CN103949192B - A kind of method that microwave-assisted aerosol prepares hollow ball - Google Patents
A kind of method that microwave-assisted aerosol prepares hollow ball Download PDFInfo
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Abstract
The present invention relates to hollow ball preparing technical field, it is specially a kind of method that microwave-assisted aerosol prepares hollow ball, the method can prepare according to the following steps: hollow ball housing presoma is scattered in polar solvent by A., adds ammonium salt and forms colloid solution or true solution, i.e. precursor solution；B. the step A precursor solution prepared is formed aerosol droplets through atomization；C. the step B aerosol droplets prepared is imported microwave generator and carry out microwave exposure, namely obtain hollow ball powder particle.The preparation method of hollow spherical powder of the present invention with short production cycle, easy and simple to handle, pollution-free, the microstructure of gained hollow spherical powder is survivable, it is easy to accomplish amplify, suitable popularization and application.
Description
Technical field
The present invention relates to hollow ball preparing technical field, is specially a kind of method that microwave-assisted aerosol prepares hollow ball.
Background technology
Having the inorganic micro/nano material of hollow ball structure and increasingly cause the concern of people because of the physicochemical properties of its uniqueness, it is respectively provided with boundless application prospect in material subject and Other subjects.Inorganic micro-/ nano hollow ball material has the characteristic of light weight, high intensity and high-specific surface area, it has relatively broad application in many emerging fields, such as: the cavity of hollow ball can be used as chemical microreactor, as the carrier of biological medium, biological medicine, medicament slow release and drug targeting release；It is alternatively arranged as effective catalyst and carrier, light wave microwave absorbing material, photoelectric conversion material, electrically insulating material, low dielectric heat-barrier material etc..
The preparation method of inorganic hollow ball material of the prior art mainly has template, ultrasonic method, spray pyrolysis, laser ablation method, layer-layer construction from part and hydro-thermal method etc., wherein, most common method is template, the main preparation process of template is to add template, and the method then pass through calcining, dissolving is removed template and obtained desirable hollow ball structure.The kind of the template added in above-mentioned preparation process is more, hard template and soft template can be divided into according to type, hard template has ion exchange resin, polymer colloidal particles, inorganic ions, metal ion etc., and soft template has micelle, vesicle, emulsifying droplet and the gas etc. generated in course of reaction.Applying template method can obtain the hollow ball material of all kinds and size, the size of gained hollow ball is determined by the size of template, but general template can cause the residual (such as the impurity such as residual carbon or cation) of impurity and subsiding or blocking of spheroid while removing template, and these unfavorable factors will certainly affect the performance of hollow ball.
In course of reaction, with the gas that generates or produce for template, as adopted aerosol spray to dry, spray pyrolysis or aerosol evaporation-induced self-assembly (EISA) method to prepare hollow ball, then can produce different effects.In recent years, the research about said method achieves some achievements, specific as follows:
Chinese patent CN100348499C adopts spray drying method to prepare mesic hole hollow ball-shape titania powder, the chloride of titanium is made the spray-dried hollow spherical powder obtaining titanium dioxide nanoparticle composition of the hydrosol by this method, then through calcining to obtain mesic hole hollow ball-shape powder body；Although this preparation method does not need to add other reagent, the impurity content of product is little, and purity is high, and productivity is high, and surface titanium atom content is high, and photocatalysis performance is good, but in preparation process, the hydrosol needs aging, and ageing time is longer, it is also desirable to high-temperature calcination.
The preparation method that US Patent No. 7744673 describes a kind of metallic oxide hollow sphere, metal alkoxide or chloride are dissolved in the inertia hydrophobic solvent (such as hexane, chloroform) of effumability by this method, aerosol droplets is produced by anhydrous carrier gas, aerosol droplets enters back into aerosol reactor and reacts with water, hydrophobic solvent is heated volatilization, and slaine hydrolysis, polycondensation form hollow ball；The advantage of the method is in that low temperature, low cost, and preparation time is shorter, without destructive, but form hollow ball and need to rely on the evaporation of hydrophobic solvent, and hydrophobic solvent used (such as hexane, chloroform) is toxic, can pollute in volatilization process.
It addition, Jiang et al. (Chem.Commun., 2010,46 (17), 3019-3021) adopts aerosol evaporation-induced self-assembly (EISA) method to prepare mesoporous SiO 2 hollow ball；This method adopts the not high ammonium salt (ammonium chloride or ammonium sulfate) of decomposition temperature as macropore template, and Surfactant CTAB is mesoporous template, and in preparation process, ammonium salt decomposes obtains macropore hollow ball, and CTAB obtains mesoporous silicon oxide through high-temperature calcination.Although this method technical process is simple, preparation time is shorter, it is easy to amplify, but need to remove CTAB and ammonium salt obtains mesoporous silica hollow ball through high-temperature calcination, can cause subsiding or blocking of hollow ball, cause the decline of voidage and the decline of specific surface area.The method that WuChunwei etc. (Langmuir, 2010,26 (6), 4327-4330) adopt the evaporation-induced self-assembly of aerosol droplets, with Fe3O4(～2.5nm) colloidal sol and SiO2(～15nm) colloidal sol is raw material, utilizes solvent rapid evaporation to be at high temperature prepared for hollow spheres, and gained hollow spheres wall is thicker, and particle diameter is at more than 100nm.
In sum, the method preparing hollow inorganic spheres at present all more or less comes with some shortcomings, and therefore provides a kind of environmental protection, the problem that with short production cycle, porosity is high, nondestructive preparation method is current research.
Summary of the invention
The technical problem to be solved in the present invention is: prepare hollow spherical powder Problems existing for aerosol spray seasoning of the prior art, it is provided that a kind of method that novel microwave-assisted aerosol prepares hollow ball.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method that microwave-assisted aerosol prepares hollow ball, prepares according to the following steps:
A. hollow ball housing presoma is scattered in polar solvent, adds ammonium salt and form colloid solution or true solution, the i.e. precursor solution of homogeneous transparent；
B. the step A precursor solution prepared is formed aerosol droplets through atomization in aerosol generator；
C. the step B aerosol droplets prepared is imported microwave generator and carry out microwave exposure, namely obtain moisture hollow ball powder particle.
Described step A hollow core global shell presoma is oxide colloid, slaine, metal alcohol oxide or water soluble polymer；Presoma, polar solvent, ammonium salt quality proportioning be 0.01-10:90-99.5:0.5-5.
The moisture hollow ball powder particle that described step C obtains can enter tube furnace and be further dried, and dried granule filter is collected, and solid matter is separated from the gas, and collected product is dry hollow ball powder particle.
Described step A Semi-polarity solvent is water, ammonia or effumability organic solvent, and organic solvent is: Methanamide, DMSO, acetonitrile, DMF, methanol, ethanol, acetic acid, isopropanol, acetone or oxolane；Polar solvent is preferably water；Ammonium salt in described step A is ammonium hydrogen carbonate, ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium nitrate or ammonium acetate；In described step B, the particle diameter of aerosol droplets is 0.01-100 μm；In described step C, the power of the microwave exposure of microwave generator is 100W-1000KW, and the microwave action time is 10-600s.
Further, described tube furnace temperature is 100-600 DEG C, and the time of staying is 1s-10min, and carrier gas is air, nitrogen, carbon dioxide, hydrogen or argon；Described oxide colloid is silicon oxide colloid, titanium oxide colloid, copper oxide colloid, colloid of iron oxide, zirconium oxide colloid or thorotrast；Described slaine is the nitrate of Fe, Al, Cu, Ti, Zn, Mn, Ce, Sn, Ni, Co, Ru, Sb, Pd or Cr, acetate or chlorate；Described metal alcohol oxide is the alcohol oxide of Si, Ti, Al, Zr, Ge, Sn, Ti, Cd, Zr, Fe, Al or Cu；Described water soluble polymer is polyacrylamide, native starch, HANSHENGJIAO, agar, sodium carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), cationic cellulose polymer, cation guar gum, polyvinyl alcohol (PVA), Polyethylene Glycol (PEG), polyvinylpyrrolidone, acrylate copolymer or polylactic acid.
Further, the particle diameter of the oxide colloid in described step A is 3nm-100nm, and wherein, oxide weight/mass percentage composition in oxide colloid is 3-50%.
Beneficial effect: the preparation method of hollow spherical powder of the present invention with short production cycle, easy and simple to handle, pollution-free, the microstructure of gained hollow spherical powder is survivable, it is easily achieved amplification, suitable popularization and application, the technical advantage of the technical solution used in the present invention is mainly reflected in:
(1) colloid solution and other slaines, metal alcohol oxide or the organic macromolecule aqueous solution that adopt nanometer particle size are precursor material, raw material is easy to get, environmental protection, less costly, the hollow ball of gained is polymeric hollow sphere, oxide hollow sphere or reduced form metal hollow ball, hollow ball wall is to be formed by mesoporous constructing, and cavity volume is bigger, it is adaptable to as the carrier of medicament slow release, biological medium, catalyst etc.；
(2) with the relatively low ammonium salt of decomposition temperature for template, ammonium salt can thermally decompose at a lower temperature, the gas produced expands in particulate, the cavity volume of hollow ball can be expanded, do not need high-temperature calcination, the residual of the impurity such as carbon-free and other metal ions, product purity is high, is absent from subsiding and blocking of spheroid；
(3) the microwave heating treatment technique in technical scheme be a kind of uniqueness molecule in mode of heating, microwave heating has heating feature quick, uniform, particulate in the application is rich in water and ammonium salt, these materials are all the materials that dielectric constant is bigger, can effectively absorb microwave energy, quickly raise temperature.Compared with traditional mode of heating, microwave heating can make aerocolloidal temperature raise uniformly rapidly, after system temperature reaches the boiling point of water, and the water molecule energy rapid evaporation within aerosol, form gas；On the other hand, the quick rising of temperature accelerates again the decomposes of ammonium salt, makes gas content increase further, thus obtaining the hollow spheres that cavity volume is bigger；Further, microwave heating makes each position of aerosol be heated evenly, and temperature is basically identical, advantageously forms the outer wall of uniform pore diameter.Additionally, the present invention is without surfactant, do not need high-temperature calcination, decrease caving in of hollow-core construction, preparation process does not need organic solvent, reduce environmental pollution.Therefore, the tiny balloon preparation method that the present invention proposes have simple to operate, with short production cycle, have wide range of applications, the advantage such as environmental protection, there is huge application potential.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described；
Fig. 1 is the structural representation of the present invention；
Fig. 2 is the SiO that comparative example one prepares2The electron micrograph of micrometre hollow sphere powder body, wherein, (a) schemes for SEM, and (b) schemes for TEM；
Fig. 3 is the SiO that embodiment one prepares2The electron micrograph of micrometre hollow sphere powder body, wherein, (a) schemes for SEM, and (b) schemes for TEM；
Fig. 4 is the transmission electron microscope photo of the ferrum oxide hollow ball powder body that embodiment four prepares.
In figure, 1. reaction unit；2. feed pipe；3. aerosol generator；31. carrier gas device；4. microwave office；5. tube furnace；6. filter chamber；61. product collection platform；7. tail gas collecting device.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.nullAs shown in Figure 1 be a kind of microwave-assisted aerosol device of preparing hollow ball，According to aforementioned preparation process，First，The precursor solution in preparation steps A in reaction unit 1，Then the feed pipe 2 connected fixing on reacted for precursor solution device 1 is entered aerosol generator 3，The outlet of feed pipe 2 is fixedly connected with carrier gas device 31，Precursor solution forms aerosol droplets through aerosol generator 3 atomization，It is step B，Then，Aerosol droplets is imported microwave office 4 and carries out microwave exposure，Obtain moisture hollow ball powder particle，It is step C，The moisture hollow ball powder particle that step C obtains can also pass through tube furnace 5 and is further dried，Dried granule filter 6 filters，Collect，Filter 6 is internally provided with product collection platform 61，The product that product collection platform 61 is collected is dry hollow ball powder particle，Tail gas collecting device 7 it is provided with bottom filter 6，Tail gas passes through the experimental situation that tail gas collecting device 7 can keep good.
Comparative example one
A. weighing 3.0g concentration be 40% particle diameter is the Ludox of 50nm, and adding pure water 40.0g, to be diluted to concentration be 2.8%, adds 1.0g ammonium hydrogen carbonate, mix homogeneously, obtains precursor solution；
B. above-mentioned precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 18psi, through being atomized prepared aerosol droplets；
C. the aerosol droplets of above-mentioned generation is imported microwave generator (power is 0), enter back into tube furnace (temperature is set as 400 DEG C) inner drying 5s, dried granule is collected on the filter, the temperature of filter maintains 80 DEG C, the product collected is hollow spherical powder, and its particle diameter and pattern are such as shown in accompanying drawing Fig. 2.
As shown in Figure 2, when particulate is without microwave exposure, gained particle is not hollow ball structure, has inclusions in particle.
Embodiment one
A. weighing 3.0g concentration be 40% particle diameter is the Ludox of 50nm, and adding pure water 40.0g, to be diluted to concentration be 2.8%, adds 1.0g ammonium hydrogen carbonate, mix homogeneously, obtains precursor solution；
B. above-mentioned precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 18psi, through being atomized prepared aerosol droplets；
C. the aerosol droplets of above-mentioned generation is imported microwave generator (microwave output power 700W, action time 17.5s), enter back into tube furnace (temperature is set as 400 DEG C) inner drying 5s, dried granule is collected on the filter, the temperature of filter maintains 80 DEG C, the product collected is dry hollow ball powder particle, and its particle diameter and pattern are such as shown in accompanying drawing Fig. 3.
By Fig. 3 (a) it can be seen that particulate is after microwave exposure, gained particle is the hollow ball with hollow structure.Finding after Fig. 2 (b) and Fig. 3 (b), after microwave exposure, the particle diameter of particle significantly increases.
Embodiment two
A. weighing 5.0g concentration be 30% particle diameter is the Ludox of 12nm, and adding pure water 45.0g, to be diluted to concentration be 3.0%, adds 1.0g ammonium hydrogen carbonate, mix homogeneously, obtains precursor solution；
B. above-mentioned precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 10psi, through being atomized prepared aerosol droplets；
C. by the aerosol droplets of above-mentioned generation through microwave generator (microwave output power 350W, action time 25s), enter back into tube furnace (temperature is set as 400 DEG C) inner drying 5s, dried granule is collected on the filter, the temperature of filter maintains 80 DEG C, and the product collected is dry hollow ball powder particle.
Embodiment three
A. weighing 3.0g concentration be 40% particle diameter is the Ludox of 22nm, and adding pure water 40.0g, to be diluted to concentration be 2.8%, adds 0.8g ammonium hydrogen carbonate, mix homogeneously, obtains precursor solution；
B. above-mentioned precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 10psi, through being atomized prepared aerosol droplets；
C. by the aerosol droplets of above-mentioned generation through microwave generator (microwave output power 700W, action time 25s), enter back into tube furnace (temperature is set as 400 DEG C) inner drying 5s, dried granule is collected on the filter, the temperature of filter maintains 80 DEG C, and the product collected is dry hollow ball powder particle.
Embodiment four
A. 0.5gFeCl is weighed3(analytical pure) is placed in beaker, and adding distilled water diluting to concentration is 1.0%, adds 1.5g ammonium sulfate, mix homogeneously, obtains precursor solution.
B. above-mentioned precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 20psi, through being atomized prepared aerosol droplets；
C. by the aerosol droplets of above-mentioned generation through microwave generator (microwave output power 700W, action time 25s), enter back into tube furnace (temperature is set as 400 DEG C) inner drying 5s, dried granule is collected on the filter, the temperature of filter maintains 80 DEG C, the product collected is dry hollow ball powder particle, and as shown in Figure 4, Fig. 4 is particle diameter is the ferrum oxide transmission electron microscope picture of 0.10-5 μm to its transmission electron microscope photo.
Embodiment five
A. weighing 0.5g PEG 20000 (analytical pure) and be placed in beaker, adding distilled water diluting to concentration is 0.1%, adds 1.0g ammonium sulfate, mix homogeneously, obtains precursor solution；
B. this precursor solution is put into aerosol generator, open nitrogen cylinder, regulate the atomisation pressure of aerosol generator to 20psi, prepare aerosol droplets；
C. by the aerosol droplets of above-mentioned generation through microwave generator (microwave output power 1000W, action time 25s), tube furnace (temperature is set as 400 DEG C) inner drying 5s is entered back into；Dried granule is collected on the filter, and the temperature of filter maintains 80 DEG C, collects dry hollow ball powder particle.
Claims (8)
1. the method that microwave-assisted aerosol prepares hollow ball, is characterized in that: prepare according to the following steps:
A. hollow ball housing presoma is scattered in polar solvent, adds ammonium salt and form colloid solution or true solution, i.e. precursor solution；
B. the step A precursor solution prepared is formed aerosol droplets through atomization in aerosol generator；
C. the step B aerosol droplets prepared is imported microwave generator and carry out microwave exposure, namely obtain moisture hollow ball powder particle；
Described step A hollow core global shell presoma is oxide colloid, slaine or water soluble polymer；Presoma, polar solvent, ammonium salt quality proportioning be 0.01-10:90-99.5:0.5-5；Oxide colloid is silicon oxide colloid, titanium oxide colloid, copper oxide colloid, colloid of iron oxide, zirconium oxide colloid or thorotrast；Described slaine is the nitrate of Mn, Sn, Ni, Co, Ru, Sb, Pd or Cr, acetate or chlorate；Water soluble polymer is polyacrylamide, native starch, HANSHENGJIAO, agar, CMC, HEC, HPC, cationic cellulose polymer, cation guar gum, PVA, PEG, polyvinylpyrrolidone, acrylate copolymer or polylactic acid；
The particle diameter of described oxide colloid is 3nm-100nm, and wherein, oxide weight/mass percentage composition in oxide colloid is 3-50%.
2. the method that microwave-assisted aerosol according to claim 1 prepares hollow ball, it is characterized in that: the moisture hollow ball powder particle that described step C obtains enters tube furnace and is further dried, dried granule filter is collected, and collected product is dry hollow ball powder particle.
3. the method that microwave-assisted aerosol according to claim 1 prepares hollow ball, is characterized in that: the ammonium salt in described step A is ammonium hydrogen carbonate, ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium nitrate or ammonium acetate；Polar solvent is water, ammonia or effumability organic solvent.
4. the method that microwave-assisted aerosol according to claim 1 prepares hollow ball, is characterized in that: in described step B, the particle diameter of aerosol droplets is 0.01-100 μm.
5. the method that microwave-assisted aerosol according to claim 1 prepares hollow ball, is characterized in that: in step C, the microwave action time is 10-600s.
6. the method that microwave-assisted aerosol according to claim 2 prepares hollow ball, is characterized in that: described tube furnace temperature is 100-600 DEG C, and the time of staying is 1s-10min, and carrier gas is air, nitrogen, carbon dioxide, hydrogen or argon.
7. the method that microwave-assisted aerosol according to claim 3 prepares hollow ball, is characterized in that: described polar solvent is water.
8. the method that microwave-assisted aerosol according to claim 3 prepares hollow ball, is characterized in that: described organic solvent is: Methanamide, DMSO, acetonitrile, DMF, methanol, ethanol, acetic acid, isopropanol, acetone or oxolane.
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| FR3043572B1 (en) * | 2015-11-12 | 2020-05-15 | Pylote | THERMALLY INSULATING MATERIALS INCORPORATING SPHERICAL AND HOLLOW INORGANIC PARTICLES |
| CN105502334A (en) * | 2015-12-21 | 2016-04-20 | 常州轻工职业技术学院 | Hollow carbon ball and preparation method thereof |
| CN107498059B (en) * | 2017-08-28 | 2019-01-22 | 西北有色金属研究院 | A kind of method that aerosolization prepares partial size refinement titanium-based spherical powder |
| CN107855539A (en) * | 2017-11-16 | 2018-03-30 | 武汉工程大学 | A kind of method for preparing superfine metal and metal oxide |
| CN107934922A (en) * | 2017-12-13 | 2018-04-20 | 武汉工程大学 | A kind of microwave radiation technology aerosol prepares nanometer TeO2Method |
| CN108329046B (en) * | 2018-02-26 | 2020-09-11 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation composite material |
| CN109607616B (en) * | 2018-12-19 | 2021-02-19 | 大连理工大学 | Method for synthesizing metal oxide hollow sphere powder and precursor thereof by spraying |
| CN112958014A (en) * | 2020-10-23 | 2021-06-15 | 武汉市格勒特新材料有限公司 | Method for producing superfine nano silver-based metal composite antibacterial agent by microwave-assisted aerosol |
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| CN101426610A (en) * | 2005-06-08 | 2009-05-06 | 丰田发动机工程及制造北美公司 | Metal oxide nanoparticles and process for producing the same |
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| CN101475146A (en) * | 2009-01-19 | 2009-07-08 | 华中师范大学 | Universal method for synthesizing metallic oxide hollow sphere by H3BO3 induced ultrasonic atomization |
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