CN112076717A - Method for preparing lithium ion sieve through melt impregnation reaction - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005470 impregnation Methods 0.000 title claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000000155 melt Substances 0.000 claims abstract description 17
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-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
- 230000035484 reaction time Effects 0.000 claims description 6
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 5
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 4
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- WNCZOFYWLAPNSS-UHFFFAOYSA-M lithium;3-carboxy-3,5-dihydroxy-5-oxopentanoate Chemical compound [Li+].OC(=O)CC(O)(C(O)=O)CC([O-])=O WNCZOFYWLAPNSS-UHFFFAOYSA-M 0.000 claims description 2
- SQWDGUOWCZUSAO-UHFFFAOYSA-L manganese(2+);diformate;dihydrate Chemical compound O.O.[Mn+2].[O-]C=O.[O-]C=O SQWDGUOWCZUSAO-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910015645 LiMn Inorganic materials 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 229910004251 HMn2O4 Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 8
- 229910004255 HMnO2 Inorganic materials 0.000 description 7
- 239000012267 brine Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- 235000006748 manganese carbonate Nutrition 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 5
- 229940093474 manganese carbonate Drugs 0.000 description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- -1 pegmatite Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
Abstract
The invention discloses a method for preparing a lithium ion sieve by a melt impregnation reaction, which comprises the steps of preparing a porous manganese source by taking a soluble manganese source and a template agent as raw materials, and preparing a spinel-type manganese-series lithium ion sieve precursor LiMn with a porous structure by taking the porous manganese source and a lithium source as raw materials and adopting a melt impregnation method2O4Then treating the precursor with an acidic solution to obtain the lithium ion sieve material HMn2O4. According to the method for preparing the porous lithium ion sieve by the melt impregnation reaction, reactants can be mixed at an atomic level, the pore structure of the porous manganese source is reserved, and the prepared lithium ion sieve material is high in adsorption speed and high in adsorption capacity.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a method for preparing a lithium ion sieve through a melt impregnation reaction.
Background
With the continuous improvement of the pursuit of people for good life and green water mountains, the demand of the market for lithium resources is increasing day by day. Lithium is an important strategic resource, and the existence form in nature is mainly divided into two types, wherein the first type is ores such as spodumene, pegmatite, lepidolite and the like, and accounts for 21.6 percent of the reserve of lithium resources. The second type is salt lake brine and seawater, accounting for 78.3% of the total lithium resources (Progress in Materials Science 84(2016) (276) -313).
Conventional lithium ore resources are being increasingly reduced. Therefore, the method has very important significance for extracting lithium resources from liquid lithium sources such as salt lake brine and seawater. Although the lithium storage capacity in salt lake brine is huge in China, the phenomena of low concentration and high magnesium-lithium ratio generally exist. The mature lithium extraction process applied to the low-magnesium lithium salt lake in other countries is not suitable for the brine of the salt lake in China, and the difficulty coefficient of extracting lithium from the brine in the China by seawater is increased.
The liquid lithium extraction method mainly comprises a precipitation method, a solvent extraction method, a salt exposure method, a membrane Separation and adsorption method (Separation and Purification Technology 172(2017)388-403) and the like, wherein the ion adsorption method is the best method for extracting lithium from the salt lake brine with high magnesium lithium and low lithium concentration. The manganese series lithium ion sieve material is the best choice by comprehensively considering the aspects of selectivity, manufacturing cost, adsorption and desorption efficiency, energy consumption and the like of the material.
However, the manganese-based lithium ion sieve material obtained by the traditional sintering method is difficult to mix at an atomic level, and the generation of a heterogeneous phase is difficult to avoid in the reaction process, so that the adsorption capacity of the material is reduced. The melt impregnation method can not only realize the atomic-scale mixing of reactants, but also retain the porous structure of the manganese source (battery, 2011,41(06): 297) 300), thereby preparing the porous lithium ion sieve material with pure spinel phase and faster ion exchange rate.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing a lithium ion sieve by a melt impregnation reaction, which improves the phase purity of a lithium ion sieve material, introduces a porous structure, enables the lithium ion sieve material to have higher adsorption capacity and ion exchange rate, and solves the problem of material adsorption capacity reduction caused by impurity phase generation in the traditional sintering method.
The technical scheme is as follows: the invention relates to a method for preparing a lithium ion sieve by a melt impregnation reaction, which comprises the following steps:
(1) respectively adding a soluble manganese source and a template agent into a solvent, and stirring to obtain a mixed solution;
(2) transferring the mixed solution to a stainless steel high-pressure reaction kettle with a Teflon lining, carrying out hydrothermal reaction at a first temperature, naturally cooling the mixed solution to room temperature after the reaction is finished, filtering, washing and drying to obtain a porous manganese source;
(3) according to a molar ratio of Li to Mn of 1: weighing the porous manganese source and the lithium source by 0.7-4, and pouring the porous manganese source and the lithium source into a mixing device for mixing until the porous manganese source and the lithium source are uniformly mixed;
(4) quickly heating the mixed solid to a second temperature for reaction, continuously heating to a third temperature for reaction after the reaction is finished, and naturally cooling to room temperature after the reaction is finished to obtain a lithium ion sieve precursor LiMn2O4Powder;
(5) and putting the lithium ion sieve precursor powder into an acid solution according to a certain solid-to-liquid ratio for elution, and then filtering, washing and drying to obtain the porous lithium ion sieve material.
Further, the soluble manganese source in the step (1) is one or more of manganese chloride tetrahydrate, manganese acetate tetrahydrate, manganese sulfate monohydrate, potassium permanganate, manganese nitrate, manganese oxalate dihydrate and manganese formate dihydrate; the template agent is one or more of PEG-1200, PVP (K-30) and urea.
Further, the solvent is one or more of ethylene glycol, water and isopropanol.
Further, the stirring time in the step (1) is 0.4-5 hours.
Further, in the step (2), the first temperature is 100-280 ℃, and the reaction time is 4-72 hours.
Further, in the step (3), the lithium source is one or more of lithium acetate, lithium hydroxide monohydrate, lithium nitrate, lithium chloride, lithium citrate tetrahydrate, lithium oxalate and dilithium oxalate.
Further, in the step (4), the second temperature is 80-400 ℃, and the reaction time is 1-8 hours; the third temperature is 400-1200 ℃, and the reaction time is 5-48 h.
Further, the solid-to-liquid ratio in the step (5) is 0.5-10 g/L.
Further, in the step (5), the acidic solution is one or more of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, ammonium persulfate and ammonium bisulfate, the concentration of the acidic solution is 0.01-10M, and the elution time is 4-72 h.
Further, filtering, washing and drying the mixed solution in the step (2), and heating or calcining to obtain the porous manganese source.
The porous manganese source is prepared by reacting a soluble manganese source, such as:
(1) preparation of porous manganese carbonate
Weighing 2-6 g of manganese chloride tetrahydrate, dissolving in 30-80 mL of ethylene glycol, and adding 0.5-1.5 g of PEG-1200 and a small amount of deionized water; weighing urea according to a molar ratio of manganese chloride tetrahydrate to urea of 1:4, and slowly dripping the mixed solution while stirring to obtain a uniform suspension; the mixture is stirred vigorously for 0.4-5 h, transferred into a Teflon lining stainless steel high-pressure reaction kettle and subjected to hydrothermal reaction at 140-280 ℃ for 4-18 h; cooling to room temperature, performing centrifugal separation, washing the sample with deionized water and absolute alcohol sequentially for one time and three times, and drying at 80 ℃ in vacuum for 12 hours to obtain the porous manganese carbonate.
(2) Preparation of porous manganese sesquioxide
Weighing a small amount of manganese acetate tetrahydrate and urea according to a molar ratio of 1:9, respectively adding 20-60 mL of ethylene glycol, continuously stirring the mixture for 0.4-5 h, transferring the mixture into a Teflon-lined stainless steel high-pressure reaction kettle, and carrying out hydrothermal reaction at 130-230 ℃ for 16-72 h; cooling to room temperature, performing centrifugal separation, washing the sample with deionized water and absolute alcohol sequentially for one time and three times, drying at 80 ℃ in vacuum for 12 hours, heating the synthesized sample under air atmosphere, and raising the temperature at the rate of 0.5-5 ℃ per minute-1And heating to 450-800 ℃ for reaction for 4-12 h to obtain the porous trimanganese tetroxide.
(3) Preparation of porous mangano-manganic oxide
Weighing a small amount of manganese sulfate monohydrate, PVP (K-30) and sodium hypochlorite according to a molar ratio of 1:1:2, adding 50mL of deionized water, violently stirring the mixture to clarify the solution, transferring the solution into a stainless steel high-pressure reaction kettle with a Teflon lining, carrying out hydrothermal reaction at 100-200 ℃ for 10-16 h, naturally cooling to room temperature, filtering pure black precipitates, washing the sample with deionized water and absolute alcohol for one time and three times in sequence, drying in the air at 60 ℃ for 5h, and carrying out reduction reaction on the sample at 250-350 ℃ for 2-6 h to obtain the porous trimanganese tetroxide.
(4) Preparation of porous manganese dioxide
Weighing a small amount of potassium permanganate and manganese sulfate according to a molar ratio of 4:5, weighing a small amount of PVP (K-30), adding into 50-100 mL of deionized water, adding 70mL of isopropanol into the mixed solution, and stirring for 0.4-5 h; transferring the mixture into a Teflon-lined stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction at 100-180 ℃ for 24-72 h, cooling the mixture to room temperature, carrying out centrifugal separation, washing the sample with deionized water and absolute alcohol for one time and three times in sequence, and calcining the powder at 300-400 ℃ for 5h in an argon atmosphere to obtain the porous manganese dioxide.
Compared with the prior art, the invention has the advantages that:
(1) the material of the invention reserves the pore structures of the porous manganese source, and the pore structures are beneficial to the diffusion of lithium ions among pore channels, thereby improving the ion exchange rate, shortening the cycle period of adsorption and desorption and harvesting higher economic benefit;
(2) the raw materials used by the material are economical and easy to obtain, and the preparation process is simple;
(3) the material has high uniformity and good adsorption selectivity, and can have good enrichment effect on liquid lithium resources from resources such as salt lake brine, seawater and the like;
(4) the material is green and environment-friendly and can be recycled for multiple times.
Drawings
FIG. 1 is an SEM scan of a porous lithium ionic sieve precursor prepared according to the present invention;
FIG. 2 is an SEM scan of a porous lithium ion sieve prepared according to the present invention;
FIG. 3 is an XRD diffraction pattern of a porous lithium ionic sieve precursor and a porous lithium ionic sieve prepared by the invention;
fig. 4 is a graph showing the adsorption performance of the porous lithium ion sieve prepared according to the present invention.
Detailed Description
The invention is further described below with reference to the following figures and examples:
example 1
Preparation of porous manganese sesquioxide
Respectively weighing 2.45g and 5.4g of manganese acetate tetrahydrate and urea according to a molar ratio of 1:9, adding 50mL of ethylene glycol, continuously stirring the mixture for 0.4h, transferring the mixture into a Teflon-lined stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, washing the sample once or three times by deionized water and absolute alcohol in sequence, drying at 80 ℃ in vacuum for 12h, heating the synthesized sample under an air atmosphere, and increasing the temperature at the rate of 2 ℃ min-1Heating to 600 ℃ and reacting for 10h to obtain porous manganese sesquioxide;
porous lithium ion sieve precursor LiMn2O4Preparation of
The porous manganese sesquioxide and the lithium nitrate are mixed according to a molar ratio of 1: 0.35 weigh 1.58g and 0.24g, respectively. Transferring the mixed powder to a planetary ball mill, setting the rotating speed to be 60r/min, changing the running direction every 30min, quickly heating the powder to 400 ℃ after ball milling for 6h, reacting for 1h at the temperature, then heating to 750 ℃, reacting for 10h at the temperature, and naturally cooling to room temperature to obtain a lithium ion sieve precursor LiMn2O4And (3) powder.
Preparation of lithium ion sieve material HMnO2
Putting the precursor powder into acetic acid with the concentration of 5M for elution for 72h at the solid-to-liquid ratio of 4g/L under magnetic stirring, then filtering, washing the sample for one time and three times by using deionized water and absolute alcohol in sequence, and drying the powder for 10h at the temperature of 80 ℃ to obtain HMnO2A lithium ion sieve material, wherein figure 1 shows a lithium ion sieve precursor LiMn2O4Fig. 2 is an SEM scan of the porous lithium ion sieve, fig. 3 is an XRD diffractogram of the porous lithium ion sieve precursor and the porous lithium ion sieve, and fig. 4 is an adsorption performance graph of the porous lithium ion sieve.
The existing manganese series lithium ion sieve adsorbent is compared with the lithium ion sieve adsorbent prepared by the invention:
reference example 1: nonferrous Metals (extraction Metals), 2008(6):31(in Chinese);
reference example 2: water Research 87(2015) 320-327;
comparative example 3 document Xuxin, microwave liquid phase synthesis of lithium ion adsorbing material and its adsorption performance [ D ]. university of east China, 2014.
TABLE 1 comparison of conventional Mn-based lithium ion sieve adsorbents with the lithium ion sieve adsorbent prepared according to the present invention
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Prepared by the invention | |
| Chemical formula (II) | HMn1.85Ni0.15O4 | HMO | H1.6Mn1.6O4 | HMnO2 |
| Adsorption capacity | 18.3mg/g | 15.2mg/g | 22.19mg/g | 24.8mg/g |
| Adsorption period | 34h | 12h | 20h | 10h |
| Desorption cycle | 10h | 24h | 24h | 2h |
| Topographic features | Nano granular morphology | Irregular morphology | Nano granular morphology | Morphology of agglomerated nanoparticles |
Example 2
Preparation of porous manganese carbonate
Respectively weighing 1.98g and 1.8g of manganese chloride tetrahydrate and urea according to the molar ratio of 1:3, adding 50mL of ethylene glycol, and dissolving; weighing 10g of deionized water, and slowly dripping the mixed solution under stirring to obtain uniform suspension; the mixture is stirred vigorously for 3h, the mixture is transferred into a Teflon-lined stainless steel high-pressure reaction kettle, hydrothermal reaction is carried out for 16h at 190 ℃, after the mixture is cooled to room temperature, centrifugal separation is carried out, the sample is washed by deionized water and absolute alcohol for one time and three times in sequence, and drying is carried out for 12h at 80 ℃ in vacuum, so as to obtain the porous manganese carbonate;
porous lithium ion sieve precursor LiMn2O4Preparation of
Porous manganese carbonate and lithium hydroxide monohydrateAccording to a molar ratio of 1:4 weigh 1.15g and 1.68g, respectively. Transferring the mixed powder into 100ml of deionized water, and carrying out ultrasonic treatment for 20min to obtain uniformly dispersed suspension; transferring the suspension to a feed port of a spray dryer, setting the drying temperature to be 170 ℃, the sample injection speed to be 1L/h, collecting the obtained mixed powder from a discharge port, quickly heating to 80 ℃, reacting for 8h at the temperature, subsequently heating to 1200 ℃, reacting for 5h at the temperature, and naturally cooling to room temperature to obtain a lithium ion sieve precursor LiMn2O4And (3) powder.
Preparation of lithium ion sieve material HMnO2
Putting the precursor powder into hydrochloric acid with the concentration of 0.01M for elution for 30 hours at the solid-to-liquid ratio of 0.5g/L under magnetic stirring; then filtering, washing the sample with deionized water and absolute alcohol sequentially for one time and three times, and drying the powder at 80 ℃ for 10h to obtain HMnO2A lithium ion sieve material.
Example 3
Preparation of porous manganese dioxide
Respectively weighing 0.47g of potassium permanganate and 1.3g of manganese sulfate according to a molar ratio of 4:5, adding 0.1g of PVP (K-30) into 50mL of deionized water to obtain a mixed solution, adding 70mL of isopropanol into the mixed solution, and stirring for 5 hours; transferring the mixture into a Teflon-lined stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 36h, cooling the mixture to room temperature, carrying out centrifugal separation, washing the sample with deionized water and absolute alcohol for one time and three times in sequence, and finally calcining the powder at 350 ℃ for 5h in an argon atmosphere to obtain porous manganese dioxide;
porous lithium ion sieve precursor LiMn2O4Preparation of
Porous manganese dioxide and lithium acetate are mixed according to a molar ratio of 1: 2.05 weighing 1.74g and 2.71g respectively, transferring the weighed materials into a watch glass filled with 5ml of deionized water, carrying out ultrasonic treatment for 15min in the watch glass to obtain uniformly dispersed slurry, placing the watch glass in a constant-temperature oven at 90 ℃ until a dry cake-shaped solid is formed, rapidly heating the cake-shaped solid to 320 ℃, reacting for 4 hours at the temperature, then heating to 400 ℃, and reacting for 48 hours at the temperature; naturally cooling to room temperature to obtain the LiMn precursor of the lithium ion sieve2O4And (3) powder.
Preparation of lithium ion sieve material HMnO2
Putting the precursor powder into 4.5M sulfuric acid with the concentration of 10g/L for elution for 12h under magnetic stirring, then filtering, washing the sample with deionized water and absolute alcohol sequentially for one time and three times, and drying the powder for 10h at 80 ℃ to obtain HMnO2A lithium ion sieve material.
Claims (10)
1. A method for preparing a lithium ion sieve by a melt impregnation reaction is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively adding a soluble manganese source and a template agent into a solvent, and stirring to obtain a mixed solution;
(2) transferring the mixed solution to a stainless steel high-pressure reaction kettle with a Teflon lining, carrying out hydrothermal reaction at a first temperature, naturally cooling the mixed solution to room temperature after the reaction is finished, filtering, washing and drying to obtain a porous manganese source;
(3) according to a molar ratio of Li to Mn of 1: weighing the porous manganese source and the lithium source by 0.7-4, and pouring the porous manganese source and the lithium source into a mixing device for mixing until the porous manganese source and the lithium source are uniformly mixed;
(4) quickly heating the mixed solid to a second temperature for reaction, continuously heating to a third temperature for reaction after the reaction is finished, and naturally cooling to room temperature after the reaction is finished to obtain a lithium ion sieve precursor LiMn2O4Powder;
(5) and putting the lithium ion sieve precursor powder into an acid solution according to a certain solid-to-liquid ratio for elution, and then filtering, washing and drying to obtain the porous lithium ion sieve material.
2. The method of claim 1, wherein the melt impregnation reaction is performed by: the soluble manganese source in the step (1) is one or more of manganese chloride tetrahydrate, manganese acetate tetrahydrate, manganese sulfate monohydrate, potassium permanganate, manganese nitrate, manganese oxalate dihydrate and manganese formate dihydrate; the template agent is one or more of PEG-1200, PVP (K-30) and urea.
3. The method of claim 1, wherein the melt impregnation reaction is performed by: the solvent is one or more of ethylene glycol, water and isopropanol.
4. The method of claim 1, wherein the melt impregnation reaction is performed by: the stirring time in the step (1) is 0.4-5 h.
5. The method of claim 1, wherein the melt impregnation reaction is performed by: the first temperature in the step (2) is 100-280 ℃, and the reaction time is 4-72 hours.
6. The method of claim 1, wherein the melt impregnation reaction is performed by: and (3) the lithium source is one or more of lithium acetate, lithium hydroxide monohydrate, lithium nitrate, lithium chloride, lithium citrate tetrahydrate, lithium oxalate and dilithium oxalate.
7. The method of claim 1, wherein the melt impregnation reaction is performed by: in the step (4), the second temperature is 80-400 ℃, and the reaction time is 1-8 h; the third temperature is 400-1200 ℃, and the reaction time is 5-48 h.
8. The method of claim 1, wherein the melt impregnation reaction is performed by: the solid-liquid ratio in the step (5) is 0.5-10 g/L.
9. The method of claim 1, wherein the melt impregnation reaction is performed by: the acidic solution in the step (5) is one or more of acetic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, ammonium persulfate and ammonium bisulfate, the concentration of the acidic solution is 0.01-10M, and the elution time is 4-72 h.
10. The method of claim 1, wherein the melt impregnation reaction is performed by: and (3) filtering, washing and drying the mixed solution in the step (2), and heating or calcining to obtain the porous manganese source.
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