CN115212844B - Composite adsorbent for extracting lithium from salt lake brine and preparation method thereof - Google Patents
Composite adsorbent for extracting lithium from salt lake brine and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 239000003463 adsorbent Substances 0.000 title claims abstract description 25
- 239000012267 brine Substances 0.000 title claims abstract description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000012265 solid product Substances 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 9
- 239000001354 calcium citrate Substances 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 9
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/048—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 phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- 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
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- Hydrology & Water Resources (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a composite adsorbent for extracting lithium from salt lake brine, which comprises the steps of disassembling waste graphite and a doping agent obtained after a waste lithium battery is disassembled according to a mass ratio of 1: mixing 0.1-0.3 (g/g), and activating at 200-600deg.C for 3-5 hr. The doped and modified graphite is prepared according to a solid-to-liquid ratio of 1: adding 0.1-0.5 (g/mL) into 1-3mol/L lithium ion electrolyte solution, ultrasonically oscillating at 20-50 ℃ for 0.5-3h, and centrifuging to separate a solid product. The solid product is prepared according to the solid-to-liquid ratio of 1:2-5 (g/mL) of the mixture is placed in a hydroxyapatite precursor solution, and after 3-8 hours of reaction at 25-60 ℃, the solid product is centrifugally separated. Roasting the separated product at 200-500 ℃ for 2-4 hours, and then, according to the solid-liquid ratio of 1:5 to 10 (g/mL) of the catalyst is placed in a dilute acid solution with the molar concentration of 0.1 to 1mol/L, and the specific composite adsorbent is obtained after the reaction for 0.5 to 2 hours and the centrifugal separation. The invention has the advantages of simple preparation process, high lithium ion selectivity, large adsorption capacity, low dissolution loss rate and the like.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to a composite adsorbent for extracting lithium from salt lake brine and a preparation method thereof.
Background
Lithium and its compounds are widely used in the fields of electronics, metallurgy, chemical industry, medicine, energy and the like with excellent physical and chemical properties, and have important strategic positions in national economy and national defense construction. In the middle of the 80 s of the last century, the world countries mainly use lithium ores as raw materials to produce lithium salts. The method has longer history and mature process, but has higher energy consumption, can pollute the environment to a certain extent, and has increasingly deficient lithium ore resources, and increasingly shows the limitation. On the other hand, the lithium reserves in the salt lake brine are rich, the cost is lower than that of the exploitation of lithium ores, and along with the exploration and development of huge salt lake brine lithium resources in south america, the lithium extraction in the salt lake gradually becomes a development trend. China is a large country of lithium resources, and reserves are in the first place of the world. Wherein, the lithium resource reserves of the salt lakes of Qinghai and Tibet account for more than 85 percent of the total reserves. Generally, the ratio of magnesium to lithium in salt lake brine determines the feasibility of producing lithium salt by utilizing brine resources and the production cost and economic benefit of lithium salt products. But the Qinghai salt lake brine has higher magnesium and lithium ratio and great difficulty in extracting lithium.
The current methods for extracting lithium from salt lake brine include precipitation, calcination leaching, extraction, membrane separation, adsorption and the like. The precipitation method is simple in process and low in cost, and is suitable for extracting lithium from salt lake brine with low magnesium-lithium ratio. However, the method can cause excessive alkali consumption and serious lithium salt loss when magnesium and lithium are relatively large. The calcination leaching method has simple process, but the hydrated magnesium chloride is difficult to completely decompose, the generated hydrogen chloride gas has large corrosion to equipment, the water quantity required to be evaporated is large, and the process energy consumption is high. The extraction method is suitable for extracting lithium from brine with high magnesium-lithium ratio, but has long process flow, equipment corrosion and dissolution loss problems, and the cost is obviously increased. The membrane separation method has high cost and is not easy to industrialize. The adsorption method has the advantages of simple process, high recovery rate, environmental friendliness and the like, and realizes industrialized Hombre Muerto salt lake with Livent control at present, and the Nalge salt lake developed in blue-branch lithium industry and Tibetan lattice lithium industry. The lithium adsorbent used in industry mainly comprises manganese-series and titanium-series ion sieve adsorbents, but the adsorbents are generally in powder form, have poor fluidity and permeability, have high dissolution loss rate in the adsorption elution process, and have certain limitation in industrial application. Therefore, how to develop an adsorbent with high lithium ion selectivity, large adsorption capacity and high material stability becomes a key problem to be solved in the adsorption method for extracting lithium.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite adsorbent for extracting lithium from salt lake brine and a preparation method thereof.
The technical scheme of the invention is as follows:
the preparation method of the composite adsorbent for extracting lithium from salt lake brine comprises the following steps:
step (1), the waste graphite and the doping agent obtained after the waste lithium battery is disassembled are mixed according to the mass ratio of 1: mixing 0.1-0.3 (g/g), and activating in a microwave oven at 200-600deg.C for 3-5 hr;
step (2), mixing the doped and modified graphite according to a solid-to-liquid ratio of 1: adding 0.1-0.5 (g/mL) into 1-3mol/L lithium ion electrolyte solution, ultrasonically oscillating at 20-50 ℃ for 0.5-3h, and centrifuging to separate a solid product;
step (3), solid products are mixed according to a solid-liquid ratio of 1:2-5 (g/mL) of the mixture is placed in a hydroxyapatite precursor solution, and after the mixture reacts for 3-8 hours at 25-60 ℃, the solid product is centrifugally separated;
step (4), roasting the separated product at 200-500 ℃ for 2-4 hours, and then, according to a solid-to-liquid ratio of 1:5 to 10 (g/mL) of the mixture is placed in a dilute acid solution with the molar concentration of 0.1 to 1mol/L, and the mixture is centrifugally separated after 0.5 to 2 hours of reaction, so as to obtain the composite adsorbent.
Preferably, in the step (1), the dopant is one or more of sodium benzenesulfonate, ammonium persulfate, sodium polysulfide, potassium permanganate, sodium sulfate, and potassium sulfate.
Preferably, in the step (2), the electrolyte is one or more of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium bistrifluoromethane sulfonyl imide, perfluoroalkyl sulfonyl methyl lithium, and lithium difluorooxalato borate.
Preferably, the hydroxyapatite precursor consists of lithium nitrate, calcium citrate and diammonium phosphate, wherein the molar concentration of the lithium nitrate, the calcium citrate and the diammonium phosphate is 0.1-0.5mol/L, 0.5-2mol/L and 0.5-2mol/L respectively, and the volume ratio is 1:10-15:5-10.
Preferably, in the step (4), the dilute acid is one or a combination of more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, in the step (4), the surface area of the composite adsorbent is 100-500m 2 Per gram, the aperture is 0.1-60nm, and the lithium ion adsorption capacity is 20-30mg/g.
The invention also provides a composite adsorbent prepared by the preparation method of the composite adsorbent for extracting lithium from salt lake brine.
The invention takes waste graphite as a core, and can remove residual organic and inorganic impurities in the waste graphite by microwave modification, thereby improving the pore structure and the specific surface area of the waste graphite. The doping modification is carried out by adding the doping agent, so that the surface functional groups of the material can be enriched, the hydrophilicity is improved, and the specific surface area of the material is further improved. The hydroxyapatite is taken as a shell, after being immersed and modified in a lithium ion electrolyte solution, the quantitative decomposition of internal graphite and the slow etching of the electrolyte solution to the hydroxyapatite can be controlled through a subsequent thermal activation process, so that a double reaming effect is achieved, a multi-stage pore structure is generated, and the adsorption capacity of lithium ions is improved. The lithium impregnated in the lithium ion electrolyte solution is eluted through subsequent acid washing, so that the selectivity of the composite material to lithium can be improved. Therefore, the invention overcomes the defects of small adsorption capacity, low selectivity and easy dissolution loss of the traditional adsorbent, has the advantages of simple preparation process, high lithium ion selectivity, large adsorption capacity, low dissolution loss rate and the like, and is easy for large-scale application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
Example 1:
(1) Waste graphite obtained after the waste lithium battery is disassembled and sodium benzenesulfonate are mixed according to the mass ratio of 1:0.1 (g/g) and then placing the mixture in a microwave oven for activation for 5 hours at 200 ℃;
(2) Mixing the doped and modified graphite according to a solid-to-liquid ratio of 1:0.1 (g/mL) is added into a lithium hexafluorophosphate solution with the molar concentration of 1mol/L, and after ultrasonic oscillation is carried out for 3 hours at 20 ℃, the solid product is centrifugally separated;
(3) The solid product is mixed according to the solid-liquid ratio of 1:2 (g/mL) are placed in lithium nitrate, calcium citrate and diammonium hydrogen phosphate solution, the molar concentration of the three is 0.1mol/L, 0.5mol/L and 0.5mol/L, and the volume ratio is 1:10:10 After 8 hours of reaction at 25 ℃, the solid product is centrifugally separated;
(4) Roasting the separated product at 200 ℃ for 4 hours, and then, according to a solid-to-liquid ratio of 1:5 (g/mL) is placed in hydrochloric acid solution with the molar concentration of 0.1mol/L, and after 2 hours of reaction, centrifugal separation is carried out to obtain the specific surface area of 500m 2 And/g, pore diameter of 0.1-30nm and lithium ion adsorption capacity of 20 mg/g.
Example 2:
(1) Waste graphite obtained after the waste lithium battery is disassembled and ammonium persulfate are mixed according to the mass ratio of 1:0.3 (g/g) and then placing the mixture in a microwave oven for activation at 600 ℃ for 3 hours.
(2) Mixing the doped and modified graphite according to a solid-to-liquid ratio of 1:0.5 (g/mL) was added to a 3mol/L lithium perchlorate solution, and the solid product was centrifuged after shaking ultrasonically at 50℃for 0.5 h.
(3) The solid product is mixed according to the solid-liquid ratio of 1:5 (g/mL) are placed in lithium nitrate, calcium citrate and diammonium hydrogen phosphate solution, the molar concentration of the three is 0.5mol/L, 2mol/L and 2mol/L respectively, and the volume ratio is 1:15: 9. after 3h reaction at 60℃the solid product was centrifuged.
(4) Roasting the separated product at 500 ℃ for 2 hours, and then, according to a solid-to-liquid ratio of 1:10 (g/mL) is placed in sulfuric acid solution with the molar concentration of 1mol/L, and after 0.5 hour of reaction, centrifugal separation is carried out to obtain the specific surface area of 100m 2 And/g, pore diameter of 0.3-60nm, and lithium ion adsorption capacity of 30mg/g.
Example 3:
(1) Waste graphite and sodium persulfate obtained after the disassembly of the waste lithium batteries are mixed according to the mass ratio of 1:0.2 (g/g) and placing the mixture in a microwave oven for activation for 4 hours at 300 ℃;
(2) Mixing the doped and modified graphite according to a solid-to-liquid ratio of 1:0.3 (g/mL) adding the solid into a lithium tetrafluoroborate solution with the molar concentration of 2mol/L, and centrifuging the solid product after ultrasonic oscillation for 1.75 hours at 35 ℃;
(3) The solid product is mixed according to the solid-liquid ratio of 1:3.5 (g/mL) is placed in lithium nitrate, calcium citrate and diammonium phosphate solution, the molar concentration of the three is 0.3mol/L, 1mol/L and 1mol/L respectively, and the volume ratio is 1:10: 6. after reacting for 4 hours at 40 ℃, centrifugally separating a solid product;
(4) Roasting the separated product at 300 ℃ for 3 hours, and then, according to a solid-to-liquid ratio of 1:7 (g/mL) is placed in a nitric acid solution with the molar concentration of 0.4mol/L, and after 1 hour of reaction, centrifugal separation is carried out to obtain the specific surface area of 200m 2 And/g, pore diameter of 10-50nm and lithium ion adsorption capacity of 22 mg/g.
Example 4:
(1) Waste graphite and potassium sulfate obtained after the waste lithium battery is disassembled are mixed according to the mass ratio of 1:0.15 (g/g) and then placing the mixture in a microwave oven for activation for 4 hours at 400 ℃;
(2) Mixing the doped and modified graphite according to a solid-to-liquid ratio of 1:0.3 (g/mL) adding the solid into 1.5mol/L lithium bistrifluoromethane sulfonyl imide solution, and centrifuging the solid product after ultrasonic oscillation for 2.5 hours at 40 ℃;
(3) The solid product is mixed according to the solid-liquid ratio of 1:4 (g/mL) are placed in lithium nitrate, calcium citrate and diammonium hydrogen phosphate solution, the molar concentration of the three is 0.4mol/L, 1mol/L and 2mol/L respectively, and the volume ratio is 1:11: 5. after reacting for 6 hours at 55 ℃, centrifugally separating a solid product;
(4) Roasting the separated product at 450 ℃ for 3.5 hours, and then, according to the solid-to-liquid ratio of 1:8 (g/mL) is placed in a nitric acid solution with the molar concentration of 0.6mol/L, and after 1.5h of reaction, centrifugal separation is carried out to obtain the specific surface area of 500m 2 And/g, pore diameter of 0.1-40nm and lithium ion adsorption capacity of 28 mg/g.
Example 5:
(1) Waste graphite and doping agent obtained after the waste lithium battery is disassembled are mixed according to the mass ratio of 1:0.3 (g/g) and then placing the mixture in a microwave oven, wherein the mass ratio of the sodium polysulfide to the potassium permanganate is 1: activating for 5 hours at the temperature of 1,550 ℃;
(2) Mixing the doped and modified graphite according to a solid-to-liquid ratio of 1:0.35 (g/mL) adding into 2.5mol/L perfluoroalkyl sulfonyl methyl lithium and difluoro oxalic acid lithium borate (volume ratio 1:1) solution, ultrasonically oscillating at 20 ℃ for 3h, and centrifuging the solid product;
(3) The solid product is mixed according to the solid-liquid ratio of 1:2-5 (g/mL) of the mixture is placed in lithium nitrate, calcium citrate and diammonium hydrogen phosphate solution, the molar concentration of the three is respectively 0.5mol/L, 1.4mol/L and 1.6mol/L, and the volume ratio is 1:14: 7.35. after 7.5h of reaction at 45 ℃, the solid product is centrifugally separated;
(4) Roasting the separated product at 300 ℃ for 4 hours, and then, according to a solid-to-liquid ratio of 1:5 (g/mL) is placed in a solution of hydrochloric acid and sulfuric acid with the molar concentration of 0.1mol/L (volume ratio of 1:1), and after 1.5h of reaction, the solution is centrifugally separated to obtain the specific surface area of 380m 2 And/g, pore diameter of 3-55nm and lithium ion adsorption capacity of 22 mg/g.
The specific surface area and pore size distribution were tested using a Micromeritics ASAP 2020 analyzer under nitrogen atmosphere.
Testing of lithium ion adsorption capacity: the adsorbent is prepared according to a solid-to-liquid ratio of 1:20 addAnd (3) adding the solution into simulated brine, adsorbing for a certain time in a constant-temperature water bath, centrifuging to obtain supernatant, and detecting the concentration of lithium ions in the brine by adopting an inductively coupled plasma emission spectrometer. Adsorption capacity Qt is equal to qt= (ρ) 0 -ρ 1 ) V/m is calculated, wherein Qt is the adsorption capacity at time t, and mg/g; ρ 0 mg/L is the mass concentration of the initial lithium ion of the solution; ρ 1 For the mass concentration of the lithium ions after adsorption, mg/L, m is the mass of the adsorbent, g; v is the volume of the adsorption liquid and L.
Compared with the prior art, the invention has the advantages of simple preparation process, high lithium ion selectivity, large adsorption capacity, low dissolution loss rate and the like.
Chen Linlin et al [ Chen Linlin, li Xiaowei, jiang Lei, ma Pengfei, yang Weiwei, zhu Xianrong, bright red nest, marshal. Titanium-based particulate adsorbent for adsorption study of lithium in salt lake brine [ J ]. Contemporary chemical study, 2021 (21): 4-7 ] studied the adsorption performance of titanium-based particulate adsorbent on lithium in brine, the adsorption capacity of the adsorbent on lithium being 12.4mg/g. Tanna et al [ Tanna, gong's warp type, army's aluminum-based lithium adsorbent preparation and its adsorption property research [ J ]. Inorganic salt industry, 2020,52 (08): 51-56 ] prepared aluminum-based lithium adsorbent by a one-step method using lithium chloride and anhydrous aluminum chloride as raw materials. The lithium adsorption capacity under the optimal adsorption condition is 8.66mg/g. Yuan Junsheng et al [ Yuan Junsheng, li Heng, meng Xingzhi ] study of adsorption performance of ion sieve type lithium adsorbent [ J ]. Inorganic salt industry, 2006 (06): 27-29 ] A granular ion sieve type lithium adsorbent was prepared, having a lithium ion adsorption capacity of 15.63mg/g in a pure lithium salt solution and a lithium ion adsorption capacity of 5.68mg/g in sea water.
While the invention has been described with respect to certain preferred embodiments, it will be apparent to those skilled in the art that various changes and substitutions can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
1. The preparation method of the composite adsorbent for extracting lithium from salt lake brine is characterized by comprising the following steps of:
step (1), the waste graphite and the doping agent obtained after the waste lithium battery is disassembled are mixed according to the mass ratio of 1: mixing 0.1-0.3, and activating in a microwave oven at 200-600deg.C for 3-5 hr; the unit of the mass ratio is g/g;
step (2), mixing the doped and modified graphite according to a solid-to-liquid ratio of 1: adding 0.1-0.5 into lithium ion electrolyte solution with the molar concentration of 1-3mol/L, ultrasonically oscillating at 20-50 ℃ for 0.5-3h, and centrifugally separating a solid product; the unit of the solid-liquid ratio is g/ml;
step (3), solid products are mixed according to a solid-liquid ratio of 1:2-5, placing the mixture in a hydroxyapatite precursor solution, reacting for 3-8 hours at 25-60 ℃, and centrifuging the solid product; the unit of the solid-liquid ratio is g/ml;
step (4), roasting the separated product at 200-500 ℃ for 2-4 hours, and then, according to a solid-to-liquid ratio of 1:5-10 of the catalyst is placed in a dilute acid solution with the molar concentration of 0.1-1mol/L, and after 0.5-2h of reaction, the catalyst is centrifugally separated to obtain a composite adsorbent, wherein the solid-liquid ratio is in g/ml;
in the step (1), the doping agent is one or a combination of more of sodium benzenesulfonate, ammonium persulfate, sodium polysulfide, potassium permanganate, sodium sulfate and potassium sulfate;
in the step (2), the electrolyte is one or more of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium bistrifluoromethane sulfonyl imide, perfluoroalkyl sulfonyl methyl lithium and lithium difluorooxalato borate;
in the step (3), the hydroxyapatite precursor consists of lithium nitrate, calcium citrate and diammonium phosphate, wherein the molar concentration of the lithium nitrate, the calcium citrate and the diammonium phosphate is 0.1-0.5mol/L, 0.5-2mol/L and 0.5-2mol/L respectively, and the volume ratio is 1:10-15:5-10.
2. The method for preparing a composite adsorbent for extracting lithium from salt lake brine according to claim 1, wherein in the step (4), the dilute acid is one or a combination of more of hydrochloric acid, sulfuric acid and nitric acid.
3. The method for preparing a composite adsorbent for extracting lithium from salt lake brine according to claim 1, wherein in the step (4), the composite adsorbentSurface area of 100-500m 2 Per gram, the aperture is 0.1-60nm, and the lithium ion adsorption capacity is 20-30mg/g.
4. A composite adsorbent produced by the method for producing a composite adsorbent for extracting lithium from salt lake brine according to any one of claims 1 to 3.
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