CN116440873A - Adsorbent for adsorbing lithium from refined liquid of alumina produced by Bayer process and use method thereof - Google Patents
Adsorbent for adsorbing lithium from refined liquid of alumina produced by Bayer process and use method thereof Download PDFInfo
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- CN116440873A CN116440873A CN202310433572.8A CN202310433572A CN116440873A CN 116440873 A CN116440873 A CN 116440873A CN 202310433572 A CN202310433572 A CN 202310433572A CN 116440873 A CN116440873 A CN 116440873A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 135
- 239000003463 adsorbent Substances 0.000 title claims abstract description 98
- 238000004131 Bayer process Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 96
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 210000000582 semen Anatomy 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 13
- 238000004458 analytical method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses an adsorbent for adsorbing lithium from refined liquid of alumina produced by Bayer process and a use method thereof, wherein the adsorbent is a porous composite adsorbent, and the preparation method comprises the following steps: inorganic aluminum salt and lithium salt are mixed under alkaline condition, and double salt is obtained through calcination, the double salt is blended with sulfonated polymer solution, and porous adsorption material is obtained through phase separation. The composite material is treated by a hydrothermal method to obtain the composite adsorbent with a porous structure. The adsorbent is mixed and contacted with Bayer semen containing lithium to realize the adsorption of lithium, and then the acid solution is adopted for desorption, so that the lithium-rich solution is obtained. The adsorbent disclosed by the invention is easy to control in preparation process, has good lithium adsorption performance under strong alkali conditions, is suitable for recovering lithium in alkaline solution containing low-concentration lithium, and has a lithium ion recovery rate of not less than 90% for Bayer semen.
Description
Technical Field
The invention belongs to the field of preparation and application of lithium adsorbents, and particularly relates to an adsorbent for adsorbing lithium from refined liquid in the production of aluminum oxide by a Bayer process and a use method thereof.
Background
Lithium and its compound are widely used in the fields of energy, chemical industry, medical treatment, etc., and are important energy materials, and are core materials of lithium batteries. In recent years, with the development of new energy automobiles and the demand of energy storage in industrial society, lithium batteries are rapidly developed as important secondary batteries, and further, the market demand of lithium and compounds thereof is driven.
Sources of lithium and its compounds are typically lithium ores and lithium-rich brines. Lithium ores are generally classified into a crystal structure, a lithium content, a composition, and the like: lepidolite, spodumene, petalite and the like. Generally, low-grade lithium ore is beneficiated and then lithium is extracted. The development of the lithium extraction technology of the lithium ore is relatively early, and the current mature lithium extraction technology of the ore is that the lithium ore is mixed with sulfuric acid or sulfate for calcination, so that the crystal mechanism of the ore is changed, then water is adopted for leaching to obtain a lithium-rich aqueous solution, and then technologies such as precipitation and the like are used for removing impurities, finally a lithium-rich solution with higher purity is obtained, and the lithium-rich solution can be crystallized, precipitated and the like to obtain basic lithium salts such as lithium sulfate, lithium carbonate and the like. The ore body lithium technology is relatively mature, and the problems of high energy consumption, pollution of water sources by fluorine-containing gas and sulfate radicals generated in the calcining process and the like are faced at present. The lithium ores in China are mainly distributed in Sichuan, yunnan, jiangxi and other places, the grade of the lithium is seriously reduced along with the exploitation of the ores, and in order to meet the requirement of the lithium, a relatively large part of the ores come from import. In addition to the source of lithium ore, salt lake brine is an important lithium resource, mainly in the 'lithium triangle' area of south america, the lithium-rich brine of China is distributed in Qinghai, tibet, xinjiang and the like, and the composition of each salt lake is different, so that the difference of lithium extraction processes is caused, and the characteristic of 'one lake one process' is formed. The current core brine lithium extraction process mainly comprises adsorption and membrane separation, namely, selectively adsorbing lithium in brine by an adsorbent, analyzing to obtain a lithium-rich solution, removing impurities by a membrane, concentrating and the like, and finally obtaining the lithium-rich solution with higher purity and concentration. The development of extracting lithium from salt lakes and ores is rapid, the capacity scale is increased year by year, and the demand of new energy sources in China on lithium is ensured to a certain extent. However, in order to further secure the safety of lithium salt supply and demand, a new lithium source is an important supplement.
In the process of Bayer process digestion, 80% of lithium enters Bayer process semen and finally alumina, which is pointed out in P10-14 in period 3 of mineral protection and utilization 2014. The part of lithium resources are not effectively utilized, and the part of lithium is finally enriched in an electrolytic tank for electrolyzing aluminum, so that the working condition of the electrolytic tank is deteriorated, and the production efficiency is affected. Therefore, the lithium is extracted from the refined liquid of the alumina produced by the Bayer process, which not only is the supplement of lithium resources in China, but also improves the quality of the alumina and the economic benefit of aluminum factories. Patent CN109650413a discloses a method for enriching lithium from sodium aluminate solution in alumina factories, which adopts an aluminum hydroxide adsorbent, and the lithium-enriched adsorbent is obtained by heat exchange, filtration, re-dissolution, filtration and re-adsorption after washing, however, the lithium-enriched aluminum hydroxide is difficult to dissolve, and the resolving process is more complicated. Patent CN107500318A discloses a method for extracting lithium carbonate from sodium aluminate solution in alumina factories, which adopts aluminum hydroxide seed crystal for lithium precipitation, then washes and hot-water leaching to obtain lithium-containing leaching solution, neutralizing by adding acid, separating aluminum gel to obtain purified lithium solution, however, aluminum gel is also a high-performance lithium adsorbent, causing lithium loss, and in addition, the energy consumption of hydrothermal method is high.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an adsorbent for adsorbing lithium from refined liquid in the production of alumina by a Bayer process and a use method thereof. The lithium in the refined solution of alumina produced by Bayer process is selectively extracted, thus providing a new source for the existing lithium resource, and simultaneously increasing the quality of alumina products and providing a new benefit source for aluminum factories.
The technical scheme of the invention is as follows:
an adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing inorganic aluminum salt and inorganic lithium salt under alkaline condition, wherein the concentration of hydroxyl in alkaline solution is controlled to be 0.1-1mol/L, heating and evaporating the solution to solid, and calcining at 200-350 ℃ for 1-6 hours to obtain the active double salt.
S2, preparing sulfonated polymer solution: mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled between 5% and 40%.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled to be 20% -60%.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium.
S5, adsorption of lithium: mixing the adsorbent obtained in the steps with the Bayer process semen containing lithium, adsorbing the lithium for 0.5 to 10 hours, washing the adsorbent by pure water, and then washing the adsorbent by 0.1 to 0.5mol/L acid solution, so as to analyze the lithium, thereby obtaining the analysis liquid rich in the lithium. Wherein the pure water is washed in an amount at least 3 times or more the total adsorbent volume to remove entrained impurities. The acidic solution used is preferably an inorganic acid such as hydrochloric acid or sulfuric acid.
Further, the molar ratio of the inorganic aluminum salt to the inorganic lithium salt in the step S1 is in the range of 1:1-5: the total molar amount of the inorganic aluminum salt and the inorganic lithium salt is 1mol/L to 5mol/L, and furthermore, hydroxide in an aqueous solution is provided by adding lithium hydroxide.
Further, in the sulfonated polymer solution described in step S2, the sulfonated polymer is one or more of sulfonated polysulfone, sulfonated polyether ether ketone, sulfonated polyether sulfone and sulfonated polyether sulfone ketone, and the solvent used is one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and 1, 4-dioxane.
Further, the post-treatment in step S4 is a hydrothermal treatment at 120-200 ℃ for 0.5-5 hours, wherein the aqueous solution is a hydrochloric acid solution, and the pH of the solution is 0.1-3, so as to separate lithium ions in the composite adsorbent and form the lithium ion composite adsorbent with adsorption capacity.
Further, the adsorption temperature in the step S5 is 20-80 ℃, and the Bayer process semen contains sodium aluminate solution with lithium ion concentration of 20-200 mg/L.
Further, the bayer process semen described in step S5 is selectively extracted with lithium ions after adsorption, and the remaining solution is directly used in the subsequent aluminum hydroxide production section.
Further, the adsorption in step S5 may be realized by adding an adsorbent, a fixed adsorption bed, or the like to bayer process semen. Wherein the adsorbent is added in a reasonable range of generally 20g/L to 100g/L.
The lithium-rich analytical solution in step S5 is a product solution, and the main components of the solution are lithium ions, aluminum ions and the like, impurities can be removed by a precipitation method or a nanofiltration membrane method, and then the final lithium salt product is obtained by evaporation concentration or sodium carbonate precipitation.
The main innovation points of the technology of the invention are as follows:
(1) The composite adsorbent is adopted to realize the recovery of lithium in the refined solution of alumina produced by the Bayer process, thus not only providing a new lithium source, but also improving the product quality of alumina, and having no interference to the existing alumina production.
(2) The composite lithium ion adsorbent is obtained by compounding the active double salt and the sulfonated polymer, and can realize high-efficiency adsorption of lithium ions in the Bayer process semen at high temperature and high alkalinity. And the analysis of lithium ions can be realized by adopting a hydrothermal method.
(3) The adsorption method is adopted to realize the extraction of lithium in the Bayer process semen, and the adsorbent is easy to prepare and has a simple process. And the adsorption process is simple, the automatic control is easy, and the lithium production cost is low.
Drawings
FIG. 1 is a schematic diagram of a preparation flow of a composite lithium adsorbent according to the present invention
FIG. 2 is a microstructure of the active double salt prepared according to the present invention
FIG. 3 shows the microstructure of the composite lithium adsorbent prepared according to the present invention, (a) the prepared adsorbent, and (b) the surface microstructure of the adsorbent.
Detailed Description
In order to facilitate an understanding of the present invention, a more complete and detailed description of an inventive adsorbent for adsorbing lithium from the semen of a bayer process for producing alumina and a method for using the same will now be provided with reference to the accompanying drawings and examples. The advantages and various effects of the present invention will be more clearly presented.
The drawings in the present specification illustrate preferred embodiments of the invention, but the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Those skilled in the art will appreciate that these specific embodiments and examples are presented to illustrate the invention, and not to limit the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1:
an adsorbent for adsorbing lithium from refined liquid of alumina produced by Bayer process and its application method are provided, the preparation and application method of the adsorbent are as follows:
s1, synthesizing an active double salt: mixing aluminum chloride and lithium chloride under alkaline condition, wherein the concentration of hydroxyl in alkaline solution is controlled to be 0.1mol/L, heating and evaporating the solution to solid, and calcining at 200 ℃ for 1 hour to obtain the active double salt. The molar ratio of aluminum salt to lithium salt is in the range of 1:1, the total molar amount is 1mol/L, and the solution adjusts the hydroxide concentration in the solution by adding lithium hydroxide.
S2, preparing sulfonated polymer solution: and mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled to be 10%. The sulfonated polymer is sulfonated polysulfone and the solvent is N, N-dimethylacetamide.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled at 20 percent.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium. The post-treatment is hydrothermal treatment for 5 hours at 120 ℃, wherein the aqueous solution is hydrochloric acid solution, the pH of the solution is 0.1, and the purpose is to separate lithium ions in the composite adsorbent to form the lithium ion composite adsorbent with adsorption capacity.
S5, adsorption of lithium: selecting Bayer process semen, wherein the concentration of lithium is 82mg/L; mixing the adsorbent obtained in the above steps with the Bayer process semen containing lithium, and adsorbing lithium at 40 ℃. The adding amount of the adsorbent is 50g/L, after adsorption for 2 hours, pure water is adopted to wash the adsorbent, then 0.1mol/L hydrochloric acid solution is adopted to wash the adsorbent, and lithium is resolved to obtain a lithium-rich resolved solution.
The concentration of lithium in the Bayer process semen after adsorption is 2.8mg/L, and the concentration of lithium ions in the analysis solution is 230mg/L.
Example 2:
an adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing aluminum chloride and lithium sulfate under alkaline conditions, wherein the concentration of hydroxyl in an alkaline solution is controlled to be 0.9mol/L, heating and evaporating the solution to solid, and calcining at 250 ℃ for 3 hours to obtain the active double salt. The molar ratio of the inorganic aluminum salt to the inorganic lithium salt is in the range of 2:1, the total molar amount of the inorganic aluminum salt and the inorganic lithium salt was 4mol/L, and furthermore, hydroxide in an aqueous solution was provided by adding lithium hydroxide.
S2, preparing sulfonated polymer solution: and mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled at 30%. The sulfonated polymer is sulfonated polyether ether ketone, and the solvent is N-methyl pyrrolidone.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled at 30 percent.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium. The post-treatment is a hydrothermal method at 200 ℃ for 2 hours, wherein the aqueous solution is hydrochloric acid solution, and the pH value of the solution is 1.5.
S5, adsorption of lithium: the Bayer process semen was selected with a lithium concentration of 82mg/L. Mixing the adsorbent obtained in the above steps with Bayer process semen containing lithium, adsorbing the lithium, wherein the adding amount of the adsorbent is 50g/L, washing the adsorbent by pure water after adsorbing for 4 hours, then washing the adsorbent by 0.3mol/L hydrochloric acid solution, and analyzing the lithium to obtain an analysis liquid rich in lithium. The adsorption temperature was 65 degrees celsius.
The concentration of lithium in the Bayer process semen after adsorption is 6.0mg/L, and the concentration of lithium ions in the analysis solution is 207mg/L.
Example 3:
an adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing aluminum sulfate and lithium chloride under alkaline condition, wherein the concentration of hydroxyl in alkaline solution is controlled to be 0.3mol/L, heating and evaporating the solution to solid, and calcining at 350 ℃ for 1 hour to obtain the active double salt. The molar ratio of the inorganic aluminum salt to the inorganic lithium salt is in the range of 5:1, the total molar amount of aluminum salt and lithium salt was 3mol/L, and furthermore, hydroxide in an aqueous solution was provided by adding lithium hydroxide.
S2, preparing sulfonated polymer solution: and mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled at 40%. The sulfonated polymer is sulfonated poly (arylene ether sulfone ketone), and the adopted solvent is 1, 4-dioxane.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled at 60 percent.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium. The post-treatment is a hydrothermal method at 200 ℃ for 5 hours, wherein the aqueous solution is hydrochloric acid solution, and the pH value of the solution is 3.
S5, adsorption of lithium: and selecting Bayer process semen, wherein the concentration of lithium is 171mg/L, mixing the adsorbent obtained in the steps with the Bayer process semen containing lithium, adsorbing the lithium, wherein the adding amount of the adsorbent is 80g/L, washing the adsorbent by pure water after adsorbing for 6 hours, and then washing the adsorbent by a sulfuric acid solution of 0.5mol/L to analyze the lithium to obtain the analysis liquid rich in lithium. The adsorption temperature was 80 degrees celsius.
The concentration of lithium in the Bayer process semen after adsorption is 7.7mg/L, and the concentration of lithium ions in the analysis solution is 263mg/L.
Example 4:
an adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing aluminum nitrate and lithium sulfate under alkaline conditions, wherein the concentration of hydroxyl in an alkaline solution is controlled to be 0.5mol/L, heating and evaporating the solution to solid, and calcining at 250 ℃ for 3 hours to obtain the active double salt. The molar ratio of the inorganic aluminum salt to the inorganic lithium salt is in the range of 3:1, the total molar amount of aluminum salt and lithium salt was 3mol/L, and furthermore, hydroxide in an aqueous solution was provided by adding lithium hydroxide.
S2, preparing sulfonated polymer solution: and mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled at 40%. The sulfonated polymer is sulfonated polyether sulfone, and the adopted solvent is 1, 4-dioxane.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled at 30 percent.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium. The post-treatment is hydrothermal treatment at 180 ℃ for 3 hours, wherein the aqueous solution is hydrochloric acid solution, and the pH value of the solution is 2.0.
S5, adsorption of lithium: and selecting Bayer process semen, wherein the concentration of lithium is 171mg/L, mixing the adsorbent obtained in the steps with the Bayer process semen containing lithium, adsorbing the lithium, wherein the adding amount of the adsorbent is 50g/L, washing the adsorbent by pure water after adsorbing for 6 hours, and then washing the adsorbent by 0.5mol/L hydrochloric acid solution, so as to analyze the lithium, thereby obtaining the analysis liquid rich in lithium, and the adsorption temperature is 80 ℃.
The concentration of lithium in the Bayer process semen after adsorption is 11.3mg/L, and the concentration of lithium ions in the analysis solution is 227mg/L.
Example 5:
an adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing aluminum nitrate and lithium sulfate under alkaline conditions, wherein the concentration of hydroxyl in an alkaline solution is controlled to be 0.5mol/L, heating and evaporating the solution to solid, and calcining at 250 ℃ for 3 hours to obtain the active double salt. The molar ratio of the inorganic aluminum salt to the inorganic lithium salt is in the range of 3:1, the total molar amount of aluminum salt and lithium salt was 3mol/L, and furthermore, hydroxide in an aqueous solution was provided by adding lithium hydroxide.
S2, preparing sulfonated polymer solution: and mixing the sulfonated polymer material with a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled at 40%. The sulfonated polymer is sulfonated polyether sulfone, and the adopted solvent is 1, 4-dioxane.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt in the polymer solution is controlled at 30 percent.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium. The post-treatment is hydrothermal treatment at 180 ℃ for 3 hours, wherein the aqueous solution is hydrochloric acid solution, and the pH value of the solution is 2.0.
S5, adsorption of lithium: selecting Bayer process semen, wherein the concentration of lithium is 171mg/L, filling the adsorbent obtained in the steps into a fixed adsorption column, adsorbing lithium, passing the Bayer process semen containing lithium through the adsorption column, washing the adsorbent by pure water, washing the adsorbent by 0.5mol/L hydrochloric acid solution, and resolving the lithium to obtain a resolved solution rich in lithium, wherein the adsorption temperature is 80 ℃.
The concentration of lithium in the Bayer process semen after adsorption is 5.0mg/L, and the concentration of lithium ions in the analysis solution is 329mg/L.
Claims (8)
1. An adsorbent for adsorbing lithium from refined solution of alumina produced by Bayer process and a use method thereof are characterized in that the preparation and use method of the adsorbent comprises the following steps:
s1, synthesizing an active double salt: mixing inorganic aluminum salt and inorganic lithium salt under alkaline condition, controlling the concentration of hydroxyl to be 0.1-1mol/L, heating and evaporating the solution to solid, and calcining for 1-6 hours at 200-350 ℃ to obtain the active double salt.
S2, preparing a sulfonated polymer material, and mixing and dissolving the sulfonated polymer and a polar solvent to obtain a uniform polymer solution, wherein the mass concentration of the sulfonated polymer is controlled to be 5% -40%.
S3, mixing the active double salt and sulfonated polymer: uniformly dispersing the active double salt obtained in the step S1 in the sulfonated polymer solution obtained in the step S2. Wherein the mass concentration of the active double salt is controlled between 20% and 60%.
S4, granulating and post-treating the composite adsorbent: and (3) separating phases of the sulfonated polymer solution containing the active double salt obtained in the step (S3) in an aqueous solution to obtain the porous composite adsorbent. And then carrying out post-treatment on the composite adsorbent, namely, adsorbing lithium.
S5, adsorption of lithium: mixing the adsorbent obtained in the above steps with Bayer process semen containing lithium, adsorbing lithium for 0.5-10 hours, washing the adsorbent with pure water, and then washing the adsorbent with 0.1-0.5mol/L acidic solution to analyze the lithium to obtain the analysis liquid rich in lithium.
2. The adsorbent for adsorbing lithium from semen of alumina production by bayer process according to claim 1, wherein the molar ratio of inorganic aluminum salt to inorganic lithium salt in step S1 is in the range of 1:1-5:1, the total molar amount of the inorganic aluminum salt and the inorganic lithium salt is 1mol/L to 5mol/L.
3. An adsorbent for adsorbing lithium from semen produced by bayer process for alumina and a method for using the same according to claim 1, wherein the hydroxide in step S1 is provided by lithium hydroxide.
4. The adsorbent for adsorbing lithium from semen produced by a bayer process according to claim 1, wherein in the sulfonated polymer solution in the step S2, the sulfonated polymer is one or more of sulfonated polysulfone, sulfonated polyether ether ketone, sulfonated polyether sulfone and sulfonated polyether sulfone ketone, and the solvent used is one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and 1, 4-dioxane.
5. The adsorbent for adsorbing lithium from semen of bayer process for producing alumina according to claim 1, wherein the post-treatment in step S4 is a hydrothermal treatment at 120-200 ℃ for 0.5-5 hours, wherein the aqueous solution is a hydrochloric acid solution, and the pH of the solution is 0.1-3.
6. The adsorbent for adsorbing lithium from semen produced by bayer process according to claim 1, wherein the adsorption temperature in step S5 is 20-80 ℃, and the semen by bayer process contains sodium aluminate solution with lithium ion concentration of 20-200 mg/L.
7. An adsorbent for adsorbing lithium from semen produced by bayer process according to claim 1, wherein the semen produced by bayer process in step S5 is directly used in the subsequent aluminum hydroxide production section after adsorption.
8. The adsorbent for adsorbing lithium from semen produced by Bayer process according to claim 1, wherein the adsorption in step S5 is realized by adding adsorbent, fixed adsorption bed, etc. in semen produced by Bayer process.
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| CN117358196B (en) * | 2023-09-20 | 2024-03-15 | 中国地质科学院矿产资源研究所 | Preparation method of bauxite-based aluminum lithium ion adsorbent and brine lithium extraction method |
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