CN106673023B - A method of extracting lithium from natural bittern - Google Patents
A method of extracting lithium from natural bittern Download PDFInfo
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- CN106673023B CN106673023B CN201710009166.3A CN201710009166A CN106673023B CN 106673023 B CN106673023 B CN 106673023B CN 201710009166 A CN201710009166 A CN 201710009166A CN 106673023 B CN106673023 B CN 106673023B
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- lithium
- lithium chloride
- solution
- brine
- chloride solution
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 52
- 241001131796 Botaurus stellaris Species 0.000 title claims abstract description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 184
- 239000000243 solution Substances 0.000 claims abstract description 83
- 239000012267 brine Substances 0.000 claims abstract description 80
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 80
- 239000003463 adsorbent Substances 0.000 claims abstract description 79
- 239000012535 impurity Substances 0.000 claims abstract description 55
- 239000008187 granular material Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 26
- 238000003795 desorption Methods 0.000 claims abstract description 23
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 53
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 239000011149 active material Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 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
- 239000000203 mixture Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229940063013 borate ion Drugs 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940050176 methyl chloride Drugs 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 description 17
- 239000012141 concentrate Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration 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
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 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
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 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
- 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 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
- 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
- 238000005185 salting out Methods 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
- 238000012546 transfer 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
A method of extracting lithium from natural bittern, including：In with the absorption desorption concentration module with granule adsorbent collector, the lithium in raw brine is adsorbed using granule adsorbent；Desorption lithium chloride obtains the primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities from granule adsorbent；Primary lithium chloride solution obtains lithium chloride solution using ion exchange removal of impurities removal impurity；Lithium chloride solution is concentrated, and obtains single water lithium chloride.
Description
Technical field
The present invention relates to purifying industrial fields, are the methods 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
It is extracted in raw mineral materials (lake bittern water, salt lake bittern, deeper subsurface brine).
With popularizing for lithium battery, the demand of lithium salts surges, and lithium salts manufacturer is more prone to selection liquid raw mineral materials, because
To use the raw material of this form that enterprise can be made to create higher economic benefit and to more environment-friendly.
The technology that lithium salts is produced from the liquid raw mineral materials containing lithium is all based on concentrating lithium concentrate.And by not
Disconnected ingredient (NaCl, KCl, KClMgCl for salting out in brine2·6H2O、MgCl26H2O), traditional liquid containing lithium is concentrated
State raw mineral materials (the halite type brine containing a small amount of calcium and magnesium) and with same method enrichment materials brine to LiCl's
Content, if it is desired to continuing to say that the concentration of lithium salts improves, then can bring about a serious problem, namely answer to peaking
Close salt LiClMgCl2·7H2O、LiCl·CaCl2·5H2O is precipitated.
Calcium oxide is added into lithium concentrate, is there is SO42-In the case of ion, Ca can be settled out2SO4With Mg (OH)2,
To remove the calcium and magnesium in brine.After removing the impurity in lithium concentrate in this way, it is high that lithium chloride is obtained by distillation
Strength solution.To obtain high-purity lithium chloride, it is necessary to boron impurities are isolated, with the method that high molecular alcohol extracts from lithium chloride height
Strength solution removes existing boron as boric acid, then the calcium in chemically removing lithium chloride highly concentrated solution and
Magnesium.
Then can be by modes such as electrolysis, further to purify LiCl solution, indented material has carried out greatly
The exploratory development of amount.
Have at present and has directly extracted lithium from brine to obtain the patent of the method for lithium concentrate, by using aluminium lithium
Component substances can form crystallite state lithium aluminium in ion exchange resin hole.
It is to extract brine containing lithium to obtain high-purity lithium solution, the method for synthesizing aluminium lithium compound is also suggested.It uses
This method can obtain the LiCl2Al (HO) with fault of construction3·mH2The compound of O ingredients.
The present invention by the study found that be improved for aluminium lithium compound, can obtain highly efficient lithium absorption at
Point, elemental lithium is extracted from brine to more efficient.Presently, there are the problem of be：The lithium adsorbance of adsorbent generally compares
It is low.By being acted on brine, before the parsing and washing for carrying out water, the amount containing lithium of lithium adsorbent is about 7.0 to 8.0mg.From
And production efficiency is relatively low.
Invention content
A method of extracting lithium from natural bittern, including：With with absorption-desorption of granule adsorbent collector
It concentrates in module, the lithium in raw brine is adsorbed using granule adsorbent；
Desorption lithium chloride obtains the primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities from granule adsorbent；
Primary lithium chloride solution obtains lithium chloride solution using ion exchange removal of impurities removal impurity；
Lithium chloride solution is concentrated, and obtains single water lithium chloride.
A method of it extracting lithium from natural bittern, adsorbs and be enriched with brine and obtain primary lithium chloride lithium solution, be
It is realized in adsorbing desorption device, by filtering initial brine, or the halogen with the prescribed volume containing different LiCl contents
Water is by upper and lower drainage system, and to increase LiCl concentration in brine, the brine filtered drains distribution collector by lower cartridge type
It is input to lower particle tubular type drainage system, then is exported by supreme cartridge type draining distribution collector by upper particle tubular type drainage system
Road.
A method of lithium is extracted from natural bittern, wherein being obtained using distilled water desorption lithium chloride from granule adsorbent
The primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities is obtained, lithium solion exchanges removal of impurities removal impurity and obtains lithium chloride
Solution.
A method of extracting lithium from natural bittern, it is characterised in that：The ion exchange removal of impurities removal impurity step
Such as one of following methods：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, until the content of lithium chloride
For 220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent removal of impurities is carried out to solution：Magnesium, calcium, sulfuric acid
Then root, borate ion clean to solution in Li type resins and obtain lithium chloride solution；
Or ion exchange removal of impurities is first carried out in Li type cation-exchangers to primary lithium chloride solution；Then to cleaning
Solution afterwards carries out reverse osmosis concentration and obtains LiCl contents to be 60-65kg/m3Transition solution and desalted water；With heating to mistake
Solution is crossed to be evaporated until LiCl contents are 190-210kg/m3, then reagent, which cleans, goes removing sulfate-borate-ion miscellaneous
Matter and obtain lithium chloride solution；
Or cleaned by primary lithium chloride solution and lithium carbonate contact, remove 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 removal of impurities go to clean
Matter obtains lithium chloride solution in turn.
A method of extracting lithium from natural bittern, wherein granule adsorbent uses the active material ingredients of high Al elements
Manufactured granule adsorbent, in 23-24 DEG C of operating temperature range, after fully being acted on brine, using distilled water to granular absorption
Agent is washed and is desorbed, to obtain the solution containing lithium ion.
A method of extracting lithium from natural bittern, the active material ingredients of aforementioned high Al elements are molten by lithium chloride
Liquid is mixed with lithium hydroxide or lithium carbonate or lithium chloride；Wherein Al:The atomic ratio of Li reaches 3.0-3.5；Then
Using use NaOH as alkaline reagent formed lithium aluminium double-hydroxide chloride：LiOH+3AlCl3+9NaOH+nH2O=
LiCl·3Al(OH)3·nH2O+9NaCl；Its 8≤n≤10.
Then, the product obtained to previous step cleans, and obtains LiCl3Al (OH)3·nH2O active constituent objects
Matter.
A method of from natural bittern extract lithium, granule adsorbent be by the active constituent of above-mentioned high Al elements,
Crush under hydrated state, screened after crushing, part with the sieve of 50 mesh carries out reciprocating gird after crushing, to obtain≤
Next the particle of the powdered granule of 0.2mm, crushing is mixed with organic compound, mixed mixture passes through extruding
A diameter of 2mm or so particle is made in comminutor.
A method of from natural bittern extract lithium, the aforementioned organic compound being granulated can be polyvinyl chloride or
Person's haloflex etc. can be dissolved in the mixing of the organic polymer containing chlorine or a variety of organic polymers containing chlorine of methyl chloride
Object..
A method of extracting lithium from natural bittern, according to granule adsorbent made from this kind of method, every gram of particle is inhaled
The adsorption capacity of the attached dose of Li element with 9mg.
A method of extracting lithium, wherein Al from natural bittern:The atomic ratio of Li reaches 3.0-3.5.
Description of the drawings
Fig. 1 shows the prototype figure of the brine adsorption-desorption device of this patent；
Fig. 2 shows the prototype figures of the brine adsorption-desorption device of this patent；
In the case of Fig. 3 shows different embodiments, the adsorption capacity of adsorption particle；
Influence of the granular size that Fig. 4, which is shown, to be used when preparing adsorption particle for adsorption capacity.
The embodiment of the present invention
Figures 1 and 2 show that the absorption of this patent and the schematic diagram of desorption apparatus.Illustrate this below with reference to attached Fig. 1 and 2
The device course of work of invention.
Fig. 1 devices include：Raw brine (1) containing lithium, the supply pump (2) of the brine containing lithium；Based on the double hydrogen of aluminium lithium containing chlorine
The dispersed phase of the defect kind of oxide flows the absorption-desorption device of bed with granule adsorbent filling adsorbent, collects system
The storage tank (11) for the lithium concentrate got, fresh water storage tank (12), fresh water supply pump (13) collect granular adsorbent and crush mutually mistake
Filter (27), the adsorbent selection container (24) adsorbed, the brine that gives up receive container (9), brine transfer pump (10).Further include：
Cartridge type is given up brine discharge system (6), in system the Absorption quantity agent of absorption-desorption part unload goods charging bucket (7), adsorbent is classified hydraulic pressure
Device (8), for removing little particle adsorbent and entering adsorbent bed dispersed phase impurity from brine.In its moving process
In, it is defeated to be located at brine by the lithium chloride adsorption zone (3) between cartridge type drainage system and brine input pipe for granule adsorbent
Enter and use lithium concentrate brine area (4) between pipe and lithium concentrate efferent duct, is located at lithium concentrate efferent duct and freshwater input pipe
Between lithium chloride desorption zone (5), there are two steps for the enrichment process of brine：Adsorbent is transported and production stage.
Realize that the device of this method includes in Fig. 2：Brine source (13) containing lithium be connected with three section storage tanks (1-1,1-2,
1-3)；It is underwater to collect tower replenishment pump -4 (4-1,4-2), on the basis of the biradical hydroxide difference defect dispersed phase of the lithium of aluminium containing chlorine
On, the lower part 3 (3-1,3-2) collected tower and fix compression bed as adsorption-desorption enriching apparatus；Filter (10), is used for back
Receive the derived adsorbent ground and the adsorbent adsorbed from device；Container (12), for collecting useless lithium brine；Salt is molten
The section consumption storage tank -14 of liquid three (14-1.14-2,14-3), is connected (22) with salt solution original storage tank；It pumps (15), for conveying
Collector -9 (9-1,9-2) on the salt solution of discharge to absorption-desorption module tower, the section consumption storage tank -16 of lithium concentrate three
(16-1,16-2,16-3) is connected for solution to be discharged with the container (24) for the lithium concentrate for collecting production；It pumps (17), it is defeated
It send in the lithium concentrate to container of discharge, is equally delivered to -18 (18-1,18-2,18- in the three section containers equipped with desorption liquid
3), which is connected with fresh water original storage tank (23), pump (19), and pump (19) is collected for conveying under stripping liquid to container
Device.In addition to this, also container (20), the salt waste liquid for collecting and extracting discharge, container (21), for collecting and extracting
Useless lithium concentrate, concentrate displacement.Adsorbent is fixed compression bed and is made of two containers, by pipeline and pneumatic between them
Valve is connected, and can thus realize in phase and produce lithium concentrate：One container is located at the step that adsorbent is saturated with lithium chloride
Suddenly, at this moment another container is located at brine and replaces and desorb lithium chloride step from saturation adsorbent.Tower has cylindrical shell, puts down
Bottom, oval lid, upper and lower part drainage system, centre are adsorbents.Lower drainage system is by being 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 collector phase
Connect (8), and for sleeve by gravel pack 5 (5-1,5-2), the size of gravel particle is 5-7mm, the gravel layer net of lower part and suction
Attached dose separates.Upper drainage system is by propping bar board group at the position of screen is consistent with the upper material position of adsorbent, and supporting has on screen
Size of mesh is the grid of 3-4mm, and gravel layer 6 (6-1,6-2) that can by adsorbent bed and above separates, gravel layer fill to
The upper material position of water drain casing tube is distributed, sleeve is equally evenly distributed on the section of tower, and is connected with each other 9 (9- with upper collector
1,9-2).Gravel layer above is covered with the screen that size of mesh is 3-4mm, can ensure tower in the case where compressing jigging bed condition in this way
Operating.The structure of this tower can increase to avoid the absorbent particles and the excessive of solid phase impurity fine crushing being ground in draining sleeve
Long, impurity is inevitably present in brine (2-5g/m3).It is found during experiment, the adsorbent in tower has one
The size of fixed pollutant carrying capacity, pollutant carrying capacity passes through the filtrate flows speed of adsorbent bed filtering by the size of impurity particle
It is determined with the size of adsorbent itself.If the particle size of impurity is 100 microns or is less than 100 microns, adsorbent
Grain cannot at least be less than 0.5mm, fill absorbent particles bed to its pollutant carrying capacity value with impurity, particle layers start to return
Also and enter the impurity of the same total amount of adsorbent, that is, final impurity dispersed phase enters drainage system gravel layer.It is inhaling
When attached or desorption, impurity in gravel layer or by brine stream (absorption) outflow, a portion by brine efferent duct from
Tower 6 (6-1,6-2) is opened, or is deposited on the surface (desorption) of draining cylindrical casing, it is defeated from tower because being exported different from brine
Go out desorbed species to drain cylindrical casing by the sleeve portion с (с -1, с -2) of upper collector and regenerate in displacement process,
Because the casing " с " that passes through of substitutional solution always from up to down enters collector and draining cylindrical sleeves.Passing through 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 set
Lower cylinder will be deposited on by the tube portion of trapping " а " (а -1, а -2) of lower collector, the absorption process in displacement by changing liquid
The impurity particle of sleeve interior surface is got off from surface washing and from tower with washing liquid stream discharge.In turn, in absorption process,
The compound particles for entering upper gravel layer from cylinder draining sleeve outer surface are easy to be discharged with brine stream from tower.If used
Conventional adsorbent, the whole cycle time that concentration is enriched in adsorbent is fixed and compresses bed are (to adsorb within 3 hours, 3 is small for 6 hours
When displacement desorption).
It is the basic explanation of device of the present invention for being adsorbed and being desorbed above.
The method of the present invention has used following method, with the absorption of granule adsorbent collector-desorption concentration
In module, the lithium in raw brine is adsorbed using granule adsorbent；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 obtains chlorine using ion exchange removal of impurities removal impurity
Change lithium solution；Lithium chloride solution is concentrated, and obtains single water lithium chloride.It adsorbs and is enriched with brine and to obtain primary lithium chloride lithium molten
Liquid realizes in adsorbing desorption device, by filtering initial brine, or with the prescribed volume for containing different LiCl contents
Brine by upper and lower drainage system, to increase LiCl concentration in brine, the brine filtered pass through lower cartridge type draining distribution receive
Storage is input to lower particle tubular type drainage system, then exports supreme cartridge type draining distribution by upper particle tubular type drainage system and collect
Device bypasses.The primary containing magnesium chloride and chlorination calcium impurities is wherein obtained using distilled water desorption lithium chloride from granule adsorbent
Lithium chloride solution, lithium solion exchange removal of impurities removal impurity and obtain lithium chloride solution.
One of described ion exchange removal of impurities removal impurity step such as following methods：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, until the content of lithium chloride
For 220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent removal of impurities is carried out to solution：Magnesium, calcium, sulfuric acid
Then root, borate ion clean to solution in Li type resins and obtain lithium chloride solution；
Or ion exchange removal of impurities is first carried out in Li type cation-exchangers to primary lithium chloride solution；Then to cleaning
Solution afterwards carries out reverse osmosis concentration and obtains LiCl contents to be 60-65kg/m3Transition solution and desalted water；With heating to mistake
Solution is crossed to be evaporated until LiCl contents are 190-210kg/m3, then reagent, which cleans, goes removing sulfate-borate-ion miscellaneous
Matter and obtain lithium chloride solution；
Or cleaned by primary lithium chloride solution and lithium carbonate contact, remove 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 removal of impurities go to clean
Matter obtains lithium chloride solution in turn.
It below will be to the present invention for being stressed the main reason for improving adsorption efficiency.
The preparation process of the active material of high Al content for the present invention is as follows：
The preparation of active material one：In the liquor alumini chloridi of 10L, AlCl3A concentration of 188g/L, be added 0.125L's
The atomic ratio of LiOH solution (0.85g/L), Al and Li are Al:Li=3.6 (Al ions excessive about 15%), it is molten to be subsequently added into NaOH
Liquid reaches 7 to PH.
Under room temperature, the mixture after above-mentioned reaction is stirred 30 minutes.Precipitation then is filtered out with filter, it is natural after cleaning
It dries, obtains LiCl3Al (OH)3·nH2O (8≤n≤10) active ingredient substance；Then, by the active matter with hydrate
Matter is ground into particle, reciprocating gird is carried out using the sieve of 60 mesh, to obtain≤the powdered granule of 0.2mm.
The preparation of active material two：In 10L liquor alumini chloridis (188g/L), the atomic ratio that Al and Li is added is Al:Li
=3.2 lithium carbonate slurry, is subsequently added into NaOH solution, until the reaction was complete, solution PH reaches 7.0.
Precipitation is isolated, then filters out precipitation with filter, naturally dry after cleaning obtains LiCl3Al (OH)3·
nH2O (8≤n≤10) active ingredient substance；Then, the active material with hydrate is ground into particle, uses the sieve of 60 mesh
Son carries out reciprocating gird, to obtain≤the powdered granule of 0.2mm.
Not necessarily active material one and active material two are mixed with for the preparation of active material in the present invention；Take work
One kind in the preparation method of property substance one or active material two, can prepare final active material.
It is prepared by the adsorption particle for the present invention：Active material one and active material two are uniformly mixed, by compounding substances
Pass through the particle of 60 mesh sieve.99% particle size≤0.2mm that powder contains, to which acquisition is prepared in final before particle
Between object.Next can be used for that particle is made.Hydration number 8≤n≤10 of active material.
Atomic ratio Al in mixture:Li=3.3.
Particle preparation is carried out in sealed stirrer.The intermediary of 800g, 80g chlorinated polyvinyl chloride second are put into blender
Alkene, dichloromethane solution, stirring to starchiness.Slurry is put into extruder, obtained fine strip shape substance is then cut into length
It is for use after dry for the particle of 2mm.
Adsorption test：In order to determine the adsorption capacity of particulate matter, 5kg particles are put into the reaction tube of diameter 4cm, water
Pass through tower with the speed of 3 cubic decimeters/hour.After processing in 8 hours, the particle of absorption stable state is obtained.
Then, stable grain size distilled water desorption will be adsorbed.After measured, the Li of 45g is obtained altogether；Equivalent every 1g adsorbents
The Li of 9mg can be adsorbed.
Embodiment one：
Adsorption particle using the present invention carries out the absorption of elemental lithium in brine, as previously mentioned, at normal temperatures, 8 as a child,
The particle of absorption stable state can be obtained.Adsorb stable grain size after measured, every gram of adsorbent can adsorb the lithium of 9mg.
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 23-24 DEG C of degree, granule adsorbent disclosed in this invention is acted on brine at such a temperature, and 5kg particles are put into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, adsorption particle distillation is hydrolyzed
Absorption.After measured, the Li of 45g is obtained altogether；The equivalent Li that 9mg can be adsorbed per 1g adsorbents.
Reference examples two：
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 24-25 DEG C of degree, granule adsorbent disclosed in this invention is acted on brine at such a temperature, and 5kg particles are put into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, adsorption particle distillation is hydrolyzed
Absorption.After measured, the Li of 45.2g is obtained altogether；The equivalent Li that 9.04mg can be adsorbed per 1g adsorbents.
Reference examples three：
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 22-23 DEG C of degree, granule adsorbent disclosed in this invention is acted on brine at such a temperature, and 5kg particles are put into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, adsorption particle distillation is hydrolyzed
Absorption.After measured, the Li of 42.1g is obtained altogether；The equivalent Li that 8.42mg can be adsorbed per 1g adsorbents.
Reference examples four：
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 21-22 DEG C of degree, granule adsorbent disclosed in this invention is acted on brine at such a temperature, and 5kg particles are put into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, adsorption particle distillation is hydrolyzed
Absorption.After measured, the Li of 40.5g is obtained altogether；The equivalent Li that 8.1mg can be adsorbed per 1g adsorbents.
Reference examples five：
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 20-21 DEG C of degree, granule adsorbent disclosed in this invention is acted on brine at such a temperature, and 5kg particles are put into diameter
In the reaction tube of 4cm, water passes through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, adsorption particle distillation is hydrolyzed
Absorption.After measured, the Li of 39.5g is obtained altogether；The equivalent Li that 7.9mg can be adsorbed per 1g adsorbents.
Reference examples six：
The method according to the invention prepares active material, is evenly heated so that hydration number 7≤n≤8.Then, according to this hair
Bright method prepares adsorption particle.
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 23-24 DEG C of degree, this reference examples granule adsorbent is acted on brine at such a temperature, by the anti-of 5kg particles input diameter 4cm
Ying Guanzhong, water pass through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, by adsorption particle distilled water desorption.Through
It measures, obtains the Li of 42.5g altogether；The equivalent Li that 8.5mg can be adsorbed per 1g adsorbents.
Reference examples seven：
The method according to the invention prepares active material, is evenly heated so that hydration number 6≤n≤7.Then, according to this hair
Bright method prepares adsorption particle.
Before brine carries out elemental lithium absorption, brine preheating, most final temperature after brine preheating are carried out using daylight, high-temperature liquid stream
About 20-21 DEG C of degree, this reference examples granule adsorbent is acted on brine at such a temperature, by the anti-of 5kg particles input diameter 4cm
Ying Guanzhong, water pass through tower with the speed of 3 cubic decimeters/hour.After processing in 4 hours, by adsorption particle distilled water desorption.Through
It measures, obtains the Li of 40g altogether；The equivalent Li that 8mg can be adsorbed per 1g adsorbents.
It is salt lake saline that the application scenario of institute of the invention, which is brine, and salt lake be in high latitude area, and in general outdoor is averaged
Temperature is relatively low, needs to preheat salt lake saline.The mode of multistage preheating may be used in preheating, right using production high temperature wastewater
Low temperature salt lake saline is preheated.Liquid after proposition can preheat salt lake saline to be extracted again.To profit as much as possible
With temperature difference, heat is made full use of.
Inventor has found that using high Al content adsorption activity ingredient, the operating temperature of granule adsorbent is right
There is larger impact in the elemental lithium adsorption capacity of granule adsorbent.As shown in embodiment one to reference examples five, active material is in 23-
Under 24 degrees Celsius, Li atomic adsorptions amount can reach 9mg, and temperature continues to increase, and the adsorbance of Li does not significantly increase, this
Perhaps related 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.
Hydration number in high Al content, active material also has certain influence for the adsorption capacity of Li.Referring to attached
Fig. 4.The high Al active materials of the present invention preferably use 8-10 hydration number.
The method of the present invention advantage is：
1, this patent method works at 23-24 DEG C；Using the preheating in other courses of work, to the aqueous salt brine of exchange
It is heated and can reach.The temperature is higher than Salt Lake Area outdoor temperature, since the optimum working temperature of active material is in this
One temperature range, therefore, the efficiency for being conducive to granule adsorbent extraction active material are far above room ambient conditions.
2, this patent method improves the service efficiency of lithium ion.LiCl·3Al(OH)3The use of ingredient is compared with LiCl
2Al(OH)3For, the utilization rate higher of single lithium ion.Adsorbent using 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).
3, this patent uses the hydrate of the active material of high Al content as granulation raw material.In granulation process and it is granulated
Afterwards, active material hydrate is lost, and to which specific surface area increases, improves the adsorption capacity of unit mass granulated pellet.
4, the primary solution that the method for this patent obtains, concentration is higher than conventional method, and the spent time is significantly lower than normal
Rule method.
The above content is combine specific optimal technical scheme it is made for the present invention be further described, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of method for extracting lithium from natural bittern, including：With dense with the de- analysis of the absorption-of granule adsorbent collector
In contracting module, the lithium in raw brine is adsorbed using granule adsorbent；
Analysis lithium chloride is taken off from granule adsorbent obtains the primary lithium chloride solution containing magnesium chloride and chlorination calcium impurities；
Primary lithium chloride solution obtains lithium chloride solution using ion exchange removal of impurities removal impurity；
Lithium chloride solution is concentrated, and obtains single water lithium chloride；
It is characterized in that：The active constituent of granule adsorbent is LiOH+3AlCl3+9NaOH+nH2O=LiCl3Al (OH)3·
nH2O+9NaCl；Its 8≤n≤10；
The active constituent of granule adsorbent is the powdered granule of grain size≤0.2mm, and granule adsorbent is the particle of a diameter of 2mm；
The operating temperature range of absorption is 23-24 DEG C.
It is in the de- analysis dress of absorption -2. method as claimed in claim 1 is adsorbed and is enriched with brine and obtains primary lithium chloride lithium solution
Middle realization is set, by the initial brine of filtering, or with the brine of the prescribed volume containing different LiCl contents by arranging up and down
Water system, to increase LiCl concentration in brine, the brine filtered drains distribution collector by lower cartridge type and is input to lower particle
Pipe drain system, then supreme cartridge type draining distribution collector bypass is exported by upper particle tubular type drainage system.
3. method as claimed in claim 1 obtains wherein taking off analysis lithium chloride from granule adsorbent using distilled water containing magnesium chloride
With the primary lithium chloride solution of chlorination calcium impurities, lithium solion exchanges removal of impurities removal impurity and obtains lithium chloride solution.
4. the method as described in claim 1, it is characterised in that：The ion exchange removal of impurities removal impurity step such as following methods
One of：
Primary lithium chloride solution is stood, until MgCl2·6H2O and CaCl2·6Н2О is precipitated, until the content of lithium chloride is
220-350kg/m3, dilution liquid phase to LiCl contents is 190-210kg/m3, reagent removal of impurities is carried out to solution：Magnesium, calcium, sulfate radical,
Then borate ion cleans to solution in Li type resins and obtains lithium chloride solution；
Or ion exchange removal of impurities is first carried out in Li type cation-exchangers to primary lithium chloride solution；Then to cleaning after
Solution carries out reverse osmosis concentration and obtains LiCl contents to be 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 removal of impurities remove removing sulfate-borate-ionic impurity and
Obtain lithium chloride solution；
Or cleaned by primary lithium chloride solution and lithium carbonate contact, remove impurity magnesium and calcium；Solution after cleaning is first
It is concentrated to give transition solution and desalted water 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 removal of impurities removal impurity into
And obtain lithium chloride solution.
5. particle is inhaled made of the active material ingredients of method as claimed in claim 1, wherein granule adsorbent using high Al elements
Attached dose, in 23-24 DEG C of operating temperature range, after fully being acted on brine, using distilled water to granule adsorbent carry out washing and
Desorption, to obtain the solution containing lithium ion.
6. method as claimed in claim 5, the active material ingredients of aforementioned high Al elements be by lithium chloride solution and lithium hydroxide,
Or lithium carbonate or lithium chloride are mixed；Wherein Al:The atomic ratio of Li reaches 3.0-3.5；Then made using NaOH solution
The chloride of lithium aluminium double-hydroxide is formed for alkaline reagent：LiOH+3AlCl3+9NaOH+nH2O=LiCl3Al (OH)3·
nH2O+9NaCl；Its 8≤n≤10；
Then, the product obtained to previous step cleans, and obtains LiCl3Al (OH)3·nH2O active ingredient substances.
7. method as claimed in claim 5, granule adsorbent be by the active constituent of above-mentioned high Al elements, under hydrated state into
Row crushes, and is screened after crushing, and part with the sieve of 50 mesh carries out reciprocating gird after crushing, to obtain≤the powdered granule of 0.2mm, powder
Next broken particle is mixed with organic compound, mixed mixture, by Squeezinggranulator, is made a diameter of
2mm particles.
8. method as claimed in claim 7, the aforementioned organic compound being granulated be polyvinyl chloride or haloflex in this way
The organic polymer containing chlorine that can be dissolved in methyl chloride or a variety of organic polymers containing chlorine mixture.
9. method as claimed in claim 5, according to granule adsorbent made from this kind of method, every gram of granule adsorbent has 9mg's
The adsorption capacity of Li elements.
10. a kind of granule adsorbent, the granule adsorbent used for claim 7 the method, it is characterised in that：Wherein
Al:The atomic ratio of Li reaches 3.0-3.5.
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| AR112849A1 (en) | 2016-11-14 | 2019-12-26 | Lilac Solutions Inc | EXTRACTION OF LITHIUM WITH COATED ION EXCHANGE PARTICLES |
| WO2019028148A1 (en) | 2017-08-02 | 2019-02-07 | Lilac Solutions, Inc. | Lithium extraction with porous ion exchange beads |
| MA52428A (en) | 2018-02-28 | 2021-06-02 | Lilac Solutions Inc | PARTICLE TRAP ION EXCHANGE REACTOR FOR LITHIUM EXTRACTION |
| EP4087825A4 (en) | 2020-01-09 | 2024-01-24 | Lilac Solutions, Inc. | Process for separating undesirable metals |
| CA3178825A1 (en) | 2020-06-09 | 2021-12-16 | David Henry SNYDACKER | Lithium extraction in the presence of scalants |
| CA3199218A1 (en) | 2020-11-20 | 2022-05-27 | David Henry SNYDACKER | Lithium production with volatile acid |
| EP4326413A1 (en) | 2021-04-23 | 2024-02-28 | Lilac Solutions, Inc. | Ion exchange devices for lithium extraction |
| 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263678A (en) * | 1997-07-12 | 2000-08-16 | 艾利森电话股份有限公司 | Method and system for performing optimised hand over |
| RU2157338C2 (en) * | 1998-08-24 | 2000-10-10 | Закрытое акционерное общество "Экостар-Наутех" | Method of production of high-purity lithium hydroxide from natural brines |
| US6280693B1 (en) * | 1993-05-24 | 2001-08-28 | Fmc Corporation | Composition for the recovery of lithium values from brine and process of making/using said composition |
| RU2193008C2 (en) * | 1998-03-25 | 2002-11-20 | Закрытое акционерное общество "Экостар - Наутех" | Method of producing lithium hydroxide from brines and plant for method embodiment |
| CN1511964A (en) * | 2002-12-27 | 2004-07-14 | 中国科学院青海盐湖研究所 | Process for extracting lithium from salt lake brine by adsorptive method |
| CN101829538A (en) * | 2010-05-19 | 2010-09-15 | 浙江海虹控股集团有限公司 | Preparation method of high-performance lithium adsorbent |
| CN102432044A (en) * | 2011-09-26 | 2012-05-02 | 江苏海龙锂业科技有限公司 | Method for extracting ultrahigh-purity lithium carbonate from salt lake brine with high magnesium-lithium ratio |
| RU2455063C2 (en) * | 2010-10-13 | 2012-07-10 | Закрытое акционерное общество (ЗАО) "Экостар-Наутех" | Method of producing granular sorbent for extracting lithium from lithium-containing brine |
| CN106076243A (en) * | 2016-06-06 | 2016-11-09 | 中国科学院青海盐湖研究所 | A kind of method of micropore aluminium salt lithium adsorbent and preparation method thereof, filler and enriching lithium ion |
-
2017
- 2017-01-06 CN CN201710009166.3A patent/CN106673023B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6280693B1 (en) * | 1993-05-24 | 2001-08-28 | Fmc Corporation | Composition for the recovery of lithium values from brine and process of making/using said composition |
| CN1263678A (en) * | 1997-07-12 | 2000-08-16 | 艾利森电话股份有限公司 | Method and system for performing optimised hand over |
| RU2193008C2 (en) * | 1998-03-25 | 2002-11-20 | Закрытое акционерное общество "Экостар - Наутех" | Method of producing lithium hydroxide from brines and plant for method embodiment |
| RU2157338C2 (en) * | 1998-08-24 | 2000-10-10 | Закрытое акционерное общество "Экостар-Наутех" | Method of production of high-purity lithium hydroxide from natural brines |
| CN1511964A (en) * | 2002-12-27 | 2004-07-14 | 中国科学院青海盐湖研究所 | Process for extracting lithium from salt lake brine by adsorptive method |
| CN101829538A (en) * | 2010-05-19 | 2010-09-15 | 浙江海虹控股集团有限公司 | Preparation method of high-performance lithium adsorbent |
| RU2455063C2 (en) * | 2010-10-13 | 2012-07-10 | Закрытое акционерное общество (ЗАО) "Экостар-Наутех" | Method of producing granular sorbent for extracting lithium from lithium-containing brine |
| CN102432044A (en) * | 2011-09-26 | 2012-05-02 | 江苏海龙锂业科技有限公司 | Method for extracting ultrahigh-purity lithium carbonate from salt lake brine with high magnesium-lithium ratio |
| CN106076243A (en) * | 2016-06-06 | 2016-11-09 | 中国科学院青海盐湖研究所 | A kind of method of micropore aluminium salt lithium adsorbent and preparation method thereof, filler and enriching lithium ion |
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