CN117339543A - Preparation method of composite titanium lithium ion sieve - Google Patents
Preparation method of composite titanium lithium ion sieve Download PDFInfo
- Publication number
- CN117339543A CN117339543A CN202311522275.7A CN202311522275A CN117339543A CN 117339543 A CN117339543 A CN 117339543A CN 202311522275 A CN202311522275 A CN 202311522275A CN 117339543 A CN117339543 A CN 117339543A
- Authority
- CN
- China
- Prior art keywords
- ion sieve
- lithium
- temperature
- zirconium composite
- titanium zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- -1 lithium titanium zirconium Chemical compound 0.000 claims abstract description 47
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 12
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims abstract description 10
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 239000004800 polyvinyl chloride Substances 0.000 claims description 15
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910052596 spinel Inorganic materials 0.000 claims description 12
- 239000011029 spinel Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 238000000605 extraction Methods 0.000 description 11
- 239000010936 titanium Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a composite titanium lithium ion sieve, which comprises the steps of preparing precursor powder of the titanium lithium ion sieve by using lithium acetate, butyl titanate and zirconyl nitrate, and finally obtaining spherical lithium titanium zirconium composite ion sieve particles by heating, acid washing, granulating and the like. According to the invention, the zirconium element is doped in the titanium ion sieve, so that the lithium titanium zirconium composite oxide is kept stable in the acid modification process, the adsorption cycle stability of the ion sieve is improved, and the cycle use times of the ion sieve are increased.
Description
Technical Field
The invention belongs to the technical field of lithium extraction, and relates to a preparation method of a composite titanium lithium ion sieve.
Background
Lithium resources were considered important energy materials and strategic resources in the 21 st century. Lithium is the least dense metal and therefore plays an important role in many industries, such as: lithium ion secondary batteries, ceramic glass, air purifiers, medicines, lubricants, nuclear industries, dyes, cement binders, and the like. With the continuous development of science and technology, the market demand of lithium resources has risen year by year. Lithium resources present on earth can be divided into two main categories: 1. the land lithium ore resources mainly comprise spodumene, lepidolite, petalite, sphalerite and the like; 2. lithium resources in the form of lithium ions in the ocean and salt lake water. Although the development on land is high, the reserves in the sea and salt lake water are huge. According to literature reports, about 60% of lithium reserves (about 26.9 Mt) have been ascertained on earth to exist in seawater and salt lake water. Among them, most of the resources are stored in China, chilean, bolivia, argentina, america, etc. Thus, there is great potential in the acquisition of lithium resources in the ocean and salt lake waters. The development of the high-efficiency liquid-phase lithium extraction technology can effectively relieve the pressure of a lithium resource market and has profound strategic significance on the national level.
Heretofore, many techniques for extracting lithium in liquid phase have been developed, such as "sun evaporation technique", "carbonization technique", "solvent extraction technique", "salting-out method", "adsorption lithium extraction technique", and the like. The lithium extraction period in the 'insolation and evaporation technology' is relatively long, and the extraction process is limited by factors such as reaction temperature, pH value of solution, molar ratio of Li and AL, and the like, so that the industrial application prospect is relatively poor; the carbonization technology cannot separate Li-containing brine with higher Na concentration content; the extractant of the solvent extraction technology is high in cost and is not beneficial to large-scale industrial popularization; the salting-out method can be performed in a closed environment, has serious corrosion to equipment and cannot be used for industrial production. The adsorption lithium extraction technology is a novel technology for extracting lithium with high cost performance and relative environmental friendliness, and particularly the application of the lithium ion sieve material, the unique surrounding lattice structure of the lithium ion sieve material is utilized to macroscopically show high-efficiency lithium ion selective adsorption. Therefore, the lithium ion sieve lithium extraction technology is considered as the liquid phase lithium extraction technical scheme with the most industrialized potential. The lithium ion sieve is obtained by introducing a template Li+ into an inorganic compound, generating a lithium ion sieve precursor through heat treatment, and then leaching Li+ in the lithium ion sieve precursor through acid. The lithium ion sieve has specific memory selectivity on Li+ ions due to size effect and sieving effect, can separate Li+ ions from other ions under the condition of multi-ion coexistence, and is commonly used for the selective extraction of Li+ in lithium-rich solutions such as seawater or brine.
At present, research on lithium ion sieve materials mainly focuses on manganese ion sieves, but the manganese ion sieves have the defects of large manganese dissolution loss, few cycle times and the like. The titanium lithium ion sieve has the advantages of less dissolution loss, stable structure and the like. However, the titanium-series lithium ion sieve prepared by the existing preparation method generally has the defects of incomplete lithium removal, incomplete ion exchange, low crystallinity of the ion sieve, high resistance of three-dimensional channels for lithium ions to enter and exit the ion sieve and the like, and is not beneficial to industrialized large-scale popularization and application. Accordingly, a novel titanium-based ion sieve is needed to solve the above-mentioned problems.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to solve the problems that the titanium-series lithium ion sieve prepared by the existing preparation method is not thorough in lithium removal, incomplete in ion exchange, low in crystallinity of the ion sieve, high in resistance of three-dimensional channels of lithium ions entering and exiting the ion sieve and the like.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the composite titanium lithium ion sieve specifically comprises the following steps:
step one: adding a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into ethylene glycol for dissolution, then adding a proper amount of citric acid, and stirring until all the materials are dissolved; wherein the molar ratio of lithium acetate to butyl titanate to zirconyl nitrate is 4.3:4.79:0.03, the ethylene glycol capacity is 4L, and the addition amount of citric acid is 0.1kg;
step two: transferring the mixed solution obtained in the step one into a reaction container for heating reaction to obtain white colloid;
step three: drying the white colloid obtained in the second step, and transferring the white colloid into a heating component for reaction to obtain a lithium titanium zirconium composite oxide;
step four: adding the lithium titanium zirconium composite oxide in the third step into an acidic solution to obtain a lithium titanium zirconium composite ion sieve, wherein the reaction process is as follows:
step five: adding polyvinyl chloride into N, N-dimethylformamide, adding the polyvinyl chloride into the lithium titanium zirconium composite ion sieve after the polyvinyl chloride is completely dissolved in the N, N-dimethylformamide, uniformly dispersing the lithium titanium zirconium composite ion sieve into solution, uniformly adding the solution into deionized water to obtain spherical lithium titanium zirconium composite ion sieve particles, drying to constant weight, and taking out for later use.
Preferably, the first step is to add a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into glycol for dissolution, then add a proper amount of citric acid, and stir until all the materials are dissolved;
wherein, stirring with a magnetic stirrer at 400-600rpm for at least 60min. By adopting the magnetic stirrer, the reaction caused by the contact of the stirrer with the solution can be avoided, and further other impurities are introduced to influence the purity of the reagent.
Preferably, the lithium titanium zirconium composite oxide is in a spinel structure, the spinel structure is a three-dimensional space system formed by interweaving nanopores, the pore diameter of the spinel structure is mostly mesoporous, and the pore diameter is 40+/-2 nm.
Preferably, the acidic solution is hydrochloric acid with the concentration of 0.15 mol/L.
Preferably, in the second step, the solution in the first step is transferred into a high-pressure reaction kettle, the temperature is controlled at 180 ℃, the reaction is controlled for 24-30 hours, and finally, the white colloid is obtained.
Preferably, the step three: drying the white colloid obtained in the second step, and transferring the white colloid into a heating component for reaction to obtain a lithium titanium zirconium composite oxide;
drying the white colloid obtained in the second step, and then raising the temperature from room temperature to 200 ℃ at a heating rate of 4 ℃/min, and keeping the temperature at 200 ℃ for 30 minutes; raising the temperature from 200 ℃ to 300 ℃ at the temperature raising rate of 2 ℃/min, and keeping the temperature at 300 ℃ for 30 minutes; raising the temperature from 300 ℃ to 400 ℃ at the temperature raising rate of 2 ℃/min, and keeping the temperature at 400 ℃ for 30 minutes; the spinel structure was formed by heating from room temperature of 400℃to 800℃at a heating rate of 4℃per minute and holding at 800℃for 150 minutes.
Preferably, in the fourth step, the lithium titanium zirconium composite oxide in the third step is added into hydrochloric acid with the concentration of 0.15mol/L, and then a constant-temperature water bath with the temperature of 40 ℃ is needed for 3d; filtering to remove solid impurities to obtain clear liquid; and finally drying the mixture at 50 ℃ to obtain the lithium titanium zirconium composite ion sieve, namely IE-H.
Preferably, in the fifth step, the mass ratio of the polyvinyl chloride to the lithium titanium zirconium composite ion sieve is 1:4, and the spherical lithium titanium zirconium composite ion sieve particles need to be dried at 75 ℃.
Preferably, the spherical lithium titanium zirconium composite ion sieve particles obtained in the step five are white spheres, and the diameter of the spheres is 1.5-2.5mm.
Compared with the prior art, the invention has the beneficial effects that:
the zirconium element is doped in the titanium ion sieve, so that the lithium titanium zirconium composite oxide is kept stable in the acid modification process, the adsorption cycle stability of the ion sieve is improved, the cycle use times are high, and the practical value is high. The three-stage roasting can remove corresponding impurities, and the ethylene glycol and the crystallization water can be volatilized and removed after the three-stage roasting is kept at 200 ℃ for 30 minutes; maintaining at 400 ℃ for 30 minutes, removing citric acid, and stabilizing the material structure; the firing time at 900 c increases and too high a temperature collapses the nanopores, causing structural damage, so 800 c is selected as the temperature for firing the composite oxide.
Detailed Description
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the description as it relates to "first", "second", etc. in the present invention is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implying an indication of the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention discloses a preparation method of a composite titanium ion sieve, which comprises the following steps of
Step one: adding a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into ethylene glycol for dissolution, then adding a proper amount of citric acid, and stirring until all the materials are dissolved; wherein the molar ratio of lithium acetate to butyl titanate to zirconyl nitrate is 4.3:4.79:0.03, the ethylene glycol is 4L, and the addition amount of the citric acid is 0.1kg;
step two: transferring the solution in the first step into a reaction container for heating to react to obtain white colloid;
step three: drying the white colloid obtained in the second step, transferring to a heating component for reaction to obtain a lithium titanium zirconium composite oxide, namely Li 4 Ti 5 O 12 ；
Step four: adding the lithium titanium zirconium composite oxide in the third step into an acidic solution to obtain a lithium titanium zirconium composite ion sieve, wherein the reaction process is as follows:
step five: adding polyvinyl chloride into N, N-dimethylformamide, adding the polyvinyl chloride into the lithium titanium zirconium composite ion sieve after the polyvinyl chloride is completely dissolved in the N, N-dimethylformamide, uniformly dispersing the lithium titanium zirconium composite ion sieve into solution, uniformly adding the solution into deionized water to obtain spherical lithium titanium zirconium composite ion sieve particles, drying to constant weight, and taking out for later use.
The application of the invention uses a solvothermal method to keep the lithium titanium zirconium composite oxide stable in the acid modification process, improves the adsorption cycle stability of the ion sieve, and recycles the zirconium for times, thus having great practical value.
Further, adding a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into ethylene glycol for dissolution, adding a proper amount of citric acid, and stirring until all the materials are dissolved; wherein, stirring with a magnetic stirrer at 400-600rpm for at least 60min. By adopting the magnetic stirrer, the reaction caused by the contact of the stirrer with the solution can be avoided, and further other impurities are introduced to influence the purity of the reagent.
Further, the lithium titanium zirconium composite oxide is of a spinel structure, the solvent and the solute interact to form nanopores in a high-pressure reaction kettle sealing high-pressure state, and the spinel structure is a three-dimensional space system formed by interweaving the nanopores, so that the contact probability of the adsorbent and the liquid is increased. The pore diameter of the spinel structure is mostly mesoporous, and the pore diameter is 40+/-2 nm.
In a specific embodiment, 8 parts by mass of the calcined lithium titanium zirconium composite oxide with the mass of 0.1g are accurately weighed and placed in a 100ml container, 0.03, 0.06, 0.09, 0.12, 0.15, 0.18, 0.21 and 0.24mol/L hydrochloric acid is respectively used as a delithiation solvent to be added into the container, the solution is leached in a constant-temperature water bath at 40 ℃ for 3d, the supernatant is removed, and Li in the solution is measured + 、Ti 4+ The contents of (2) are shown in the following table:
TABLE 1 ion extraction Rate at different hydrochloric acid concentrations
| Hydrochloric acid concentration (mol/L) | Li + (wt) | Ti 4+ (wt) |
| 0.03mol/L | 10.05％ | 0.05％ |
| 0.06mol/L | 19.57％ | 0.09％ |
| 0.09mol/L | 39.87％ | 0.14％ |
| 0.12mol/L | 64.54％ | 0.22％ |
| 0.15mol/L | 84.81％ | 0.37％ |
| 0.18mol/L | 84.92％ | 1.92％ |
| 0.21mol/L | 85.23％ | 3.62％ |
| 0.24mol/L | 86.12％ | 7.41％ |
Acid leaching experiments are carried out on the lithium titanium zirconium composite oxide to obtain the concentration of HCl and Li + 、Ti 4+ When the hydrochloric acid concentration is 0.15mol/L, li + The leaching rate of (a) is as high as 84.81%, and Ti 4+ The extraction rates were all below 0.37% and therefore a suitable acid leaching concentration of 0.165mol/L was determined.
Further, in the second step, the solution in the first step is transferred into a high-pressure reaction kettle, the temperature is controlled at 180 ℃, the reaction is controlled for 24-30 hours, and finally white colloid is obtained.
Further, the step three: drying the white colloid obtained in the second step, transferring to a heating component for reaction to obtain a lithium titanium zirconium composite oxide, namely Li 4 Ti 5 O 12 ；
Drying the white colloid obtained in the second step, heating from room temperature of 20 ℃ to 200 ℃ at a heating rate of 4 ℃/min, and keeping at 200 ℃ for 30 minutes to volatilize and remove ethanol and crystal water; raising the temperature from 200 ℃ to 300 ℃ at the temperature raising rate of 2 ℃/min, and keeping the temperature at 300 ℃ for 30 minutes; at a heating rate of 2 ℃/min, heating from 300 ℃ to 400 ℃ at room temperature, maintaining at 400 ℃ for 30 minutes, removing citric acid, and stabilizing the material structure; the spinel structure was formed by heating from room temperature of 400℃to 800℃at a heating rate of 4℃per minute and holding at 800℃for 150 minutes.
The roasting process is mainly divided into three stages:
the first stage: in the temperature range of 0-200 ℃, the weight of the product is reduced in a straight line, the change rate is high, and the lost quality can reach 50%, which is caused by rapid volatilization of the adsorbed water and ethanol solvent in the sample along with the temperature rise.
And a second stage: in the range of 250 to 400 ℃, the weight of the product is slowly decreased, and an endothermic peak occurs at 300 ℃, because the product absorbs heat to decompose citric acid and organic matters in the material. Thus, a suitable air flow rate and a stable temperature rise rate contribute to the formation of the oxide space frame.
And a third stage: after 500 ℃, the curve is basically in a horizontal state, the weight of the product has no obvious change, a small exothermic peak appears at 450 ℃, the composite oxide forms a spinel-type structure to release a certain amount of heat, and after 550 ℃, the composite oxide is basically formed. The product has a small amount of TiO when baked at 600 DEG C 2 The diffraction peak intensity of the sample baked at 700 ℃ is increased and the peak shape is sharp, but TiO is still present 2 And (3) generating. The roasting time at 900 ℃ is increased, and the nano holes collapse due to the too high temperature, so that the structure is damaged, and the temperature of 800 ℃ is selected as the temperature for roasting the composite oxide.
Further, the lithium titanium zirconium composite oxide in the third step is added into hydrochloric acid with the concentration of 0.15mol/L, and then constant-temperature water bath at the temperature of 40 ℃ is needed for 3d; filtering to remove solid impurities to obtain clear liquid; and finally drying the mixture at 50 ℃ to obtain the lithium titanium zirconium composite ion sieve, namely IE-H.
In another embodiment, the granulation process comprises the steps of: 0.30, 0.45, 0.60, 0.75g of polyvinyl chloride (PVC) was weighed into four small beakers of DMF having 10mL and stirred. When the PVC is completely dissolved in N, N-Dimethylformamide (DMF), 2.7 g, 2.55 g, 2.4 g and 2.25g of lithium titanium zirconium composite ion sieve powder are respectively added, and four granular ion sieves with the addition amounts of 10%, 15%, 20% and 25% of the PVC are obtained. After the ion sieve is uniformly dispersed in the solution, dripping the ion sieve into deionized water at a uniform speed to obtain spherical lithium titanium zirconium composite ion sieve particles. The granular lithium ion is screened and washed, and then dried at 75 ℃ until the weight is constant, and the granular lithium ion can be taken out for standby.
When the content of polyvinyl chloride in the spherical lithium titanium zirconium composite ion sieve particles is 20%, the particle-loaded lithium ion sieve with better shock resistance can be obtained, the spherical lithium titanium zirconium composite ion sieve particles are white spheres, and the diameter of the spheres is 1.5-2.5mm.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The preparation method of the composite titanium lithium ion sieve is characterized by comprising the following steps of:
step one: adding a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into ethylene glycol for dissolution, then adding a proper amount of citric acid, and stirring until all the materials are dissolved; wherein the molar ratio of lithium acetate to butyl titanate to zirconyl nitrate is 4.3:4.79:0.03, the ethylene glycol capacity is 4L, and the addition amount of citric acid is 0.1kg;
step two: transferring the mixed solution obtained in the step one into a reaction container for heating reaction to obtain white colloid;
step three: drying the white colloid obtained in the second step, and transferring the white colloid into a heating component for reaction to obtain a lithium titanium zirconium composite oxide;
step four: adding the lithium titanium zirconium composite oxide in the third step into an acidic solution to obtain a lithium titanium zirconium composite ion sieve, wherein the reaction process is as follows:
step five: adding polyvinyl chloride into N, N-dimethylformamide, adding the polyvinyl chloride into the lithium titanium zirconium composite ion sieve after the polyvinyl chloride is completely dissolved in the N, N-dimethylformamide, uniformly dispersing the lithium titanium zirconium composite ion sieve into solution, uniformly adding the solution into deionized water to obtain spherical lithium titanium zirconium composite ion sieve particles, drying to constant weight, and taking out for later use.
2. The method for preparing the composite titanium ion sieve according to claim 1, wherein the method comprises the following steps: firstly, adding a certain amount of lithium acetate, butyl titanate and zirconyl nitrate into ethylene glycol for dissolution, then adding a proper amount of citric acid, and stirring until the materials are completely dissolved;
wherein, stirring with a magnetic stirrer at 400-600rpm for at least 60min.
3. The method for preparing a composite titanium ion sieve according to claim 1, wherein the lithium titanium zirconium composite oxide is a spinel structure, the spinel structure is a three-dimensional space system formed by interweaving nanopores, the pore diameter of the spinel structure is mostly mesoporous, and the pore diameter is 40+/-2 nm.
4. The method for preparing a composite titanium ion sieve according to claim 1, wherein the acidic solution is hydrochloric acid with a concentration of 0.15 mol/L.
5. The method for preparing a composite titanium ion sieve according to claim 1, wherein in the second step, the solution in the first step is transferred into a high-pressure reaction kettle, the temperature is controlled at 180 ℃, and the reaction is controlled for 24-30 hours, so that a white colloid is finally obtained.
6. The method for preparing a composite titanium ion sieve according to claim 1, wherein the step three: drying the white colloid obtained in the second step, and transferring the white colloid into a heating component for reaction to obtain a lithium titanium zirconium composite oxide;
drying the white colloid obtained in the second step, and then raising the temperature from room temperature to 200 ℃ at a heating rate of 4 ℃/min, and keeping the temperature at 200 ℃ for 30 minutes; raising the temperature from 200 ℃ to 300 ℃ at the temperature raising rate of 2 ℃/min, and keeping the temperature at 300 ℃ for 30 minutes; raising the temperature from 300 ℃ to 400 ℃ at the temperature raising rate of 2 ℃/min, and keeping the temperature at 400 ℃ for 30 minutes; the spinel structure was formed by heating from room temperature of 400℃to 800℃at a heating rate of 4℃per minute and holding at 800℃for 150 minutes.
7. The method for preparing the composite titanium ion sieve according to claim 1, wherein the method comprises the following steps: adding the lithium titanium zirconium composite oxide in the step three into hydrochloric acid with the concentration of 0.15mol/L, and requiring constant-temperature water bath at the temperature of 40 ℃ for 3d; filtering to remove solid impurities to obtain clear liquid; and finally drying the mixture at 50 ℃ to obtain the lithium titanium zirconium composite ion sieve, namely IE-H.
8. The method according to claim 1, wherein in the fifth step, the mass ratio of the polyvinyl chloride to the lithium titanium zirconium composite ion sieve is 1:4, and the spherical lithium titanium zirconium composite ion sieve particles are required to be dried at 75 ℃.
9. The method for preparing a composite titanium ion sieve according to claim 1, wherein the spherical lithium titanium zirconium composite ion sieve particles obtained in the fifth step are white spheres with diameters of 1.5-2.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522275.7A CN117339543A (en) | 2023-11-15 | 2023-11-15 | Preparation method of composite titanium lithium ion sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522275.7A CN117339543A (en) | 2023-11-15 | 2023-11-15 | Preparation method of composite titanium lithium ion sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117339543A true CN117339543A (en) | 2024-01-05 |
Family
ID=89371170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311522275.7A Pending CN117339543A (en) | 2023-11-15 | 2023-11-15 | Preparation method of composite titanium lithium ion sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117339543A (en) |
-
2023
- 2023-11-15 CN CN202311522275.7A patent/CN117339543A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Orooji et al. | Recent advances in nanomaterial development for lithium ion-sieving technologies | |
| Wei et al. | Porous lithium ion sieves nanofibers: General synthesis strategy and highly selective recovery of lithium from brine water | |
| CN112871127B (en) | Preparation method of high-porosity lithium ion sieve particles | |
| CN101961634B (en) | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof | |
| CN107376827B (en) | Zirconium dioxide coated manganese lithium ion sieve and preparation method and application thereof | |
| JP7376862B2 (en) | Wet synthesis method of NCMA high nickel quaternary precursor | |
| CN109999750B (en) | Lithium zirconate coated manganese lithium ion sieve and preparation and application thereof | |
| CN109173976B (en) | Synthesis method of metatitanic acid type lithium adsorbent for efficiently separating and extracting lithium in brine | |
| EP3538266A1 (en) | Lithium extraction with coated ion exchange particles | |
| CN109317087B (en) | Doped lithium titanate adsorbent and preparation method thereof | |
| CN103958412A (en) | Process for producing lithium carbonate from concentrated lithium brine | |
| CN103121724A (en) | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 | |
| CN113274971A (en) | Titanium type lithium ion sieve and preparation method thereof | |
| CN113731371A (en) | Preparation method of lithium ion adsorption material | |
| CN110898794A (en) | Preparation method of lithium ion sieve | |
| CA3167584A1 (en) | Orthosilicate-based adsorbent and selective metal adsorption from brines using orthosilicate-based adsorbent | |
| CN106315690A (en) | Porous cobalt tetroxide nanosheet and preparation method thereof | |
| CN109289756B (en) | Porous manganese-based lithium ion sieve adsorbent and preparation method thereof | |
| CN115301196A (en) | Titanium-doped modified manganese-based lithium ion sieve and preparation method thereof | |
| CN110106356B (en) | Method for separating lithium from salt lake brine by using powder type titanium ion exchanger | |
| CN111892071B (en) | Method for purifying lithium carbonate | |
| CN117339543A (en) | Preparation method of composite titanium lithium ion sieve | |
| CN105060266A (en) | Hydro-thermal synthesis method for nano LiFePo4 | |
| CN116159531A (en) | Preparation method of hollow fiber membrane lithium ion adsorbent | |
| CN107473242B (en) | A method of high-purity lithium oxide is prepared using lithium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |