CN106673023A - Method for extracting lithium from natural brine - Google Patents
Method for extracting lithium from natural brine Download PDFInfo
- Publication number
- CN106673023A CN106673023A CN201710009166.3A CN201710009166A CN106673023A CN 106673023 A CN106673023 A CN 106673023A CN 201710009166 A CN201710009166 A CN 201710009166A CN 106673023 A CN106673023 A CN 106673023A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- lithium chloride
- salt
- granule
- Prior art date
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- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 52
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 239000012267 brine Substances 0.000 title claims abstract description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 182
- 239000000243 solution Substances 0.000 claims abstract description 91
- 239000003463 adsorbent Substances 0.000 claims abstract description 75
- 239000012535 impurity Substances 0.000 claims abstract description 63
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 73
- 239000008187 granular material Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000010521 absorption reaction Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 23
- 238000003795 desorption Methods 0.000 claims description 21
- 239000011575 calcium Substances 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 241001131796 Botaurus stellaris Species 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229940063013 borate ion Drugs 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- ZSYZSZTWBOHQQK-UHFFFAOYSA-L dilithium;dichloride Chemical compound [Li+].[Li+].[Cl-].[Cl-] ZSYZSZTWBOHQQK-UHFFFAOYSA-L 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 80
- 239000013543 active substance Substances 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 10
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 chloride aluminum lithium Chemical compound 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 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 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C01D15/04—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a method for extracting lithium from natural brine. The method comprises the steps of adsorbing lithium in raw material brine by using a granular adsorbent in an adsorption-desorption concentration module with a granular adsorbent collector; adsorbing lithium chloride from the granular adsorbent to obtain a primary lithium chloride solution containing magnesium chloride and calcium chloride impurities; removing the impurities from the primary lithium chloride solution by adopting ion exchange to obtain a lithium chloride solution; concentrating the lithium chloride solution and obtaining lithium chloride monohydrate.
Description
Technical field
The present invention relates to purifying industrial field, is the method that elemental lithium is extracted from lake water containing lithium salts particularly.
Background technology
In the past, lithium salts was from the solid mineral (spodumene, lepidolite, petalite) containing lithium, also from the liquid containing lithium
Extract in raw mineral materials (lake bittern water, salt lake bittern, deeper subsurface salt).
With the popularization of lithium battery, the demand of lithium salts surges, and lithium salts manufacturer is more prone to select liquid raw mineral materials, because
It is using the raw material of this form enterprise can be made to create higher economic benefit and to more environment-friendly.
From containing lithium liquid raw mineral materials in produce lithium salts technology be all to concentrate lithium concentrate based on.And pass through not
Disconnected composition (NaCl, KCl, KClMgCl for salting out in salt2·6H2O、MgCl26H2O), traditional liquid containing lithium is concentrated
State raw mineral materials (the halite type salt containing a small amount of calcium and magnesium) and with same method enrichment materials salt to LiCl's
Content is to peaking, if it is desired to continuing to say that the concentration of lithium salts is improved, subsequently can bring about a serious problem, namely occurs multiple
Close salt LiClMgCl2·7H2O、LiCl·CaCl2·5H2O is precipitated.
Calcium oxide is added in lithium concentrate, is there is SO42-In the case of ion, Ca can be settled out2SO4With Mg (OH)2,
Calcium and magnesium in so as to remove salt.After removing the impurity in lithium concentrate in this way, lithium chloride is obtained by distillation high
Strength solution.To obtain high-purity lithium chloride, it is necessary to removing foreign matter boron, the method extracted with high molecular alcohol is high from lithium chloride
Strength solution removes the boron that exists as boric acid, then in the calcium chemically removed in lithium chloride highly concentrated solution and
Magnesium.
Subsequently can be by modes such as electrolysis, further purification LiCl solution, indented material has been carried out greatly
The exploratory development of amount.
There is at present from salt extracting directly lithium to obtain the patent of the method for lithium concentrate, by using aluminum lithium
Component substances, can form crystallite state lithium aluminum in ion exchange resin hole.
To extract salt containing lithium to obtain high-purity lithium solution, the method for synthesizing aluminum lithium complex is also suggested.Use
This method can obtain the LiCl2Al (HO) with fault of construction3·mH2The compound of O compositions.
The present invention is had found by studying, for aluminum lithium complex is improved, it is possible to obtain highly efficient lithium adsorbs into
Point, elemental lithium is extracted from salt so as to more efficient.The problem that presently, there are is：The lithium adsorbance of adsorbent generally compares
It is low.By acting on salt, before the parsing and washing for entering water-filling, the amount containing lithium of lithium adsorbent is about 7.0 to 8.0mg.From
And production efficiency is relatively low.
The content of the invention
A kind of method that lithium is extracted from natural bittern, comprising：With with the absorption-desorption of granule adsorbent catcher
In concentration module, using granule adsorbent the lithium in raw brine is adsorbed；
Desorption lithium chloride obtains the primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities from granule adsorbent；
Primary lithium chloride solution goes the removal of impurity using ion exchange remove impurity, obtains lithium chloride solution；
Concentration lithium chloride solution, and obtain single water lithium chloride.
A kind of method that lithium is extracted from natural bittern, adsorbs and is enriched with salt and obtain primary lithium chloride lithium solution, is
Realize in absorption desorption device, by filtering initial salt, or with the halogen of the prescribed volume for containing difference LiCl contents
Water by upper and lower drainage system, to increase salt in LiCl concentration, the salt for being filtered distributes catcher by lower cartridge type draining
It is input into lower granule tubular type drainage system, then supreme cartridge type draining is exported by upper granule tubular type drainage system and distributes by catcher
Road.
A kind of method that lithium is extracted from natural bittern, wherein desorption lithium chloride is obtained from granule adsorbent using distilled water
Primary lithium chloride solution that must be containing magnesium chloride and chlorination calcium impurities, lithium solion exchanges remove impurity and goes the removal of impurity to obtain lithium chloride
Solution.
A kind of method that lithium is extracted from natural bittern, it is characterised in that：Removal of impurity step is gone in the ion exchange remove impurity
Such as one of following methods：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, to the content of lithium chloride
For 220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent remove impurity is carried out to solution：Magnesium, calcium, sulphuric acid
Root, borate ion, then carry out remove impurity and obtain lithium chloride solution to solution in Li type resins；
Or first ion exchange remove impurity is carried out in Li type cationites to primary lithium chloride solution；Then to cleaning
Solution afterwards carries out reverse osmosis concentration and obtains LiCl contents for 60-65kg/m3Transition solution and desalted water；With heating to mistake
Cross solution to be evaporated until LiCl contents are 190-210kg/m3, then reagent remove impurity goes removing sulfate-borate-ion miscellaneous
Matter and obtain lithium chloride solution；
Or remove impurity is carried out by primary lithium chloride solution and lithium carbonate contact, remove removal of impurity magnesium and calcium；It is molten after cleaning
Liquid is first concentrated to give transition solution and desalted water with hyperfiltration；Then transition solution is evaporated until LiCl with heating
Content is 450kg/m3NaCl is salted out, subsequent dilute solution is until LiCl 190-210kg/m3, then reagent remove impurity goes remove impurity
Matter further obtains lithium chloride solution.
A kind of method that lithium is extracted from natural bittern, wherein granule adsorbent adopt the active material ingredients of high Al elements
Made by granule adsorbent, in 23-24 DEG C of operating temperature range, after fully acting on salt, using distilled water to granular absorption
Agent is washed and desorbing, so as to obtain the solution containing lithium ion.
A kind of method that lithium is extracted from natural bittern, the active material ingredients of aforementioned high Al elements are molten by lithium chloride
Liquid is mixed with Lithium hydrate or lithium carbonate or lithium chloride；Wherein Al:The atomic ratio of Li reaches 3.0-3.5；Subsequently
Using with NaOH as alkaline reagent formed lithium aluminum double-hydroxide chloride：LiOH+3AlCl3+9NaOH+nH2O=
LiCl·3Al(OH)3·nH2O+9NaCl；Its 8≤n≤10.
Subsequently, the product that previous step is obtained is cleaned, obtains LiCl3Al (OH)3·nH2O active component things
Matter.
It is a kind of from natural bittern extract lithium method, granule adsorbent be by the active component of above-mentioned high Al elements,
Crushed under hydrated state, screened after crushing, part is carried out reciprocating gird after crushing with the sieve of 50 mesh, so as to obtaining≤
Next the powdered granule of 0.2mm, the granule of crushing is mixed with organic compound, mixed mixture, by extruding
Comminutor, is obtained a diameter of 2mm or so granule.
It is a kind of from natural bittern extract lithium method, the aforementioned organic compound for carrying out pelletize can be polrvinyl chloride or
Person's chlorinated polyethylene etc. can be dissolved in the chloride organic polymer of methyl chloride, or the mixing of various chloride organic polymers
Thing..
A kind of method that lithium is extracted from natural bittern, according to granule adsorbent obtained in this kind of method, every gram of granule is inhaled
The absorbability of the attached dose of Li element with 9mg.
A kind of method that lithium is extracted from natural bittern, wherein Al:The atomic ratio of Li reaches 3.0-3.5.
Description of the drawings
Fig. 1 shows the prototype figure of the salt adsorption-desorption device of this patent；
Fig. 2 shows the prototype figure of the salt adsorption-desorption device of this patent；
Fig. 3 shown in the case of different embodiments, the absorbability of adsorption particle；
Fig. 4 shows the granular size used when preparing adsorption particle for the impact of absorbability.
Embodiments of the invention
Figures 1 and 2 show that the absorption of this patent and the schematic diagram of desorption apparatus.Below with reference to attached Fig. 1 and 2 explanations originally
The device course of work of invention.
Fig. 1 devices include：Raw brine (1) containing lithium, the supply pump (2) containing lithium salt；Based on the double hydrogen of chloride aluminum lithium
The dispersion phase of the defect kind of oxide, with granule adsorbent the absorption-desorption device of adsorbent flowing bed is filled, and collects system
The storage tank (11) of the lithium concentrate got, fresh water storage tank (12), fresh water supply pump (13) is collected granular adsorbent and crushes mutually mistake
Filter (27), adsorbed adsorbent selects container (24), and the salt that gives up receives container (9), salt transhipment pump (10).Also include：
Cartridge type is given up salt discharge system (6), and goods charging bucket (7), adsorbent classification hydraulic pressure are unloaded in absorption-desorption part Absorption quantity agent in system
Device (8), for removing little particle adsorbent and entering adsorbent bed dispersion phase impurity from salt.In its moving process
In, granule adsorbent is defeated positioned at salt through the lithium chloride adsorption zone (3) being located between cartridge type drainage system and salt input pipe
Enter use lithium concentrated solution salt area (4) between pipe and lithium concentrated solution outlet tube, positioned at lithium concentrated solution outlet tube and freshwater input pipe
Between lithium chloride desorption zone (5), the enrichment process of salt has two steps：Adsorbent is transported and production stage.
The device of this method is realized in Fig. 2 to be included：Salt containing lithium source (13), be connected with three section storage tanks (1-1,1-2,
1-3)；Tower replenishment pump -4 (4-1,4-2) is collected under water, on the basis of chloride aluminum lithium double-basis hydroxide difference defect dispersion phase
On, it is lower to collect the part 3 (3-1,3-2) that tower fixes compression bed as adsorption-desorption enriching apparatus；Filter (10), for returning
Receive the derived adsorbent for grinding and adsorbed adsorbent from device；Container (12), for collecting useless lithium salt；Sal is molten
The section of liquid three consumes storage tank -14 (14-1.14-2,14-3), is connected (22) with salt solution original storage tank；Pump (15), for conveying
The salt solution of discharge to catcher -9 (9-1,9-2) on absorption-desorption module tower, the section of lithium concentrated solution three consume storage tank -16
(16-1,16-2,16-3), for discharging solution, is connected with the container (24) of the lithium concentrated solution for collecting production；Pump (17), it is defeated
The lithium concentrated solution for sending discharge is delivered to -18 (18-1,18-2,18- in equipped with desorbing liquid three section containers into container, equally
3), the three section container is connected with fresh water original storage tank (23), pump (19), and pump (19) is collected for conveying stripping liquid to container
Device.In addition, also container (20), for collecting and extracting the Sal waste liquid of discharge, container (21), for collecting and extracting
Useless lithium concentrated solution, concentrated solution displacement.Adsorbent is fixed compression bed and is made up of two containers, by pipeline and pneumatic between them
Valve is connected, and thus can realize in phase producing lithium concentrated solution：One container is located at the step of lithium chloride saturation adsorbent
Suddenly, at this moment another container is located at salt displacement and from saturation adsorbent desorbing lithium chloride step.Tower has cylindrical shell, puts down
Bottom, oval lid, upper and lower drainage system, centre is adsorbent.Lower drainage system be by be fixed on cylindrical shape distribution
Water drain casing tube bottom structure composition 4 (4-1,4-2), sleeve is evenly distributed on the section of tower, and with lower catcher phase
Connect (8), and by gravel pack 5 (5-1,5-2), the size of gravel particle is 5-7mm, the gravel layer net of bottom and suction to sleeve
Attached dose separates.Upper drainage system is by supporting screen to constitute, and the position of screen is consistent with the upper material position of adsorbent, and support has on screen
Size of mesh for 3-4mm grid, gravel layer 6 (6-1,6-2) that can by adsorbent bed and above separates, gravel layer fill to
The upper material position of distribution water drain casing tube, sleeve is equally evenly distributed on the section of tower, and is connected with each other 9 (9- with upper catcher
1,9-2).Gravel layer size of mesh above is that the screen of 3-4mm is covered, and so can ensure that tower under compression jigging bed condition
Operating.The structure of this tower can avoid the excessive increasing of the absorbent particles being ground in draining sleeve and solid phase impurity in small, broken bits
Long, impurity is inevitably present in salt (2-5g/m3).Find during experiment, the adsorbent in tower has one
Fixed water environment capacity, the size of water environment capacity by impurity particle size, by the filtrate flows speed of adsorbent bed filtration
Determine with the size of adsorbent itself.If the particle size of impurity is for 100 microns or less than 100 microns, then adsorbent
Grain at least can not be less than 0.5mm, with impurity fill absorbent particles bed to its water environment capacity value, particle layers start to return
Also and into the impurity of the same total amount of adsorbent, that is, final impurity dispersion phase enter into drainage system gravel layer.Inhaling
During attached or desorbing, impurity in gravel layer or flowed out by salt stream (absorption), a portion by salt outlet tube from
Tower 6 (6-1,6-2) is opened, or is deposited on the surface (desorbing) of draining cylindrical casing, it is defeated from tower because exporting different from salt
Going out desorbed species will be regenerated by the sleeve portion с (с -1, с -2) of upper catcher, draining cylindrical casing in displacement operation,
Because always top-down enters catcher and draining cylindrical sleeves to substitutional solution through sleeve pipe " с ".By water drain casing tube
When filtering substitutional solution, the impurity for being deposited on the upper surface of draining cylindrical sleeves is transferred in gravel layer.Because removing is put
Changing liquid will be deposited on lower cylinder by the tube portion of trapping " а " (а -1, а -2) of lower catcher, the absorption process in displacement
The impurity particle of sleeve interior surface is got off from surface washing and is discharged with cleaning mixture stream from tower.In turn, in absorption process,
It is easy to be discharged with salt stream from tower from cylinder draining sleeve outer surface into the compound particles of upper gravel layer.If used
Conventional adsorbent, the whole cycle time that concentration is enriched with adsorbent fixes compression bed is (to adsorb within 3 hours, 3 is little for 6 hours
When displacement desorption).
It is more than that the present invention is used to carry out adsorbing the basic explanation with the device of desorbing.
The method of the present invention has used following method, with the absorption of granule adsorbent catcher-desorption concentration
In module, using granule adsorbent the lithium in raw brine is adsorbed；Desorption lithium chloride is obtained containing chlorination from granule adsorbent
The primary lithium chloride solution of magnesium and chlorination calcium impurities；Primary lithium chloride solution goes the removal of impurity using ion exchange remove impurity, obtains chlorine
Change lithium solution；Concentration lithium chloride solution, and obtain single water lithium chloride.Absorption and it is enriched with salt and to obtain primary lithium chloride lithium molten
Liquid, is realized in absorption desorption device, by filtering initial salt, or with containing the prescribed volume of difference LiCl contents
Salt by upper and lower drainage system, to increase salt in LiCl concentration, the salt for being filtered received by lower cartridge type draining distribution
Storage is input into lower granule tubular type drainage system, then exports supreme cartridge type draining distribution collection by upper granule tubular type drainage system
Device is bypassed.Wherein using distilled water, desorption lithium chloride obtains the primary containing magnesium chloride and chlorination calcium impurities from granule adsorbent
Lithium chloride solution, lithium solion exchanges remove impurity and goes the removal of impurity to obtain lithium chloride solution.
Removal of impurity step such as one of following methods are removed in the ion exchange remove impurity：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, to the content of lithium chloride
For 220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent remove impurity is carried out to solution：Magnesium, calcium, sulphuric acid
Root, borate ion, then carry out remove impurity and obtain lithium chloride solution to solution in Li type resins；
Or first ion exchange remove impurity is carried out in Li type cationites to primary lithium chloride solution；Then to cleaning
Solution afterwards carries out reverse osmosis concentration and obtains LiCl contents for 60-65kg/m3Transition solution and desalted water；With heating to mistake
Cross solution to be evaporated until LiCl contents are 190-210kg/m3, then reagent remove impurity goes removing sulfate-borate-ion miscellaneous
Matter and obtain lithium chloride solution；
Or remove impurity is carried out by primary lithium chloride solution and lithium carbonate contact, remove removal of impurity magnesium and calcium；It is molten after cleaning
Liquid is first concentrated to give transition solution and desalted water with hyperfiltration；Then transition solution is evaporated until LiCl with heating
Content is 450kg/m3NaCl is salted out, subsequent dilute solution is until LiCl 190-210kg/m3, then reagent remove impurity goes remove impurity
Matter further obtains lithium chloride solution.
The present invention will be stressed for the main cause for improving adsorption efficiency below.
Preparation process for the active substance of the high Al content of the present invention is as follows：
The preparation of active substance one：In the liquor alumini chloridi of 10L, AlCl3Concentration be 188g/L, add 0.125L
LiOH solution (0.85g/L), the atomic ratio of Al and Li is Al:Li=3.6 (Al ions excessive about 15%), is subsequently added into NaOH molten
Liquid to PH reaches 7.
Under room temperature, above-mentioned reacted mixture is stirred 30 minutes.Subsequently precipitation is leached with filter, it is natural after cleaning
Dry, obtain LiCl3Al (OH)3·nH2O (8≤n≤10) active ingredient substance；Subsequently, by the active matter with hydrate
Matter is ground into granule, and using the sieve of 60 mesh reciprocating gird is carried out, so as to obtaining≤powdered granule of 0.2mm.
The preparation of active substance two：In 10L liquor alumini chloridis (188g/L), the atomic ratio for adding Al and Li is Al:Li
=3.2 lithium carbonate slurry, is subsequently added into NaOH solution, and complete to reacting, solution PH reaches 7.0.
Precipitation is isolated, subsequently precipitation is leached with filter, is dried naturally after cleaning, obtain LiCl3Al (OH)3·
nH2O (8≤n≤10) active ingredient substance；Subsequently, the active substance with hydrate is ground into into granule, using the sieve of 60 mesh
Son carries out reciprocating gird, so as to obtaining≤powdered granule of 0.2mm.
Not necessarily active substance one and active substance two are mixed with for the preparation of the active substance in the present invention；Take work
One kind in the preparation method of property material one or active substance two, can prepare final active substance.
It is prepared by the adsorption particle for the present invention：Active substance one and active substance two are uniformly mixed, by compounding substances
By the microgranule of 60 mesh sieve.Powder contain 99% particle size≤0.2mm, so as to obtain prepare before granule it is final in
Between thing.Next can be used for making granule.Hydration number 8≤n≤10 of active substance.
Atomic ratio Al in mixture:Li=3.3.
Particle preparation is carried out in sealed stirrer.The intermedium of 800g, 80g chlorinated polyvinyl chloride second are put in agitator
Alkene, dichloromethane solution, stir to starchiness.Slurry is put into into extruder, then the fine strip shape material for obtaining length is cut into into
It is stand-by after being dried for the granule of 2mm.
Adsorption test：In order to determine the absorbability of particulate matter, 5kg granules are put in the reaction tube of diameter 4cm, water
Tower is passed through with the speed of 3 cubic decimeters/hour.After 8 hours are processed, the granule of absorption stable state is obtained.
Subsequently, by absorption stable grain size distilled water desorption.Jing is determined, and the Li of 45g is obtained altogether；Equivalent every 1g adsorbents
The Li of 9mg can be adsorbed.
Embodiment one：
The absorption of elemental lithium in salt is carried out using the adsorption particle of the present invention, as it was previously stated, at normal temperatures, 8 as a child,
The granule of absorption stable state can be obtained.Absorption stable grain size Jing is determined, and every gram of adsorbent can adsorb the lithium of 9mg.
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 23-24 DEG C of degree, granule adsorbent disclosed in this invention is acted at such a temperature with salt, and 5kg granules are put into into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distillation hydrolysis
Absorption.Jing is determined, and the Li of 45g is obtained altogether；The equivalent Li that can adsorb 9mg per 1g adsorbents.
Reference examples two：
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 24-25 DEG C of degree, granule adsorbent disclosed in this invention is acted at such a temperature with salt, and 5kg granules are put into into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distillation hydrolysis
Absorption.Jing is determined, and the Li of 45.2g is obtained altogether；The equivalent Li that can adsorb 9.04mg per 1g adsorbents.
Reference examples three：
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 22-23 DEG C of degree, granule adsorbent disclosed in this invention is acted at such a temperature with salt, and 5kg granules are put into into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distillation hydrolysis
Absorption.Jing is determined, and the Li of 42.1g is obtained altogether；The equivalent Li that can adsorb 8.42mg per 1g adsorbents.
Reference examples four：
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 21-22 DEG C of degree, granule adsorbent disclosed in this invention is acted at such a temperature with salt, and 5kg granules are put into into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distillation hydrolysis
Absorption.Jing is determined, and the Li of 40.5g is obtained altogether；The equivalent Li that can adsorb 8.1mg per 1g adsorbents.
Reference examples five：
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 20-21 DEG C of degree, granule adsorbent disclosed in this invention is acted at such a temperature with salt, and 5kg granules are put into into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distillation hydrolysis
Absorption.Jing is determined, and the Li of 39.5g is obtained altogether；The equivalent Li that can adsorb 7.9mg per 1g adsorbents.
Reference examples six：
Active substance is prepared according to the method for the present invention, uniform heating so that hydration number 7≤n≤8.Subsequently, according to this
Bright method prepares adsorption particle.
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 23-24 DEG C of degree, this reference examples granule adsorbent is acted at such a temperature with salt, and 5kg granules are put into into the anti-of diameter 4cm
Ying Guanzhong, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distilled water desorption.Jing
Determine, the Li of 42.5g is obtained altogether；The equivalent Li that can adsorb 8.5mg per 1g adsorbents.
Reference examples seven：
Active substance is prepared according to the method for the present invention, uniform heating so that hydration number 6≤n≤7.Subsequently, according to this
Bright method prepares adsorption particle.
Before salt carries out elemental lithium absorption, using daylight, high-temperature liquid stream salt preheating, most final temperature after salt preheating are carried out
About 20-21 DEG C of degree, this reference examples granule adsorbent is acted at such a temperature with salt, and 5kg granules are put into into the anti-of diameter 4cm
Ying Guanzhong, water passes through tower with the speed of 3 cubic decimeters/hour.After 4 hours are processed, by adsorption particle distilled water desorption.Jing
Determine, the Li of 40g is obtained altogether；The equivalent Li that can adsorb 8mg per 1g adsorbents.
It is salt lake saline that the application scenario of institute of the invention is salt, and salt lake is in high latitude area, in general it is outdoor averagely
Temperature is relatively low, needs to preheat salt lake saline.Preheating can be right using production high temperature wastewater with by the way of multistage preheating
Low temperature salt lake saline is preheated.Liquid after proposition, can preheat again to salt lake saline to be extracted.So as to profit as much as possible
With temperature difference, heat is made full use of.
Inventor has found that in the case of using high Al content adsorption activity composition, the operating temperature of granule adsorbent is right
There is considerable influence in the elemental lithium absorbability of granule adsorbent.As shown in embodiment one to reference examples five, active substance is in 23-
Under 24 degrees Celsius, Li atomic adsorptions amount can reach 9mg, and temperature continues to increase, and the adsorbance of Li is not significantly increased, this
Perhaps it is relevant with the saturated extent of adsorption of adsorbent.And after temperature is substantially reduced, the Li adsorbances of adsorbent are substantially reduced.Referring to Fig. 3.
In the case of high Al content, the absorbability of the hydration number of active substance for Li also has certain impact.Referring to attached
Fig. 4.The high Al active substances of the present invention, preferably use 8-10 hydration number.
The inventive method advantage is：
1st, this patent method works at 23-24 DEG C；Using the preheating in other courses of work, to the aqueous salt brine for exchanging
Heated and can reach.The temperature is higher than Salt Lake Area outdoor temperature, because the optimum working temperature of active substance is in this
One temperature range, therefore, the efficiency for extracting active substance beneficial to granule adsorbent is far above room ambient conditions.
2nd, this patent method improves the service efficiency of lithium ion.LiCl·3Al(OH)3The use of composition is compared with LiCl
2Al(OH)3For, the utilization rate of single lithium ion is higher.Using the adsorbent of the present invention, the suction of lithium ion in unit adsorbent
Attached amount can reach 9mg/g (every gram of adsorbent can adsorb 9mg elemental lithiums).
3rd, this patent uses the hydrate of the active substance of high Al content as pelletize raw material.In granulation process and pelletize
Afterwards, active substance hydrate is lost, and so as to specific surface area increase, improves the absorbability of unit mass granulated pellet.
4th, the primary solution that the method for this patent is obtained, concentration is higher than conventional method, and the spent time is significantly lower than normal
Rule method.
Above content is to combine specific optimal technical scheme further description made for the present invention, it is impossible to assert
The present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of without departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. it is a kind of from natural bittern extract lithium method, comprising：With dense with the absorption-desorption of granule adsorbent catcher
In contracting module, using granule adsorbent the lithium in raw brine is adsorbed；
Desorption lithium chloride obtains the primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities from granule adsorbent；
Primary lithium chloride solution goes the removal of impurity using ion exchange remove impurity, obtains lithium chloride solution；
Concentration lithium chloride solution, and obtain single water lithium chloride.
2. method as claimed in claim 1, adsorbs and is enriched with salt and obtain primary lithium chloride lithium solution, is in absorption desorption device
Middle realization, by filtering initial salt, or with the salt of the prescribed volume for containing difference LiCl contents by upper and lower draining
System, to increase salt in LiCl concentration, the salt for being filtered by lower cartridge type draining distribute catcher be input into lower particle pipe
Formula drainage system, then supreme cartridge type draining distribution catcher bypass is exported by upper granule tubular type drainage system.
3. method as claimed in claim 1, wherein desorption lithium chloride is obtained containing magnesium chloride from granule adsorbent using distilled water
With the primary lithium chloride solution of chlorination calcium impurities, lithium solion exchange remove impurity go the removal of impurity obtain lithium chloride solution.
4. the method for claim 1, it is characterised in that：Removal of impurity step such as following methods are removed in the ion exchange remove impurity
One of：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, and the content to lithium chloride is
220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent remove impurity is carried out to solution：Magnesium, calcium, sulfate radical,
Borate ion, then carries out remove impurity and obtains lithium chloride solution to solution in Li type resins；
Or first ion exchange remove impurity is carried out in Li type cationites to primary lithium chloride solution；Then to cleaning after
Solution carries out reverse osmosis concentration and obtains LiCl contents for 60-65kg/m3Transition solution and desalted water；It is molten to transition with heating
Liquid is evaporated until LiCl contents are 190-210kg/m3, then reagent remove impurity remove removing sulfate-borate-ionic impurity and
Obtain lithium chloride solution；
Or remove impurity is carried out by primary lithium chloride solution and lithium carbonate contact, remove removal of impurity magnesium and calcium；Solution elder generation after cleaning
Transition solution and desalted water are concentrated to give with hyperfiltration；Then transition solution is evaporated until LiCl contents with heating
For 450kg/m3NaCl is salted out, subsequent dilute solution is until LiCl 190-210kg/m3, then reagent remove impurity goes the removal of impurity to enter
And obtain lithium chloride solution.
5. method as claimed in claim 1, wherein granule adsorbent using high Al elements active material ingredients made by granule inhale
Attached dose, in 23-24 DEG C of operating temperature range, after fully acting on salt, using distilled water to granule adsorbent carry out washing and
Desorbing, so as to obtain the solution containing lithium example.
6. method as claimed in claim 5, the active material ingredients of aforementioned high Al elements be by lithium chloride solution and Lithium hydrate,
Or lithium carbonate or lithium chloride are mixed；Wherein Al:The atomic ratio of Li reaches 3.0-3.5；Subsequently use and use NaOH conducts
The chloride of lithium aluminum double-hydroxide is formed as alkaline reagent：LiOH+3AlCl3+9NaOH+nH2O=LiCl3Al
(OH)3·nH2O+9NaCl；Its 8≤n≤10.
Subsequently, the product that previous step is obtained is cleaned, obtains LiCl3Al (OH)3·nH2O active ingredient substances.
7. method as claimed in claim 5, granule adsorbent is, by the active component of above-mentioned high Al elements, to enter under hydrated state
Row is crushed, and is screened after crushing, and part carries out reciprocating gird after crushing with the sieve of 50 mesh, so as to obtaining≤powdered granule of 0.2mm, powder
Next broken granule is mixed with organic compound, mixed mixture, by Squeezinggranulator, is obtained a diameter of
2mm or so granules.
8. method as claimed in claim 7, the aforementioned organic compound for carrying out pelletize can be polrvinyl chloride or chlorinated polyethylene
Etc. the chloride organic polymer that can be dissolved in methyl chloride, or the mixture of various chloride organic polymers.
9. method as claimed in claim 5, according to granule adsorbent obtained in this kind of method, every gram of granule adsorbent has 9mg's
The absorbability of Li elements.
10. a kind of granule adsorbent, for claim 1-9 methods described, it is characterised in that：Wherein Al:The atomic ratio of Li reaches
To 3.0-3.5.
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| US11986816B2 (en) | 2021-04-23 | 2024-05-21 | Lilac Solutions, Inc. | Ion exchange devices for lithium extraction |
| US12076662B2 (en) | 2022-03-28 | 2024-09-03 | Lilac Solutions, Inc. | Devices for efficient sorbent utilization in lithium extraction |
| CN115739004A (en) * | 2022-11-25 | 2023-03-07 | 中国科学院青海盐湖研究所 | Lithium-aluminum adsorption material prepared from salt lake brine with high magnesium-lithium ratio and method thereof |
| CN115739004B (en) * | 2022-11-25 | 2024-04-16 | 中国科学院青海盐湖研究所 | Lithium-aluminum adsorption material prepared from salt lake brine with high magnesium-lithium ratio and method thereof |
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