CN103043695A - Aluminum oxide hollow microsphere and preparation method thereof - Google Patents
Aluminum oxide hollow microsphere and preparation method thereof Download PDFInfo
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- CN103043695A CN103043695A CN2013100061886A CN201310006188A CN103043695A CN 103043695 A CN103043695 A CN 103043695A CN 2013100061886 A CN2013100061886 A CN 2013100061886A CN 201310006188 A CN201310006188 A CN 201310006188A CN 103043695 A CN103043695 A CN 103043695A
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Abstract
The invention provides an aluminum oxide hollow microsphere and a preparation method thereof. The preparation method comprises the steps of adding aluminum alkoxide to an organic solvent to prepare an aluminum alkoxide solution, adding oxalic acid to the aluminum alkoxide solution at a molar ratio of 1:(1-10), stirring, conducting reaction at 100-220 DEG C for 2-48h, conducting pressure reducing suction filtration and alcohol washing, roasting a dried precursor at 400-900 DEG C, and obtaining the aluminum oxide hollow microsphere with a diameter of 1-2 micrometers and a maximum specific surface area of 326m<2>/g. The method is simple in technological flow, economical and environment-friendly.
Description
Technical field
What the present invention relates to is a kind of inorganic functional material and preparation method thereof, specifically a kind of hollow aluminum oxide microspheres and preparation method thereof.
Background technology
The pattern of material, size and spatial arrangement have a great impact its performance, so the design and assembly of material have attracted the interest of Many researchers.Aluminum oxide is a kind of very important inorganic functional material, can be applicable to the numerous areas such as catalysis, absorption, separation, pottery.At present, people have adopted diverse ways to synthesize the nano aluminium oxide with different morphologies.The human template such as Zhu take polyethylene oxide as synthesis of surfactant alumina nano fiber [Zhu, H.Y.; Riches.J.D.; Barry.J.C.Chem.Mater.2002,14,2086.]; The human anonizings such as Zhang are at porous anodic alumina films surface growth one dimension aluminium oxide nano structure [Zhang, L.; Cheng, B.; Shi, W.S; Samulski, E.T.J.Mater.Chem.2005,15,4889.].In recent decades, the hollow ball shaped material has attracted the interest of Many researchers, because hollow ball has the size of good distribution, homogeneous, lower density and high specific surface area, these characteristics have a wide range of applications at catalysis, absorption, biologic applications, sensor numerous areas so that the spherical material of inorganic hollow is more superior than the performance of material of the same type.The preparation and application of alumina hollow ball also cause people's extensive concern recently.For example, the human hard template method such as Lu are prepared a kind of alumina hollow ball [Lu, J.; Liu, S.S.; Deng.C.H.Chem.Commun.2011,47,5334.], the people such as Hu successfully synthesize hollow alumina nanometer ball [Hu, Y.J. as the drop stabilizer with the flame spraying thermal decomposition method with tensio-active agent; Ding, H.Q.; Li, C.Z.Particuology 2011,9, and 528.].Although and can obtain desirable pattern by the material that these methods make, but all more or less exist some defectives, perhaps need harsh synthesis condition, complexity and expensive equipment, perhaps need exhibiting high surface promoting agent or some other certain moduli version, this can have a negative impact to environment.
Summary of the invention
The purpose of this invention is to provide the high hollow aluminum oxide microspheres of a kind of specific surface area.The present invention also aims to provide the preparation method of simple, the economic environmental protection hollow aluminum oxide microspheres of a kind of flow process.
The object of the present invention is achieved like this:
Hollow aluminum oxide microspheres of the present invention is aluminium alcoholates to be joined be mixed with pure aluminum solutions in the organic solvent, be that the ratio of 1:1-10 adds oxalic acid in pure aluminum solutions according to the mol ratio of aluminium alcoholates and oxalic acid, stir, under 100-220 ℃ of temperature, react 2-48h, decompress filter, alcohol wash, dried presoma are 400-900 ℃ of calcining, resulting hollow ball diameter is between 1～2 μ m, and the high specific surface-area reaches 326.4m
2The hollow aluminum oxide microspheres of/g.
The preparation method of hollow aluminum oxide microspheres of the present invention is:
Aluminium alcoholates joined be mixed with pure aluminum solutions in the organic solvent, be that the ratio of 1:1-10 adds oxalic acid in pure aluminum solutions according to the mol ratio of aluminium alcoholates and oxalic acid, stir, react 2-48h under 100-220 ℃ of temperature, decompress filter, alcohol wash, dried presoma obtain hollow aluminum oxide microspheres 400-900 ℃ of calcining.
Described aluminium alcoholates is aluminum isopropylate or trimethyl carbinol aluminium.
Described organic solvent is dehydrated alcohol or Virahol.
Calcining temperature the best is 500 ℃.
The present invention is under the condition without any template, and take aluminium alcoholates as the aluminium source, oxalic acid is hydrolytic reagent, and the water that utilizes the oxalic acid pyrolytic decomposition to produce progressively is hydrolyzed aluminium alcoholates.In reaction process, oxalic acid meeting and solvent form a large amount of esters; The alcohol that simultaneously aluminium alcoholates hydrolysis produces also can with solution in the oxalic acid reaction.As from masterplate, low water concentration can reduce the speed of aluminium alcoholates hydrolysis and condensation in the system, and then causes aluminum ion to be gathered in step by step around a large amount of ester mixtures, the formation core-shell structure with a large amount of ester mixtures of forming.At a certain temperature roasting, ester mixture is removed, and forms alumina hollow ball.Specific surface area is maximum after 500 ℃ of roastings, reaches 326.4m
2/ g.
Simple, the economic environmental protection of the technical process of method of the present invention.
Description of drawings
Fig. 1 is the XRD figure of the hollow aluminum oxide microspheres that obtains of 800 ℃ of lower roastings.
Fig. 2 A is the TEM figure of presoma, and Fig. 2 B is the TEM figure of 500 ℃ of product of roasting hollow aluminum oxide microspheres.
Embodiment
The invention will be further described for example for the below.
Embodiment 1: take trimethyl carbinol aluminium as the aluminium source, ethanol is solvent, and oxalic acid is hydrolytic reagent.Trimethyl carbinol aluminium joins in the ethanol, and the room temperature lower magnetic force is mixed with the ethanolic soln of aluminum isopropylate to fully dissolving.Mol ratio according to aluminum isopropylate and oxalic acid is the ratio adding oxalic acid of 1:3, continues to stir the formation settled solution.The solution that obtains has been transferred in the teflon-lined reactor 200 ℃ of reaction 12h.Suction filtration is used the dehydrated alcohol repetitive scrubbing, and drying obtains presoma.Presoma is 500 ℃ of roasting 4h in retort furnace, can obtain hollow aluminum oxide microspheres.
Embodiment 2:
Be Virahol with solvent replacement, other conditions such as embodiment 1.
Embodiment 3:
The mol ratio that changes aluminium alcoholates and hydrolytic reagent oxalic acid is 1:5 or 1:7, other conditions such as embodiment 1.
Embodiment 4:
The temperature that changes hydro-thermal reaction is 120 ℃, 160 ℃ or 180 ℃, other conditions such as embodiment 1.
Embodiment 6:
Changing calcining temperature is 600 ℃ or 800 ℃, other condition such as embodiment 1.
Claims (8)
1. hollow aluminum oxide microspheres, it is characterized in that: be aluminium alcoholates to be joined be mixed with pure aluminum solutions in the organic solvent, be that the ratio of 1:1-10 adds oxalic acid in pure aluminum solutions according to the mol ratio of aluminium alcoholates and oxalic acid, stir, under 100-220 ℃ of temperature, react 2-48h, decompress filter, alcohol wash, dried presoma are 400-900 ℃ of calcining, and resulting hollow ball diameter is between 1～2 μ m, and the high specific surface-area reaches 326.4m
2The hollow aluminum oxide microspheres of/g.
2. hollow aluminum oxide microspheres according to claim 1, it is characterized in that: described aluminium alcoholates is aluminum isopropylate or trimethyl carbinol aluminium.
3. hollow aluminum oxide microspheres according to claim 1 and 2, it is characterized in that: described organic solvent is dehydrated alcohol or Virahol.
4. the preparation method of a hollow aluminum oxide microspheres, it is characterized in that: aluminium alcoholates is joined be mixed with pure aluminum solutions in the organic solvent, be that the ratio of 1:1-10 adds oxalic acid in pure aluminum solutions according to the mol ratio of aluminium alcoholates and oxalic acid, stir, react 2-48h under 100-220 ℃ of temperature, decompress filter, alcohol wash, dried presoma obtain hollow aluminum oxide microspheres 400-900 ℃ of calcining.
5. the preparation method of hollow aluminum oxide microspheres according to claim 4, it is characterized in that: described aluminium alcoholates is aluminum isopropylate or trimethyl carbinol aluminium.
6. according to claim 4 or the preparation method of 5 described hollow aluminum oxide microspheres, it is characterized in that: described organic solvent is dehydrated alcohol or Virahol.
7. it is characterized in that according to claim 4 or the preparation method of 5 described hollow aluminum oxide microspheres: calcining temperature is selected 500 ℃.
8. the preparation method of hollow aluminum oxide microspheres according to claim 6 is characterized in that: 500 ℃ of calcining temperature selections.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126686A (en) * | 2018-08-29 | 2019-01-04 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of hierarchical structure Hollow Compound nano aluminium oxide |
Citations (3)
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| US3674461A (en) * | 1965-04-15 | 1972-07-04 | Canadian Patents Dev | Hollow spherical articles |
| CN101367535A (en) * | 2008-10-09 | 2009-02-18 | 武汉理工大学 | Hydrothermal method for preparing gamma-AL2O3 hollow microsphere polishing material without mould plate |
| CN101885502A (en) * | 2010-07-05 | 2010-11-17 | 西南科技大学 | Method for preparing hollow aluminum oxide microspheres |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674461A (en) * | 1965-04-15 | 1972-07-04 | Canadian Patents Dev | Hollow spherical articles |
| CN101367535A (en) * | 2008-10-09 | 2009-02-18 | 武汉理工大学 | Hydrothermal method for preparing gamma-AL2O3 hollow microsphere polishing material without mould plate |
| CN101885502A (en) * | 2010-07-05 | 2010-11-17 | 西南科技大学 | Method for preparing hollow aluminum oxide microspheres |
Non-Patent Citations (4)
| Title |
|---|
| 《JOURNAL OF MATERIALS SCIENCE》 19981221 M. CHATTERJEE et al. "Hollow alumina microspheres from boehmite sols" 第4937-4942页 1-8 第33卷, * |
| 《中国陶瓷》 20060228 王细凤等 《晶种的加入对异丙醇铝水解制备alpha -Al2O3 的影响》 第25-27页 1-8 第42卷, 第2期 * |
| M. CHATTERJEE ET AL.: ""Hollow alumina microspheres from boehmite sols"", 《JOURNAL OF MATERIALS SCIENCE》, vol. 33, 21 December 1998 (1998-12-21), pages 4937 - 4942 * |
| 王细凤等: "《晶种的加入对异丙醇铝水解制备α -Al2O3 的影响》", 《中国陶瓷》, vol. 42, no. 2, 28 February 2006 (2006-02-28), pages 25 - 27 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126686A (en) * | 2018-08-29 | 2019-01-04 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of hierarchical structure Hollow Compound nano aluminium oxide |
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