CN108658108A - A kind of preparation method of hollow aluminum oxide microspheres - Google Patents
A kind of preparation method of hollow aluminum oxide microspheres Download PDFInfo
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- CN108658108A CN108658108A CN201810522070.1A CN201810522070A CN108658108A CN 108658108 A CN108658108 A CN 108658108A CN 201810522070 A CN201810522070 A CN 201810522070A CN 108658108 A CN108658108 A CN 108658108A
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- aluminum oxide
- alooh
- hollow aluminum
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- oxide microspheres
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- 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
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- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a kind of preparation methods of hollow aluminum oxide microspheres, and aluminum soluble salt is added in absolute ethyl alcohol and the mixed solution of deionized water first, after mixing in certain temperature sealing, a certain amount of propylene oxide are added, makes its fast sol gel；Then by gel in the organic solvents such as isopropanol aging certain time, after drying process, obtain γ AlOOH tiny balloons, then calcine γ AlOOH tiny balloons to get to the hollow aluminum oxide microspheres of different crystal forms in different temperatures.This method is simple for process, at low cost, controllability is good and is easy to prepare on a large scale, prepared tiny balloon large specific surface area, homogeneous grain diameter and good dispersion.
Description
Technical field
The invention belongs to inorganic functional material fields, are related to a kind of preparation method of hollow aluminum oxide microspheres.
Background technology
Aluminium oxide is widely used in as a kind of important industrial materials in people's life, such as：Catalyst carrier, suction
Attached dose, ceramics and grinding agent.Micro-nano rank hollow aluminum oxide microspheres not only have the distinctive high rigidity of aluminium oxide itself, Gao Rong
Point and the characteristics such as corrosion-resistant, and due to hollow structure, it also has the characteristics that more high adsorption, low-density.
The preparation process of tiny balloon probably divides two major classes, one kind to be templates, and another kind of is template-free method.Currently, big
Majority report concentrates on template, template have the hard templates such as polymer, charcoal ball, inorganic material, metal nanoparticle and micella,
The soft templates such as drop.However, these template prevailing prices are expensive, and preparation process complicated and time consumption effort.Template-free method is main
It is to prepare tiny balloon by Ostwald ripening mechanisms, advantage is the introducing and removing without template, is eliminated
Complicated pilot process, has saved time and cost of material.
Sun et al. prepares charcoal ball using hydro-thermal method, then prepares hollow aluminum oxide microspheres using charcoal ball as template.However, this
Technique due to cumbersome, and the cost for preparing template program, be not suitable for industrialization large-scale production [X.M.Sun, Y.D.Li,
Colloidal Carbon Spheres and Their Core/Shell Structures with Noble-Metal
Nanoparticles[J].Angew.Chem.Int.Ed.,2004,43(5):597-601].Chemical induction self assembly method saves
Expensive template and complicated preparation flow have been gone, has been effective, the simple technique for preparing tiny balloon.Cai et al.
Using this principle, using hydrothermal synthesis method be prepared for γ-AlOOH tiny balloons [W.Q.Cai, J.G.Yu, S.Mann,
Template-free hydrothermal fabrication of hierarchically organizedγ-AlOOH
hollow microspheres[J].Microporous Mesoporous Mater.,2009,122:42-47], it prepares
Tiny balloon size can be controlled by the time of hydro-thermal, however, hydro-thermal reaction needs to provide a complicated external environment.
Therefore, consider, a kind of simple, controllable, environmentally friendly preparation process prepare hollow aluminum oxide microspheres need it is further
Research.
Invention content
The technical problem to be solved by the present invention is to provide a kind of aluminium oxide in view of the deficiency of the prior art
The preparation method of tiny balloon can prepare various crystal form hollow aluminum oxide microspheres by controlling calcination temperature, simple, controllable,
It is environmental-friendly, and be produced on a large scale.
The present invention be solve the problems, such as it is set forth above used by technical solution be：
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles；
γ-AlOOH full particles are changed by solvent-induced completion village hollowing, it is hollow to obtain γ-AlOOH by step 2
Microballoon；
Step 3, γ-AlOOH tiny balloons are by the calcination processing of different temperatures, to obtain the oxidation of different crystal forms
Aluminium tiny balloon.
By said program, Fast sol-gel prepare γ-AlOOH full particles the step of it is as follows：By soluble inorganic aluminium
Salt is added in the mixed solvent, is uniformly mixed in 40 DEG C -70 DEG C；Then propylene oxide, which is added, makes its Fast sol-gel, molten
The time of glue-gel is 15s or so, as γ-AlOOH full particles gel.Wherein, presoma inorganic aluminate is in mixed solvent
A concentration of 1-3mmol/mL, mixed solvent is that deionized water and alcohol miscible with water mix；Propylene oxide and solubility
The molar ratio of Al is 3-8 in aluminium salt.
By said program, the preparation process of γ-AlOOH tiny balloons is as follows：By γ-AlOOH full particle gels different
Aging certain time in the organic solvents such as propyl alcohol after drying process, obtains γ-AlOOH tiny balloons.Wherein, aging solvent is
Isopropanol, ethyl alcohol and acetone and other organic solvent；Aging temperature be 50 DEG C -70 DEG C, ageing time 0h-48h, aging solvent every
8-16h replaces primary.
By said program, the γ-AlOOH tiny balloons have " sea urchin shape " shell, and grain size is at 2-3 μm.
By said program, the temperature of the calcination processing is within the scope of 600 DEG C -1200 DEG C, and calcination time is in 1-3h.Its
In, the corresponding hollow aluminum oxide microspheres type of calcination processing of different temperatures is respectively：Room temperature do not calcine for γ-AlOOH it is hollow
Microballoon, 600 DEG C of calcinings are γ-Al2O3Tiny balloon, 1000 DEG C of calcinings are δ-Al2O3Tiny balloon, 1200 DEG C of calcinings are α-
Al2O3Tiny balloon.
By said program, the hollow aluminum oxide microspheres of the different crystal forms obtained by the calcination processing of different temperatures have all had
Good hollow-core construction and grain size concentrates on 2-3 μm.
Compared with existing hollow aluminum oxide microspheres technology of preparing, the beneficial effects of the invention are as follows：
Mainly in two steps, first is Fast sol gel process to the present invention, this process time is short (15s or so),
Manufacturing cycle is greatly accelerated, propylene oxide (is also attempted some other as a kind of efficient proton remover in research process
Substance cannot obtain the PhastGel effect), the polymerization of aluminium ion fast hydrolyzing can be made to generate three-dimensional net structure；Second
A step is village hollowing transition process, this process carries out in organic solvent, without the environment such as external special high temperature, this aging
Journey equipment requirement is simple and environmentally protective, at low cost.Whole preparation process is simple for process, environmentally protective without template, process, at
This is low, controllability is good and is easy to prepare on a large scale, obtained tiny balloon large specific surface area, homogeneous grain diameter and good dispersion.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates using 1-5 of the embodiment of the present invention hollow aluminum oxide microspheres prepared.
Fig. 2 is scanning electron microscope (SEM) photo that hollow aluminum oxide microspheres are prepared using 1-5 of the embodiment of the present invention；
Wherein, (a) room temperature, (b) 600 DEG C, (c) 900 DEG C, (d) 1000 DEG C, (e) 1200 DEG C of difference corresponding embodiment 1-5.
Fig. 3 is the TEM figures that embodiment 1 prepares γ-AlOOH tiny balloons.
Specific implementation mode
Below by specific embodiment, invention is further described in detail, but present disclosure not only limits
In the embodiment.
Embodiment 1
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles：By 20mmolAlCl3·6H2O is dissolved in 4ml
The in the mixed solvent of deionized water and 6ml absolute ethyl alcohols is stirred evenly in 60 DEG C；Being then quickly added into 0.1mol propylene oxide makes
Its PhastGel, sol-gel time just complete in 15s or so, as γ-AlOOH full particles gel；
Step 2, by above-mentioned gel in 60 DEG C of aging 48h in isopropanol, isopropanol replaces primary, drying every 12h
Afterwards, γ-AlOOH tiny balloons are obtained.
Embodiment 2
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles：By 20mmolAlCl3·6H2O is dissolved in 4ml
The in the mixed solvent of deionized water and 6ml absolute ethyl alcohols is stirred evenly in 60 DEG C；Being then quickly added into 0.1mol propylene oxide makes
Its PhastGel, sol-gel time just complete in 15s or so, as γ-AlOOH full particles gel.；
Step 2, by above-mentioned gel in 60 DEG C of aging 48h in isopropanol, isopropanol replaces primary, drying every 12h
Afterwards, γ-AlOOH tiny balloons are obtained；
Above-mentioned gained γ-AlOOH tiny balloons are calcined 2h in 600 DEG C, obtain γ-Al by step 32O3Tiny balloon.
Embodiment 3
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles：By 20mmolAlCl3·6H2O is dissolved in 4ml
The in the mixed solvent of deionized water and 6ml absolute ethyl alcohols is stirred evenly in 60 DEG C；Being then quickly added into 0.1mol propylene oxide makes
Its PhastGel, sol-gel time just complete in 15s or so, as γ-AlOOH full particles gel.；
Step 2, by above-mentioned gel in 60 DEG C of aging 48h in isopropanol, isopropanol replaces primary, drying every 12h
Afterwards, γ-AlOOH tiny balloons are obtained；
Above-mentioned gained γ-AlOOH tiny balloons are calcined 2h in 900 DEG C, obtain δ-Al by step 32O3Tiny balloon.
Embodiment 4
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles：By 20mmolAlCl3·6H2O is dissolved in 4ml
The in the mixed solvent of deionized water and 6ml absolute ethyl alcohols is stirred evenly in 60 DEG C；Being then quickly added into 0.1mol propylene oxide makes
Its PhastGel, sol-gel time just complete in 15s or so, as γ-AlOOH full particles gel.；
Step 2, by above-mentioned gel in 60 DEG C of aging 48h in isopropanol, isopropanol replaces primary, drying every 12h
Afterwards, γ-AlOOH tiny balloons are obtained；
Above-mentioned gained γ-AlOOH tiny balloons are calcined 2h in 1000 DEG C, obtain δ-Al by step 32O3Tiny balloon.
Embodiment 5
A kind of preparation method of hollow aluminum oxide microspheres, key step are as follows：
Step 1, Fast sol-gel prepare γ-AlOOH full particles：By 20mmolAlCl3·6H2O is dissolved in 4ml
The in the mixed solvent of deionized water and 6ml absolute ethyl alcohols is stirred evenly in 60 DEG C；Being then quickly added into 0.1mol propylene oxide makes
Its PhastGel, sol-gel time just complete in 15s or so, as γ-AlOOH full particles gel；
Step 2, by above-mentioned gel in 60 DEG C of aging 48h in isopropanol, isopropanol replaces primary, drying every 12h
Afterwards, γ-AlOOH tiny balloons are obtained.
Above-mentioned gained γ-AlOOH tiny balloons are calcined 2h in 1200 DEG C, obtain α-Al by step 32O3Tiny balloon.
As can be seen from Figure 1：γ-AlOOH tiny balloons are γ-Al after 600 DEG C of calcinings2O3Tiny balloon is calcined through 1000 DEG C
It is δ-Al afterwards2O3Tiny balloon is α-Al after 1200 DEG C of calcinings2O3Tiny balloon.
As shown in Figure 2：Calcination processing is carried out to γ-AlOOH tiny balloons, with the raising of calcination temperature, microsphere surface
Pattern does not vary widely, is " sea urchin shape " shell, and the size of tiny balloon is not shunk, size is on a 2-3 μm of left side
It is right；When improving calcination temperature to 1200 DEG C, " sea urchin shape " nanometer sheet of outer surface completely disappears, and occurs many holes on shell,
Shell is accumulated by nano particle, is still hollow-core construction, larger contraction does not occur for size.
Embodiment described above is better embodiment of the present invention, but the specific implementation mode of the present invention is not by above-mentioned implementation
The limitation of example, under without departing from the principle of the present invention and technical process made by it is other it is any change, substitute, simplify etc., be
Equivalent displacement should be all included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of hollow aluminum oxide microspheres, it is characterised in that key step is as follows：
Step 1, using propylene oxide as coagulant, uses sol-gel to prepare in a solvent using aluminium salt as presomaγ-
AlOOH full particles；
Step 2, willγ- AlOOH full particles are induced by organic solvent completes village hollowing transformation, obtainsγ- AlOOH is hollow
Microballoon；
Step 3,γ- AlOOH tiny balloons are by the calcination processing of different temperatures, to which the aluminium oxide for obtaining different crystal forms is empty
Heart microballoon.
2. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that the sol-gel
Time be no more than 20s.
3. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that aluminium salt is in a solvent
A concentration of 1-3mmol/mL.
4. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that described；Propylene oxide
Molar ratio with Al in aluminium salt is 3-8.
5. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that the solvent is water
With the mixed solvent of alcohol miscible with water.
6. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that the step 2 tool
Body is：It willγAfter aging, γ-AlOOH tiny balloons are obtained through being dried in organic solvent for-AlOOH full particles gel.
7. a kind of preparation method of hollow aluminum oxide microspheres according to claim 6, it is characterised in that aging temperature 50
DEG C -70 DEG C, ageing time is no more than 48h.
8. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that the calcination processing
Temperature within the scope of 600 DEG C -1200 DEG C, calcination time 1h-3h.
9. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1, it is characterised in that different temperatures is forged
Burning the corresponding hollow aluminum oxide microspheres crystal form of processing is respectively：Room temperature is not calcined as γ-AlOOH, and 600 DEG C of calcinings are γ-Al2O3,
1000 DEG C of calcinings are δ-Al2O3, 1200 DEG C of calcinings are α-Al2O3。
10. a kind of preparation method of hollow aluminum oxide microspheres according to claim 1-9, it is characterised in that obtained by step 3
Different crystal forms hollow aluminum oxide microspheres, all have intact hollow-core construction and grain size concentrate on 2-3 μm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504370A (en) * | 2018-12-12 | 2019-03-22 | 长飞光纤光缆股份有限公司 | A kind of Al2O3:Eu3+Hollow microspheres and preparation method thereof |
| CN112960681A (en) * | 2021-04-19 | 2021-06-15 | 陕西科技大学 | Method for preparing self-assembled hollow alumina microspheres by using sesbania gum as template |
| CN112980334A (en) * | 2021-03-03 | 2021-06-18 | 杭州智华杰科技有限公司 | Method for improving suspension property of aluminum oxide polishing powder |
| CN112978774A (en) * | 2021-04-19 | 2021-06-18 | 陕西科技大学 | Method for preparing self-assembled hollow alumina microspheres by using double precipitants |
| CN113735614A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of spherical alumina |
| CN114644352A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Double-hole distribution alumina spherical particle and preparation method thereof |
| CN115448338A (en) * | 2021-05-21 | 2022-12-09 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
-
2018
- 2018-05-28 CN CN201810522070.1A patent/CN108658108A/en active Pending
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504370A (en) * | 2018-12-12 | 2019-03-22 | 长飞光纤光缆股份有限公司 | A kind of Al2O3:Eu3+Hollow microspheres and preparation method thereof |
| CN113735614A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of spherical alumina |
| CN114644352A (en) * | 2020-12-17 | 2022-06-21 | 中国石油化工股份有限公司 | Double-hole distribution alumina spherical particle and preparation method thereof |
| CN114644352B (en) * | 2020-12-17 | 2024-02-13 | 中国石油化工股份有限公司 | Double-pore distribution alumina spherical particle and preparation method thereof |
| CN112980334A (en) * | 2021-03-03 | 2021-06-18 | 杭州智华杰科技有限公司 | Method for improving suspension property of aluminum oxide polishing powder |
| CN112960681A (en) * | 2021-04-19 | 2021-06-15 | 陕西科技大学 | Method for preparing self-assembled hollow alumina microspheres by using sesbania gum as template |
| CN112978774A (en) * | 2021-04-19 | 2021-06-18 | 陕西科技大学 | Method for preparing self-assembled hollow alumina microspheres by using double precipitants |
| CN115448338A (en) * | 2021-05-21 | 2022-12-09 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
| CN115448338B (en) * | 2021-05-21 | 2024-02-20 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
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Application publication date: 20181016 |