CN106673033A - Core-shell-structure alumina microspheres and preparation method thereof - Google Patents
Core-shell-structure alumina microspheres and preparation method thereof Download PDFInfo
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- CN106673033A CN106673033A CN201510761642.8A CN201510761642A CN106673033A CN 106673033 A CN106673033 A CN 106673033A CN 201510761642 A CN201510761642 A CN 201510761642A CN 106673033 A CN106673033 A CN 106673033A
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- C—CHEMISTRY; METALLURGY
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/60—Compounds characterised by their crystallite size
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- 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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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/50—Agglomerated particles
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- 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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Abstract
The invention discloses core-shell-structure alumina microspheres and a preparation method thereof. The alumina microspheres have the following properties: the diameter of the core-shell-structure alumina microspheres is 3-5 mu m; the outer shell is 0.5-1 mu m thick, and is assembled from tabular alumina with the grain size of 0.2-0.5 mu m and the thickness of 0.05-0.1 mu m, and the tabular alumina interpenetrates to be assembled into the flower structure; and the inner core has the diameter of 2-4 mu m, and is formed by closely packing alumina granules with the diameter of 10-20nm. The preparation method of the core-shell-structure alumina microspheres comprises the following steps: dissolving AlCl3.6H2O, urea and epoxy alkane in anhydrous ethanol, and reacting in a closed reactor; and after the reaction finishes, filtering to obtain the precipitate, washing, drying and roasting to obtain the core-shell-structure alumina microspheres. The core-shell-structure alumina microspheres have the advantages of high purity, low cost and uniform particle size. The preparation method is simple, and can easily implement industrial production.
Description
Technical field
The present invention relates to a kind of aluminum oxide micro-sphere of core shell structure and preparation method thereof.
Background technology
Hierarchical structure nano material is referred to and forms secondary structure unit by self assembly or oriented growth by nano-scale, then forms the micron and scale above material of Special Sequence Structures by certain effect.Aluminum oxide has unique catalysis, absorption, optics and Electronic Performance, and cheap, thus becomes one of most widely used material.Hierarchy nano aluminium oxide is due to the construction unit with nanoscale and the overall pattern of micron and scale above, and the coupling effect and cooperative effect of micro-nano yardstick, while making it have high surface energy and special surface property, can prevent liquid phase from reuniting, and can improve its production and using when separation and recovery, moreover it is possible to strengthen mechanical endurance.Core shell structure aluminum oxide micro-sphere is one kind of hierarchy nano aluminium oxide, and in recent years, the preparation and application of core shell structure aluminum oxide micro-sphere also result in the interest of people.
《The Journal of Physical
Chemistry C》（2009, volume 113, page 14739 ~ 14746）, " Synthesis of Boehmite Hollow
Core/Shell and Hollow Microspheres via Sodium Tartrate- Mediated Phase
In Transformation and Their Enhanced Adsorption Performance in Water Treatment ", using Al2(SO4)3·18H2O、CO(NH2)2, sodium tartrate the boehmite of core shell structure is prepared for raw material, the method adopts Al2(SO4)3·18H2O is raw material, SO4 2-The more difficult cleaning of ion, is easily caused product purity reduction.
《Chinese Journal of Inorganic Chemistry》（2008, volume 24（5）, page 760 ~ 764）In " hydro-thermal method prepares core-shell structure boehmite superfine powder ", with aluminum sulfate aqueous solution and urea as raw material, amphiphilic block copolymer PS-b-PAA -2- hydroxy methacrylates (P (St)-b-P (HEA)) are structure directing agent, and by hydro-thermal method nucleocapsid shape boehmite superfine powder has been synthesized.The method equally exists SO4 2-The more difficult cleaning of ion, is easily caused the shortcoming of product purity reduction.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of aluminum oxide micro-sphere of core shell structure and preparation method thereof.Core shell structure aluminum oxide micro-sphere purity height of the present invention, low cost, homogeneous grain diameter, preparation method is simple, it is easy to industrial production.
The aluminum oxide micro-sphere of the core shell structure of the present invention, with following property：A diameter of 3 ~ 5 μm of the aluminum oxide micro-sphere of core shell structure, shell shell thickness is 0.5 ~ 1 μm, by crystallite dimension be 0.2 ~ 0.5 μm, thick 0.05-0.1 μm of tabular alumina assembles, tabular alumina is mutually interspersed to be assembled into flower-like structure, kernel is a diameter of 2 ~ 4 μm, is formed by the particulate oxidation aluminum particulate of a diameter of 10-20nm is tightly packed；Specific surface area is 210-260m2/g。
The preparation method of the aluminum oxide micro-sphere of the core shell structure of the present invention, including：By AlCl3·6H2O, urea and epoxyalkane are dissolved in absolute ethyl alcohol, are reacted in closed reactor, after reaction terminates, precipitation filtered, washed, be dried and roasting, obtain core shell structure aluminum oxide micro-sphere.
In the inventive method, described epoxyalkane is one or more mixing in oxirane, expoxy propane or epoxy butane.
In the inventive method, described urea and AlCl3·6H2The mass ratio of O is 0.8:1-1.5:1；Described epoxyalkane and AlCl3·6H2The mass ratio of O is 0.03:1-0.15:1.
In the inventive method, described absolute ethyl alcohol and AlCl3·6H2The mass ratio of O is 3:1-6:1.
In the inventive method, described closed reactor is autoclave, can be dynamic response kettle or static reaction kettle, preferred static reaction kettle；Described reaction temperature be 160-220 DEG C, preferred 170-190 DEG C, the reaction time be 18-36 hours, preferred 24-30 hours.
In the inventive method, washing can also adopt conventional wash, deionized water cyclic washing 4-5 time, till Cl ion concentration ＜ 0.2m% in hydrated alumina using supersound washing.
In the inventive method, described drying condition：Baking temperature is 100-130 DEG C, and drying time is 1-10 hours；Described roasting condition is：Sintering temperature is 450-600 DEG C, and roasting time is 2-6 hours.
Compared with prior art, the raw material that the present invention is adopted is cheap, and reaction preparation process is simple, it is not necessary to special template agent, equipment and technique.Core shell structure aluminum oxide micro-sphere of the present invention, with specific surface area is big, uniform particle sizes the features such as, the field such as can be used to being catalyzed, adsorb, be especially suitable for the adsorbing domains such as sewage disposal.
Description of the drawings
Fig. 1 is the stereoscan photograph of hollow aluminum oxide microspheres prepared by embodiment 1.
Fig. 2 is the stereoscan photograph of hollow aluminum oxide microspheres prepared by comparative example 1.
Fig. 3 is the stereoscan photograph of aluminum oxide prepared by comparative example 2.
Fig. 4 is the stereoscan photograph of aluminum oxide prepared by comparative example 3.
Specific embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following examples.
The preparation method of the aluminum oxide micro-sphere of the core shell structure of the present invention, concrete preparation process is as follows：
（1）By appropriate AlCl3.6H2O, urea, epoxyalkane are dissolved into appropriate ethanol solution, and magnetic agitation is completely dissolved solid matter；
（2）By step（1）Solution proceed in autoclave, by reactor be placed in baking oven in 160-220 DEG C be heat-treated 18-36 hours；
（3）By step（2）Precipitation Jing of gained is filtered, washed, being dried, roasting is obtained core shell structure aluminum oxide micro-sphere.
Embodiment 1
By 12.45 grams of AlCl3·6H2O, 10 grams of urea, 0.75 gram of expoxy propane are placed in beaker, add 50ml absolute ethyl alcohols, magnetic agitation to be completely dissolved solid matter in beaker.The solution for obtaining is proceeded in autoclave, reactor is placed in baking oven and is heat-treated 24 hours in 160 DEG C.Naturally cool to precipitate after room temperature Jing filter, washing, 120 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, core shell structure aluminum oxide micro-sphere is obtained, scanning electron microscopic picture is as shown in Figure 1.
Embodiment 2
With embodiment 1, simply the addition of urea is 15 grams, and expoxy propane is changed to oxirane, and addition is 0.4 gram, and the addition of absolute ethyl alcohol is 37ml, and heat treatment temperature is 200 DEG C, and process time is 18 hours, obtains the aluminum oxide micro-sphere of core shell structure.
Embodiment 3
With embodiment 1, simply the addition of urea is 12.45 grams, and expoxy propane is changed to epoxy butane, and addition is 1.5 grams, and the addition of absolute ethyl alcohol is 62ml, and heat treatment temperature is 220 DEG C, and process time is 30 hours, obtains the aluminum oxide micro-sphere of core shell structure.
Embodiment 4
With embodiment 1, simply the addition of urea is 18.7 grams, and expoxy propane is changed to mass ratio for 1:1 oxirane and the mixture of expoxy propane, addition is 1.1 grams, and the addition of absolute ethyl alcohol is 74.7ml, and heat treatment temperature is 180 DEG C, and process time is 36 hours, obtains the aluminum oxide micro-sphere of core shell structure.
Embodiment 5
With embodiment 1, simply the addition of urea is 17.4 grams, and the addition of expoxy propane is 1.9 grams, and the addition of absolute ethyl alcohol is 56ml, and heat treatment temperature is 190 DEG C, and process time is 32 hours, obtains the aluminum oxide micro-sphere of core shell structure.
Comparative example 1
With embodiment 1, simply silicon source is the Al (NO with the aluminium ion equimolar amounts of example 13)3·9H2O；The scanning electron microscopic picture of the aluminum oxide for obtaining is as shown in Figure 2.
Comparative example 2
With embodiment 1, absolute ethyl alcohol is simply changed to the deionized water of phase homogenous quantities；The scanning electron microscopic picture of the aluminum oxide for obtaining is as shown in Figure 3.
Comparative example 3
With embodiment 1, simply epoxyalkane is not added in raw material；The scanning electron microscopic picture for obtaining aluminum oxide is as shown in Figure 4.
Claims (10)
1. a kind of aluminum oxide micro-sphere of core shell structure, it is characterised in that：With following property：A diameter of 3 ~ 5 μm of the aluminum oxide micro-sphere of core shell structure, shell shell thickness is 0.5 ~ 1 μm, by crystallite dimension be 0.2 ~ 0.5 μm, thick 0.05-0.1 μm of tabular alumina assembles, tabular alumina is mutually interspersed to be assembled into flower-like structure, kernel is a diameter of 2 ~ 4 μm, is formed by the particulate oxidation aluminum particulate of a diameter of 10-20nm is tightly packed.
2. according to the aluminum oxide micro-sphere described in claim 1, it is characterised in that：The specific surface area of aluminum oxide micro-sphere is 210-260m2/g。
3. the preparation method of the aluminum oxide micro-sphere of the core shell structure described in a kind of claim 1, it is characterised in that include：By AlCl3·6H2O, urea and epoxyalkane are dissolved in absolute ethyl alcohol, are reacted in closed reactor, after reaction terminates, precipitation filtered, washed, be dried and roasting, obtain core shell structure aluminum oxide micro-sphere.
4. in accordance with the method for claim 3, it is characterised in that：Described epoxyalkane is one or more mixing in oxirane, expoxy propane or epoxy butane.
5. in accordance with the method for claim 3, it is characterised in that：Described urea and AlCl3·6H2The mass ratio of O is 0.8:1-1.5:1.
6. in accordance with the method for claim 3, it is characterised in that：Described epoxyalkane and AlCl3·6H2The mass ratio of O is 0.03:1-0.15:1.
7. in accordance with the method for claim 3, it is characterised in that：Described absolute ethyl alcohol and AlCl3·6H2The mass ratio of O is 3:1-6:1.
8. in accordance with the method for claim 3, it is characterised in that：Described reaction temperature is 160-220 DEG C, and the reaction time is 18-36 hours.
9. in accordance with the method for claim 3, it is characterised in that：Described drying condition：Baking temperature is 100-130 DEG C, and drying time is 1-10 hours.
10. in accordance with the method for claim 3, it is characterised in that：Described roasting condition is：Sintering temperature is 450-600 DEG C, and roasting time is 2-6 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021078292A1 (en) | 2019-10-25 | 2021-04-29 | 中国石油化工股份有限公司 | Alumina grain, preparation method therefor and use thereof |
| CN113019310A (en) * | 2021-03-30 | 2021-06-25 | 中国建筑设计研究院有限公司 | Alumina ball with building garbage core aggregate coated by active alumina and preparation method |
| CN115465875A (en) * | 2022-09-22 | 2022-12-13 | 齐鲁工业大学 | Heavy-petal hollow-petal spherical gamma-alumina microsphere and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021078292A1 (en) | 2019-10-25 | 2021-04-29 | 中国石油化工股份有限公司 | Alumina grain, preparation method therefor and use thereof |
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| CN113019310B (en) * | 2021-03-30 | 2024-03-29 | 中国建筑设计研究院有限公司 | Alumina ball with activated alumina coated with building rubbish core aggregate and preparation method |
| CN115465875A (en) * | 2022-09-22 | 2022-12-13 | 齐鲁工业大学 | Heavy-petal hollow-petal spherical gamma-alumina microsphere and preparation method thereof |
| CN115465875B (en) * | 2022-09-22 | 2023-08-22 | 齐鲁工业大学 | Heavy-petal hollow flower spherical gamma-alumina microsphere and preparation method thereof |
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