CN116947076A - Lithium extraction method of carbonate raw halogen - Google Patents
Lithium extraction method of carbonate raw halogen Download PDFInfo
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- CN116947076A CN116947076A CN202310741094.7A CN202310741094A CN116947076A CN 116947076 A CN116947076 A CN 116947076A CN 202310741094 A CN202310741094 A CN 202310741094A CN 116947076 A CN116947076 A CN 116947076A
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- manganese
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- carbonate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 52
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000000605 extraction Methods 0.000 title claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 title claims description 16
- 150000002367 halogens Chemical class 0.000 title claims description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 119
- 239000011572 manganese Substances 0.000 claims abstract description 102
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 93
- 238000001179 sorption measurement Methods 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000012267 brine Substances 0.000 claims abstract description 16
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003480 eluent Substances 0.000 claims abstract description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000011550 stock solution Substances 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010306 acid treatment Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 61
- 239000000843 powder Substances 0.000 claims description 48
- 239000002243 precursor Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 150000002696 manganese Chemical class 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 29
- 238000004090 dissolution Methods 0.000 description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 14
- 238000001514 detection method Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000003361 porogen Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- -1 boron ions Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application relates to the field of development and utilization of carbonate brine, and particularly discloses a lithium extraction method of carbonate raw brine. The method comprises the following steps: s1, carrying out acid treatment on an adsorption column filled with an adsorbent, then carrying out an adsorption process on brine stock solution through the adsorption column, and desorbing the adsorption column after the adsorption column is saturated to obtain eluent; s2, regulating the pH value of the eluent, and then performing reverse osmosis treatment to obtain reverse osmosis concentrated water; s3, treating reverse osmosis concentrated water by adopting a calcium-containing precipitator, then introducing the reverse osmosis concentrated water into a salt field, and carrying out freezing-sun concentration to obtain LiCl concentrated solution after salt precipitation; wherein the adsorbent is a granular manganese adsorbent. The lithium extraction method has better lithium extraction effect and higher lithium recovery rate.
Description
Technical Field
The application relates to the field of development and utilization of carbonate brine, in particular to a lithium extraction method of carbonate raw brine.
Background
Lithium is used as an important new energy material, and is widely applied to the fields of automobiles, wind power, electronics and the like, and the demand of the international market for lithium products is continuously increased. The method is characterized in that the method is a large country of lithium resources, the total storage capacity of the lithium resources accounts for 21% of the total storage capacity of the world, wherein the storage capacity of salt lake brine lithium accounts for more than 62% of the total storage capacity of the country, and the lithium requirements of the country on lithium cannot be met due to complex ore extraction process flow, high cost and high energy consumption, so that the salt lake lithium extraction is a main source of a lithium market.
Salt lakes are classified into sulfate type salt lakes, chloride type salt lakes and carbonate type salt lakes according to the type of water chemistry. The carbonate type salt lake is a lake in which anions in lake water are mainly carbonate ions and bicarbonate ions, and salts which are likely to be precipitated in a solid phase are mainly carbonate, so that the salt lake is an important brine lithium resource, is rich in valuable metal ions such as lithium, potassium, rubidium, cesium and the like, and has considerable reserves. At present, a plurality of techniques for extracting lithium from carbonate type salt lakes mainly comprise a precipitation method, a calcination leaching method, a solvent extraction method, an electrodialysis method and an adsorption method. Among them, the adsorption method is considered as one of the most promising industrial methods because of its simple process, good selectivity and high lithium recovery rate. The key point of the method is to prepare the adsorbent with large adsorption capacity and good cycle performance, and the manganese-based adsorbent and the titanium-based adsorbent are the most widely studied in the following.
The traditional Chinese patent with publication number of CN 115321561A provides a method for extracting lithium from carbonate brine, which adopts a lithium ion sieve adsorbent to treat brine stock solution, and mainly adsorbs and desorbs lithium into eluent in the form of lithium chloride, while carbonate is largely trapped in adsorbed tail brine, thereby realizing the efficient separation of lithium and carbonate, and the yield of lithium in the obtained eluent can reach more than 87%. However, the adsorbent adopted in the method is hydrated lithium aluminate or manganese dioxide, and the two are powdery, are not easy to permeate, have poor fluidity, high dissolution loss rate and low recycling rate, and seriously influence the lithium extraction effect.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for extracting lithium from carbonate raw halogen.
The application provides a lithium extraction method of carbonate raw halogen, which adopts the following technical scheme:
a method for extracting lithium from carbonate raw halogen, comprising the following steps:
s1, carrying out acid treatment on an adsorption column filled with an adsorbent, then carrying out an adsorption process on brine stock solution through the adsorption column, and desorbing the adsorption column after the adsorption column is saturated to obtain eluent;
s2, regulating the pH value of the eluent, and then performing reverse osmosis treatment to obtain reverse osmosis concentrated water;
s3, treating reverse osmosis concentrated water by adopting a calcium-containing precipitator, then introducing the reverse osmosis concentrated water into a salt field, and carrying out freezing-sun concentration to obtain LiCl concentrated solution after salt precipitation;
wherein the adsorbent is a granular manganese adsorbent.
Preferably, the granular manganese-based adsorbent comprises manganese-based lithium ion sieve adsorbent powder, EVA40W binder, lithium carbonate pore-forming agent and hexamethylphosphoric triamide, wherein the weight ratio of the manganese-based lithium ion sieve adsorbent powder is (74-80): 10-14): 4-6): 2-3.
Preferably, the granular manganese-based adsorbent is prepared by the following method:
uniformly mixing manganese series lithium ion sieve adsorbent powder, EVA40W binder, lithium carbonate pore-forming agent and hexamethylphosphoric triamide, extruding and granulating at 50-52 ℃, cooling, filtering and drying to obtain the granular manganese series adsorbent.
By adopting the technical scheme, the granular manganese-based adsorbent is prepared by a method of bonding components such as manganese-based lithium ion sieve adsorbent powder and the like by adopting an EVA40W binder and then extruding and forming. Compared with the common powdery adsorbent, the granular manganese adsorbent prepared by the method has stronger mechanical stability, higher water permeability, higher adsorption capacity, lower wear rate, stable adsorption-desorption cycle performance and extremely low manganese ion dissolution loss rate, and can greatly improve the lithium extraction effect.
Meanwhile, the application also adopts lithium carbonate as a pore-forming agent, lithium ions and carbon dioxide can be generated by dissolution in an acid solution, and the remained pore channels can improve the mass transfer efficiency of the lithium ions on the surface and inside of the granular manganese-based adsorbent, so that the possibility that the adsorption pore channels are blocked after the manganese-based lithium ion sieve adsorbent powder is wrapped and bonded by an EVA40W binder is reduced, thereby being unfavorable for ion diffusion mass transfer. Although an increase in the amount of the pore-forming agent is advantageous for improving the adsorption capacity of the particulate manganese-based adsorbent, an excessive amount of the pore-forming agent increases the attrition rate of the particulate manganese-based adsorbent. Therefore, the application further controls the dosage of the pore-forming agent, so that the granular manganese adsorbent can keep higher adsorption capacity and also has lower wear rate.
In addition, hexamethylphosphoric triamide is added into the granular manganese adsorbent, so that the dispersibility of each component in the granular manganese adsorbent can be obviously improved, a smaller amount of binder can be used for coating a larger amount of manganese lithium ion sieve adsorbent powder, the use amount of the binder is reduced, and the possibility of reduction of the effective adsorption area caused by adhesion and coating of the powder by excessive binder is reduced.
In summary, the granular manganese-based adsorbent is adopted to replace the traditional powdery adsorbent to be buried in the adsorption column, so that the lithium extraction effect can be greatly improved, and the recovery rate of lithium ions in the eluent is increased.
Preferably, the manganese-based lithium ion sieve adsorbent powder is prepared by the following method:
a. dissolving manganese chloride and lithium hydroxide in water and uniformly stirring, then dropwise adding an oxidant, continuously stirring for 2-2.5 h until a gel substance is obtained, and aging for 10-12 h; wherein n (Mn) 2+ ):n(Li + ) 1 (3.5-4.0);
b. carrying out hydrothermal treatment on the obtained product in the step a, filtering, washing, drying and grinding the obtained precipitate, and then heating at 360-400 ℃ for 5-5.5 h to obtain a precursor;
c. and (3) carrying out acid leaching and lithium extraction on the cooled precursor, filtering, washing and drying the obtained precipitate to obtain manganese series lithium ion sieve adsorbent powder.
By adopting the technical scheme, the manganese-series lithium ion sieve adsorbent powder is prepared by adopting the hydrothermal synthesis method, and in the method, the ratio of the lithium and manganese substances in the raw materials and the heating temperature in the step b are controlled, so that the manganese oxidation number of the precursor prepared by the method is larger, and the lithium and manganese in the molecular formula of the precursor are larger, and the adsorption capacity is higher.
Preferably, the oxidant in the step a is a hydrogen peroxide solution with the mass fraction of 30% -35%.
By adopting the technical scheme, the hydrogen peroxide solution which has strong oxidizing property and does not bring in interference elements is selected as the oxidant in the sol-gel process, and divalent manganese ions are oxidized into trivalent manganese ions, so that the manganese oxidation number of the synthesized precursor is larger, the lithium and manganese ratio is larger, and the adsorption capacity is higher.
Preferably, the hydrothermal treatment in the step b specifically includes: and c, putting the product obtained in the step a into a high-pressure reaction kettle, adding deionized water to 70-80% of the volume of the high-pressure reaction kettle, and keeping the temperature at 110-130 ℃ for 24-26 h.
Preferably, the temperature of the hydrothermal treatment is (120+ -1) deg.C.
By adopting the technical scheme, as the hydrothermal synthesis is a continuous exothermic reaction, the method ensures that the monoclinic LiMnO in the hydrothermal synthesis product is realized by accurately controlling the temperature of the hydrothermal treatment 2 The content of the precursor is extremely low, the prepared precursor is almost spinel type lithium manganese oxide with pure phase, the manganese oxidation number is larger than that of lithium manganese, the adsorption capacity is higher, and the manganese dissolution loss rate is lower.
Preferably, the acid leaching and lithium extraction process in the step c specifically comprises the following steps: adding the cooled precursor into dilute hydrochloric acid with the concentration of 0.5mol/L, and stirring for 20-24h; wherein the mass volume ratio of the precursor and the dilute hydrochloric acid is 0.75g/L-0.8g/L.
Preferably, n (Mn in the step a 2+ ):n(Li + ) Is 1:4.
By adopting the technical scheme, the method further controls the ratio of manganese to lithium in the raw materials, so that monoclinic LiMnO in the hydrothermal synthesis product 2 The content of the precursor is extremely low, and the prepared precursor is almost spinel type lithium manganese oxide with pure phase, so that the adsorption capacity of the manganese series lithium ion sieve adsorbent powder is further improved.
Preferably, in the step b, the particle size after grinding is 20-100 mesh.
In summary, the application has the following beneficial technical effects:
1. according to the application, the granular manganese adsorbent is used for replacing the traditional powdery adsorbent to be buried in the adsorption column, so that the lithium extraction effect can be greatly improved, and the recovery rate of lithium ions in the eluent is increased;
2. the granular manganese adsorbent prepared by the application has the advantages of larger adsorption capacity, lower wear rate and stable adsorption-desorption cycle performance; 3. the precursor manganese oxidation number of the manganese-based lithium ion sieve adsorbent powder prepared by the method is larger, the lithium manganese is larger, the adsorption capacity of the manganese-based lithium ion sieve adsorbent powder is higher, and the manganese dissolution loss rate is lower.
Detailed Description
The present application will be described in further detail with reference to preparation examples, comparative examples and application examples.
<Material source>
The raw materials used in the application are all commercial products except for special descriptions, and the specific materials are:
EVA40W binder, produced by DuPont, U.S., with a melting point of 47 ℃;
hexamethylphosphoric triamide, available from Shijia Chengcheng and Xincheng chemical Co., ltd;
the calcium-containing precipitant of the application is specifically calcium chloride;
in the brine stock solution, the content of lithium ions is 0.87g/L, the content of sodium ions is 139g/L, the content of potassium ions is 50g/L, the content of chloride ions is 183.6g/L, the content of sulfate ions is 28.52g/L, the content of carbonate is 42.13g/L, and the content of boron ions is 5.90g/L.
<Preparation example>
Preparation example 1
The preparation method of the manganese-series lithium ion sieve adsorbent powder comprises the following steps:
a. dissolving manganese chloride and lithium hydroxide in water and uniformly stirring, slowly dropwise adding 95mL of 30% hydrogen peroxide solution, continuously stirring for 2 hours to obtain a gel-like substance, and aging for 12 hours; wherein n (Mn) 2+ ):n(Li + ) 1:3.5;
b. putting the product obtained in the step a into a high-pressure reaction kettle, adding deionized water to 70% of the volume of the high-pressure reaction kettle, keeping the temperature at 130 ℃ for 24 hours, filtering the obtained precipitate, washing the precipitate with deionized water for 5 times, drying the precipitate at 60 ℃ for 12 hours, grinding the precipitate to 20 meshes, and heating the precipitate at 360 ℃ for 5.5 hours to obtain a precursor;
c. adding the cooled precursor into a dilute hydrochloric acid solution with the concentration of 0.5mol/L, stirring for 20 hours, filtering the obtained precipitate, washing the precipitate with deionized water for 6 times, and drying the precipitate at the temperature of 60 ℃ for 5 hours to obtain manganese-series lithium ion sieve adsorbent powder, wherein the mass-volume ratio of the precursor to the dilute hydrochloric acid is 0.75g/L.
Preparation example 2
The preparation method of the manganese-series lithium ion sieve adsorbent powder comprises the following steps:
a. dissolving manganese chloride and lithium hydroxide in water and uniformly stirring, slowly dropwise adding 95mL of 35% hydrogen peroxide solution, continuously stirring for 2.5h to obtain a gel-like substance, and aging for 10h; wherein n (Mn) 2+ ):n(Li + ) 1:4;
b. putting the product obtained in the step a into a high-pressure reaction kettle, adding deionized water to 80% of the volume of the high-pressure reaction kettle, keeping the temperature at 110 ℃ for 26 hours, filtering the obtained precipitate, washing the precipitate with deionized water for 5 times, drying the precipitate at 60 ℃ for 12 hours, grinding the precipitate to 100 meshes, and heating the precipitate at 400 ℃ for 5 hours to obtain a precursor;
c. adding the cooled precursor into a dilute hydrochloric acid solution with the concentration of 0.5mol/L, stirring for 24 hours, filtering the obtained precipitate, washing the precipitate with deionized water for 6 times, and drying the precipitate at the temperature of 60 ℃ for 5 hours to obtain manganese-series lithium ion sieve adsorbent powder, wherein the mass-volume ratio of the precursor to the dilute hydrochloric acid is 0.8g/L.
Preparation example 3
The preparation method of the manganese-based lithium ion sieve adsorbent powder is different from that of preparation example 1 in that: n (Mn) in step a 2+ ):n(Li + ) 1:4, the remainder being the same as in preparation example 1.
Preparation example 4
The preparation method of the manganese-based lithium ion sieve adsorbent powder is different from that of preparation example 1 in that: the temperature of the hydrothermal treatment in the step b was (120.+ -. 1) ℃ and the remainder was the same as in production example 1.
Preparation example 5
The preparation method of the manganese-based lithium ion sieve adsorbent powder is different from that of preparation example 1 in that: n (Mn) in step a 2+ ):n(Li + ) 1:4.5, the remainder being the same as in preparation example 1.
Preparation example 6
The preparation method of the manganese-based lithium ion sieve adsorbent powder is different from that of preparation example 1 in that: in the step b, the curing heating temperature was 320℃and the remainder was the same as in preparation example 1.
<Examples>
Example 1
The preparation method of the granular manganese adsorbent comprises the following steps:
74g of the manganese-based lithium ion sieve adsorbent powder prepared in preparation example 1, 14g of an EVA40W binder, 4g of a lithium carbonate pore-forming agent and 3g of hexamethylphosphoric triamide are uniformly mixed, extruded and granulated at a temperature of 50 ℃, cooled, filtered and dried in an oven at 105 ℃ to obtain the granular manganese-based adsorbent.
Example 2
The preparation method of the granular manganese adsorbent comprises the following steps:
80g of the manganese series lithium ion sieve adsorbent powder prepared in preparation example 1, 10g of EVA40W binder, 6g of lithium carbonate pore-forming agent and 2g of hexamethylphosphoric triamide are uniformly mixed, extruded and granulated at the temperature of 52 ℃, cooled, filtered and dried in an oven at the temperature of 105 ℃ to obtain the granular manganese series adsorbent.
Example 3
The preparation method of the granular manganese adsorbent comprises the following steps:
77g of the manganese-based lithium ion sieve adsorbent powder prepared in preparation example 1, 12g of EVA40W binder, 5g of lithium carbonate pore-forming agent and 2.5g of hexamethylphosphoric triamide are uniformly mixed, extruded and granulated at the temperature of 51 ℃, cooled, filtered and dried in an oven at 105 ℃ to obtain the granular manganese-based adsorbent.
Examples 4 to 8
The process for producing the granular manganese-based adsorbent is different from example 3 in that: the manganese-based lithium ion sieve adsorbent powders used in the examples were selected from various preparations, as shown in Table 1.
Table 1 manganese-based lithium ion sieve adsorbent powders selected for use in examples 4-8
| Examples | Manganese series lithium ion sieve adsorbent powder |
| 4 | Preparation example 2 |
| 5 | Preparation example 3 |
| 6 | Preparation example 4 |
| 7 | Preparation example 5 |
| 8 | Preparation example 6 |
<Comparative example>
Comparative example 1
The difference from example 3 is that: no lithium carbonate porogen was added and the remainder was the same as in example 3.
Comparative example 2
The difference from example 3 is that: hexamethylphosphoric triamide was not added, and the rest was the same as in example 3.
Comparative example 3
The difference from example 3 is that: the amount of lithium carbonate porogen was 2g, the remainder being the same as in example 3.
Comparative example 4
The difference from example 3 is that: the amount of lithium carbonate porogen used was 8g, the remainder being the same as in example 3.
Comparative example 5
The difference from example 3 is that: the EVA40W binder was used in an amount of 5g, and the remainder was the same as in example 3.
Comparative example 6
The difference from example 3 is that: the EVA40W binder was used in an amount of 18g, and the remainder was the same as in example 3.
<Application example>
Application example 1
A method for extracting lithium from carbonate raw halogen, comprising the following steps:
s1, an adsorption column filled with 30kg of the granular manganese-based adsorbent obtained in example 1 was subjected to acid treatment, and then 0.63m was introduced 3 Adsorbing the brine stock solution subjected to vacuum filtration through an adsorption column, and desorbing the adsorption column by adopting 0.5mol/L dilute hydrochloric acid after the adsorption column is saturated to obtain eluent;
s2, regulating the pH value of the eluent to 2.2, and then adopting a reverse osmosis device to carry out reverse osmosis treatment to obtain reverse osmosis concentrated water;
s3, adding calcium chloride into the reverse osmosis concentrated water, uniformly stirring, then introducing the mixture into an evaporation pond, and performing freezing-sun concentration to gradually separate out salts such as calcium sulfate, sodium chloride, potassium chloride and the like, thereby obtaining the LiCl concentrate, wherein the adding amount of the calcium chloride is 1.9g/L of the reverse osmosis concentrated water.
Application examples 2 to 8
The lithium extraction method of carbonate raw halogen is different from the application example 1 in that: the granular manganese-based adsorbents prepared in examples 2 to 8 were used as the granular manganese-based adsorbent in step S1.
<Comparative application example>
Comparative application example 1
The difference from application example 1 is that: the granular manganese-based adsorbent in step S1 was replaced with a manganese dioxide ion sieve adsorbent, purchased from the national institute of industry technology.
Comparative application example 2
The difference from application example 1 is that: the particulate manganese-based adsorbent in step S1 was replaced with a hydrated lithium aluminate adsorbent available from ekostarnutech ltd.
Comparative application examples 3 to 8
The difference from application example 1 is that: the granular manganese-based adsorbents prepared in comparative examples 1 to 6 were used as the granular manganese-based adsorbent in step S1, respectively.
<Performance detection>
Performance detection of manganese series lithium ion sieve adsorbent powder
1. The precursors in preparation examples 1-6 were dissolved with a mixed solution of hydrogen peroxide and nitric acid in a volume ratio of 1:1, and the manganese oxide number was determined by potassium permanganate back titration;
2. adding the manganese-series lithium ion sieve adsorbent powder prepared in preparation examples 1-6 into LiCl solution, magnetically stirring, measuring the content of lithium ions in the solution before and after adsorption and the content of manganese ions in the solution after adsorption by adopting an atomic absorption spectrophotometry, and calculating the adsorption capacity and the manganese dissolution loss rate;
wherein the adsorption capacity Q (mg/g) is calculated according to the following formula:
Q＝(C 1 V 1 -C 2 V 2 )/m (1)
in the formula (1), C 1 And C 2 The mass concentration (mg/L) of lithium ions in the solution before and after adsorption, V 1 And V 2 The volumes (L) of the solution before and after adsorption are respectively shown, and m is the mass (g) of the manganese series lithium ion sieve adsorbent powder;
the manganese dissolution loss (%) was calculated according to the following formula:
L Mn ＝CV/m×100％ (2)
in the formula (2), C is the mass concentration (g/L) of manganese ions in the solution after adsorption, V is the volume (L) of the solution after adsorption, and m is the mass (g) of manganese-series lithium ion sieve adsorbent powder;
the results of the above detection are shown in Table 2.
Table 2 table of performance test results
| Project | Manganese oxidation number of precursor | Adsorption capacity (mg/g) | Loss rate of manganese (%) |
| Preparation example 1 | 3.62 | 37.74 | 3.64 |
| Preparation example 2 | 3.77 | 36.24 | 3.84 |
| Preparation example 3 | 4.02 | 50.11 | 2.56 |
| Preparation example 4 | 3.92 | 41.02 | 3.06 |
| Preparation example 5 | 3.64 | 33.22 | 3.68 |
| Preparation example 6 | 3.42 | 27.15 | 3.65 |
As can be seen from Table 1, the manganese oxide number of the precursor prepared in preparation examples 1-2 is 3.62-3.77, the adsorption capacity of the manganese-based lithium ion sieve adsorbent powder is 36.24mg/g-37.74mg/g, the manganese dissolution loss rate is 3.64% -3.84%, the manganese oxide number of the precursor prepared in preparation example 3 is 4.02, which is improved by 11.05% compared with preparation example 1, the adsorption capacity of the manganese-based lithium ion sieve adsorbent powder is 50.11mg/g, which is improved by 32.78% compared with preparation example 1, the manganese dissolution loss rate is 2.56%, which is reduced by 29.67% compared with preparation example 1, which means that the lithium-manganese ratio in the raw materials can be further controlled, the manganese oxide number in the precursor can be further increased, the adsorption capacity can be improved, and the manganese dissolution loss rate can be reduced.
The manganese oxidation number of the precursor prepared in preparation example 4 is 3.92, which is improved by 8.29% compared with preparation example 1, the adsorption capacity of the manganese-based lithium ion sieve adsorbent powder is 41.02mg/g, which is improved by 8.69% compared with preparation example 1, the manganese dissolution loss rate is 3.06% and is reduced by 15.93% compared with preparation example 1, which indicates that the application can further increase the manganese oxidation number in the precursor, improve the adsorption capacity and reduce the manganese dissolution loss rate by precisely controlling the temperature of the hydrothermal treatment.
The manganese oxide number of the precursor prepared in preparation example 5 was 3.64, which is slightly higher than that in preparation example 1, but the adsorption capacity of the manganese-based lithium ion sieve adsorbent powder was 33.22mg/g, which was lower than that in preparation example 1 by 11.98%, the manganese dissolution loss rate was 3.68%, and higher than that in preparation example 1 by 1.1%, which means that when the lithium-manganese ratio in the raw material was too high, the content of monoclinic form in the precursor was increased, thereby reducing the adsorption capacity and increasing the manganese dissolution loss rate.
The precursor obtained in preparation example 6 had a manganese oxide number of 3.42, 5.52% lower than that in preparation example 1, an adsorption capacity of 27.15mg/g for the manganese-based lithium ion sieve adsorbent powder, 28.06% lower than that in preparation example 1, and a manganese dissolution loss rate of 3.65% almost the same as that in preparation example 1, which means that the curing temperature is out of the range of the present application, and the manganese oxide number in the precursor was reduced, and the adsorption capacity was reduced.
In conclusion, the manganese-series lithium ion sieve adsorbent powder prepared by the preparation method has higher adsorption capacity and lower manganese dissolution loss rate.
Performance detection of particulate manganese-based sorbents
3. Adding the granular manganese-based adsorbents prepared in examples 1-8 and comparative examples 1-6 into LiCl solution, performing vibration adsorption for 48 hours at room temperature, taking supernatant, measuring the lithium ion content in the solution before and after adsorption by adopting an atomic absorption spectrophotometry, and calculating the adsorption capacity Q (mg/g):
Q＝(C 3 V 3 -C 4 V 4 )/m(3)
in the formula (3), C 3 And C 4 The mass concentration (mg/L) of lithium ions in the solution before and after adsorption, V 3 And V 4 The volumes (L) of the solution before and after adsorption are respectively shown, and m is the mass (g) of the granular manganese adsorbent;
because the phenomenon of adsorbent fragmentation can be caused in the vibration adsorption process, the percent of the part which is dried, screened and removed and occupies the original particles after adsorption is called the abrasion rate, and the calculation formula of the abrasion rate (N) is as follows:
N＝(1-M 1 /M 0 )×100％ (4)
in the formula (4), M 0 The mass (g) of the granular manganese adsorbent before adsorption and M 1 The mass (g) of the screen residue part after the adsorption of the granular manganese-based adsorbent;
the results of the above detection are shown in Table 3.
TABLE 3 Table for detecting the Performance of particulate manganese-based adsorbents
| Project | Adsorption capacity (mg/g) | Wear Rate (%) |
| Example 1 | 38.32 | 1.2 |
| Example 2 | 40.16 | 1.9 |
| Example 3 | 39.46 | 1.7 |
| Example 4 | 38.24 | 1.1 |
| Example 5 | 50.05 | 1.2 |
| Example 6 | 41.06 | 1.2 |
| Example 7 | 32.25 | 1.1 |
| Example 8 | 27.02 | 1.0 |
| Comparative example 1 | 25.11 | 1.8 |
| Comparative example 2 | 16.08 | 1.9 |
| Comparative example 3 | 30.02 | 1.9 |
| Comparative example 4 | 49.26 | 3.8 |
| Comparative example 5 | 39.22 | 20.2 |
| Comparative example 6 | 35.64 | 0.8 |
As can be seen from Table 3, the adsorption capacity of the granular manganese adsorbent prepared by the application can reach 50.05mg/g at the highest, and the abrasion rate is lower than 1.9%, which shows that the application adopts EVA40W adhesive to bond manganese lithium ion sieve adsorbent powder, lithium carbonate pore-forming agent and hexamethylphosphoric triamide and then extrusion molding, so that the abrasion rate of the adsorbent can be effectively reduced, and the adsorbent also has higher adsorption capacity.
The adsorption capacity of comparative example 1 was reduced by 36.37% compared to example 3, which indicates that if no lithium carbonate pore-forming agent was added, the adsorption channels in the manganese-based lithium ion sieve adsorbent powder would be blocked after the powder was bound by EVA40W binder, thereby affecting ion diffusion mass transfer, but rather reducing the adsorption capacity of the adsorbent.
The adsorption capacity of comparative example 2 is reduced by 59.25% compared with example 3, which shows that the application adds hexamethylphosphoric triamide into the adsorbent, which can greatly improve the dispersibility of each component in the adsorbent, so that the application can use less binder to wrap more manganese series lithium ion sieve adsorbent powder, and greatly improve the adsorption capacity of the adsorbent.
The adsorption capacity of comparative example 3 was reduced by 23.92% as compared with example 3, which suggests that if the addition amount of the lithium carbonate porogen is too low, the mass transfer efficiency of lithium ions on the surface and inside of the adsorbent cannot be well improved, thereby reducing the adsorption capacity of the adsorbent.
The adsorption capacity of comparative example 4 was higher than that of example 3, but the attrition rate was increased by 123.53% as compared with example 3, which suggests that the increase in the amount of the lithium carbonate pore-forming agent contributes to the increase in adsorption capacity, but the addition of too large an amount greatly increases the attrition rate of the adsorbent.
The adsorption capacity of comparative example 5 was slightly reduced by 0.61% compared to example 3, and the attrition rate was increased by 1088.2% compared to example 3, which indicates that when the amount of EVA40W binder was too low, good encapsulation of the manganese-based lithium ion sieve adsorbent powder could not be achieved, reducing the adsorption capacity of the adsorbent, and greatly improving the attrition rate of the adsorbent.
The adsorption capacity of comparative example 6 was reduced by 9.68% compared to example 3 and the attrition rate was reduced by 52.94% compared to example 3, which means that when the EVA40W binder was used in too much amount, although good coating was formed on the manganese-based lithium ion sieve adsorbent powder, the attrition rate of the adsorbent was reduced, but the manganese-based lithium ion sieve adsorbent powder was coated by the binder adhesion, resulting in a reduction in the effective adsorption area, and thus a reduction in adsorption capacity.
Performance detection of granular manganese-based adsorbent in practical application process
4. Measuring the concentration of lithium ions in the eluent obtained in the step S1 in application examples 1-8 and comparative application examples 1-8 by adopting an atomic absorption spectrophotometry, and calculating the yield of the lithium ions;
5. the adsorption columns of application examples 1 to 8 and comparative application examples 1 to 8 were subjected to adsorption-desorption for 20 times, and then subjected to adsorption column chromatography for 0.63m 3 Adsorbing the brine stock solution subjected to vacuum filtration through an adsorption column, desorbing the adsorption column by adopting 0.5mol/L dilute hydrochloric acid after the adsorption column is saturated to obtain an eluent, measuring the concentration of lithium ions in the eluent by adopting an atomic absorption spectrophotometry, and calculating the yield of the lithium ions;
the results of the above detection are shown in Table 4.
TABLE 4 adsorption-desorption Performance test results Table
As can be seen from Table 4, the recovery rate of lithium ions of the granular manganese-based adsorbent of the present application can be as high as 97.3%, and the recovery rate of 96.6% can be maintained after 20 times of recycling, while the recovery rate of lithium ions of comparative application examples 1-2 is reduced by 5.06% -8.23% as compared with application example 1, and the recovery rate is reduced by a larger extent after 20 times of recycling, which indicates that the granular manganese-based adsorbent of the present application has a higher adsorption capacity, and at the same time, the adsorption-desorption cycle performance is stable, and the lithium extraction effect is stronger, as compared with the conventional powdery adsorbent.
The embodiments of the present application are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (10)
1. A method for extracting lithium from carbonate raw halogen, which is characterized by comprising the following steps:
s1, carrying out acid treatment on an adsorption column filled with an adsorbent, then carrying out an adsorption process on brine stock solution through the adsorption column, and desorbing the adsorption column after the adsorption column is saturated to obtain eluent;
s2, regulating the pH value of the eluent, and then performing reverse osmosis treatment to obtain reverse osmosis concentrated water;
s3, treating reverse osmosis concentrated water by adopting a calcium-containing precipitator, then introducing the reverse osmosis concentrated water into a salt field, and carrying out freezing-sun concentration to obtain LiCl concentrated solution after salt precipitation;
wherein the adsorbent is a granular manganese adsorbent.
2. The method for extracting lithium from carbonate raw halogen according to claim 1, wherein the granular manganese-based adsorbent comprises manganese-based lithium ion sieve adsorbent powder, EVA40W binder, lithium carbonate pore-forming agent and hexamethylphosphoric triamide in a weight ratio of (74-80): (10-14): (4-6): (2-3).
3. The method for extracting lithium from carbonate raw halogen according to claim 2, wherein the granular manganese adsorbent is prepared by the following method:
uniformly mixing manganese series lithium ion sieve adsorbent powder, EVA40W binder, lithium carbonate pore-forming agent and hexamethylphosphoric triamide, extruding and granulating at 50-52 ℃, cooling, filtering and drying to obtain the granular manganese series adsorbent.
4. A method for extracting lithium from a carbonate raw halogen according to claim 2 or 3, wherein the manganese-based lithium ion sieve adsorbent powder is prepared by the following method:
a. dissolving manganese chloride and lithium hydroxide in water and uniformly stirring, then dropwise adding an oxidant, continuously stirring for 2-2.5 h until a gel substance is obtained, and aging for 10-12 h; wherein n (Mn) 2+ ）:n（Li + ) 1 (3.5-4.0);
b. carrying out hydrothermal treatment on the obtained product in the step a, filtering, washing, drying and grinding the obtained precipitate, and then heating at 360-400 ℃ for 5-5.5 h to obtain a precursor;
c. and (3) carrying out acid leaching and lithium extraction on the cooled precursor, filtering, washing and drying the obtained precipitate to obtain manganese series lithium ion sieve adsorbent powder.
5. The method for extracting lithium from a carbonate raw halogen according to claim 4, wherein the oxidant in the step a is a hydrogen peroxide solution with a mass fraction of 30% -35%.
6. The method for extracting lithium from a carbonate raw halogen according to claim 4, wherein the hydrothermal treatment in the step b is specifically: and c, putting the product obtained in the step a into a high-pressure reaction kettle, adding deionized water to 70-80% of the volume of the high-pressure reaction kettle, and keeping the temperature at 110-130 ℃ for 24-26 h.
7. The method for extracting lithium from a carbonate raw halogen of claim 6, wherein the temperature of the hydrothermal treatment is (120+ -1) °c.
8. The method for extracting lithium from carbonate raw halogen according to claim 4, wherein the acid leaching and lithium extracting process in the step c is specifically: adding the cooled precursor into dilute hydrochloric acid with the concentration of 0.5mol/L, and stirring for 20-24h; wherein the mass volume ratio of the precursor and the dilute hydrochloric acid is 0.75g/L-0.8g/L.
9. The method for extracting lithium from a carbonate raw halogen of claim 4, wherein n (Mn 2+ ）:n（Li + ) Is 1:4.
10. The method for extracting lithium from a carbonate raw brine according to claim 4, wherein in the step b, the particle size after grinding is 20-100 mesh.
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