CN115837265A - Manganese-based oxide lithium ion sieve and preparation method and application thereof - Google Patents
Manganese-based oxide lithium ion sieve and preparation method and application thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 24
- 239000011572 manganese Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims abstract description 23
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000008247 solid mixture Substances 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 239000012467 final product Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- SAEVTEVJHJGDLY-UHFFFAOYSA-N dilithium;manganese(2+);oxygen(2-) Chemical compound [Li+].[Li+].[O-2].[O-2].[Mn+2] SAEVTEVJHJGDLY-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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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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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of submarine optical cables, and discloses a manganese-based oxide lithium ion sieve and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1: directly mixing a solid self-polymerization monomer reagent and solid total metal salt, wherein the solid total metal salt is the mixture of solid manganese salt and solid lithium salt; s2: putting the solid mixture obtained in the step S1 into a crucible and placing the crucible into a muffle furnace; s3: directly taking air as atmosphere, heating the solid mixture to 750-950 ℃ at the heating rate of 1-10 ℃, and maintaining the temperature for 1-3 h; s4: and (3) immersing the lithium manganese oxide material in the S3 into a hydrochloric acid solution for lithium ion exchange to obtain a lithium ion sieve material, wherein the method has a simple process, a final product can be obtained in one step, and the prepared lithium ion sieve material has a good application prospect and economic benefits in the fields of lithium extraction in salt lakes and the like.
Description
Technical Field
The invention belongs to the technical field of lithium element extraction, and particularly relates to a manganese-based oxide lithium ion sieve and a preparation method and application thereof.
Background
The Qinghai salt lake in China has a large amount of lithium resources, lithium is extracted from salt lake brine, a lithium chloride mixed solution with higher concentration can be obtained, and then the lithium chloride mixed solution reacts with carbonate to precipitate lithium, so that a lithium carbonate product can be prepared, a Lithium Ion Sieve (LIS) is a lithium ion adsorbent which is low in toxicity, low in cost, high in chemical stability and strong in lithium absorption capacity and is considered as the most promising lithium extraction reagent, generally, the LIS is divided into Lithium Manganese Oxide (LMO) and Lithium Titanium Oxide (LTO) types, the LMO type LIS is the most popular lithium adsorbent because of superior lithium selectivity, high lithium absorption capacity and excellent regeneration performance, and compared with the LMO type LIS, the LTO type LIS has a more stable molecular structure due to larger titanium-oxygen bond energy, but the lithium absorption rate of the LTO type LIS is relatively slow.
For example, chinese patent (CN 202210732462.7) discloses a titanium-based lithium ion sieve inorganic composite adsorption lithium extraction material and a preparation method thereof, the method is to mix a titanium-based lithium ion sieve or a precursor thereof with a regulator, a curing agent and a resin monomer, a high molecular monomer is subjected to polymerization reaction and gradually cured at a certain temperature, in the process, a particle material with a specific shape is prepared by extrusion or spray drying, then high-temperature roasting is carried out under an anaerobic condition, and a carbon-supported titanium-based lithium ion sieve inorganic/inorganic composite lithium extraction material is obtained after acid treatment; chinese patent (CN 202110062640.5) discloses a preparation method of high-adsorption-capacity lithium ion sieve particles, wherein the lithium ion sieve particles are prepared by sanding lithium ion sieve powder, mixing the sanded lithium ion sieve powder with an inorganic binder, spray-drying the mixture, mixing the prepared micron-sized particles with a template pore-forming agent, mixing the mixture with an aqueous resin emulsion in granulation equipment for granulation, heating to complete drying and curing processes, and finally performing acid leaching and water washing.
Disclosure of Invention
In order to solve the problems, the invention provides a manganese-based oxide lithium ion sieve and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a manganese-based oxide lithium ion sieve comprises the following steps:
s1: directly mixing a solid self-polymerization monomer reagent and solid total metal salt, wherein the solid total metal salt is the mixture of solid manganese salt and solid lithium salt;
s2: putting the solid mixture obtained in the step S1 into a crucible and placing the crucible in a muffle furnace;
s3: directly taking air as atmosphere, heating the solid mixture to 750-950 ℃ at the heating rate of 1-10 ℃, maintaining the temperature for 1-3 h, and obtaining lithium manganese oxide after calcination;
s4: and (3) immersing the lithium manganese oxide material in the S3 into a hydrochloric acid solution for lithium ion exchange to obtain the lithium ion sieve material.
Further, the solid self-polymerization monomer reagent in step S1 is one or more of citric acid, maleic acid and ethylenediamine tetraacetic acid.
Further, the solid manganese salt in the step S1 is solid manganese acetate, manganese sulfate or manganese chloride.
Further, the solid lithium salt in step S1 is solid lithium acetate, lithium chloride, lithium sulfate and lithium nitrate.
Further, the molar ratio of the solid self-polymerization monomer reagent to the solid total metal salt in the step S1 is 0.5.
Further, the molar ratio of the solid manganese salt to the solid lithium salt in the solid total metal salts is 2:1.
Further, the concentration of the hydrochloric acid solution in the step S4 is 0.1-3 mol/L, and the immersion exchange time is 5-24 h.
The invention also provides the manganese-based oxide lithium ion sieve prepared by the preparation method.
The invention also provides an application of the manganese-based oxide lithium ion sieve in lithium extraction.
In conclusion, the beneficial effects of the invention are as follows:
(1) The manganese-based oxide lithium ion extractant is directly prepared by calcining the solid mixture in one step, the raw materials are cheap and easy to obtain, the process operation is simple and convenient, and the production cost is saved.
(2) The complex derivative polymer formed by the self-polymerization reaction of the heated solid self-polymerization monomer is beneficial to forming the lithium manganese oxide lithium ion sieve with a special structure, and the capture capability of the material to lithium ions can be improved.
Drawings
FIG. 1 is an SEM photograph of a manganese-based oxide lithium ion sieve prepared in example 1 of the present invention.
Detailed Description
In order to further understand the present invention, the following examples are further detailed below, and the following examples are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
A method for preparing a manganese-based oxide lithium ion sieve, comprising the steps of:
s1: directly and fully mixing a solid self-polymerization monomer reagent and solid total metal salt, wherein the solid total metal salt is the mixture of solid manganese salt and solid lithium salt, and liquid solvents such as water and the like are not needed in the mixing process;
s2: putting the solid mixture obtained in the step S1 into a crucible and placing the crucible into a muffle furnace;
s3: directly taking air as atmosphere, heating the solid mixture to 750-950 ℃ at the heating rate of 1-10 ℃, maintaining the temperature for 1-3 h, and obtaining lithium manganese oxide after calcination;
s4: and (3) immersing the lithium manganese oxide material in the S3 into a hydrochloric acid solution for lithium ion exchange to obtain the lithium ion sieve material.
The solid self-polymerization monomer reagent in the step S1 is one or more of citric acid, maleic acid and ethylene diamine tetraacetic acid.
In the step S1, the solid manganese salt is solid manganese-containing metal salt such as solid manganese acetate, manganese sulfate, manganese chloride and the like.
In the step S1, the solid lithium salt is solid lithium acetate, lithium chloride, lithium sulfate and lithium nitrate.
The molar ratio of the solid self-polymerization monomer reagent to the solid total metal salt in the step S1 is 0.5.
The molar ratio of solid manganese salt to solid lithium salt in the total solid metal salts is 2:1.
In the step S4, the concentration of the hydrochloric acid solution is 0.1-3 mol/L, and the immersion exchange time is 5-24 h.
Example 1
S1: directly mixing 10mmol of manganese acetate, 5mmol of lithium acetate and 22.5mmol of citric acid in a solid state;
s2: placing the solid mixture into a crucible and placing the crucible in a muffle furnace;
s3: heating to 850 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and maintaining the temperature for 2h to obtain lithium manganese oxide;
s4: and (3) placing the lithium manganese oxide in a 1.0mol/L hydrochloric acid solution for 12h to completely remove lithium per se, thus obtaining the high-efficiency lithium ion sieve material.
Referring to fig. 1, fig. 1 is an SEM image of the prepared lithium manganese oxide lithium ion sieve, and the prepared lithium ion sieve has a sponge-like structure with a porous structure, which can improve the extraction efficiency of lithium.
1.0g of manganese-based oxide lithium ion sieve prepared in example 1 was used for adsorption extraction of lithium from 1.0L of saturated lithium chloride solution, followed by delithiation in 1.0L of 1mol/L hydrochloric acid solution, and the concentration of lithium in hydrochloric acid was 38.65mg/L as determined by atomic absorption spectrophotometry.
Example 2
S1: directly mixing 10mmol of manganese acetate, 5mmol of lithium acetate and 22.5mmol of maleic acid in a solid state;
s2: placing the solid mixture into a crucible and placing the crucible in a muffle furnace;
s3: heating to 750 ℃ in a muffle furnace at a heating rate of 1 ℃/min, and maintaining the temperature for 3 hours to obtain lithium manganese oxide;
s4: and (3) putting the lithium manganese oxide into a 1.0mol/L hydrochloric acid solution for exchange for 12 hours, and completely removing lithium per se to obtain the high-efficiency lithium ion sieve material.
1.0g of manganese-based oxide lithium ion sieve prepared in example 2 was used for adsorption extraction of lithium from 1.0L of saturated lithium chloride solution, followed by delithiation in 1.0L of 1mol/L hydrochloric acid solution, and the lithium concentration in hydrochloric acid was determined to be 28.31mg/L by atomic absorption spectrophotometry.
Example 3
S1: directly mixing 10mmol of manganese acetate, 5mmol of lithium acetate and 22.5mmol of ethylene diamine tetraacetic acid in a solid state;
s2: placing the solid mixture into a crucible and placing the crucible in a muffle furnace;
s3: heating to 800 ℃ in a muffle furnace at a heating rate of 3 ℃/min, and maintaining the temperature for 3 hours to obtain lithium manganese oxide;
s4: and (3) putting the lithium manganese oxide into a 1.0mol/L hydrochloric acid solution for exchange for 12 hours, and completely removing lithium per se to obtain the high-efficiency lithium ion sieve material.
1.0g of manganese-based oxide lithium ion sieve prepared in example 3 was used for adsorption extraction of lithium from 1.0L of saturated lithium chloride solution, followed by delithiation in 1.0L of 1mol/L hydrochloric acid solution, and the lithium concentration in hydrochloric acid was 29.87mg/L as determined by atomic absorption spectrophotometry.
Example 4
S1: directly mixing 10mmol of manganese acetate, 5mmol of lithium acetate, 7.5mmol of maleic acid, 7mmol of ethylene diamine tetraacetic acid and 8mmol of citric acid in a solid state;
s2: placing the solid mixture into a crucible and placing the crucible in a muffle furnace;
s3: heating to 900 ℃ in a muffle furnace at the heating rate of 4 ℃/min, and maintaining the temperature for 1.5h to obtain lithium manganese oxide;
s4: and (3) putting the lithium manganese oxide into a 1.0mol/L hydrochloric acid solution for exchange for 12 hours, and completely removing lithium per se to obtain the high-efficiency lithium ion sieve material.
1.0g of manganese-based oxide lithium ion sieve prepared in example 4 was used for adsorption extraction of lithium from 1.0L of saturated lithium chloride solution, followed by delithiation in 1.0L of 1mol/L hydrochloric acid solution, and the lithium concentration in hydrochloric acid was 32.34mg/L as determined by atomic absorption spectrophotometry.
Example 5
S1: directly mixing 10mmol of manganese acetate, 5mmol of lithium acetate, 14mmol of maleic acid and 8.5mmol of citric acid in a solid state;
s2: placing the solid mixture into a crucible and placing the crucible in a muffle furnace;
s3: heating to 950 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and maintaining the temperature for 3 hours to obtain lithium manganese oxide;
s4: and (3) putting the lithium manganese oxide into a 1.0mol/L hydrochloric acid solution for exchange for 12 hours, and completely removing lithium per se to obtain the high-efficiency lithium ion sieve material.
1.0g of manganese-based oxide lithium ion sieve prepared in example 4 was used for adsorption extraction of lithium from 1.0L of saturated lithium chloride solution, followed by delithiation in 1.0L of 1mol/L hydrochloric acid solution, and the lithium concentration in hydrochloric acid was 34.61mg/L as measured by atomic absorption spectrophotometry.
Comparative example
The method for preparing the manganese-based oxide lithium ion sieve by the solid phase synthesis method comprises the following steps:
s1: mixing 10mmol LiCO 3 、20mmolλ-MnO 2 Fully mixing, putting into a crucible and placing into a muffle furnace;
s2: calcining for 2h at 850 ℃, and obtaining the lithium manganese oxide after the reaction is finished.
S3: and (3) putting the lithium manganese oxide into a 1.0mol/L hydrochloric acid solution for exchange for 12 hours, and completely removing lithium per se to obtain the high-efficiency lithium ion sieve material.
1.0g of manganese-based oxide lithium ion sieve prepared in the comparative example is used for absorbing and extracting lithium from 1.0L of saturated lithium chloride solution, then delithiation is carried out in 1mol/L of 1.0L of hydrochloric acid solution, and the lithium concentration in the hydrochloric acid is 14.27mg/L through atomic absorption spectrophotometry.
The above examples 1 to 5 and the comparative example were subjected to tests of lithium adsorption effect, and the specific test results are shown in table 1:
| lithium concentration in solution (mg/L) | |
| Example 1 | 38.65 |
| Example 2 | 28.31 |
| Example 3 | 29.87 |
| Example 4 | 32.34 |
| Example 5 | 34.61 |
| Comparative example | 14.27 |
TABLE 1
As can be seen from the adsorption effect of the materials prepared in the above-mentioned examples and comparative examples on lithium, the effect of adsorbing and extracting lithium ions of the manganese-based lithium ion sieve material prepared by the conventional solid phase synthesis method is far less than that of the manganese-based lithium ion sieve material prepared by the method provided by the present invention, and meanwhile, in the present invention, example 1 is the most preferred example.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the manganese-based oxide lithium ion sieve is characterized by comprising the following steps of:
s1: directly mixing a solid self-polymerization monomer reagent and solid total metal salt, wherein the solid total metal salt is a mixture of solid manganese salt and solid lithium salt;
s2: putting the solid mixture obtained in the step S1 into a crucible and placing the crucible in a muffle furnace;
s3: directly taking air as atmosphere, heating the solid mixture to 750-950 ℃ at the heating rate of 1-10 ℃, maintaining the temperature for 1-3 h, and obtaining lithium manganese oxide after calcination;
s4: and (3) immersing the lithium manganese oxide material in the S3 into a hydrochloric acid solution for lithium ion exchange to obtain the lithium ion sieve material.
2. The method of claim 1, wherein the solid self-polymerizing reagent in step S1 is one or more selected from the group consisting of citric acid, maleic acid, and ethylenediaminetetraacetic acid.
3. The method of claim 1, wherein the solid manganese salt in step S1 is solid manganese acetate, manganese sulfate or manganese chloride.
4. The method of claim 1, wherein the solid lithium salt in step S1 is solid lithium acetate, lithium chloride, lithium sulfate or lithium nitrate.
5. The method of claim 1, wherein the molar ratio of the solid self-polymerizing monomer reagent to the solid total metal salt in step S1 is 0.5 to 5:1.
6. The method of claim 5, wherein the molar ratio of solid manganese salt to solid lithium salt in the total solid metal salts is 2:1.
7. The method of claim 1, wherein the hydrochloric acid solution has a concentration of 0.1 to 3mol/L and the immersion exchange time is 5 to 24 hours in step S4.
8. The manganese-based oxide lithium ion sieve prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the manganese-based oxide lithium ion sieve of claim 8 in lithium extraction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461064A (en) * | 2003-06-19 | 2003-12-10 | 南京大学 | Method for preparing lithium manganese oxide by using low-heat solid phase reaction |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461064A (en) * | 2003-06-19 | 2003-12-10 | 南京大学 | Method for preparing lithium manganese oxide by using low-heat solid phase reaction |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
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