set of the step raw material and product.
In addition, though in above-mentioned steps S1, if in order to reach separating magnesium and lithium purpose, can use has monovalent ion selection
The electrodialysis plant of property, there is ion interchange unit of adsorption effect etc. to magnesium ion to substitute nanofiltration separation method, but these
Alternative can not realize good coupling with other follow-up techniques, to realize optimal production efficiency and process energy consumption；
Because the electrodialysis of monovalent ion selectivity is, it is necessary to which there is feeding liquid higher ion concentration can just obtain optimal place
Efficiency is managed, for the concentration conditions of the nanofiltration stoste of this patent requirement, although identical separating effect can be reached, its energy
Consumption is higher；Demagging is carried out using the method for ionic adsorption, can reduce magnesium so as to reduce Mg/Li ratio, but simultaneously can by from
It is sub to exchange the sodium ion (and this phenomenon is not present in nanofiltration process) for introducing the magnesium equimolar amounts with removing, due to introducing sodium ion
The salt content of production water is added, so as to which the concentration effect of lithium in subsequent concentration enrichment process will be influenceed.
The method of the present invention will be embodied by specific embodiment below.
Salt lake bittern is specially Qinghai salt lake caused old halogen after carrying potassium and carrying sodium used by the present embodiment, and this is old
Li in halogen+Content be 4.30g/L, B2O3Content be 16.90g/L, Mg/Li ratio 25.
Step A, pretreatment of raw material.
The fresh water that 14 times of volumes are mixed into old halogen is diluted, the Li after dilution in bittern+Content be 0.26g/L,
Mg2+Content be 6.5g/L, Mg/Li ratio 25, B2O3Content be 1.13g/L；Filtered off after dilution except organic matter therein and
Suspension, the lithium-containing solution of acquisition are standby as nanofiltration raw water.
Step B, separating magnesium and lithium.
Separating magnesium and lithium is carried out to nanofiltration raw water using nanofiltration film separation system, nanofiltration film separation system is two in the present embodiment
Level nanofiltration system, controlling nanofiltration to enter, film pressure is 3.0MPa, one-level producing water ratio is 80%, two level producing water ratio is 70%, is obtained
Li in two level nanofiltration production water+Content be 0.40g/L, Mg2+Content be 0.02g/L, Mg/Li ratio 0.05, B2O3Content be
0.65g/L, pH 6.8, it is standby that two level nanofiltration production water enters nanofiltration water producing tank；Li in the nanofiltration concentrated water of acquisition+Content be
0.08g/L, Mg/Li ratio 180.24, B2O3Content be 1.74g/L, nanofiltration concentrated water is discharged into salt pan.
The producing water ratio refers to that the nanofiltration production water volume that nanofiltration process obtains accounts for the percentage of nanofiltration raw water volume.
In the present embodiment, NF membrane that nanofiltration process uses for GE companies of the U.S. DK series NF membranes.
Step C, depth demagging.
The two level nanofiltration production water of above-mentioned acquisition is subjected to depth demagging in ion exchange system.Specifically, make first
Ion exchange resin is handled with the hydrochloric acid solution that mass percent is 6%, then is washed to neutral standby；Then by two level
Nanofiltration production water is adsorbed by ion exchange resin column, and obtained efflux is that depth removes magnesium liquid, wherein Li+Content be
0.39g/L、Mg2+Content be 0.002g/L, Mg/Li ratio 0.01, B2O3Content be 0.63g/L, pH 5.5.
In the present embodiment, the ion exchange resin that ion exchange system uses is phosphoramidic acid type chelating resin.
Step D, acidity adjustment.
Removed to depth in magnesium liquid and add hydrochloric acid, it is 4.5 to adjust its pH, obtains acidifying depth and removes magnesium liquid.
Step E, enrichment concentration.
By acidifying depth except magnesium liquid is concentrated into film concentration systems, reverse osmosis is controlled to penetrate film pressure as 2.5MPa, production
Water rate is 87.5%, obtains Li in rich lithium concentrate+Content be 3.59g/L, Mg2+Content be 0.02g/L, Mg/Li ratio be
0.01、B2O3Content be 5.80g/L, it is standby that rich lithium concentrate enters concentration liquid case；Li in desalination production water+Content be
0.03g/L、Mg2+Content be 0g/L, B2O3Content be 0.06g/L, desalination production water section is back to the dilution of old halogen.
Film concentration systems described in the present embodiment are specially counter-infiltration system, and its producing water ratio refers to reverse osmosis concentrated compression process and obtained
The rich lithium volume of concentrate account for acidifying depth remove magnesium liquid product percentage.
It is preferred that BW series reverse osmosis membrane of the reverse osmosis membrane that uses of the present embodiment counter-infiltration system for LG-DOW.
Step F, bipolar membrane electrodialysis.
In the bipolar membrane electrodialysis device of the present embodiment, its membrane stack include be alternately arranged 20 Bipolar Membranes, 19 the moon
Film and 19 anode membranes, in order to form sour room, alkali room and feed liquid room, typically also need to be separated by compartment spacers.
Specifically, the lithium hydroxide solution that concentration is 0.05mol/L is store in alkali liquid tank, concentration is store in acid solution tank
For 0.05mol/L hydrochloric acid solution, sodium chloride solution that concentration is 0.5mol/L is store in the flow container of pole as pole liquid.
Pole liquid is set to circulate between anode chamber and pole flow container and be followed between cathode chamber and pole flow container by pole liquid pump
Ring；Rich lithium concentrate is set to be circulated between feed liquid room and material liquid tank by feed pump；Lithium hydroxide solution is set to exist by lye pump
Circulated between alkali room and alkali liquid tank；Hydrochloric acid solution is set to be circulated between sour room and acid solution tank by acid pump.
After above-mentioned various circulation pump circulation 20min, the voltage of the bipolar membrane electrodialysis system is set as 20V, each room solution
In ion in cyclic process due to producing displacement under DC electric field and the collective effect of amberplex, so as to feed liquid
Li in room+Into alkali room so that lithium hydroxide is enriched with alkali room, Cl-Into sour room so that hydrochloric acid obtains in sour room
Enrichment, and uncharged B2O3It is retained in feed liquid room, so as to which the boron in feed liquid room is efficiently separated with lithium.
After the completion of bipolar membrane electrodialysis, boron-rich feed liquid is obtained in material liquid tank, lithium hydroxide pregnant solution is obtained in alkali liquid tank,
Hydrochloric acid pregnant solution is obtained in acid solution tank.
Wherein, Li in boron-rich feed liquid+Content be 0.24g/L, Na+Content be 0.02g/L, Mg/Li ratio 0.07, B2O3
Content be 5.67g/L, boric acid product can be prepared by further concentrating and crystallizing in the boron-rich feed liquid；Hydrochloric acid pregnant solution
Middle Li+Content be 0.10g/L, Na+Content be 0.01g/L, Mg/Li ratio 0, B2O3Content be 0.05g/L, Cl-Content
For 30.50g/L, pH 0.5, the pH of magnesium liquid is removed available for regulation depth, and Li in lithium hydroxide pregnant solution+Content be
3.25g/L、Na+Content be 1.30g/L, Mg/Li ratio 0, B2O3Content be 0.08g/L, be used directly for lithium hydroxide
The preparation of product.
Step G, LITHIUM BATTERY lithium hydroxide is prepared.
Main component in lithium hydroxide pregnant solution is lithium hydroxide, and contains a small amount of sodium hydroxide.Pass through steaming first
Hair, crystallization obtain coarse lithium hydroxide monohydrate, after then being recrystallized to coarse lithium hydroxide monohydrate, are dried to obtain high single
Water lithium hydroxide product, the main content fraction of the Lithium hydroxide monohydrate product is 99.85%, can be used as LITHIUM BATTERY hydroxide
Lithium.
The old halogen and the composition of each phase solution used in above-described embodiment is as shown in table 1.
The composition of old halogen and each phase solution in the embodiment of table 1
By above-described embodiment, using certain salt lake brine with high magnesium-lithium ratio as raw material, pass through separating magnesium and lithium, depth demagging, richness
The methods of collection concentration and bipolar membrane electrodialysis, boron-rich feed liquid and lithium hydroxide pregnant solution, hydrochloric acid enrichment is finally prepared
Liquid.Wherein, the purity for the LITHIUM BATTERY lithium hydroxide product being prepared by lithium hydroxide pregnant solution has reached 99.85%；It is boron-rich
B in feed liquid2O3Concentration be 5.72g/L, the content of remaining foreign ion has controlled very low degree, can be directly used for boron
The preparation of acid product；The pH of hydrochloric acid pregnant solution is 0.5, can be directly used for adjusting the pH of rich lithium concentrate, or for boric acid product
Preparation process.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (13)
1. a kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method, it is characterised in that including step：
Separating magnesium and lithium：Using lithium-containing solution as nanofiltration raw water, and separating magnesium and lithium is carried out by nano filtering process, obtain nanofiltration production water and receive
Filter concentrated water；Wherein, in the lithium-containing solution, Li+Concentration be 0.05g/L~2.0g/L, Mg2+Concentration for 0.25g/L~
20.0g/L, Mg/Li ratio are no more than 200；In water is produced in the nanofiltration, Li+Concentration be 0.10g/L~2.50g/L, Mg2+It is dense
It is 0.01~3.0 to spend for 0.01g/L~2.4g/L, Mg/Li ratio；
Depth demagging：Water is produced into the nanofiltration and carries out depth demagging by ion-exchange or the precipitation method or ultrafiltration, it is described to receive
Magnesium ion and calcium ion in filter production water are removed, and are obtained depth and are removed magnesium liquid；Wherein, in the depth removes magnesium liquid, Li+It is dense
Spend for 0.05g/L~2.0g/L, Mg2+Concentration be 0.1mg/L~20.0mg/L；
Acidity adjustment：By the depth except the pH of magnesium liquid is adjusted to 3.0~7.0, obtain acidifying depth and remove magnesium liquid；
Enrichment concentration：The acidifying depth is subjected to enrichment concentration except magnesium liquid by film concentration systems, obtain rich lithium concentrate with
Desalination production water；Wherein, in the rich lithium concentrate, Li+Concentration be 2.0g/L~20.0g/L；In the desalination production water,
Li+Concentration be 0.01g/L~0.10g/L；
Bipolar membrane electrodialysis：The rich lithium concentrate is handled by bipolar membrane electrodialysis system, the bipolar membrane electrodialysis system
System includes anode chamber and the cathode chamber being oppositely arranged, and is folded between the anode chamber and the cathode chamber by Bipolar Membrane, cavity block
The membrane stack of composition is alternately arranged with anode membrane, the Bipolar Membrane includes the anode film and cathodic coating mutually attached, the moon of the Bipolar Membrane
Pole film and the anode membrane form alkali room relatively, and the anode film of the Bipolar Membrane and the cavity block form sour room, the anode membrane relatively
It is relative with the cavity block to form feed liquid room；Pole liquid is passed through into the anode chamber and the cathode chamber, is passed through into the alkali room
Lithium hydroxide solution, hydrochloric acid solution is passed through in the sour room, while the rich lithium concentrate is passed through into the feed liquid room, straight
In the presence of flowing electric field, the Li in the rich lithium concentrate+Enter the alkali room through the anode membrane, and hydrogen is formed in the alkali room
Lithia pregnant solution；Cl in the rich lithium concentrate-Enter the sour room through the cavity block, and hydrochloric acid is formed in the sour room
Pregnant solution；Boron-rich feed liquid is formed in the feed liquid room；
It is prepared by lithium hydroxide：The lithium hydroxide pregnant solution is through evaporating, crystallizing acquisition coarse lithium hydroxide monohydrate；The one water hydrogen
Lithia crude product is through recrystallizing, dry acquisition LITHIUM BATTERY lithium hydroxide.
2. LITHIUM BATTERY lithium hydroxide preparation method according to claim 1, it is characterised in that the boron-rich feed liquid is through evaporation
Crystallization, and separation of solid and liquid, obtain boric acid.
3. LITHIUM BATTERY lithium hydroxide preparation method according to claim 1 or 2, it is characterised in that by by salt lake bittern
It is diluted, filtering and impurity removing, obtains the lithium-containing solution.
4. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that the desalination production water is back to
In the separating magnesium and lithium step, for diluting the salt lake bittern.
5. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that in the lithium-containing solution,
Li+Concentration be 0.10g/L~0.40g/L, Mg2+Concentration be 0.5g/L~10.0g/L, Mg/Li ratio is 20~50；Described
In nanofiltration production water, Li+Concentration be 0.30g/L~0.60g/L, Mg2+Concentration be 0.01g/L~0.6g/L, Mg/Li ratio is
0.02~1.0.
6. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that remove magnesium liquid in the depth
In, Li+Concentration be 0.30g/L~0.60g/L, Mg2+Concentration be 0.1mg/L~5.0mg/L.
7. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that in the acidity adjustment step
In, by the depth except the pH of magnesium liquid is adjusted to 4.5~5.5, obtain the acidifying depth and remove magnesium liquid.
8. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that in the rich lithium concentrate
In, Li+Concentration be 3.0g/L~6.0g/L；In the desalination production water, Li+Concentration be 0.04g/L~0.08g/L.
9. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that the pole liquid is that sodium chloride is molten
Liquid or metabisulfite solution.
10. LITHIUM BATTERY lithium hydroxide preparation method according to claim 9, it is characterised in that the desalination production water returns
Into the bipolar membrane electrodialysis step, for preparing the pole liquid and/or the lithium hydroxide solution.
11. LITHIUM BATTERY lithium hydroxide preparation method according to claim 3, it is characterised in that the hydrochloric acid pregnant solution returns
It is back in the acidity adjustment step, the pH of magnesium liquid is removed for adjusting the depth, magnesium liquid is removed to obtain the acidifying depth.
12. LITHIUM BATTERY lithium hydroxide preparation method according to claim 1, it is characterised in that the film concentration systems choosing
From counter-infiltration system, common electrodialysis system or the counter-infiltration system and electrodialysis system being sequentially connected.
13. LITHIUM BATTERY lithium hydroxide preparation method according to claim 1, it is characterised in that in the lithium-containing solution,
Mg/Li ratio is 20~200.
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| CN115196655A (en) * | 2022-08-23 | 2022-10-18 | 杭州科锐环境能源技术有限公司 | Method and system for removing boron and concentrating lithium from high-boron-content lithium liquid |
| CN115784503A (en) * | 2022-11-24 | 2023-03-14 | 安徽启迪清源新材料有限公司 | A system and method for extracting lithium from salt lake brine and preparing battery-grade lithium carbonate |
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