CN108217703B - Preparation method of hollow alumina microspheres - Google Patents
Preparation method of hollow alumina microspheres Download PDFInfo
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- CN108217703B CN108217703B CN201810081028.0A CN201810081028A CN108217703B CN 108217703 B CN108217703 B CN 108217703B CN 201810081028 A CN201810081028 A CN 201810081028A CN 108217703 B CN108217703 B CN 108217703B
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- 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
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- C01P2004/34—Spheres hollow
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Abstract
The invention discloses a preparation method of hollow alumina microspheres, which comprises the following steps of 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution; step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 30-60min, then adding into a mold, and rapidly cooling to obtain high-molecular spherical particles; step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles; step 4, putting the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 3-5 hours to obtain cured spherical particles; and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolysis for 3-5h, taking out after the reaction is finished, cleaning, and drying to obtain the hollow alumina microspheres. The invention solves the problem of difficult preparation of the inorganic hollow sphere, and the preparation method is simple and quick, has stable structure and larger specific surface area.
Description
Technical Field
The invention belongs to the field of functional ceramics, and particularly relates to a preparation method of hollow alumina microspheres.
Background
Compared with the bulk material, the nano material (especially with a hollow structure) has the characteristics of low density, high specific surface area, good stability, strong surface permeability, special optical properties and the like, and is one of the directions of interest in the field of material research. The alumina hollow structure has a hollow structure, has a larger specific surface area, can adsorb and fill particles, has high chemical stability, can remarkably improve catalytic efficiency due to large specific surface area and pore size and high activity when the size of the alumina hollow structure is reduced to a nano scale, can be used as a packaged very small reactor, and is widely applied to catalytic cracking of heavy oil macromolecules, heterogeneous catalysis, novel reactors in chemical engineering, adsorption separation and immobilized enzyme conversion in petrochemical engineering, carriers in automobile exhaust treatment, carriers for drug delivery, development of artificial batteries, protection of bioactive agents such as proteins, enzymes or deoxyribonucleic acid (DNA), and the like.
A range of materials have been fabricated into hollow spherical structures by various methods, including carbon, polymers, metals and other inorganic materials. The main methods for preparing hollow microspheres are nozzle reaction processes, emulsion/phase separation processes, and removable core technologies. The latter two methods can be broadly classified as a template method, and there are two types of templates that are generally used as a core, a soft template serving as the former and a hard template serving as the latter. The templates used in common use are mainly: lyotropic liquid crystals, copolymer mesophases, bicontinuous microemulsion droplets, emulsion foams, monodisperse inorganic spheres, stacks thereof, bacterial supramolecules, polystyrene emulsion spheres.
The preparation of the inorganic hollow spheres mainly comprises metal oxides and metals, and most of the previous works are difficult to control, and the operation process is generally complex, so that the application of the inorganic hollow spheres is limited to a great extent. Reports on the synthesis of alumina core-shell, hollow spheres are rare.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of hollow alumina microspheres, which solves the problem of difficulty in preparation of inorganic hollow spheres, and has the advantages of simple and rapid preparation method, stable structure and larger specific surface area.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of hollow alumina microspheres comprises the following steps:
step 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution;
step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 30-60min, then adding into a mold, and rapidly cooling to obtain high-molecular spherical particles;
step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles;
step 4, putting the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 3-5 hours to obtain cured spherical particles;
and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolytic reaction for 3-5h, taking out after the reaction is finished, cleaning, and drying to obtain the hollow alumina microspheres.
The mass concentration of the polyvinyl alcohol in the deionized water in the step 1 is 10-30g/L, and the ultrasonic stirring frequency is 2-4 kHz.
The adding amount of the polylactic acid powder in the step 2 is 40-60% of the mass of the polyvinyl alcohol, the adding amount of the curing agent is 3-5% of the mass of the polyvinyl alcohol, and the curing agent adopts diaminodiphenylmethane.
The power of the microwave reaction in the step 2 is 200-500W, and the temperature is 190-220 ℃.
The adding amount of the ammonium aluminum carbonate in the step 3 is 50-70% of the mass of the polyvinyl alcohol, the concentration of the ammonium aluminum carbonate in the absolute ethyl alcohol is 50-80g/L, and the adding amount of the polyvinylpyrrolidone is 30-50% of the mass of the polyvinyl alcohol.
The stirring speed in the step 3 is 2000-5000r/min, the coating adopts spraying, and the coating amount is 30-50g/cm2。
The temperature of the heating and pressurizing reaction in the step 4 is 70-100 ℃, and the pressure is 3-5 MPa.
The current intensity of the micro-electrolysis in the step 5 is 20-40mA/cm2The voltage is 20-30V, and the temperature is 40-60 ℃.
And 5, cleaning by using absolute ethyl alcohol, wherein the drying temperature is 80-90 ℃.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of difficult preparation of the inorganic hollow sphere, and the preparation method is simple and quick, has stable structure and larger specific surface area.
2. The invention takes polyvinyl alcohol and polylactic acid as main components of the inner core, not only has good dispersion system, but also has good degradability, and forms the degradable soft mold of alumina.
3. The invention adopts polyvinylpyrrolidone as the dispersant of ammonium aluminum carbonate, thereby not only ensuring the good dispersibility of ammonium aluminum titanate, but also playing a good bonding effect and ensuring the bonding effect of aluminum oxide.
4. The invention adopts a heating and pressurizing mode to remove the absolute ethyl alcohol to form a compact alumina structure.
5. The invention adopts a micro-electrolysis mode to electrolyze and oxidize polyvinylpyrrolidone, polyvinyl alcohol and polylactic acid to form stable hollow alumina, and takes methanol as electrolyte, thereby having good conductivity and being convenient for subsequent cleaning.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of hollow alumina microspheres comprises the following steps:
step 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution;
step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 30min, then adding the mixture into a mold, and rapidly cooling to obtain high-molecular spherical particles;
step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles;
step 4, placing the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 3 hours to obtain cured spherical particles;
and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolytic reaction for 3 hours, taking out after the reaction is finished, cleaning and drying to obtain the hollow alumina microspheres.
The mass concentration of the polyvinyl alcohol in the deionized water in the step 1 is 10g/L, and the ultrasonic stirring frequency is 2 kHz.
The adding amount of the polylactic acid powder in the step 2 is 40% of the mass of the polyvinyl alcohol, the adding amount of the curing agent is 3% of the mass of the polyvinyl alcohol, and the curing agent adopts diaminodiphenylmethane.
The power of the microwave reaction in the step 2 is 200W, and the temperature is 190 ℃.
The adding amount of the ammonium aluminum carbonate in the step 3 is 50% of the mass of the polyvinyl alcohol, the concentration of the ammonium aluminum carbonate in the absolute ethyl alcohol is 50g/L, and the adding amount of the polyvinylpyrrolidone is 30% of the mass of the polyvinyl alcohol.
The stirring speed in the step 3 is 2000r/min, the coating adopts spray coating, and the coating amount is 30g/cm2。
The temperature of the heating and pressurizing reaction in the step 4 is 70 ℃, and the pressure is 3 MPa.
The steps areThe current intensity of the microelectrolysis in step 5 is 20mA/cm2The voltage is 20V and the temperature is 40 ℃.
And 5, cleaning by using absolute ethyl alcohol, wherein the drying temperature is 80 ℃.
Example 2
A preparation method of hollow alumina microspheres comprises the following steps:
step 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution;
step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 60min, then adding the mixture into a mold, and rapidly cooling to obtain high-molecular spherical particles;
step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles;
step 4, placing the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 5 hours to obtain cured spherical particles;
and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolytic reaction for 5 hours, taking out after the reaction is finished, cleaning and drying to obtain the hollow alumina microspheres.
The mass concentration of the polyvinyl alcohol in the deionized water in the step 1 is 30g/L, and the ultrasonic stirring frequency is 4 kHz.
The adding amount of the polylactic acid powder in the step 2 is 60% of the mass of the polyvinyl alcohol, the adding amount of the curing agent is 5% of the mass of the polyvinyl alcohol, and the curing agent adopts diaminodiphenylmethane.
The microwave reaction in the step 2 has the power of 500W and the temperature of 220 ℃.
The adding amount of the ammonium aluminum carbonate in the step 3 is 70% of the mass of the polyvinyl alcohol, the concentration of the ammonium aluminum carbonate in the absolute ethyl alcohol is 80g/L, and the adding amount of the polyvinylpyrrolidone is 50% of the mass of the polyvinyl alcohol.
The stirring speed in the step 3 is 5000r/min, and the coating adopts sprayingCoating amount of 50g/cm2。
The temperature of the heating and pressurizing reaction in the step 4 is 100 ℃, and the pressure is 5 MPa.
The current intensity of the micro-electrolysis in the step 5 is 40mA/cm2The voltage is 30V and the temperature is 60 ℃.
And 5, cleaning by using absolute ethyl alcohol, wherein the drying temperature is 90 ℃.
Example 3
A preparation method of hollow alumina microspheres comprises the following steps:
step 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution;
step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 45min, then adding the mixture into a mold, and rapidly cooling to obtain high-molecular spherical particles;
step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles;
step 4, placing the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 4 hours to obtain cured spherical particles;
and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolytic reaction for 4 hours, taking out after the reaction is finished, cleaning and drying to obtain the hollow alumina microspheres.
The mass concentration of the polyvinyl alcohol in the deionized water in the step 1 is 20g/L, and the ultrasonic stirring frequency is 2-4 kHz.
The adding amount of the polylactic acid powder in the step 2 is 50% of the mass of polyvinyl alcohol, the adding amount of the curing agent is 4% of the mass of polyvinyl alcohol, and the curing agent adopts diaminodiphenylmethane.
The microwave reaction in the step 2 has the power of 400W and the temperature of 210 ℃.
The adding amount of the ammonium aluminum carbonate in the step 3 is 60% of the mass of the polyvinyl alcohol, the concentration of the ammonium aluminum carbonate in the absolute ethyl alcohol is 70g/L, and the adding amount of the polyvinylpyrrolidone is 30-50% of the mass of the polyvinyl alcohol.
The stirring speed in the step 3 is 4000r/min, the coating adopts spraying, and the coating amount is 40g/cm2。
The temperature of the heating and pressurizing reaction in the step 4 is 80 ℃, and the pressure is 4 MPa.
The current intensity of the micro-electrolysis in the step 5 is 30mA/cm2The voltage was 25V and the temperature was 50 ℃.
And 5, cleaning by using absolute ethyl alcohol, wherein the drying temperature is 85 ℃.
In summary, the invention has the following advantages:
1. the invention solves the problem of difficult preparation of the inorganic hollow sphere, and the preparation method is simple and quick, has stable structure and larger specific surface area.
2. The invention takes polyvinyl alcohol and polylactic acid as main components of the inner core, not only has good dispersion system, but also has good degradability, and forms the degradable soft mold of alumina.
3. The invention adopts polyvinylpyrrolidone as the dispersant of ammonium aluminum carbonate, thereby not only ensuring the good dispersibility of ammonium aluminum titanate, but also playing a good bonding effect and ensuring the bonding effect of aluminum oxide.
4. The invention adopts a heating and pressurizing mode to remove the absolute ethyl alcohol to form a compact alumina structure.
5. The invention adopts a micro-electrolysis mode to electrolyze and oxidize polyvinylpyrrolidone, polyvinyl alcohol and polylactic acid to form stable hollow alumina, and takes methanol as electrolyte, thereby having good conductivity and being convenient for subsequent cleaning.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (9)
1. A preparation method of hollow alumina microspheres is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, adding polyvinyl alcohol into deionized water, and ultrasonically stirring until the polyvinyl alcohol is completely dissolved to obtain a dispersed alcohol solution;
step 2, adding polylactic acid powder and a curing agent into the dispersed alcohol solution for microwave reaction for 30-60min, then adding into a mold, and rapidly cooling to obtain high-molecular spherical particles;
step 3, adding ammonium aluminum carbonate and polyvinylpyrrolidone into absolute ethyl alcohol, uniformly stirring, and uniformly coating the mixture on the surface of the polymer spherical particles to obtain inorganic-organic spherical particles;
step 4, putting the inorganic-organic spherical particles into a reaction kettle, heating and pressurizing for 3-5 hours to obtain cured spherical particles;
and 5, putting the solidified spherical particles into a methanol reaction solution, carrying out micro-current electrolytic reaction for 3-5h, taking out after the reaction is finished, cleaning, and drying to obtain the hollow alumina microspheres.
2. The method for preparing hollow alumina microspheres according to claim 1, wherein: the mass concentration of the polyvinyl alcohol in the deionized water in the step 1 is 10-30g/L, and the ultrasonic stirring frequency is 2-4 kHz.
3. The method for preparing hollow alumina microspheres according to claim 1, wherein: the adding amount of the polylactic acid powder in the step 2 is 40-60% of the mass of the polyvinyl alcohol, the adding amount of the curing agent is 3-5% of the mass of the polyvinyl alcohol, and the curing agent adopts diaminodiphenylmethane.
4. The method for preparing hollow alumina microspheres according to claim 1, wherein: the power of the microwave reaction in the step 2 is 200-500W, and the temperature is 190-220 ℃.
5. The method for preparing hollow alumina microspheres according to claim 1, wherein: the adding amount of the ammonium aluminum carbonate in the step 3 is 50-70% of the mass of the polyvinyl alcohol, the concentration of the ammonium aluminum carbonate in the absolute ethyl alcohol is 50-80g/L, and the adding amount of the polyvinylpyrrolidone is 30-50% of the mass of the polyvinyl alcohol.
6. The method for preparing hollow alumina microspheres according to claim 1, wherein: the stirring speed in the step 3 is 2000-5000r/min, the coating adopts spraying, and the coating amount is 30-50g/cm2。
7. The method for preparing hollow alumina microspheres according to claim 1, wherein: the temperature of the heating and pressurizing reaction in the step 4 is 70-100 ℃, and the pressure is 3-5 MPa.
8. The method for preparing hollow alumina microspheres according to claim 1, wherein: the current intensity of the micro-electrolysis in the step 5 is 20-40mA/cm2The voltage is 20-30V, and the temperature is 40-60 ℃.
9. The method for preparing hollow alumina microspheres according to claim 1, wherein: and 5, cleaning by using absolute ethyl alcohol, wherein the drying temperature is 80-90 ℃.
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| CN101367535B (en) * | 2008-10-09 | 2012-04-25 | 武汉理工大学 | Hydrothermal method for preparing gamma-AL2O3 hollow microsphere polishing material without mould plate |
| CN101585708B (en) * | 2009-06-18 | 2011-09-28 | 西南科技大学 | Method for preparing corundum hollow microsphere |
| CN103508475B (en) * | 2012-06-19 | 2015-06-03 | 同济大学 | Preparation methods of alumina hollow microspheres |
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