CN117069082A - Preparation method and application of mesoporous zirconium phosphate type lithium ion adsorption material - Google Patents
Preparation method and application of mesoporous zirconium phosphate type lithium ion adsorption material Download PDFInfo
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- CN117069082A CN117069082A CN202311130593.9A CN202311130593A CN117069082A CN 117069082 A CN117069082 A CN 117069082A CN 202311130593 A CN202311130593 A CN 202311130593A CN 117069082 A CN117069082 A CN 117069082A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 32
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 26
- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 3
- 239000011574 phosphorus Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 21
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical group [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 15
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910001463 metal phosphate Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 zirconium organic compound Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000012257 stirred material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 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
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- 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
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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Abstract
The preparation method of the mesoporous zirconium phosphate type lithium ion adsorption material comprises the following steps: mechanically mixing a zirconium source, a phosphorus source and a template agent according to a proportion; transferring the mixed materials into a drying box for drying; and calcining the material in an air atmosphere to obtain the mesoporous zirconium phosphate for lithium ion adsorption. The invention relates to a preparation method of a mesoporous zirconium phosphate type lithium ion adsorption material and a performance study of selective adsorption separation of lithium ions. The preparation method adopts zirconium organic precursors and phosphate as raw materials, a segmented copolymer as a template agent, and the mesoporous zirconium phosphate is obtained after mechanical mixing, solidification and calcination according to a certain proportion.
Description
Technical field:
the invention relates to a lithium ion adsorption material, in particular to a preparation method of a mesoporous zirconium phosphate type lithium ion adsorption material.
The background technology is as follows:
in recent years, due to the widespread use of lithium ion batteries in electronic products and electric automobiles, the global consumption of lithium has rapidly increased, and battery-grade lithium hydroxide and lithium carbonate mainly come from LiCl concentration in solar evaporation ponds in south america and hard rock mining in australia. Because of the first two relatively complex, geothermal brines have been identified as a possible alternative source of lithium, particularly in the united states, and various adsorbents have been developed to exploit this resource. Other more sustainable sources of lithium include recycling scrap lithium ion batteries. How to efficiently extract lithium from geothermal brine, other land lithium resources, and lithium ion battery waste streams is a topic of great scientific and industrial interest to continue the "lithium revolution" and strive to achieve a green, more sustainable future.
About 76% of the global lithium resources are present in brine, and lithium, a common alkali metal, has strong electrochemical activity and is a valuable element in the battery industry. The existing lithium extraction method comprises an evaporation crystallization method, a 3-membrane filtration method, a 4-calcination leaching method, a 5-precipitation method, a 6-ion exchange method and a 7-adsorption method, wherein the adsorption method has the advantages of easy regeneration, simple operation, high recovery rate and the like, and is one of the most promising lithium extraction methods.
The lithium ion exchange process is based on a material that absorbs and releases Li according to a change in pH, and when the pH is low, the material absorbs H and releases Li. At high pH, the material absorbs Li, releasing H. The existing preparation method has the defects of low specific surface area, incapability of fully contacting with lithium-containing solution, slower speed of the deintercalation process, poor adsorption quantity and the like, and cannot be industrialized, so that the method is a difficult problem to be solved urgently.
Disclosure of Invention
Aiming at the production technical defects of higher synthesis cost, poor lithium adsorption capacity, inapplicability to industrial production and the like, the invention provides the preparation method of the mesoporous zirconium phosphate type lithium ion adsorption material, which has simple and feasible operation steps and environment-friendly raw materials.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the mesoporous zirconium phosphate type lithium ion adsorption material comprises the following steps:
a, putting a zirconium organic compound, phosphate and a template agent into a small bottle according to a certain proportion;
b, uniformly stirring the medicines;
c, placing the stirred material in an oven for drying;
d, calcining the obtained product after drying is finished to obtain the mesoporous zirconium phosphate material for lithium ion adsorption;
e, washing the obtained material with an acid solution, removing inorganic salt, and washing with deionized water to be neutral.
The steps are as follows
The molar ratio of the zirconium n-butoxide to the triethyl phosphate in the step a is preferably 1:1 to 3:1, and the required template agent is 1-2 g for every 10mmol of zirconium n-butoxide.
And b, stirring for 6-8h.
The drying temperature in the step c is preferably 60-70 ℃ and the time is 12-24h.
The calcination temperature in step d is preferably 400-600 ℃ and the time is 1-8h.
And e, stirring each 40mg of the final product in 20-50mL of 1M hydrochloric acid solution for 12-24 hours, washing to be neutral, and drying.
The beneficial effects of the invention are as follows:
(1) The invention relates to a preparation method of a mesoporous zirconium phosphate type lithium ion adsorption material and a performance study of selective adsorption separation of lithium ions. The preparation method adopts zirconium organic precursors and phosphate as raw materials, a segmented copolymer as a template agent, and the mesoporous zirconium phosphate is obtained after mechanical mixing, solidification and calcination according to a certain proportion. On the basis, the mesoporous zirconium phosphate and a lithium source are ground and calcined at high temperature, so that the aim that lithium ions uniformly enter a zirconium phosphate skeleton is fulfilled, and then the lithium ions are extracted and intercalated by an acid treatment method, so that rich ion cavities are formed.
(2) The mesoporous zirconium phosphate is prepared by a simple and green solvent-free method, and has the characteristics of short time consumption in the synthesis process and no pollution to the environment;
(3) The mesoporous zirconium phosphate prepared by the method has the characteristics of large specific surface and uniform pore diameter;
(4) The product prepared by the method has no toxicity and is easy to recycle, and is an ideal adsorption material;
(5) The preparation method of the invention adopts zirconium organic compounds and phosphate as raw materials, and the segmented copolymer is used as a template agent, and mesoporous zirconium phosphate is obtained after mechanical mixing, solidification and calcination.
(6) The preparation method has the advantages of simple and easy operation steps, environment-friendly raw materials, and no wastewater in the preparation process.
Description of the drawings:
FIG. 1 is a XRD spectrum for the preparation of ZrPO-1, zrPO-2, zrPO-3;
FIG. 2 is a FI-TR diagram of ZrPO-1, zrPO-2, zrPO-3;
FIG. 3 is a graph showing the low temperature nitrogen adsorption and desorption curves for ZrPO-1, zrPO-2, zrPO-3.
FIG. 4 is a graph showing adsorption capacity versus adsorption time for ZrPO-1, zrPO-2, zrPO-3
The specific implementation method comprises the following steps:
the following describes the specific implementation method of the present invention in detail. The specific embodiments described herein are offered by way of illustration and explanation only, and are not intended to limit the invention.
The preparation method of the mesoporous zirconium phosphate type lithium ion adsorption material comprises the following steps:
c, putting the zirconium organic compound, phosphate and template agent into a small bottle according to a certain proportion;
d, uniformly stirring the medicines;
c, placing the stirred material in an oven for drying;
d, calcining the obtained product after drying is finished to obtain the mesoporous zirconium phosphate material for lithium ion adsorption; washing the obtained material with an acid solution to remove inorganic salts, and washing with deionized water to neutrality; every 40mg of the final product is stirred in 20-50mL of 1M hydrochloric acid solution for 12-24 hours, washed to be neutral and dried.
The method for removing Li ions by using the material comprises the following steps: 40mg of the final product is stirred in 20-50mL of 0.5M hydrochloric acid solution for 12-24h, washed to neutrality and dried.
The method for removing Li ions by using the material can also be as follows: the Li ion removing method comprises the following steps: 40mg of the final product is stirred in 20-50mL of 1M hydrochloric acid solution for 12-24h, washed to be neutral and dried.
The product prepared by the method is compared with the existing product:
example 1
4.84g of zirconium n-butoxide (80%), 1.82g of triethyl phosphate and 1.5g of P123 are weighed into a small flask, stirred for 6 hours in magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-1.
Example 2
4.84g of zirconium n-butoxide (80%), 1.82g of triethyl phosphate and 1.5g of F127 are weighed into a small flask, stirred for 6 hours in magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-2.
Example 3
4.84g zirconium n-butoxide (80%), 1.82g triethyl phosphate and 1.5g CTAB are weighed into a small flask, stirred in magnetic force for 6 hours to be uniformly mixed, then spread on a surface dish, put into an oven to keep the constant temperature at 65 ℃ for 24 hours, and heated to 500 ℃ at 2 ℃/min under the air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-3.
Example 4
4.84g of zirconium n-butoxide (80%), 1.82g of triethyl phosphate and 2g of P123 are weighed into a small flask, stirred for 6 hours under magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-4.
Example 5
4.84g of zirconium n-butoxide (80%), 1.82g of triethyl phosphate and 2g of F127 are weighed into a small flask, stirred for 6 hours under magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-5.
Example 6
5.0g of zirconium n-butoxide (80%), 1.82g of triethyl phosphate and 2g of F127 are weighed into a small flask, stirred for 6 hours under magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-6.
Example 7
4.84g of zirconium n-butoxide (80%), 2g of triethyl phosphate and 2g of F127 are weighed into a small flask, stirred for 6 hours under magnetic force, uniformly mixed, then spread on a surface dish, put into an oven at constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-7.
Example 8
5g of zirconium n-butoxide (80%), 2g of triethyl phosphate and 2g of F127 are weighed into a small flask, stirred for 6 hours in a magnetic force to be uniformly mixed, then spread on a surface dish, put into an oven to be kept at a constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under an air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-8.
Example 9
5g of zirconium n-butoxide (80%), 2g of triethyl phosphate and 2g of F127 are weighed into a small flask, stirred for 10 hours in a magnetic force to be uniformly mixed, then spread on a surface dish, put into an oven to be kept at a constant temperature of 65 ℃ for 24 hours, heated to 500 ℃ at 2 ℃/min under an air atmosphere, and calcined for 6 hours. The resulting sample was labeled ZrPO-9.
Comparative example 1
5g of zirconium n-butoxide (80%), 2g of triethyl phosphate, 2g of F127 are stirred in a magnetic stirrer for 10h. The resulting product was then washed to neutrality with 50mL of 1M dilute sulfuric acid, washed with deionized water, and the initial product was directly placed in an oven and dried at 900℃for 18h, followed by mixing the product with Li 2 CO 3 The mass ratio is 1:1, calcining for 4 hours at 900 ℃ in air after grinding uniformly, and finally, washing the obtained product to be neutral and drying after stirring for 24 hours in 1M hydrochloric acid solution, and marking the product as ZrPO-10.
Comparative example 2
Pouring 20g of absolute ethyl alcohol and a certain amount of ethylenediamine alkaline modifier into a beaker, standing for 30min, then filling the solution into a three-neck flask, weighing 5g of alkaline-washed activated carbon, and pouring into the three-neck flask. The three-neck flask is placed in a constant-temperature water bath kettle, sealed and stirred for 24 hours at the temperature of 80 ℃, and dried at the temperature of 120 ℃ for standby after the reaction is finished, and is marked as ZrPO-11.
Lithium ion adsorption performance test: the adsorbents prepared in the above examples were ground into powder for evaluation of adsorption performance of pure lithium solution. The test conditions were as follows: the amount of the adsorbent was 40mg, 50mL of a solution having an initial lithium ion concentration of 100ppm was used as the lithium-containing solution, the solution was pH=7 and pH=10, the reaction was carried out at 25℃for 12 hours, and the adsorption amount was measured.
Table 1 is a statistical table of the lithium absorption properties of the inventive examples 1-3 in a 100ppm pure lithium solution
FIG. 1 is the XRD patterns of examples 1-3. It can be seen from the figure that the synthesized ZrPO-1, zrPO-2 and ZrPO-3 have no obvious corresponding crystal diffraction peaks, and that the ZrPO-1 and the ZrPO-2 have an amorphous broad peak only in the range of 2θ=15° -35 °, and that the ZrPO-3 has a broad peak in the range of 2θ=15 ° -35 ° and 40 ° -70 °, respectively, which is consistent with the mesoporous metal phosphate reported in most documents. The amorphous peaks of the XRD patterns indicate that the three metal phosphates synthesized are amorphous or low in crystallinity and porous.
FIG. 2 is the FT-IR chart of examples 1-3. To further analyze the radical composition of the three metal phosphates, FT-IR spectroscopic analysis was performed on the samples. As can be seen from FIG. 2, all three phosphates are at 1033cm -1 ，1639cm -1 ，3450cm -1 The infrared absorption peaks appear and are respectively attributed to symmetrical vibration of P-O bonds in-PO 4, stretching vibration of hydroxyl groups and stretching vibration of surface water molecules. The infrared analysis result shows that the metal phosphate skeletonIs formed to assist the XRD results.
The catalyst was analyzed for texture parameters by low temperature nitrogen adsorption-desorption characterization, with nitrogen adsorption-desorption isotherms as shown in fig. 3, and structural parameters as shown in table 2 (either providing no 3-1 missing or table 1). As can be seen from FIG. 3, all three phosphates show IV type isothermal adsorption and desorption curves, which indicate that mesoporous structures exist, wherein ZrPO-2 shows H3 type hysteresis loops which are commonly found in lamellar porous structures generating slits, and have more obvious N in a low specific pressure region 2 The adsorption quantity is related to micropore filling, and the adsorption isotherm still has an ascending trend in the range of the specific pressure of 0.7-1, which shows that the adsorption quantity has larger mesopores and the pore size distribution is irregular; the ZrPO-1 and ZrPO-3 have a saturated adsorption platform and an H1 type hysteresis loop in the interval of the relative specific pressure of 0.5-1, which indicates that the material has a uniform mesoporous structure. As can be seen from the texture parameters summarized in Table 3-2, zrPO-1 had the largest specific surface area (402.2 m 2 Per g), followed by ZrPO-2 (367.8 m) 2 /g)、ZrPO-3(136.7m 2 /g). The large specific surface area can carry more active sites, provides a larger contact surface for molecular reaction, and the large pore size can provide a larger molecular movement space, so that the specific surface area and the pore size are both important factors for determining the catalytic performance of the catalytic material.
FIG. 4 shows the relationship between the adsorption capacity of the mesoporous zirconium phosphate type lithium ion sieve material and the adsorption time at room temperature. The result shows that the adsorption capacity of lithium ions has an ascending trend along with the adsorption time, and the performance of the mesoporous zirconium phosphate type lithium ion sieve material is obviously better than that of the comparative example. In the test process, when the adsorption time reaches 15h, the adsorption capacities of the adsorbents ZrPO-1 and ZrPO-2 reach a saturation value of 22.5mg/g, and the adsorption efficiency is obviously better than that of the comparative adsorbent ZrPO-3 under the same condition.
TABLE 2 structural parameters of zirconium phosphates prepared in examples 1-3
The series of materials show excellent performance in lithium solution selective adsorption lithium ion experiments. In summary, the preparation method has the outstanding advantage of adopting a green and simple solvent-free synthesis technology. The preparation method is simple, mild in condition, large in specific surface and uniform in aperture, is favorable for full contact of lithium-containing liquid and is convenient for lithium ion deintercalation. The adsorption material has stable structure, low dissolution loss and long cycle life, and is favorable for showing important potential industrial application value in the fields of lithium ion adsorption and purification.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. Various components mentioned in the present invention are common in the art, and it should be understood by those skilled in the art that the present invention is not limited by the above embodiments, and the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications can be made in the present invention without departing from the spirit and scope of the invention, which is defined in the claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the mesoporous zirconium phosphate type lithium ion adsorption material comprises the following steps:
the first step: mechanically mixing a zirconium source, a phosphorus source and a template agent according to a proportion;
and a second step of: transferring the mixed materials into a drying box for drying;
and a third step of: and calcining the material in an air atmosphere to obtain the mesoporous zirconium phosphate for lithium ion adsorption.
2. The method of manufacturing according to claim 1, characterized in that: the zirconium source is zirconium n-butoxide, zirconium phosphate or zirconium acetylacetonate; the phosphate is triethyl phosphate, tributyl phosphate or diethyl phosphate.
3. The method of manufacturing according to claim 1, characterized in that: the mol ratio of the zirconium n-butoxide to the triethyl phosphate is 1:1 to 3:1, and the required template agent is 1 to 2g per 10mmol of zirconium n-butoxide.
4. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the zirconium source to the phosphorus source is 1-6:1.
5. The method of manufacturing according to claim 1, characterized in that: the template agent is a block copolymer.
6. The method of manufacturing according to claim 1, characterized in that: the template agent is P123, F127 or CTAB.
7. The method of manufacturing according to claim 1, characterized in that: the mechanical mixing method is that a zirconium source, phosphate and a template agent are placed in a small flask and magnetically stirred for 6-8h.
8. The method of manufacturing according to claim 1, characterized in that: the drying temperature is 60-70 ℃ and the drying time is 12-24h.
9. The method of manufacturing according to claim 1, characterized in that: the calcination temperature is 300-600 ℃, and the calcination time is 1-8h.
10. Use of the mesoporous zirconium phosphate obtained by the preparation method according to any one of claims 1 to 9 as a lithium ion adsorbing material.
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