CN116040667A - Micron-sized boehmite powder material and preparation method thereof - Google Patents
Micron-sized boehmite powder material and preparation method thereof Download PDFInfo
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- CN116040667A CN116040667A CN202310159364.3A CN202310159364A CN116040667A CN 116040667 A CN116040667 A CN 116040667A CN 202310159364 A CN202310159364 A CN 202310159364A CN 116040667 A CN116040667 A CN 116040667A
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- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 133
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 133
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 86
- 239000002243 precursor Substances 0.000 claims abstract description 68
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 108
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- -1 aluminum ions Chemical class 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 64
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000877 morphologic effect Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000000926 separation method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
- C01F7/145—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process characterised by the use of a crystal growth modifying agent other than aluminium hydroxide seed
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a micron-sized boehmite powder material and a preparation method thereof. The preparation method comprises the following steps: step S1, adding seed crystals into a sodium aluminate solution, stirring for a period of time after the seed crystals are added, and filtering to obtain a boehmite precursor; and S2, dispersing the boehmite precursor in water, performing hydrothermal reaction, filtering and drying after the reaction is finished to obtain the micron-sized boehmite powder. The preparation method of the boehmite powder material utilizes the structural instability of sodium aluminate solution to obtain boehmite precursors with certain morphological characteristics and particle size, and further aggregates and grows up the boehmite precursors through hydrothermal reaction to obtain the micron-sized boehmite powder material. The controllability of the preparation method is high, and the micron-sized boehmite powder material with high purity and uniform particle size can be obtained by controlling the decomposition condition of the sodium aluminate solution and seed crystal iteration. The preparation method is suitable for mass production and is convenient for large-scale application.
Description
Technical Field
The invention relates to the technical field of inorganic materials, in particular to a micron-sized boehmite powder material and a preparation method thereof.
Background
Boehmite, also known as boehmite or boehmite, is chemically composed as AlOOH, belongs to orthorhombic systems, is a precursor of many aluminum-containing oxides, and has a layered structure. Due to the unique lamellar structure, the boehmite has the advantages of zero charge, high interfacial free energy, good colloid-melting property, large porosity, large specific surface area, good dispersibility and the like. Accordingly, boehmite is widely used in industry for preparing alumina precursors, catalyst carriers, catalysts, adsorbents, separator coatings, flame retardants, and the like.
Alumina is widely used in the field of inorganic separator coating. However, boehmite as a precursor has a greater potential for development in the lithium battery field than alumina. Boehmite has a lower hardness than alumina, which allows for reduced mechanical wear during battery separator coating; the boehmite density is smaller, the boehmite of the same quality can be coated with 25% more area than the high purity alumina, and the boehmite coating can significantly improve the thermal stability of the separator at lower coating thickness.
Boehmite powder materials used for coating materials of power battery separator in the market at present can be divided into flake, needle and block according to the microscopic morphology of particles. Based on the test results, boehmite materials with a particularly good morphology in bulk form perform best. The current preparation method of the domestic micron-sized blocky boehmite powder material takes a medium-sized aluminum Zhengzhou mechanochemical segmented energy storage (MTCG) method as a main material, and the method adopts a template agent and crude aluminum hydroxide to prepare nanoscale boehmite and aluminum oxide.
However, the boehmite material prepared by the prior method has uneven phase components, non-centralized particle size distribution and easy agglomeration among particles, and is difficult to meet the use requirement.
Disclosure of Invention
The invention mainly aims to provide a micron-sized boehmite powder material and a preparation method thereof, which are used for solving the problem that the particle size of the boehmite powder material is not concentrated in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a micro-sized boehmite powder material, the method comprising: step S1, adding seed crystals into a sodium aluminate solution, stirring for a period of time after the seed crystals are added, and filtering to obtain a boehmite precursor; and S2, dispersing the boehmite precursor in water, performing hydrothermal reaction, filtering and drying after the reaction is finished to obtain the micron-sized boehmite powder.
Further, the sodium aluminate solution is prepared by the following steps: step S01, fully dissolving soluble aluminum salt in an aqueous solution to obtain an aluminum salt aqueous solution, adding a first alkali solution to adjust the pH value of the aluminum salt aqueous solution to generate aluminum hydroxide precipitate, and filtering to obtain an aluminum hydroxide precursor; step S02, mixing an aluminum hydroxide precursor, a second alkali reagent and water to obtain a sodium aluminate solution, wherein the second alkali reagent is sodium hydroxide; preferably, a sodium aluminate solution is formed at 85-100 ℃;
preferably, the soluble aluminum salt comprises any one or more of aluminum chloride, aluminum sulfate and aluminum nitrate;
preferably, the soluble aluminum salt has a purity of 95% or more.
Further, in the step S01, the aluminum hydroxide precipitate is aged for 12 to 24 hours and then filtered; preferably, the filter cake obtained by filtration is washed by deionized water at 70-90 ℃;
preferably, the concentration of aluminum ions in the aluminum salt aqueous solution is 0.5-0.7 mol/L;
preferably, the first alkali solution is any one or more of sodium hydroxide solution, calcium hydroxide solution and potassium hydroxide solution;
preferably, the concentration of the first alkali solution is 0.5-1 mol/L;
preferably, in step S01, the pH of the aqueous aluminum salt solution is adjusted to 6 to 10.
Further, in the sodium aluminate solution, according to Na 2 O is calculated to have the concentration of 150-160 g/L, preferably, the ratio of sodium hydroxide to aluminum hydroxide precursor in the sodium aluminate solution is converted into Na 2 O and Al 2 O 3 The molar ratio of (2) to (3).
Further, step S1 includes: adding seed crystal into sodium aluminate solution at 45-65 deg.c; preferably, stirring is carried out in the process of adding the seed crystal, and the stirring rotating speed is 30-100 rpm; preferably, the seed crystal is added in multiple times or at a constant speed over a period of time;
preferably, after the seed crystal is added, the temperature is maintained at 45-65 ℃, and the stirring duration is 12-24 hours.
Further, the seed crystal is a dried aluminum hydroxide precursor or a boehmite precursor; preferably, the seed placement seed crystal coefficient is 0.15 to 0.3.
Further, step S1 further comprises washing the solid obtained after filtration with deionized water to obtain a boehmite precursor, preferably, the temperature of deionized water used for washing is 70-90 ℃.
Further, in step S2, the dispersion concentration of the aluminum element in the boehmite precursor in water is 0.5 to 1.0mol/L.
Further, the temperature of the thermal reaction is 180-220 ℃; preferably, the hydrothermal reaction time is 4 to 12 hours.
According to another aspect of the present invention, there is provided a micro-sized boehmite powder material prepared by any one of the preparation methods described above.
By applying the technical scheme of the invention, the preparation method of the boehmite powder material utilizes the structural instability of sodium aluminate solution to obtain boehmite precursors with certain morphological characteristics and particle size, and further aggregates and grows up the boehmite precursors through hydrothermal reaction to obtain the micron-sized boehmite powder material. The controllability of the preparation method is high, and the micron-sized boehmite powder material with high purity and uniform particle size can be obtained by controlling the decomposition condition of the sodium aluminate solution and seed crystal iteration. The preparation method is suitable for mass production and is convenient for large-scale application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a schematic process flow diagram of a preparation method according to an embodiment of the invention;
FIG. 2 shows XRD phase diagrams of boehmite products according to example 1 of the invention;
FIG. 3 shows SEM microcosmic morphology of boehmite products according to example 1 of the invention;
fig. 4 shows a particle size distribution graph of the boehmite product of example 1 of the invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As analyzed by the background art of the present application, the problems of uneven phase components, uneven particle size distribution, and easy agglomeration among particles of the boehmite material exist in the prior art, and in order to solve the problems, the present application provides a micron-sized boehmite powder material and a preparation method thereof.
According to an exemplary embodiment of the present application, there is provided a method for preparing a micro-sized boehmite powder material, which is characterized by comprising: step S1, adding seed crystals into a sodium aluminate solution, stirring for a period of time after the seed crystals are added, and filtering to obtain a boehmite precursor; and S2, dispersing the boehmite precursor in water, performing hydrothermal reaction, filtering and drying after the reaction is finished to obtain boehmite powder.
The preparation method of the boehmite powder material utilizes the structural instability of sodium aluminate solution to obtain boehmite precursors with certain morphological characteristics and particle size, and further causes the boehmite precursors to aggregate and grow up through hydrothermal reaction to obtain the micron-sized boehmite powder material. The controllability of the preparation method is high, and the micron-sized boehmite powder material with high purity and uniform particle size can be obtained by controlling the decomposition condition of the sodium aluminate solution and seed crystal iteration. The preparation method is suitable for mass production and is convenient for large-scale application.
The sodium aluminate and sodium metaaluminate mentioned in the present application, the sodium aluminate solution in step S1 may be prepared by adding water to sodium aluminate solid to prepare an aqueous solution thereof, or may be prepared by corresponding reaction of aluminum-containing oxide, aluminum-containing hydroxide or aluminum salt, and the present application is not particularly limited.
In some preferred embodiments, to further improve the purity and uniformity of particle size of the boehmite particles, the sodium aluminate solution is treated with Na as contained in the solution 2 O is measured with the concentration of 150-160 g/L, namely Na contained in solute in each liter of sodium aluminate solution 2 The weight of O is 150-160 g, and the ratio of NaOH to aluminum salt is converted into Na 2 O and Al 2 O 3 The molar ratio is 2-3.
In some typical embodiments of the present application, the sodium aluminate solution is prepared by the steps of: step S01, fully dissolving soluble aluminum salt in an aqueous solution to obtain an aluminum salt aqueous solution, adding a first alkali solution to adjust the pH value of the aluminum salt aqueous solution to generate aluminum hydroxide precipitate, and filtering to obtain an aluminum hydroxide precursor; step S02, mixing an aluminum hydroxide precursor, a second alkali reagent and water to obtain a sodium aluminate solution, wherein the second alkali reagent is sodium hydroxide. By adopting the method to prepare the sodium aluminate solution, a soluble aluminum salt product with low price or easy acquisition can be selected as an aluminum source according to market conditions, so that the preparation method has wider raw material range; in addition, the purity of the aluminum salt product is not required to be high, and most impurities can be left in the solution in the process of preparing the aluminum hydroxide precursor so as to be removed, so that the boehmite product with high purity can be obtained more easily.
The soluble aluminum salt includes any one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; in some embodiments of the present application, the soluble aluminum salt has a purity of 93% or more, preferably, the soluble aluminum salt has a purity of 95% or more. In some preferred embodiments of the present application, in order to facilitate mixing the aluminum hydroxide precursor, the second alkaline reagent and water to prepare a sodium aluminate solution, the system is stirred at 60-100 ℃ to prepare the sodium aluminate solution, preferably, the sodium aluminate solution is formed by stirring at 85-100 ℃, so that the formed sodium aluminate solution is relatively uniform and stable, and the particle size of the boehmite precursor obtained by decomposing the seed crystal is more concentrated. In some preferred embodiments of the present application, in the step S01, the aluminum hydroxide precipitate is aged for 12-24 hours and then filtered, so that the generated aluminum hydroxide precipitate particles are mutually bonded and grown to form larger particles, which is beneficial to the subsequent use as seed crystals in sodium aluminate solution; preferably, the filter cake obtained by filtration is washed with deionized water at 70-90 ℃, so that the purity of aluminum hydroxide in the aluminum hydroxide precursor is further improved, and the purity of boehmite powder material is further improved.
In some embodiments of the present application, in order to better compromise the purity and conversion of aluminum hydroxide in the aluminum hydroxide precursor, the pH of the aqueous aluminum salt solution is adjusted to 6 to 10 in step S01. In some embodiments of the present application, in order to further increase the precipitation efficiency of aluminum ions, in step S01, the concentration of aluminum ions in the aluminum salt solution prepared using the soluble aluminum salt is 0.5 to 0.7mol/L. The first alkali solution may be selected from alkali aqueous solutions in the prior art, and the cations thereof may not form a precipitate with anions in the aluminum salt solution, for example, the first alkali solution may be any one or more of sodium hydroxide solution, calcium hydroxide solution, and potassium hydroxide solution. The concentration of the first alkali solution is not particularly limited, and in some embodiments of the present application, in order to facilitate pH adjustment, a suitable solution concentration is provided, the concentration of the first alkali solution is 0.5 to 1mol/L, and the aluminum hydroxide precursor formed by using the alkali solution with the concentration is used as a seed crystal in step S1, which is helpful for preparing boehmite powder materials with more uniform particle sizes.
In some typical embodiments of the present application, step S01 comprises slowly adding or spraying 0.5 to 1mol/L sodium hydroxide solution to the aluminum chloride solution using a peristaltic pump, adjusting the pH of the solution to 6 to 10, precipitating aluminum element in the solution as aluminum hydroxide, and aging the solution for 12 to 24 hours. Filtering to separate solid from liquid, and washing filter cake with deionized water at 70-90 deg.c to obtain aluminum hydroxide precursor with excellent filtering performance and aluminum element recovering rate over 90%.
In some preferred embodiments of the present application, in the above step S02, the ratio of the molar amount of hydroxyl groups in the second base reagent to the molar amount of aluminum hydroxide in the aluminum hydroxide precursor is 2 to 3 (in Na 2 O and Al 2 O 3 Calculated) is favorable for further improving the conversion amount of the subsequent sodium aluminate into precipitate and forming boehmite powder with better comprehensive performance. In some embodiments of the present application, step S02 includes mixing an aluminum hydroxide precursor with NaOH solids, adding a small amount of deionized water, first to achieve a concentration of NaOH in the solution of 300-320 g/L (converted to Na 2 Calculated by O), the addition ratio of NaOH to aluminum hydroxide precursor is 2-3:1 (converted into Na 2 O and Al 2 O 3 In terms of mole ratio), heated to boiling, stirred, and deionized water is added into the system to dilute the concentration of NaOH in the solution to 150-160 g/L (according to Na) 2 O), and the sodium aluminate solution is prepared, and the sodium aluminate solution is placed in an oil/water bath kettle with the temperature of 85-100 ℃.
In some exemplary embodiments of the present application, the step S1 includes: seed crystals are added into the sodium aluminate solution with the temperature of 45-65 ℃ to help to form boehmite precursors with uniform particle size; preferably, stirring is carried out in the process of adding the seed crystal, and the stirring rotating speed is 30-100 rpm; the seed crystal is added for multiple times or at constant speed within a period of time, so that the particle size of the finally formed boehmite powder is more uniform, the effect of slowly adding the seed crystal is better, and preferably, the seed crystal is uniformly distributed within 1-2 hours in the process of adding the seed crystal. In some exemplary embodiments of the present application, after the seed addition is completed, the temperature is maintained at 45-65 ℃ and the stirring is continued for 12-24 hours to allow the sodium aluminate to fully decompose and convert to boehmite precursors.
The seed crystal may be aluminum hydroxide or boehmite powder, or may be aluminum hydroxide precursor or boehmite precursor obtained by the above-mentioned production method, preferably, the median particle diameter of the seed crystal is 0.1 μm to 2 μm, more preferably 1.5 μm; when the aluminum hydroxide precursor prepared in the step S01 is used as a seed crystal, the number of seed crystal iterations, that is, the number of seed crystal cycles is 1, and when the boehmite precursor finally obtained in the step S1 or the boehmite finally obtained in the step S2 is used for seed crystal decomposition, the number of seed crystal iterations becomes 2. The seed crystal can be cyclically participated in the decomposition for a plurality of times, namely the iteration times can be a plurality of times. In some preferred embodiments of the present application, the seed addition is at a seed factor of 0.15 to 0.3, the crystallization efficiency is high, and the crystal size is relatively uniform, wherein the seed factor represents the ratio of the weight of seed added to the sum of the weights of equivalent aluminum hydroxide and seed in the pre-formulated sodium aluminate solution.
In some exemplary embodiments of the present application, the preparation process of the micro-scale boehmite is shown in fig. 1, specifically as follows: dissolving soluble aluminum salt in deionized water to prepare a solution with the concentration of aluminum element of 0.5-0.7 mol/L; slowly adding or spraying 0.5-1 mol/L sodium hydroxide solution into the aluminum chloride (or aluminum salt solution) solution by adopting a peristaltic pump, adjusting the pH value of the solution to 6-10, precipitating aluminum element in the crystalline aluminum chloride in the form of aluminum hydroxide, and stirring and aging the solution for 12-24 hours; filtering to perform solid-liquid separation, and washing a filter cake with deionized water at 70-90 ℃ to obtain an aluminum hydroxide precursor; mixing the aluminum hydroxide precursor with sodium hydroxide under the condition of heating and stirring, and adding water to prepare a solution to obtain a sodium aluminate solution; adding seed crystals for multiple times into a sodium aluminate solution, decomposing the sodium aluminate into aluminum hydroxide under a stirring state, continuously growing aluminum hydroxide crystals, filtering to obtain a boehmite precursor, dispersing the boehmite precursor into water, performing hydrothermal reaction, and filtering to obtain micron-sized boehmite; wherein the seed crystal adopts any one of the following two schemes: seed crystal scheme 1, using an aluminum hydroxide precursor as a seed crystal for seed crystal decomposition; seed regimen 2 boehmite precursor, i.e., aluminum hydroxide subjected to 1 or more iterations, was seeded.
In some embodiments of the present application, in order to further improve uniformity and purity of particle size distribution of the finally obtained boehmite powder material, remove soluble impurities including sodium aluminate, and wash the solid obtained after filtration with deionized water to obtain boehmite precursor, preferably, the temperature of deionized water used for washing is 70-90 ℃, and the washing effect is better.
And S2, dispersing the boehmite precursor in water, performing a hydrothermal reaction to further aggregate and grow the boehmite precursor, and obtaining the micron-sized boehmite powder with regular shape and concentrated particle size distribution. In some embodiments of the present application, to further enhance the effectiveness of the hydrothermal reaction, the boehmite precursor has a concentration of aluminum dispersed in water of 0.5 to 1.0mol/L. In some embodiments of the present application, the temperature of the hydrothermal reaction is 180-220 ℃; preferably, the hydrothermal reaction time is 4 to 12 hours. The temperature and time of the hydrothermal reaction are controlled, and the dispersion concentration of the boehmite precursor in the reaction is controlled, so that the purity and the particle size uniformity of the boehmite powder material are further improved. In some typical embodiments of the present application, boehmite precursors are dispersed in deionized water, the concentration of aluminum element in the system is kept at 0.5-1.0 mol/L, the mixture is stirred uniformly, the pH value of the solution is kept at 6-8, and the solution is placed in a high-pressure reaction kettle and subjected to hydrothermal reaction at 200 ℃ for 12 hours. And after the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating, washing the obtained solid product with deionized water, and drying to obtain boehmite crystals.
According to another exemplary embodiment of the present application, there is provided a micro-sized boehmite powder material prepared by any one of the preparation methods described above. The preparation method of the boehmite powder material utilizes the structural instability of sodium aluminate solution to obtain boehmite precursors with certain morphological characteristics and particle size, and further causes the boehmite precursors to gather for a large length through hydrothermal reaction, thereby obtaining the micron-sized boehmite powder material. Because the preparation method has high controllability, the micron-sized boehmite powder material obtained by controlling the decomposition condition of the sodium aluminate solution and the iteration of the seed crystal has higher purity, uniform particle size and less agglomeration phenomenon among particles. The preparation method is suitable for batch production and convenient for large-scale application, so that the micron-sized boehmite powder material has low cost and good application value.
In some preferred embodiments of the present application, the purity of the above-mentioned micro-sized boehmite powder material is more than 99%, and boehmite powder materials having concentrated particle size distribution can be obtained, and the average particle size of the boehmite powder materials can be controlled in the range of 0.5 to 5 μm.
The advantages that can be achieved by the present application will be further described below in connection with examples and comparative examples.
Example 1
(1) First, 41.5260g of crystalline aluminum chloride (i.e., a soluble aluminum salt raw material, denoted by A) was dissolved in deionized water to a volume of 250mL to prepare a 0.7mol/L aluminum salt solution. And adding 1mol/L sodium hydroxide solution into the aluminum salt solution at a flow rate of 5mL/min by adopting a peristaltic pump, adjusting the pH value of the solution to B, precipitating aluminum dissolved in the solution in the form of aluminum hydroxide, and aging the solution for 12 hours. And (3) performing solid-liquid separation by adopting a filter pressing tank (the filtering pressure is 0.6 MPa), and cleaning a filter cake with deionized water at 80 ℃ for 3 times. The filter cake of the aluminum hydroxide has good filtering performance. In the process of transferring aluminum element from aluminum salt to aluminum hydroxide, the recovery rate of the aluminum element reaches more than G%. And drying the aluminum hydroxide wet filter cake at 120 ℃ for 12 hours to prepare the dry No. 1 aluminum hydroxide.
(2) Mixing 7.94g of the aluminum hydroxide solid obtained in the step (1) with 10.32g of NaOH solid, fixing the volume to 50mL by using deionized water, heating to boiling, stirring to dissolve the aluminum hydroxide solid sufficiently, and placing a beaker containing the sodium aluminate solution in an oil bath pot to keep the temperature at 90 ℃ to obtain the sodium aluminate solution.
(3) 2.0124g of aluminum hydroxide powder (i.e., seed crystal, represented by C) having a median particle diameter of 2 μm was weighed as seed crystal. The seed crystal was divided into several portions and added to the sodium aluminate solution of (2) at 65℃every 10 minutes for a total of 2 hours. The sodium aluminate solution is slowly cooled in the process of adding the seed crystal, and finally is stabilized at D ℃, and is slowly stirred during the period of time, and the stirring speed is E rpm.
(4) After the end of the seed addition, the system temperature was kept at D ℃ for F h and the stirring speed E rpm was continued. During the period, sodium aluminate solution is decomposed and seed crystal grows up.
(5) After the seed crystal is decomposed, a filter pressing tank (the filtering pressure is 0.6 MPa) is adopted to carry out solid-liquid separation, and deionized water at 80 ℃ is adopted to clean a filter cake for 3 times, so that a No. 2 precursor aluminum hydroxide wet filter cake is obtained.
(6) Dispersing the aluminum hydroxide wet filter cake in deionized water, keeping the concentration of aluminum element in the system to be 0.5mol/L, uniformly stirring, wherein the pH value of the solution is about 7, placing the solution in a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 200 ℃. And after the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration and separation, washing the obtained solid product with deionized water for 3 times, and drying at 110 ℃ for 24 hours to obtain a dried boehmite product.
In this example, the process conditions or parameters A-G involved are shown in Table 1 below.
TABLE 1
The experiment shows that 6.09g of boehmite crystals with chemical purity higher than 99.6% have a median particle diameter Dv50 of 3.27 μm and a mode particle diameter Dv90 of 6.85 μm, the XRD phase pattern of the boehmite crystals is shown in fig. 2, the ordinate is the intensity (a.u.), the SEM micro morphology photograph is shown in fig. 3, and the particle size distribution is shown in fig. 4.
Example 2
(1) First, 41.5260g of crystalline aluminum chloride (i.e., a soluble aluminum salt raw material, denoted by A) was dissolved in deionized water to a volume of 250mL to prepare a 0.7mol/L aluminum salt solution. And adding 1mol/L sodium hydroxide solution into the aluminum salt solution at a flow rate of 5mL/min by adopting a peristaltic pump, adjusting the pH value of the solution to B, precipitating aluminum dissolved in the solution in the form of aluminum hydroxide, and aging the solution for 12 hours. And (3) performing solid-liquid separation by adopting a filter pressing tank (the filtering pressure is 0.6 MPa), and cleaning a filter cake with deionized water at 80 ℃ for 3 times. The filter cake of the aluminum hydroxide has good filtering performance. In the process of transferring aluminum element from aluminum salt to aluminum hydroxide, the recovery rate of the aluminum element reaches more than G%. The wet cake of aluminum hydroxide was dried at 120℃for 12 hours to give dried aluminum hydroxide No. 1 having a Dv50 of 0.1. Mu.m, and a Dv90 of 0.23. Mu.m.
(2) Mixing 7.94g of the No. 1 aluminum hydroxide solid obtained in the step (1) with 10.32g of NaOH solid, fixing the volume to 50mL by using deionized water, heating to boiling, stirring to dissolve the solid sufficiently, and placing a beaker containing the sodium aluminate solution in an oil bath pot to keep the temperature at 90 ℃ to obtain the sodium aluminate solution.
(3) 2.0124g of the aluminum hydroxide # 1 (i.e., seed crystal, represented by C) obtained in step (1) was weighed as a seed crystal. The seed crystal was divided into several portions and added to the sodium aluminate solution of (2) at 65℃every 10 minutes for a total of 2 hours. The sodium aluminate solution is slowly cooled in the process of adding the seed crystal, and finally is stabilized at D ℃, and is slowly stirred during the period of time, and the stirring speed Erpm is increased.
(4) After the end of the seed addition, the system temperature was kept at D ℃ for F h and the stirring speed E rpm was continued. During the period, sodium aluminate solution is decomposed and seed crystal grows up.
(5) After the seed crystal is decomposed, a filter pressing tank (the filtering pressure is 0.6 MPa) is adopted to carry out solid-liquid separation, and deionized water at 80 ℃ is adopted to clean a filter cake for 3 times, so that a No. 2 precursor aluminum hydroxide wet filter cake is obtained.
(6) Dispersing the aluminum hydroxide wet filter cake in deionized water, keeping the concentration of aluminum element in the system to be 0.5mol/L, uniformly stirring, wherein the pH value of the solution is about 7, placing the solution in a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 200 ℃. And after the reaction is finished, cooling the reaction kettle to room temperature, carrying out suction filtration and separation, washing the obtained solid product with deionized water for 3 times, and drying at 110 ℃ for 24 hours to obtain a dried boehmite product.
In this example, the process conditions or parameters A-G involved are shown in Table 2 below.
TABLE 2
The experiment gave 6.21g of boehmite crystals having a chemical purity of more than 99.3% and a median particle diameter Dv50 of 0.51 μm and a mode particle diameter Dv90 of 2.05. Mu.m.
Example 3
(1) First, 41.5260g of crystalline aluminum chloride (i.e., a soluble aluminum salt raw material, denoted by A) was dissolved in deionized water to a volume of 250mL to prepare a 0.7mol/L aluminum salt solution. And adding 1mol/L sodium hydroxide solution into the aluminum salt solution at a flow rate of 5mL/min by adopting a peristaltic pump, adjusting the pH value of the solution to B, precipitating aluminum dissolved in the solution in the form of aluminum hydroxide, and aging the solution for 12 hours. And (3) performing solid-liquid separation by adopting a filter pressing tank (the filtering pressure is 0.6 MPa), and cleaning a filter cake with deionized water at 80 ℃ for 3 times. The filter cake of the aluminum hydroxide has good filtering performance. In the process of transferring aluminum element from aluminum salt to aluminum hydroxide, the recovery rate of the aluminum element reaches more than G%. The wet cake of aluminum hydroxide was dried at 120℃for 12 hours to give dried aluminum hydroxide No. 1 having a Dv50 of 0.05. Mu.m, and a Dv90 of 0.16. Mu.m.
(2) Mixing 7.94g of the No. 1 aluminum hydroxide solid obtained in the step (1) with 10.32g of NaOH solid, fixing the volume to 50mL by using deionized water, heating to boiling, stirring to dissolve the solid sufficiently, and placing a beaker containing the sodium aluminate solution in an oil bath pot to keep the temperature at 90 ℃ to obtain the sodium aluminate solution.
(3) 2.0124g of the aluminum hydroxide # 1 obtained in the step (1) was weighed as seed crystals. The seed crystal was divided into several portions and added to the sodium aluminate solution of (2) at 65℃every 10 minutes for a total of 2 hours. The sodium aluminate solution is slowly cooled in the process of adding the seed crystal, and finally is stabilized at D ℃, and is slowly stirred during the period of time, and the stirring speed Erpm is increased.
(4) After the end of the seed addition, the system temperature was kept at D ℃ for F h and the stirring speed E rpm was continued. During the period, sodium aluminate solution is decomposed and seed crystal grows up.
(5) After the seed crystal is decomposed, a filter pressing tank (the filtering pressure is 0.6 MPa) is adopted to carry out solid-liquid separation, and deionized water at 80 ℃ is adopted to clean a filter cake for 3 times, so that a No. 2 precursor aluminum hydroxide wet filter cake is obtained.
(6) Dispersing the aluminum hydroxide wet filter cake in deionized water, keeping the concentration of aluminum element in the system to be 0.5mol/L, uniformly stirring, wherein the pH value of the solution is about 7, placing the solution in a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 200 ℃. After the reaction, the reaction vessel was cooled to room temperature, and the solid product obtained was separated by suction filtration, washed 3 times with deionized water, and dried at 110℃for 24 hours to give dried boehmite having a Dv50 of 0.46. Mu.m, and a Dv90 of 2.18. Mu.m.
(7) Repeating steps (3) to (6) with 2.0124g of boehmite (i.e., seed, indicated by C) prepared in step (6) as seed, to obtain a boehmite product.
In this example, the process conditions or parameters A-G involved are shown in Table 3 below.
TABLE 3 Table 3
The final boehmite product obtained by the experiment is 6.30g boehmite crystals with chemical purity more than 99.6%, the median particle diameter Dv50 is 1.33 μm, and the mode particle diameter Dv90 is 3.54 μm.
Example 4
The difference from example 3 is that the boehmite products obtained in example 3 were obtained by repeating steps (3) to (6) twice, i.e., seed crystals (i.e., denoted by C) and then repeating steps (3) to (6).
In this example, the process conditions or parameters A-G involved are shown in Table 4 below.
TABLE 4 Table 4
The experiment gave 6.44g of boehmite crystals having a chemical purity of more than 99.6% and a median particle diameter Dv50 of 2.58 μm and a mode particle diameter Dv 90.40 of μm.
Example 5
The difference from example 3 is that the boehmite products obtained in example 4 were obtained by repeating the steps (3) to (6) three times, namely, the boehmite products obtained in example 4 were used as seed (i.e., seed, denoted by C), and then the steps (3) to (6) were repeated to obtain the boehmite products of this example.
In this example, the process conditions or parameters A-G involved are shown in Table 5 below.
TABLE 5
The experiment gave 6.52g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 4.95 μm and a mode particle diameter Dv90 of 8.56. Mu.m.
Example 6
The same preparation as in example 1 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 6 below.
TABLE 6
The experiment gave 6.12g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 1.85 μm and a mode particle diameter Dv90 of 11.37. Mu.m.
Example 7
The same preparation as in example 1 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 7 below.
TABLE 7
The experiment gave 6.25g of boehmite crystals having a chemical purity of more than 99.6% and a median particle diameter Dv50 of 5.02 μm and a mode particle diameter Dv90 of 13.06 μm.
Example 8
The same preparation as in example 1 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 8 below.
TABLE 8
The experiment gave 6.40g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 1.94 μm and a mode particle diameter Dv90 of 8.49. Mu.m.
Example 9
The same preparation as in example 1 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 9 below.
TABLE 9
The experiment gave 6.20g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 1.70 μm and a mode particle diameter Dv90 of 4.43. Mu.m.
Example 10
The same preparation as in example 1 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 10 below.
Table 10
The experiment gave 6.50g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 2.41 μm and a mode particle diameter Dv90 of 9.53. Mu.m.
Example 11
The difference from example 1 is that: omitting the step (1), adopting 25.0g of analytically pure sodium metaaluminate in the step (2), using deionized water to fix the volume to 50ml, and heating to boil to prepare the sodium aluminate solution. The subsequent processing steps were the same as in example 1.
The experiment gave 11.89g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 4.32 μm and a mode particle diameter Dv90 of 6.62 μm.
Example 12
The difference from example 2 is that in step (1), the wet cake of aluminum hydroxide was not dried, and the wet cake was directly used in step (2), and the seed crystal in step (3) was aluminum hydroxide obtained in step (1) in the same amount as in example 2 after being dried, and the other conditions were the same as in example 2.
The experiment gave 5.88g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 1.27 μm and a mode particle diameter Dv90 of 3.62. Mu.m.
Example 13
The difference from example 1 is that in step (3), the crystals are added to the sodium aluminate solution at once.
The experiment gave 5.43g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 1.75 μm and a mode particle diameter Dv90 of 2.07. Mu.m.
Example 14
The same preparation as in example 2 is carried out, except that the process conditions or parameters A to G involved are as specified in Table 11 below.
TABLE 11
The experiment gave 5.27g of boehmite crystals having a chemical purity of more than 99.5%, a median particle diameter Dv50 of 3.54 μm and a mode particle diameter Dv90 of 5.81 μm.
Example 15
The difference from example 1 is that 41.5260g of crystalline aluminum chloride was replaced with 57.26g of aluminum sulfate octadecabydrate as the soluble aluminum salt raw material A.
The experiment gave 6.35g of boehmite crystals having a chemical purity of more than 99.6%, a median particle diameter Dv50 of 2.87 μm and a mode particle diameter Dv90 of 6.32. Mu.m.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the preparation method of the boehmite powder material utilizes the structural instability of sodium aluminate solution to obtain boehmite precursors with certain morphological characteristics and particle size, and further aggregates and grows up the boehmite precursors through hydrothermal reaction to obtain the micron-sized boehmite powder material. The controllability of the preparation method is high, and the micron-sized boehmite powder material with high purity and uniform particle size can be obtained by controlling the decomposition condition of the sodium aluminate solution and seed crystal iteration. The preparation method is suitable for mass production and is convenient for large-scale application.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the micron-sized boehmite powder material is characterized by comprising the following steps:
step S1, adding seed crystals into a sodium aluminate solution, stirring for a period of time after the seed crystals are added, and filtering to obtain a boehmite precursor;
and S2, dispersing the boehmite precursor in water, performing hydrothermal reaction, filtering and drying after the reaction is finished to obtain the micron-sized boehmite powder.
2. The preparation method according to claim 1, wherein the sodium aluminate solution is prepared by:
step S01, fully dissolving soluble aluminum salt in an aqueous solution to obtain an aluminum salt aqueous solution, adding a first alkali solution to adjust the pH value of the aluminum salt aqueous solution to generate aluminum hydroxide precipitate, and filtering to obtain an aluminum hydroxide precursor;
step S02, mixing the aluminum hydroxide precursor, a second alkali reagent and water to obtain a sodium aluminate solution, wherein the second alkali reagent is sodium hydroxide; preferably, the sodium aluminate solution is formed at 85-100 ℃;
preferably, the soluble aluminum salt comprises any one or more of aluminum chloride, aluminum sulfate and aluminum nitrate;
preferably, the soluble aluminum salt has a purity of 95% or more.
3. The preparation method according to claim 2, wherein in the step S01, the aluminum hydroxide precipitate is aged for 12 to 24 hours and then filtered; preferably, the filter cake obtained by filtering is washed by deionized water with the temperature of 70-90 ℃;
preferably, the concentration of aluminum ions in the aluminum salt aqueous solution is 0.5-0.7 mol/L;
preferably, the first alkali solution is any one or more of sodium hydroxide solution, calcium hydroxide solution and potassium hydroxide solution;
preferably, the concentration of the first alkali solution is 0.5-1 mol/L;
preferably, in the step S01, the pH of the aqueous aluminum salt solution is adjusted to 6 to 10.
4. The method according to claim 2, wherein the sodium aluminate solution is prepared by Na 2 O is calculated to have a concentration of 150-160 g/L, preferably, the ratio of the sodium hydroxide to the aluminum hydroxide precursor in the sodium aluminate solution is converted into Na 2 O and Al 2 O 3 The molar ratio of (2) to (3).
5. The method according to claim 1, wherein the step S1 comprises: adding seed crystal into sodium aluminate solution at 45-65 deg.c; preferably, stirring is performed in the process of adding the seed crystal, and the stirring speed is 30-100 rpm; preferably, the seed crystal is added in multiple times or at a constant speed over a period of time;
preferably, after the seed crystal is added, the temperature is maintained at 45-65 ℃, and the stirring duration is 12-24 hours.
6. The method of preparation according to claim 2, characterized in that the seed is the dried aluminium hydroxide precursor or the boehmite precursor;
preferably, the seed crystal coefficient of the seed crystal is 0.15 to 0.3.
7. The method according to claim 1, wherein step S1 further comprises washing the solid obtained after the filtration with deionized water to obtain the boehmite precursor, preferably, the temperature of deionized water used for the washing is 70 to 90 ℃.
8. The method according to claim 1, wherein in the step S2, the dispersion concentration of the aluminum element in the boehmite precursor in water is 0.5 to 1.0mol/L.
9. The method of claim 1, wherein the hydrothermal reaction is at a temperature of 180-220 ℃;
preferably, the hydrothermal reaction time is 4-12 hours.
10. A micron-sized boehmite powder material prepared by the preparation method according to any one of claims 1 to 9.
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