CN104961143B - The method that lithium is extracted from salt lake bittern - Google Patents
The method that lithium is extracted from salt lake bittern Download PDFInfo
- Publication number
- CN104961143B CN104961143B CN201510392024.0A CN201510392024A CN104961143B CN 104961143 B CN104961143 B CN 104961143B CN 201510392024 A CN201510392024 A CN 201510392024A CN 104961143 B CN104961143 B CN 104961143B
- Authority
- CN
- China
- Prior art keywords
- lithium
- magnesium
- clear liquid
- liquid
- separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 183
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 70
- 241001131796 Botaurus stellaris Species 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 133
- 239000011777 magnesium Substances 0.000 claims abstract description 121
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 102
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000000926 separation method Methods 0.000 claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 239000012141 concentrate Substances 0.000 claims abstract description 47
- 238000001556 precipitation Methods 0.000 claims abstract description 27
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000013049 sediment Substances 0.000 claims abstract description 7
- 230000001174 ascending effect Effects 0.000 claims abstract description 6
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 claims abstract description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 20
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001471 micro-filtration Methods 0.000 claims description 5
- 239000010451 perlite Substances 0.000 claims description 5
- 235000019362 perlite Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 229940009662 edetate Drugs 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 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 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010889 donnan-equilibrium Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QMPFJHZFXOPGIK-UHFFFAOYSA-N P.P.OC=C Chemical compound P.P.OC=C QMPFJHZFXOPGIK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-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
- C01D15/08—Carbonates; Bicarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of method of the separation and Extraction lithium from bittern, including：1) acidifying removes boron, and into bittern, acid adding is settled out boric acid, and separation of solid and liquid obtains the first clear liquid；2) pre-process, part sulfate radical and magnesium ion in first clear liquid are removed in the way of precipitation, the second clear liquid is obtained；3) Separation of Li and Mg, using the lithium and magnesium in the second clear liquid described in Separation of Li and Mg UF membrane, obtains the low lithium production water of high magnesium and the low magnesium production water of high lithium；4) lithium is concentrated, and the high low magnesium of lithium for concentrating the gained of film concentration step 3 using lithium produces water, obtains concentrate and light liquid；5) sinker, the pH of the gained concentrate of ascending step 4, by Mg are refined2+With Mg (OH)2The form of precipitation is removed, and obtains the 3rd clear liquid, CO is introduced in the 3rd clear liquid3 2‑, Li+With Li2CO3Form precipitation, isolate sediment and wash dry after obtain battery-level lithium carbonate product.
Description
Technical field
This disclosure relates to which technical field of membrane separation, more particularly to chemical precipitation method and membrane separation process are combined and carried from salt lake saline
The method for taking lithium.
Background technology
The mankind have been working hard find the new energy of alternative fossil energy in recent decades, and the most common profit of new energy
It is that various forms of energy are converted into electrical power storage with mode.Specific capacity is high, work temperature due to possessing for lithium ion battery
The prominent advantages such as scope is wide, self-discharge rate is low, has extended cycle life, have a safety feature are spent, in mobile communication equipment and various numbers
It is widely applied in code product, and is acknowledged as the ideal source of electric automobile.Thus, even if global economy in recent years
Slowdown in growth, lithium industry performance is but especially protruded, lithium product is one of a small number of industrial goods of rise in price, thus lithium resource obtains
Take the focus for also becoming countries in the world concern.
In explored world's lithium resource, bittern lithium resource accounts for 61%, ore lithium resource and accounts for 34%, oil field and GEOTHERMAL WATER
Lithium resource accounts for 5%.For current economy, the state of the art, lithium is extracted from salt lake bittern no matter equal in cost and scale
Lithium is carried better than ore, the lithium product that the whole world has 70% comes from salt lake bittern.China's salt lake bittern lithium reserves account for gross reserves
More than 80%, but the lithium extracted from salt lake bittern but only accounts for the 8% of total extracted amount, reason is many.Wherein most
It is mainly due to, saline lakes of China bittern is the bittern of high Mg/Li ratio mostly, due to Mg2+With Li+In physicochemical properties
It is closely similar, cause separating magnesium and lithium difficult, it is impossible to directly to extract lithium with simple chemical method (such as precipitation method), it is existing at present
The method of lithium is extracted from high Mg/Li ratio bittern includes organic solvent extractionprocess, ion-exchange, electroosmose process, Nanofiltering membrane
Deng.Organic solvent extractionprocess production cost is high, serious to equipment corrosion, at present also in experimental stage；What ion-exchange was used
Adsorbent price is very high, and productivity ratio is low, and is easily contaminated, it is impossible to mass produce；Electrodialysis rule needs to consume a large amount of electricity
Can, and a large amount of poisonous chlorine are produced in production process；Nanofiltering membrane has very big advantage with respect to the above method.Come from principle
Say, NF membrane is a kind of pressure drive membrane, charged group carried on film, by electrostatic interaction, produce Donnan effects,
There are different selective penetrated properties to the ion of different valence state, so as to realize the separation of different valence state ion.In general, nanofiltration
Film is 10%~80% to the rejection of monovalention, and with sizable permeability, and divalence and the rejection of multivalent salts are equal
More than 90%, so as to realize the separation of monovalence lithium ion and divalence magnesium ion.Existing enterprise of the country utilizes the technology from salt lake
Lithium is extracted in bittern, but still there is some problem causes that production efficiency is low, cost remains high.
The content of the invention
Embodiments of the invention provide a kind of method of the separation and Extraction lithium from bittern, including：
1) acidifying removes boron, and the acid adding into bittern is settled out boric acid, and separation of solid and liquid obtains the first clear liquid；
2) pre-process, part sulfate radical and magnesium ion in first clear liquid are removed in the way of precipitation, second is obtained clear
Liquid；
3) Separation of Li and Mg, using the lithium and magnesium in the second clear liquid described in Separation of Li and Mg UF membrane, obtains the low lithium production water of high magnesium
Water is produced with the low magnesium of high lithium；
4) lithium is concentrated, and the high low magnesium of lithium for concentrating the gained of film concentration step 3 using lithium produces water, obtains concentrate and light liquid；
5) sinker, the pH of the gained concentrate of ascending step 4, by Mg are refined2+With Mg (OH)2The form of precipitation is removed, and is obtained
3rd clear liquid, CO is introduced in the 3rd clear liquid3 2-, Li+With Li2CO3Form precipitation, isolate sediment and wash drying
After obtain battery-level lithium carbonate product.
In one embodiment of the invention, the low lithium of the high magnesium of above-mentioned steps 3 can for example be produced water, step 4 it is light
The return of at least one of liquid merges with second clear liquid of step 2.
In one embodiment of the invention, for example, the step 2 of pretreatment includes step 2A and step 2B,
Step 2A includes：SO in the pH to 7-9 of first clear liquid of regulating step 1, bittern4 2-And Mg2+A part
Precipitated in the form of calcium sulfate and magnesium hydroxide, clear liquid 2A is obtained after separation of solid and liquid and is continued with into step 2B or into step
Rapid 3 continue with；
Step 2B includes：After merging with the return clear liquid of subsequent step, remaining SO in bittern4 2-And Mg2+A part after
It is continuous to be precipitated in the form of calcium sulfate and magnesium hydroxide, obtain clear liquid 2B after separation of solid and liquid and continued with into step 3.
In one embodiment of the invention, for example, the step 3 of Separation of Li and Mg includes step 3A and step 3B,
Step 3A includes：Acid is added in step 2 gained clear liquid, pH to 7-8.5 is adjusted, it is clear using Separation of Li and Mg UF membrane
Liquid obtains the low lithium production water 3A of high magnesium and the low magnesium production water 3A of high lithium, wherein the low lithium production water 3A of high magnesium is returned after the enrichment method of salt pan, then
Merge with raw brine, the high low magnesium production water 3A of lithium is then continued with or continued with into step 4 into step 3B；
Step 3B includes：Complexing agent is added in the low magnesium production water 3A of high lithium, is produced using the low magnesium of the high lithium of Separation of Li and Mg UF membrane
Water 3A obtains the low lithium production water 3B of high magnesium and the low magnesium production water 3B of high lithium, wherein the low lithium production water 3B of high magnesium is returned and step 2A clear liquid is closed
And, the high low magnesium production water 3B of lithium is then continued with into step 4.
In one embodiment of the invention, for example, the step 4 of lithium concentration includes step 4A, step 4B and step 4C,
Step 4A includes：Film is concentrated using lithium to concentrate the low magnesium production water of high lithium of step 3, obtains concentrate 4A and light
Liquid 4A, merges wherein light liquid 4A is returned with step 2A clear liquid, and then entrance step 4B is continued with or into step 5 concentrate 4A
Continue with；
Step 4B includes：Step 4A concentrate 4A is concentrated using lithium concentration film, concentrate 4B and light liquid is obtained
4B, wherein light liquid 4B return merge with step 2A clear liquid, concentrate 4B then entrance step 4C continue with or into step 5 after
Continuous processing；
Step 4C includes：Step 4B concentrate 4B is concentrated using lithium concentration film, concentrate 4C and light liquid is obtained
4C, merges wherein light liquid 4C is returned with step 2A clear liquid, and concentrate 4C is then continued with into step 5.
In one embodiment of the invention, for example, above-mentioned steps 1 are acidified except boron includes：Acid adding adjusts salt lake bittern
PH is that 2-4 crystallizes precipitation to boric acid, and separation of solid and liquid obtains clear liquid and thick boric acid.
In one embodiment of the invention, for example, above-mentioned steps 2B includes：Filter aid is added in clear liquid 2A, with
After the return clear liquid of subsequent step merges, remaining SO in bittern4 2-And Mg2+A part continue with calcium sulfate and magnesium hydroxide
Form precipitation, using polytetrafluoroethylene (PTFE) microfiltration membranes by CaSO4、Mg(OH)2Clear liquid 2B is obtained after floccule separation into step 3
Continue with.
In one embodiment of the invention, for example, lithium concentration is less than in the low lithium production water 3A of above-mentioned high magnesium
Lithium concentration is more than 300ppm in 150ppm, the high low magnesium production water 3A of lithium；Lithium concentration is more than in the high low magnesium production water 3B of lithium
300ppm and lithium magnesium mass ratio are more than 1.
In one embodiment of the invention, for example, lithium concentration is more than 1000ppm and lithium in above-mentioned concentrate 4A
Magnesium mass ratio is more than 1；Lithium concentration is more than 2000ppm in concentrate 4B and lithium magnesium mass ratio is more than 1；In concentrate 4C lithium from
Sub- concentration is more than 16000ppm and lithium magnesium mass ratio is more than 1.
In one embodiment of the invention, for example, in step 2A, first clear liquid of the regulating step 1
PH mode includes：Add NaOH, NH4OH, KOH or Ca (OH)2。
In one embodiment of the invention, it is described for example, the filter aid is perlite, diatomite or cellulose
The addition of filter aid is 30-50ppm.
In one embodiment of the invention, for example, in step 3A, the acid added in step 2 gained clear liquid is wrapped
Include one kind in hydrochloric acid, sulfuric acid, nitric acid or its combination.
In one embodiment of the invention, for example, in step 3B, the complexing added in water 3A is produced in the low magnesium of high lithium
Agent is sub- for compounding EDETATE SODIUM salt, ethylenediamine tetra-acetic acid, edetate, ATMP, divinyl triammonium five
Methylphosphonic acid, hydroxy ethylene diphosphonic acid or calgon, concentration are 3-6ppm.
In one embodiment of the invention, for example, the method that clear liquid is wherein obtained in step 5 is：Toward the dense of step 4
Sodium hydroxide is added in contracting liquid, slurry is obtained, part Mg in this slurry2+With Mg (OH)2Form precipitation, by above-mentioned slurry solid-liquid
Isolated magnesium hydrate precipitate and a lixivium, magnesium hydrate precipitate carry out the leaching more than once with water or filtrate again, Gu
Liquid separates to obtain magnesium hydrate precipitate and filtrate, this filtrate is used to configure sodium hydroxide continuation reuse, a lixivium is filtrated to get
Clear liquid.
In one embodiment of the invention, for example, the method for the separation of solid and liquid includes：Be centrifuged at a high speed, plate
Frame separation of solid and liquid, polytetrafluoroethylene (PTFE) micro-filtration UF membrane and/or filtering.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will simply be situated between to the accompanying drawing of embodiment below
Continue, it should be apparent that, drawings in the following description merely relate to some embodiments of the present invention, rather than limitation of the present invention.
A kind of method flow diagram for separation and Extraction lithium from bittern that Fig. 1 provides for one embodiment of the invention；
A kind of method flow diagram for separation and Extraction lithium from bittern that Fig. 2 provides for further embodiment of this invention；
A kind of method flow diagram for separation and Extraction lithium from bittern that Fig. 3 provides for third embodiment of the invention；
A kind of method flow diagram for separation and Extraction lithium from bittern that Fig. 4 provides for fourth embodiment of the invention.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
Accompanying drawing, the technical scheme to the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair
Bright a part of embodiment, rather than whole embodiments.Based on described embodiments of the invention, ordinary skill
All other embodiment that personnel are obtained on the premise of without creative work, belongs to the scope of protection of the invention.
Unless otherwise defined, technical term or scientific terminology used herein should be in art of the present invention and had
The ordinary meaning that the personage of general technical ability is understood.Used in present patent application specification and claims " the
One ", " second " and similar word are not offered as any order, quantity or importance, and are used only to distinguish different
Part.Equally, the similar word such as " one " or " one " does not indicate that quantity is limited yet, but represents there is at least one.
Unless otherwise defined, ppm herein is mass ratio, Chinese with chemical formula state implication it is identical, such as magnesium from
Son and Mg2+, sulfate ion and SiO4 2-Deng.
The technology of the existing some NF membranes separation and Extraction lithium from bittern in this area, Qinghai Lake research institute of the Chinese Academy of Sciences
Chinese Patent Application No. 0310808088.X by the multistage NF membrane of commercialization separating magnesium and enriching lithium from salt lake bittern,
But bittern does not remove the foreign ions such as sulfate radical, borate before nanofiltration UF membrane is entered, and causes UF membrane efficiency low, and
The duct of NF membrane is often blocked by flocky precipitate during use, influence production and cost rise, is carried using the technology
Pure obtained rich lithium bittern does not reach the concentration and purity of practical application in industry yet；Wang Hui Chinese Patent Application No.
The raw brine of high saliferous is first diluted with water in 201010295933.X, then by one or more levels NF membrane separating magnesium and lithium,
Concentrated finally by reverse osmosis membrane or membrane distillation system, the technology is also without in view of other ion pairs beyond demagging
The influence of separation process, UF membrane is inefficient, and the method is by NF membrane plural serial stage in addition, and next stage concentrated water returns to upper level
Charging, can so cause Mg/Li ratio to raise, and reduce UF membrane efficiency.
For the above-mentioned problems in the prior art, embodiments of the invention provide one kind combine chemical method,
Comprehensive lithium ion (the Li of the methods such as physics impurity removal method, nanofiltration membrane separation process, concentration embrane method+) extracting method, pass through chemical drugs
Other method beyond the membrane separation processes such as agent method, physics impurity removal method, is removed big present in salt lake bittern in advance before UF membrane
Partial impurities ion, such as Mg2+、SO4 2-、B2+Deng being that UF membrane creates good condition, substantially increase UF membrane efficiency, excellent
Separating effect is changed；In membrane separating process and after UF membrane, also in conjunction with the above method, extraction lithium is further increased
Efficiency and purity.Before the present invention occurs, lithium is extracted from salt lake using membrane separation process and is typically only capable of reaching technical grade, and
Due to the presence of a large amount of foreign ions, often produce a large amount of precipitations in membrane separating process and cause the dirt of film to block up, on the one hand influence
Manufacturing schedule, on the other hand also increases production cost.And it is then reachable to use method of the invention to extract lithium from salt lake bittern
To the purity of LITHIUM BATTERY, while a large amount of foreign ions were removed before UF membrane, problem is blocked up in the dirt in membrane separating process
It is resolved, substantially prolongs the production cycle, reduces production cost.
It should be noted that herein, " the low lithium production water of high magnesium " in Separation of Li and Mg step does not mean that wherein magnesium
Concentration ratio lithium is high, " the high low magnesium production water of lithium " does not mean that the concentration ratio magnesium of wherein lithium is high yet, but said in same step (such as step
In 3A), the lithium magnesium ratio (mass ratio) in " the high low lithium production water of magnesium " will be less than the lithium magnesium ratio (mass ratio) in " the high low magnesium production water of lithium ".
Embodiment 1
As shown in figure 1, raw material is the bittern containing lithium from salt lake or the bittern containing lithium in other sources.In the embodiment of the present invention
The salt lake bittern of use is all the salt lake bittern of high Mg/Li ratio, Mg/Li ratio (Mg2+:Li+Mass ratio) it is general more than 20.
The acid adding into raw brine, regulation bittern pH is that 2-4 crystallizes precipitation to boric acid, and separation of solid and liquid obtains clear liquid and thick boron
Acid.Thick boric acid can further handle sale, and clear liquid is then pre-processed into step 2.
In pre-treatment step, part sulfate radical and magnesium ion (sulfate radical clearance in bittern are removed in the way of precipitation
90% or so, magnesium ion clearance 10-15% or so), separation of solid and liquid, clear liquid is continued with into next step.The side of precipitation
Formula includes conventional chemically or physically intermediate processing, and such as adding alkali lye makes magnesium ion be precipitated in the form of magnesium hydroxide, adds barium
Ion precipitates sulfate ion, or change solution temperature causes calcium sulfate solubility to change to precipitate.
Separation of Li and Mg is carried out to the clear liquid of pre-treatment step using Separation of Li and Mg film, the low lithium production water of high magnesium is obtained and high lithium is low
Magnesium produces water, wherein the low magnesium production water of high lithium is continued with into next step.Lithium ion content in the low magnesium production water of high lithium is big
In 300PPM, lithium magnesium mass ratio is more than 1：1.The Separation of Li and Mg film, which can be used, can separate monovalent ion and bivalent ions
NF membrane.NF membrane is a kind of pressure drive membrane, due to often carrying charged group on film or in film, passes through electrostatic phase interaction
With generation Donnan effects, to the ion of different valence state, with different selectivity, so as to realize point of different valence state ion
From.The Separation of Li and Mg film of the existing commercialization in this area, such as Membrane Products, Nitto, Osmonics companies are all
There is the product line of correlation.Certainly, above-mentioned technique provided in an embodiment of the present invention can also utilize the Separation of Li and Mg voluntarily prepared
Film.
The low magnesium production water of high lithium obtained by previous step is concentrated, concentrate and light liquid are obtained, under wherein concentrate enters
One step is continued with.The method of concentration can be using the low magnesium production water of the lithium concentration high lithium of film process.The lithium concentration film is generally
Reverse osmosis membrane, can use commercialization product, such as Tao Shi (DOW), Coriolis (KOCH), Hydranautics (HYDRANAUTICS), GE,
The series of products of eastern beautiful (TORAY) etc..Above-mentioned technique provided in an embodiment of the present invention can also utilize the lithium concentration voluntarily prepared
Film.Lithium content is more than 16000PPM in concentrate obtained by concentration, and lithium magnesium mass ratio is more than 1:1.
Refined sinker, raises the pH of the concentrate of previous step, by Mg2+With Mg (OH)2The form of precipitation is removed, and obtains clear
Liquid, introduces CO in clear liquid3 2-, Li+With Li2CO3Form precipitation, isolate sediment and wash be dried to obtain LITHIUM BATTERY carbonic acid
Lithium product, purity>99.5%.
Embodiment 2
As shown in Fig. 2 another embodiment of the present invention provides a kind of method of the separation and Extraction lithium from bittern, with embodiment
1 method provided is compared, the step of method that the present embodiment is provided has more subdivisions, including：
1) acidifying removes boron, and clear liquid is continued with into next step；
2) pre-process, part sulfate radical and magnesium ion in bittern are removed in the way of precipitation；Pre-treatment step 2 includes step
2A and step 2B, step 2A include：The pH of the clear liquid of ascending step 1, adjusts the SO in pH to 7-9, bittern4 2-And Mg2+One
Divide and precipitated in the form of calcium sulfate and magnesium hydroxide, obtain clear liquid 2A after separation of solid and liquid continues with into step 2B；Step 2B
Including：Remaining SO in filter aid (such as equal grain perlite, addition is 30-50ppm), bittern is added in clear liquid 2A4 2-With
Mg2+A part continue to precipitate in the form of calcium sulfate and magnesium hydroxide, obtain clear liquid 2B after separation of solid and liquid continues into step 3
Processing.
3) Separation of Li and Mg, using Separation of Li and Mg UF membrane lithium and magnesium, obtains the low lithium production water of high magnesium and the low magnesium production water of high lithium；Step
Rapid 3 include step 3A and step 3B, and step 3A includes：Acid is added in clear liquid obtained by step 2B, pH to 7-8.5 is adjusted, utilized
Separation of Li and Mg UF membrane clear liquid obtains the low lithium production water 3A of high magnesium and high lithium low magnesium production water 3A, the high low magnesium production water 3A of lithium enter step 3B
Continue with；Step 3B includes：Adding complexing agent in the low magnesium production water 3A of high lithium, (complexing agent can use water treatment field
Conventional antisludging agent, for example, can be compounding EDETATE SODIUM salt, ethylenediamine tetra-acetic acid, edetate, aminotrimethylene
Phosphonic acids, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphonic acid or calgon, concentration is 3-6ppm), utilize lithium
The low magnesium production water 3A of the magnesium separation high lithium of UF membrane obtains the low lithium production water 3B of high magnesium and the low magnesium production water 3B of high lithium, and the high low magnesium of lithium produces water 3B and entered
Enter step 4 to continue with.
4) lithium is concentrated, and the low magnesium of high lithium for concentrating the gained of film concentration step 3 using lithium produces water, obtains concentrate and light liquid, wherein
Concentrate is continued with into next step；The step 4 of lithium concentration includes step 4A, step 4B and step 4C, and step 4A includes：
Film is concentrated using lithium to concentrate the low magnesium production water of high lithium of step 3, obtains concentrate 4A and light liquid 4A, concentrate 4A enters step
Rapid 4B is continued with；Step 4B includes：Using lithium concentration film step 4A concentrate 4A is concentrated, obtain concentrate 4B with
Light liquid 4B, concentrate 4B are continued with into step 4C；Step 4C includes：Step 4B concentrate 4B is entered using lithium concentration film
Row concentration, obtains concentrate 4C and light liquid 4C, concentrate 4C is continued with into step 5.
5) sinker, the pH of the concentrate of ascending step 4, by Mg are refined2+With Mg (OH)2The form of precipitation is removed, and obtains clear
Liquid, introduces CO in clear liquid3 2-, Li+With Li2CO3Form precipitation, isolate sediment and be dried to obtain battery-level lithium carbonate production
Product, purity>99.7%.It is above-mentioned obtain clear liquid method be：Sodium hydroxide is added into the concentrate of step 4, slurry is obtained, this
Part Mg in slurry2+With Mg (OH)2Form precipitation, above-mentioned slurry separation of solid and liquid is obtained into magnesium hydrate precipitate and a leaching
Liquid, magnesium hydrate precipitate carries out the leaching more than once with water or filtrate again, and separation of solid and liquid obtains magnesium hydrate precipitate and filtrate, will
This filtrate recycle is filtrated to get clear liquid in configuration sodium hydroxide solution, a lixivium.
The above method that embodiment 2 is provided has more fine division steps, on the one hand can cause Separation of Li and Mg effect more
Good, the purity for obtaining final products lithium carbonate is also higher；On the other hand it is sediment removal in bittern is more thorough, reduce film
Situation is blocked up in dirt in separation process so that the time that this method is continuously run greatly prolongs, and improves the automation of whole technique
Degree., can be by the sulfate ion and magnesium in bittern using two pre-treatment steps of 2A and 2B by taking pre-treatment step 2 as an example
Ion reduces more, reduces the sediment into next step, so as to reduce dirty stifled probability in membrane separating process, favorably
In follow-up Separation of Li and Mg.It should be noted that step 2,3,4 and need not be finely divided simultaneously, can be according to actual needs
To certain, some steps are finely divided, and then a step is completed other steps.The lithium carbonate purity that the present embodiment is finally obtained>
99.6%.
Embodiment 3
As shown in figure 3, another embodiment of the present invention provides a kind of method of the separation and Extraction lithium from bittern, with embodiment
2 methods provided are compared, and the method that the present embodiment is provided reclaims the Li of each step generation+The relatively low solution of content, to improve
Overall lithium ion extraction rate.Content same as Example 2 will be omitted in the present embodiment, the part that emphasis description is differed.
As shown in figure 3, the low lithium production water 3A of high magnesium that step 3A is obtained is returned after the enrichment method of salt pan, then merge with raw brine, step
The low lithium production water 3B of high magnesium that 3B is obtained is returned to be merged with step 2A clear liquid, and the light liquid 4A that step 4A is obtained is returned with step 2A's
Clear liquid merges, and the light liquid 4B that step 4B is obtained is returned to be merged with step 2A clear liquid, and the light liquid 4C that step 4C is obtained is returned and step
Rapid 2A clear liquid merges.The Li produced due to each step+The relatively low solution of content is recycled, Li in bittern+Overall
Recovery rate is improved, and can bring up to more than 80% by 40%.It should be noted that above-mentioned Li+The relatively low solution of content is simultaneously
It need not simultaneously reclaim, according to circumstances reasonable selection a portion can be recycled in actual production, to take into account cost and lithium
The ion extraction rate.The lithium carbonate purity that the present embodiment is finally obtained>99.7%, the lithium rate of recovery is more than 80% in bittern.
Embodiment 4
As shown in figure 4, another embodiment of the present invention provides a kind of method of the separation and Extraction lithium from bittern, with embodiment
3 methods provided are compared, and the method that the present embodiment is provided adds auxiliary agent, further to optimize the treatment effect of each step.This
It will be omitted with previous embodiment identical content in embodiment, the part that emphasis description is differed.As shown in figure 4, step 2A bags
Include：SO in the pH of the clear liquid of ascending step 1 to 7-9, bittern4 2-And Mg2+A part in the form of calcium sulfate and magnesium hydroxide
Precipitation.Rise pH mode includes but is not limited to, and NaOH, KOH, Ca (OH) are added into solution2Or ammoniacal liquor, formed after precipitation and led to
High speed centrifugation or sheet frame separation of solid and liquid are crossed, solid content can further be handled as the raw material of magnesium products.PH rise can promote
Enter the place to go of magnesium, this process can remove 20~30% magnesium.
As shown in figure 4, introducing filter aid in pretreatment 2B.Filter aid is added in clear liquid 2A, such as equal grain perlite, plus
Enter amount for 30-50ppm, remaining SO in bittern4 2-And Mg2+A part continue in the form of calcium sulfate and magnesium hydroxide precipitate,
Using polytetrafluoroethylene (PTFE) microfiltration membranes by CaSO4、Mg(OH)2Clear liquid 2B is obtained after floccule separation to continue with into step 3.Help
Filtering agent is to improve the material of filtrate filter efficiency.In general, to prevent filter residue accumulation excessively closely knit, making filtering smoothly enter
OK, filter aid can be using the different insoluble inert material of granularity.The example of above-mentioned filter aid is included but not in the present invention
It is limited to perlite, diatomite, cellulose etc..
As shown in figure 4, complexing agent can be introduced in step 3B.Complexing agent is added in the low magnesium production water 3A of high lithium, is such as compounded
EDETATE SODIUM salt, 3-6ppm obtains the low lithium of high magnesium using the low magnesium production water 3A of the high lithium of Separation of Li and Mg UF membrane and produces water 3B and the low magnesium of high lithium
Water 3B is produced, wherein the low lithium production water 3B of high magnesium is returned and merged with step 2A clear liquid, the high low magnesium production water 3B of lithium then continues into step 4
Processing.The effect of above-mentioned complexing agent is complexed with calcium, barium, strontium etc., prevents calcium sulfate, calcium carbonate, strontium sulfate, barium sulfate etc. in film
Surface scale, is damaged to film.The example of above-mentioned complexing agent includes but is not limited to compounding EDETATE SODIUM salt, ethylenediamine in the present invention
Tetraacethyl, edetate, ATMP, divinyl triammonium pentamethylene phosphonic acids, hydroxy ethylene diphosphine
Acid or calgon etc..
Described above is only the exemplary embodiment of the present invention, not for limiting the scope of the invention, this hair
Bright protection domain is determined by appended claim.
Claims (13)
1. a kind of method of the separation and Extraction lithium from bittern, including：
1 acidifying removes boron, and the acid adding into bittern is settled out boric acid, then carries out separation of solid and liquid, obtains the first clear liquid；
2 pretreatments, acidifying is removed in the way of precipitation and removes part sulfate radical and magnesium ion in first clear liquid obtained after boron,
Obtain the second clear liquid；
3 Separation of Li and Mg, using the lithium and magnesium in the second clear liquid described in Separation of Li and Mg UF membrane, obtain the low lithium production water of high magnesium and high lithium
Low magnesium produces water；
4 lithiums are concentrated, and the high low magnesium of lithium for concentrating the gained of film concentration step 3 using lithium produces water, obtains concentrate and light liquid；
5 refined sinkers, the pH value of the gained concentrate of ascending step 4, by Mg2+With Mg (OH)2The form of precipitation is removed, and obtains the 3rd
Clear liquid, CO is introduced in the 3rd clear liquid3 2-, Li+With Li2CO3Form precipitation, isolate sediment and wash dry after
To battery-level lithium carbonate product；
Wherein, step 2 includes step 2A and step 2B, and step 2A includes：With Ca (OH)2First clear liquid of regulating step 1
PH value is to 7-9 so that the SO in the bittern4 2-And Mg2+A part precipitated in the form of calcium sulfate and magnesium hydroxide, carry out
Clear liquid 2A is obtained after separation of solid and liquid, the clear liquid 2A is continued with into step 2B or continued with into step 3；Step
2B includes：Remaining SO in bittern4 2-And Mg2+A part continue in the form of calcium sulfate and magnesium hydroxide precipitate, separation of solid and liquid
After obtain clear liquid 2B, the clear liquid 2B is continued with into step 3；
Step 3 includes step 3A and step 3B, and step 3A includes：Acid, regulation pH value to 7- are added in step 2 gained clear liquid
8.5, obtain the low lithium of high magnesium using the Separation of Li and Mg UF membrane clear liquid and produce water 3A and the low magnesium production water 3A of high lithium, wherein the low lithium of high magnesium
Produce water 3A to return after the enrichment method of salt pan, then merge with raw brine, the high low magnesium production water 3A of lithium, which then enters step 3B, to be continued
Processing；Step 3B includes：Add complexing agent in the low magnesium production water 3A of the high lithium, using Separation of Li and Mg film described in step 3A or
The high low magnesium production water 3A of lithium, obtains the low lithium production water 3B of high magnesium and the low magnesium production water 3B of high lithium described in the new Separation of Li and Mg UF membrane of person, its
Described in the low lithium production water 3B of high magnesium return and merge with step 2A clear liquid, the high low magnesium of lithium produces water 3B, and then entrance step 4 continues
Processing.
2. according to the method described in claim 1, wherein, the low lithium of the high magnesium of step 3 is produced into water 3A, the low lithium of high magnesium of step 3 is produced
The return of at least one of water 3B, the light liquid of step 4 merges with second clear liquid of step 2.
3. according to the method described in claim 1, wherein, step 4 include step 4A, step 4B and step 4C,
Step 4A includes：Film is concentrated using the lithium water 3A and/or the low magnesium production water 3B progress of high lithium are produced to the low magnesium of high lithium of step 3
Concentration, obtains concentrate 4A and light liquid 4A, wherein the light liquid 4A is returned and merged with step 2A clear liquid, the concentrate 4A is then
Continue with or continued with into step 5 into step 4B；
Step 4B includes：Film is concentrated using lithium described in step 4A or new lithium concentration film is carried out to step 4A concentrate 4A
Concentration, obtains concentrate 4B and light liquid 4B, wherein the light liquid 4B is returned and merged with step 2A clear liquid, the concentrate 4B is then
Continue with or continued with into step 5 into step 4C；
Step 4C includes：Lithium concentration film described in film or step 4B or the concentration of new lithium are concentrated using lithium described in step 4A
Film is concentrated to step 4B concentrate 4B, obtains concentrate 4C and light liquid 4C, wherein the light liquid 4C is returned and step 2A
Clear liquid merge, the concentrate 4C is then continued with into step 5.
4. method according to claim 1 or 2, wherein, in step 1, plus the pH value of the acid regulation bittern is 2-4
Crystallize and separate out to the boric acid, then carry out the separation of solid and liquid and obtain first clear liquid and thick boric acid.
5. according to the method described in claim 1, wherein, in the step 2B, filter aid is added in the clear liquid 2A, then
The clear liquid returned with subsequent step merges, remaining SO in resulting treatment fluid4 2-And Mg2+A part continue with calcium sulfate
Precipitated with the form of magnesium hydroxide, then use polytetrafluoroethylene (PTFE) microfiltration membranes by the calcium sulfate being settled out and magnesium hydroxide floccule
After separation, obtain clear liquid 2B and continued with into step 3.
6. according to the method described in claim 1, wherein, lithium concentration is less than 150ppm in the low lithium production water 3A of high magnesium,
Lithium concentration is more than 300ppm in the low magnesium production water 3A of high lithium；Lithium concentration is more than in the low magnesium production water 3B of high lithium
300ppm and lithium magnesium mass ratio are more than 1.
7. method according to claim 3, wherein, lithium concentration is more than 1000ppm and lithium magnesium in the concentrate 4A
Mass ratio is more than 1；Lithium concentration is more than 2000ppm in the concentrate 4B and lithium magnesium mass ratio is more than 1；The concentrate 4C
Middle lithium concentration is more than 16000ppm and lithium magnesium mass ratio is more than 1.
8. method according to claim 5, wherein, the filter aid is perlite, diatomite or cellulose, the drainage
The addition of agent is 30-50ppm.
9. according to the method described in claim 1, wherein, in step 3A, the acid added in step 2 gained clear liquid include salt
One kind or its combination in acid, sulfuric acid, nitric acid.
10. according to the method described in claim 1, wherein, in step 3B, the complexing agent added in high lithium low magnesium production water 3A
It is sub- including compounding EDETATE SODIUM salt, ethylenediamine tetra-acetic acid, edetate, ATMP, divinyl triammonium five
Methylphosphonic acid, hydroxy ethylene diphosphonic acid or calgon, the concentration of the complexing agent is 3-6ppm.
11. method according to claim 1 or 2, wherein, in steps of 5, hydroxide is added into the concentrate of step 4
Sodium, obtains slurry, by the Mg in the slurry2+With Mg (OH)2Form precipitation, by above-mentioned slurry progress separation of solid and liquid obtain hydrogen
Magnesium oxide precipitation and immersion liquid, the 3rd clear liquid is filtrated to get by the immersion liquid.
12. method according to claim 11, wherein, by the magnesium hydrate precipitate carried out again with water or immersion liquid once with
On leaching, separation of solid and liquid obtains magnesium hydrate precipitate and filtrate, and the filtrate is used to configuring sodium hydroxide and continues reuse.
13. method according to claim 1 or 2, wherein the method for the separation of solid and liquid includes：It is centrifuged at a high speed, gathers
Tetrafluoroethene micro-filtration UF membrane and/or filtering.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392024.0A CN104961143B (en) | 2015-07-03 | 2015-07-03 | The method that lithium is extracted from salt lake bittern |
| PCT/CN2016/087443 WO2017005113A1 (en) | 2015-07-03 | 2016-06-28 | Method for extracting lithium from salt lake brine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392024.0A CN104961143B (en) | 2015-07-03 | 2015-07-03 | The method that lithium is extracted from salt lake bittern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104961143A CN104961143A (en) | 2015-10-07 |
| CN104961143B true CN104961143B (en) | 2017-08-01 |
Family
ID=54215275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510392024.0A Active CN104961143B (en) | 2015-07-03 | 2015-07-03 | The method that lithium is extracted from salt lake bittern |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN104961143B (en) |
| WO (1) | WO2017005113A1 (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961143B (en) * | 2015-07-03 | 2017-08-01 | 青海恒信融锂业科技有限公司 | The method that lithium is extracted from salt lake bittern |
| CN105586499A (en) * | 2016-02-15 | 2016-05-18 | 华陆工程科技有限责任公司 | Deep boron removing method for lithium chloride solution |
| WO2018089932A1 (en) | 2016-11-14 | 2018-05-17 | Lilac Solutions, Inc. | Lithium extraction with coated ion exchange particles |
| CN108341419A (en) * | 2017-01-24 | 2018-07-31 | 马培华 | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio |
| CN111163852A (en) | 2017-08-02 | 2020-05-15 | 锂莱克解决方案公司 | Lithium extraction using porous ion exchange beads |
| US10439200B2 (en) | 2017-08-02 | 2019-10-08 | Lilac Solutions, Inc. | Ion exchange system for lithium extraction |
| US10648090B2 (en) | 2018-02-17 | 2020-05-12 | Lilac Solutions, Inc. | Integrated system for lithium extraction and conversion |
| US11865531B2 (en) | 2018-02-28 | 2024-01-09 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
| CN110217806B (en) * | 2019-07-04 | 2022-03-11 | 中国科学院青海盐湖研究所 | Method for preparing large-particle lithium carbonate from salt lake lithium-rich brine |
| WO2021053514A1 (en) | 2019-09-16 | 2021-03-25 | InCoR Lithium | Selective lithium extraction from brines |
| CN110980775A (en) * | 2019-12-03 | 2020-04-10 | 广西天源新能源材料有限公司 | Production method for producing multi-grade lithium carbonate through continuous carbonization |
| CN110894078B (en) * | 2019-12-26 | 2023-09-26 | 合肥天晟锂业科技有限公司 | Method and device for purifying battery-grade lithium carbonate |
| CA3166921A1 (en) | 2020-01-09 | 2021-07-15 | Lilac Solutions, Inc. | Process for separating undesirable metals |
| CN111362285A (en) * | 2020-03-29 | 2020-07-03 | 衢州学院 | Method for utilizing boron resource in salt lake brine |
| CA3178825A1 (en) | 2020-06-09 | 2021-12-16 | David Henry SNYDACKER | Lithium extraction in the presence of scalants |
| EP4247759A1 (en) | 2020-11-20 | 2023-09-27 | Lilac Solutions, Inc. | Lithium production with volatile acid |
| CN112695211A (en) * | 2020-12-01 | 2021-04-23 | 西安蓝深环保科技有限公司 | Continuous ion exchange method for separating lithium from salt lake brine |
| CN112624160B (en) * | 2020-12-17 | 2023-02-28 | 宝武水务科技有限公司 | Method for extracting lithium carbonate from carbonate type salt lake brine |
| CA3216001A1 (en) | 2021-04-23 | 2022-10-27 | David Henry SNYDACKER | Ion exchange devices for lithium extraction |
| CN114381614A (en) * | 2021-12-20 | 2022-04-22 | 恒信润丰科技开发（北京）有限公司 | Method for extracting lithium from salt lake and brine |
| CN114538660A (en) * | 2022-02-28 | 2022-05-27 | 瑜华科技(上海)有限公司 | Boron removing method for salt lake water |
| CN115028149A (en) * | 2022-03-15 | 2022-09-09 | 瑜华科技(上海)有限公司 | Membrane method lithium extraction process for salt lake |
| EP4499260A1 (en) | 2022-03-28 | 2025-02-05 | Lilac Solutions, Inc. | Devices for efficient sorbent utilization in lithium extraction |
| AR128953A1 (en) | 2022-04-01 | 2024-06-26 | Lilac Solutions Inc | LITHIUM EXTRACTION WITH CHEMICAL ADDITIVES |
| CN115094247B (en) * | 2022-07-07 | 2023-10-20 | 辽宁石油化工大学 | Method for extracting lithium from salt lake brine |
| CN115321705B (en) * | 2022-07-15 | 2024-08-06 | 浙江工业大学 | Method for separating magnesium and lithium from salt lake brine with high magnesium-lithium ratio |
| CN115400604B (en) * | 2022-09-06 | 2023-08-18 | 西北工业大学 | Positive charge nanofiltration membrane coating for magnesium-lithium separation and preparation method thereof |
| CN115571951B (en) * | 2022-09-26 | 2024-06-11 | 西藏矿业发展股份有限公司 | Lithium production system is carried in salt lake |
| CN115571950B (en) * | 2022-09-26 | 2024-06-11 | 倍杰特集团股份有限公司 | Salt lake lithium extraction process |
| CN117230322A (en) * | 2023-08-04 | 2023-12-15 | 苏州工业园区蒙纳士科学技术研究院 | Method and system for efficiently extracting lithium from mixed salt solution |
| CN118307005B (en) * | 2024-04-08 | 2024-11-26 | 上海鲲赛科技发展有限公司 | A method for recovering boron element in boron-containing solution |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100528753C (en) * | 2007-01-30 | 2009-08-19 | 西部矿业集团有限公司 | Method for combined extracting boron, magnesium and lithium from salt lake bittern |
| CN101712481A (en) * | 2009-12-08 | 2010-05-26 | 耿世达 | Method for preparing high-purity lithium carbonate and other available byproducts from salt lake brine |
| CN102433434A (en) * | 2010-09-29 | 2012-05-02 | 王辉 | Method for improving recovery rate of lithium separated by lithium-containing brine membrane method by using water as circulating working substance (water washing circulation method) |
| KR101431697B1 (en) * | 2012-01-06 | 2014-08-22 | 주식회사 포스코 | Method for extracting dissolved substance of lithium bearing solution and system using the same |
| CN103572071B (en) * | 2013-11-15 | 2016-03-02 | 中国科学院青海盐湖研究所 | A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio |
| CN103570048A (en) * | 2013-11-15 | 2014-02-12 | 中国科学院青海盐湖研究所 | Method for refining lithium from salt lake brine with high magnesium-lithium ratio |
| WO2015096549A1 (en) * | 2013-12-26 | 2015-07-02 | 江苏久吾高科技股份有限公司 | Process and apparatus for extracting battery grade lithium from brine |
| CN104961143B (en) * | 2015-07-03 | 2017-08-01 | 青海恒信融锂业科技有限公司 | The method that lithium is extracted from salt lake bittern |
-
2015
- 2015-07-03 CN CN201510392024.0A patent/CN104961143B/en active Active
-
2016
- 2016-06-28 WO PCT/CN2016/087443 patent/WO2017005113A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN104961143A (en) | 2015-10-07 |
| WO2017005113A1 (en) | 2017-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104961143B (en) | The method that lithium is extracted from salt lake bittern | |
| CN103074502B (en) | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine | |
| CN106186002B (en) | A kind of preparation method of battery-level lithium carbonate | |
| CN103572071B (en) | A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio | |
| CN104338441B (en) | Sinker mother liquor treatment process | |
| US9133229B2 (en) | Economic process for producing xylose from hydrolysate using electrodialysis and direct recovery method | |
| CN207375760U (en) | A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio | |
| CN107399747A (en) | A kind of method and device that lithium is carried from salt lake brine with high magnesium-lithium ratio | |
| CN1542147A (en) | Nano-filtration method for separating magnesium and enriching lithium from salt lake brine | |
| CN107720786A (en) | A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method | |
| CN106882816B (en) | A kind of method of concentration and separation boron in salt lake brine containing lithium | |
| CN107720785A (en) | A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method | |
| CA3132970C (en) | Method for concentrating and purifying eluate brine for the production of a purified lithium compound | |
| CN103570048A (en) | Method for refining lithium from salt lake brine with high magnesium-lithium ratio | |
| CN106629786B (en) | A kind of highly selective salt lake bittern puies forward lithium method | |
| CN205653294U (en) | Salinity matter device | |
| CN105018754A (en) | Extraction technology of ion-absorbed rare earth mine | |
| CN106379919A (en) | Comprehensive utilization method of lithium-containing waste fluids | |
| JP2024509488A (en) | Systems and methods for direct lithium hydroxide production | |
| CN108658345A (en) | A kind of method and system of high-salt wastewater purified salt | |
| CN107473483A (en) | A kind of method of electroplating wastewater zero processing | |
| CN103341320A (en) | Novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method | |
| CN106365183A (en) | Recovery method of electrode discharge solution in high-magnesium solution electrodialysis lithium extraction process | |
| CN103341321A (en) | Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method | |
| CN214060200U (en) | Salt lake lithium extraction system based on membrane separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |