CN112744851B

CN112744851B - Raspberry type oxide microsphere and preparation method and application thereof

Info

Publication number: CN112744851B
Application number: CN201911053524.6A
Authority: CN
Inventors: 侯朝鹏; 李学锋; 夏国富; 孙霞; 吴玉; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-11-15
Anticipated expiration: 2039-10-31
Also published as: CN112744851A

Abstract

The invention provides a raspberry type oxide microsphere and a preparation method and application thereof, wherein the raspberry type oxide microsphere is a hollow microsphere with a large hole on the surface, a hollow structure is arranged in the hollow microsphere, and the large hole is communicated with the hollow structure to form a cavity with an opening at one end; wherein the oxide in the raspberry type oxide microspheres is selected from one or more of alumina, silica, zirconia, magnesia, calcium oxide and titanium oxide. The raspberry type oxide microsphere has better mass transfer and heat transfer characteristics, the strength is obviously higher than that of the existing product with a similar structure, and meanwhile, the raspberry type oxide microsphere can be prepared by taking a precursor of an oxide as a raw material, and the raspberry type oxide microsphere is simple in preparation method, low in cost, high in efficiency and suitable for large-scale industrial application.

Description

Raspberry type oxide microsphere and preparation method and application thereof

Technical Field

The invention relates to the field of synthesis of micron materials, in particular to raspberry type oxide microspheres and a preparation method and application thereof.

Background

In the past decades, a great deal of literature has been studying and reporting inorganic hollow microsphere materials. Compared with a common dense sphere, the hollow material has smaller density and larger specific surface area, is widely applied to various fields such as drug catalyst carriers, gas adsorbents and the like, and in recent years, the research and application of the inorganic hollow microsphere material are receiving more and more attention.

The alumina composition cavity ball is a new-type high-temp. heat-insulating material made up by using industrial alumina through the processes of smelting and blowing in electric furnace, and its crystal form is a-Al ₂ O ₃ A microcrystal. The alumina hollow ball is used as main body, and can be made into various shaped products, and the product has high mechanical strength which is several times that of general light products, but the volume density is far less than that of solid products. The energy-saving furnace is widely applied to high-temperature and ultra-high-temperature furnaces such as petrochemical industry gasification furnaces, carbon black industry reaction furnaces, metallurgical industry induction furnaces and the like, and obtains a very satisfactory energy-saving effect. The existing preparation methods of alumina cavity materials include a high-temperature melting and spray reaction method, a template method, a layer-by-layer self-assembly method (L-b-L) and a microemulsion method.

The silica hollow microsphere has the advantages of good biocompatibility, easily available raw materials, low price and the like, and is widely applied to the fields of drug carriers, biological signal markers, coatings and the like, and the preparation technology of the inorganic hollow microsphere is also widely concerned by researchers. The most widely reported method is to use polystyrene microspheres as a template, wrap a silicon oxide shell layer on the surface of the polystyrene microspheres, and remove a polystyrene core to obtain the silicon oxide hollow microspheres. The preparation methods reported in the literature at present mainly comprise (1) an electrostatic adsorption method; (2) a silicon crosslinking agent modification method; and (3) a Layer-by-Layer method.

The hollow spherical zirconia powder is a plasma spraying heat-insulating material for surface modification of mechanical parts such as aircraft engines, gas turbines, heat treatment equipment and the like, and a coating prepared from the powder has the characteristics of good thermal shock resistance and high-temperature hot corrosion resistance, so that the hollow spherical zirconia powder is sprayed on high-temperature parts such as aircraft engines and the like, the mechanical property of the engines can be improved, and the service life of the high-temperature parts can be prolonged. The hollow porous zirconia microspheres have stable chemical properties, can be used as a micro controlled release carrier (such as a drug sustained release agent) of active substances, do not react with loaded drug active ingredients, have good biocompatibility, do not pollute the environment, and can effectively control the nanometer pore canal of the particle size and the pore diameter. The prior methods for producing the hollow zirconia comprise a plasma spheroidization method and a spray drying granulation method. The plasma spheroidizing method is a process method for preparing hollow sphere powder by using a plasma spray gun as a heat source and carrying out heat treatment on porous zirconia agglomerated powder prepared by other methods.

The titanium dioxide hollow microsphere structure can enlarge the specific surface area of titanium dioxide, can provide more active sites for catalytic reaction, and the higher crystallinity of the titanium dioxide hollow microsphere structure can reduce the recombination rate of photo-generated electrons and active holes, thereby improving the catalytic activity. On the other hand, from the modification perspective, the hollow structure may provide space for further modification of the titanium dioxide material. At present, various methods for synthesizing hollow titanium oxide exist, such as a template method, a flame combustion method, a template-free method and the like, wherein the pore diameter and the shell thickness of the microsphere are easy to control by the template method, and the dispersion is relatively uniform. However, the template method has complex steps, and the shell layer is easily damaged in the process of removing the template; the flame combustion method and the template-free method have the advantages of continuous preparation process, simple operation, no pollution and the like, but the prepared product is irregular.

In summary, the existing preparation methods of inorganic hollow microsphere materials generally have the problems of small scale and difficult expansion, and some preparation methods have low preparation efficiency and high raw material cost.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to provide raspberry type oxide microspheres and a preparation method and application thereof aiming at the defects of the prior art, and the raspberry type oxide microspheres can be prepared into large-particle hollow-structure oxide microspheres with better mass transfer and heat transfer characteristics.

In order to achieve the purpose, the invention adopts the following technical scheme:

a raspberry type oxide microsphere is a hollow microsphere with a large hole on the surface, a hollow structure is arranged inside the hollow microsphere, and the large hole and the hollow structure are communicated to form a cavity with an opening at one end; wherein the oxide in the raspberry type oxide microspheres is selected from one or more of alumina, silica, zirconia and titania.

In some embodiments, the raspberry type oxide microspheres have a particle size of 3 to 2500 μm, preferably 10 to 500 μm. .

In some embodiments, the hollow structures have a diameter of 1 to 2000 μm, preferably 1 to 400 μm.

In some embodiments, the macropores have a pore size of 0.2 to 1000. Mu.m, preferably 0.5 to 200. Mu.m.

In some embodiments, the shell thickness of the hollow microspheres is 0.2 to 1000 μm, preferably 0.5 to 200 μm.

In some embodiments, the raspberry-type oxide microspheres have a sphericity of 0.50 to 0.99.

In some embodiments, the raspberry-type oxide microspheres have a breakage rate of 0 to 1%.

On the other hand, the invention provides a preparation method of the raspberry type oxide microsphere, which comprises the following steps:

sequentially adding nitrate, peptizing agent, pore-forming agent, oxide and/or precursor thereof into the dispersing agent and stirring to obtain dispersed slurry;

aging the dispersed slurry; and

sending the aged dispersed slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; drying and forming under the condition that the air outlet temperature is 50-300 ℃, preferably 120-200 ℃ to obtain the raspberry type oxide microspheres.

In some embodiments, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

In some embodiments, the peptizing agent is selected from one or more of acids, bases, and salts.

In some embodiments, the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohols, and surfactants.

In some embodiments, the oxide and/or its precursor is selected from one or more of an aluminum source selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium hydroxycarbonate, and zirconium tetrabutoxide, and a titanium source selected from one or more of titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetra-isopropyl titanate.

In some embodiments, the dispersant is selected from one or more of water, alcohols, ketones, and acids.

In some embodiments, the mass ratio of the nitrate, the peptizing agent, the pore former, and the oxide and/or a precursor thereof is (10-500): (1-10): (10-500): (10-1000).

In some embodiments, further comprising adding a blasting agent to the dispersant, the blasting agent selected from one or more of picric acid, trinitrotoluene, mercury fulminate, digested glycerol, nitrocotton, danesel, hexogen, lead azide, and C4 plastic explosives.

In some embodiments, the blasting agent is added in an amount of 0 to 1% of the total dry basis weight of the nitrate, peptizer, pore former, and oxide and/or precursor thereof.

In some embodiments, the drying device is a flash drying device or a spray drying device.

In some embodiments, the temperature of the aging treatment is 0 to 90 ℃, preferably 20 to 60 ℃.

The method for producing the microscopic powder with the cavity structure has strong controllability, low cost and high efficiency and is suitable for large-scale industrial application.

The raspberry type oxide microsphere provided by the invention can be applied to various fields, such as the field of heat-resistant materials, the field of biological materials, the field of photochemical materials and the like, and can show special advantages. Particularly in the field of catalysts, the catalyst has better mass transfer and heat transfer characteristics, and the strength of the catalyst is remarkably higher than that of the existing products with similar structures. In a fixed bed filling reactor (such as a microreactor, a microchannel reactor, a microchemical reactor and a mesoscopic reactor), the porosity is large, the pressure drop is small, and the method can be applied to the fields of petrochemical industry and the like.

Drawings

FIGS. 1 to 4 are SEM photographs of the raspberry type oxide microspheres obtained in examples 1 to 4.

FIG. 5 is a microphotograph of the raspberry type oxide microspheres obtained in example 1.

FIG. 6 is a microphotograph of raspberry type oxide microspheres obtained in example 5.

FIG. 7 is a microphotograph of raspberry type oxide microspheres obtained in example 9.

FIG. 8 is a microphotograph of raspberry type oxide microspheres obtained in example 13.

FIG. 9 is a microphotograph of oxide microspheres obtained in comparative example 1.

FIG. 10 is a microphotograph of oxide microspheres obtained in comparative example 6.

FIG. 11 is a microphotograph of oxide microspheres prepared in comparative example 7.

Detailed Description

The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.

In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.

All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a raspberry type oxide microsphere, which has a hollow microsphere with a raspberry type structure, wherein the surface of the hollow microsphere has a large pore, the interior of the hollow microsphere has a hollow structure, and the large pore and the hollow structure are communicated to form a cavity with one open end.

The oxide in the raspberry type oxide microspheres is an inorganic oxide, and can be selected from one or more of alumina, silica, zirconia, magnesia, calcium oxide and titanium oxide, and preferably is one or more of alumina, silica, zirconia and titanium oxide.

The raspberry type oxide microsphere has the particle size of 3-2500 microns, preferably 10-500 microns, the diameter of a hollow structure of 1-2000 microns, preferably 1-400 microns, and the pore diameter of a surface macropore of 0.2-1000 microns, preferably 0.5-200 microns. The raspberry type oxide microsphere has a shell layer surrounding a cavity, and the thickness of the shell layer is 0.2-1000 μm, preferably 0.5-200 μm.

The appearance of the raspberry type oxide microsphere is close to a sphere, and the sphericity of the raspberry type oxide microsphere is 0.50-0.99.

Sphericity of microbead blank

σ＝4πA/L ²

And (6) calculating. In the formula: sigma is sphericity; a is the projected area of the microsphere in m ² (ii) a L is the projection perimeter of the microsphere, and the unit is m; a and L are obtained from SEM pictures of microspheres and processed by Image processing software Image-Pro Plus.

The raspberry type oxide microsphere of the invention is roasted at 400-1300 ℃, preferably 450-1100 ℃, and then preferably 500-700 ℃ to obtain an oxide with the specific surface of about 0.1-900 m ² A ratio of 10 to 300 m/g is preferred ² A pore volume of about 0.01 to 3.6ml/g, preferably 0.1 to 0.9ml/g.

The breakage rate of the raspberry type oxide microspheres is 0-1%, the breakage rate is measured according to a method provided by a similar strength standard number Q/SH 3360-2010, and the specific method comprises the following steps:

firstly, selecting sieves S1 and S2 with the mesh numbers of M1 and M2 respectively, wherein M1 is less than M2, enabling microspheres to be detected to firstly pass through the sieve S1 with the mesh number of M1, then enabling the sieved microsphere powder to pass through the sieve S2 with the mesh number of M2, and finally enabling the microsphere powder intercepted by the sieve S2 to be used as a sample to be detected.

Adding a sample to be tested with a certain mass into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure to microspheres through a cylinder for a certain time, screening the pressed microsphere powder by using a screen S2 with the mesh number of M2, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total mass of the added microspheres to obtain the breaking rate of the microspheres.

In the present invention, M1 may be 100 mesh, M2 may be 150 mesh, the pressure may be 100N, and the time may be 10s.

The strength of the microspheres can be evaluated by using the breakage rate; the strength of the microspheres is higher when the breakage rate is lower.

The raspberry type oxide microspheres of the invention have low breaking rate and strength significantly higher than that of the existing known oxide microspheres under the condition of pressurization, for example, the apple-shaped hollow molecular sieve microspheres disclosed by CN108404970A, which are determined by the difference of raw materials and preparation methods thereof. The higher strength enables the porosity of the raspberry type oxide microspheres to be larger, the pressure drop to be greatly reduced, meanwhile, the raspberry type oxide microspheres have excellent processing performance and loss resistance, the reaction diffusion distance in the field of catalysts prepared by using the raspberry type oxide microspheres as carriers is short, the raspberry type oxide microspheres have wide application prospects, and the raspberry type oxide microspheres can also be prepared into high-temperature heat-insulating materials, biological materials and photochemical materials.

The raspberry type oxide microspheres can be prepared by the following method, including:

adding nitrate, peptizing agent, pore-forming agent and oxide precursor into a dispersing agent and stirring to obtain dispersed slurry;

aging the dispersed slurry; and

feeding the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; drying and forming under the condition that the air outlet temperature is 50-300 ℃, preferably 120-200 ℃, so as to obtain the raspberry type oxide microspheres.

In the preparation method of the invention, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate. Nitrate ions in nitrates promote their ability to act as pore formers as oxidants at high temperatures, which undergo self-propagating combustion reactions at high temperatures to produce gases and vapors that form cavities in the oxide material.

In the preparation method of the invention, the peptizing agent is selected from one or more of acids, alkalis and salts. The acids can be selected from: inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid and the like), organic acid (formic acid, acetic acid, oxalic acid and the like) and one or more of inorganic acid or organic acid; alkalies can be selected from: inorganic bases (sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, soda ash (anhydrous sodium carbonate), sodium carbonate (monohydrate, heptahydrate, decahydrate), sodium bicarbonate (baking soda), potassium carbonate, potassium bicarbonate, etc.), organic bases (such as amine compounds, alkali metal salts of alcohols, alkaloids, lithium alkylmetal compounds, etc.), and one or more of inorganic acids or organic acids; the salts can be selected from: inorganic acid salt (such as hydrochloric acid, sulfate, nitrate, etc.), organic acid salt (formate, acetate, oxalate, etc.), and one or more of inorganic acid salt or organic acid salt.

In the preparation method of the invention, the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol and surfactant. Wherein the synthetic cellulose is preferably one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymer alcohol is preferably one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol PPG; the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, acrylic acid copolymer with molecular weight of 200-2000000 and maleic acid copolymer.

In the preparation method of the present invention, the oxide and/or its precursor may be directly alumina, silica, zirconia and titania, or may be a precursor for forming these oxides, specifically may be one or more selected from an aluminum source, a silicon source, a zirconium source and a titanium source, wherein the aluminum source is one or more selected from pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, the silicon source is one or more selected from silicate, sodium silicate, water glass and silica sol, the zirconium source is one or more selected from zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconium oxynitrate, zirconium nitrate, zirconium hydroxycarbonate and tetrabutoxyzirconium, and the titanium source is one or more selected from titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate and tetra-isopropyl titanate.

When the above aluminum source, silicon source, zirconium source and titanium source are used, they may further include a chemical agent for precipitating or gelling them, such as acids (e.g., inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, or organic acids such as acetic acid), and/or alkalis (e.g., sodium carbonate and sodium hydroxide).

When it is necessary to prepare an oxide composition containing other components, oxides such as vanadium oxide, chromium oxide, manganese oxide, molybdenum oxide, tungsten oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide may be added, and precursors that can form these oxides may also be added.

In the preparation method, the dispersing agent is selected from one or more of water, alcohols, ketones and acids, wherein the alcohols can be methanol, ethanol, propanol and the like, the ketones can be acetone, butanone and the acids can be formic acid, acetic acid, propionic acid and the like. The preferable dispersing agent is a mixture of water and a small amount of ethanol, the small amount of ethanol can play a better dispersing effect in water and can be used as a boiling point regulator, and the water evaporation effect and the liquid drop shrinkage effect are matched and matched more through regulating the dispersing agent, so that the appearance effect of the microsphere is more regular and smooth.

In the preparation method, the mass ratio of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof is (10-500): (1-10): (10-500): (10-1000).

In the preparation method, the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof can be sequentially added into the dispersing agent or simultaneously added, the adding sequence can be adjusted according to the dissolution condition of the raw materials, and the raw materials are stirred to be uniformly mixed while being added.

The preparation method of the invention can also comprise adding a blasting agent into the dispersing agent, wherein the blasting agent can be added before or after the oxide. The blasting agent is selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, dana explosive, hexogen and C4 plastic explosive. Before drying and forming, the blasting agent is mixed with other materials uniformly. The addition amount of the blasting agent is 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof.

In the preparation method, the nitrate, the peptizing agent, the pore-forming agent and the precursor of the oxide are sequentially added into the dispersing agent for pulping, and the slurry is pumped into a sand mill or a colloid mill for grinding after being uniformly stirred to obtain the dispersed slurry. The solid content of the slurry is generally 5-60 wt% during pulping, and the grinding time is 1-30 minutes. After mixing and grinding, the average grain diameter of the aluminum source, the silicon source, the zirconium source and the titanium source grains in the slurry can be ground to 0.01-10 mu m.

After the raw materials are mixed and ground, the raw materials are fully dissolved and dispersed, so that the dispersed slurry is uniform. The milling equipment used may be a colloid mill, sand mill or other equipment, the criterion being selected such that the catalyst fines, after grinding thereof, reach the desired average particle size, i.e. less than 10 μm.

Then, the dispersion slurry is aged at 0 to 90 ℃ for 0.1 to 24 hours, preferably 0.5 to 2 hours.

After aging treatment, the dispersion slurry is sent into a spray drying device, drying and forming are carried out at the air inlet temperature of 400-1200 ℃, preferably 450-700 ℃, the air outlet temperature is 50-300 ℃, preferably 120-200 ℃, and the pressure in a spray tower is similar to that of conventional spraying, thus obtaining the raspberry type oxide microspheres.

The drying apparatus used in the present invention may be a flash drying apparatus and a spray drying apparatus, preferably a spray drying apparatus. Flash drying and spray drying are common methods applied for material drying. After the wet material is dispersed in a drying tower, the moisture is quickly vaporized in the contact with hot air, and a dry product is obtained. The spray drying method can directly dry the solution and emulsion into powder or granular products, and can omit the procedures of evaporation, pulverization and the like.

The working principle of spray drying is to disperse the material to be dried into fine mist-like particles by mechanical action (such as pressure, centrifugation, air-flow type spraying), increase the water evaporation area, accelerate the drying process, contact with hot air, remove most of the water in a short time, and dry the solid matter in the material into powder.

The spray drying apparatus used in the present invention is a conventional apparatus in the existing flow path, and the present invention is not particularly limited thereto. The spray drying apparatus generally comprises: the device comprises a feeding system, a hot air system, a drying tower system, a receiving system and a sealing system. The feeding system is connected with the drying tower system in the middle of the top end, the hot air system is connected with the side face of the top end of the drying tower system, the receiving system is connected with the bottom end of the drying tower system, and the sealing system is connected with the hot air system. In the spray drying process, it is essentially necessary to have a spray of the stock solution; drying the tiny droplets in the spray; three functions of separating and recovering fine powder products. In the spray drying apparatus, an atomizer, a drying chamber, and a fine powder recoverer corresponding to the above functions are generally equipped.

Because of the many control parameters and complex factors in the spray drying process, the particle size and the particle shape after spray drying are very complex. The size range of the product is generally in micron order, and the product is generally a mixture of shapes including a sphere, a disc, an apple shape, a grape shape, a cavity shape, a meniscus shape and the like, and how to selectively form an ideal single shape, such as a cavity shape, is a difficulty in the formation of the product.

One method in the prior art is to form spherical emulsion under the action of surface tension of a surfactant, and then at the moment of spray forming at a lower temperature, a pore-forming agent is vaporized or pyrolyzed in the spherical emulsion, and gas generated by vaporization and pyrolysis can cause a cavity in the microsphere emulsion; and (3) slowly releasing gas to form macropores on the surface to be communicated with the internal hollow structure, forming secondary stacking holes on the molecular sieve particles in the spray forming process to form mesopores on the surface of the molecular sieve microspheres, and combining the subsequent roasting process to obtain the large-particle hollow molecular sieve microspheres.

In the method, under the high temperature of 400-1200 ℃, the oxide and the reducing agent in the slurry generate strong oxidation-reduction self-propagating combustion reaction to instantly generate a large amount of gas; meanwhile, the liquid drops enter a high-temperature area for spraying, the liquid drops are strongly evaporated, and the surface tension formed by the thickened slurry causes the liquid drops to shrink rapidly. The strong explosion of the inside and the strong contraction of the outside form a raspberry type hollow material with good strength. The prepared raspberry type oxide microspheres have high strength, high sphericity and high yield.

The raspberry type oxide microspheres can be used as a carrier after being roasted, and can be prepared into various catalysts after being loaded with corresponding active components. The roasting temperature can be 400-1300 ℃, the preferred temperature is 450-1100 ℃, and the further preferred temperature is 500-700 ℃; the calcination time may be 1 to 12 hours, preferably 2 to 8 hours, and more preferably 3 to 4 hours.

In addition, the raspberry type oxide microsphere can also be used as a high-temperature heat insulation material, a biological material, a drug material, a photochemical material and a catalyst carrier material.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

Examples

Reagents, instruments and tests

In the following examples, preparations and comparative examples, some of the raw material specifications used were as follows:

pseudo-boehmite powder (produced by Changling catalyst factory, solid content 69.5 wt%; gamma-Al) ₂ O ₃ Content of not less than 98 wt%);

alumina sol (produced by Zhou village catalyst works, containing 22 wt% Al) ₂ O ₃ )；

Sodium silicate (Jinan Yifengda chemical limited company, modulus 3.1-3.4, insoluble substance less than 0.4%)

Ammonia, hydrochloric acid, nitric acid, sulfuric acid, aluminum sulfate, aluminum chloride, zirconium hydroxide, zirconium oxychloride, titanium tetrachloride, titanium dioxide (national chemical group, ltd., industrial grade);

polyethylene glycol PEG4000 powder (Wenzhou Shuanghoi rubber and plastic materials Co., ltd.);

methylcellulose (Hubei Jiang Mintai Walschemical Limited);

tetraethoxysilane (TEOS, jonan hua special chemical limited, content about 99%);

aluminum nitrate, titanium nitrate, zirconium nitrate, yttrium nitrate, magnesium nitrate (Fishtstage Ji Xin chemical Co., ltd., industrial grade)

The breakage of the support and the catalyst can be measured according to the following method:

the microspheres to be measured firstly pass through a 100-mesh sieve, then the sieved microsphere powder passes through a 150-mesh sieve, and finally the microsphere powder intercepted by the 150-mesh sieve is used as a sample to be measured. Adding microspheres with a certain mass (the granularity is 100-150 meshes) into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure (100N) to the microspheres through a cylinder for a certain time (10 seconds), screening the pressed microsphere powder by using a 150-mesh screen, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total mass of the added microspheres to obtain the breaking rate of the microspheres.

Example 1

20kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated nitric acid is added into the reaction kettle, 2.3kg of PEG4000 is added into the reaction kettle, and finally 4kg of pseudo-boehmite powder is added into the reaction kettle, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 35 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 580 ℃, and the air outlet temperature of drying termination is 160 ℃.

The SEM photograph of the raspberry type oxide microspheres is shown in FIG. 1, and the photomicrograph is shown in FIG. 5.

Example 2

20kg of water is added into a reaction kettle, 0.5kg of zirconium nitrate is added into the reaction kettle, 175g of concentrated nitric acid is added into the reaction kettle, 2kg of PEG4000 and 5g of digestive glycerin are added into the reaction kettle, and finally 4.6kg of pseudo-boehmite powder is added into the reaction kettle, and the mixture is uniformly stirred and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 0.5 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 140 ℃.

The SEM photograph of the raspberry type oxide microspheres is shown in fig. 2.

Example 3

30kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated nitric acid and 4.5kg of sodium carbonate are added into the reaction kettle, 2.3kg of methyl cellulose and 10g of picric acid are added into the reaction kettle, and finally 14kg of aluminum sulfate is added into the reaction kettle, stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 30 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 580 ℃, and the air outlet temperature of drying termination is 130 ℃.

SEM photographs of raspberry type oxide microspheres are shown in FIG. 3.

Example 4

40kg of water is added into a reaction kettle, 1.2kg of yttrium nitrate is added into the reaction kettle, 230g of concentrated nitric acid and 4.8kg of sodium carbonate are added into the reaction kettle, 2.8kg of methyl cellulose and 15g of nitrocotton are added into the reaction kettle, and finally 12.5kg of aluminum chloride is added into the reaction kettle, stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 30 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 141 ℃.

SEM photographs of raspberry type oxide microspheres are shown in FIG. 4.

Example 5

40kg of water was added to a reaction kettle, 1.2kg of aluminum nitrate was added thereto, 200g of concentrated nitric acid was then added, 2kg of PEG4000 and 2g of digestive fiber were then added, and 5.5kg of sodium silicate was finally added, stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 120 ℃.

A photomicrograph of raspberry-type oxide microspheres is shown in FIG. 6.

Example 6

40kg of water is added into a reaction kettle, 0.5kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated sulfuric acid is added into the reaction kettle, 1kg of PEG4000 and 5g of picric acid are added into the reaction kettle, and 3kg of sodium silicate is added into the reaction kettle, stirred uniformly and ground to obtain dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 600 ℃, and the air outlet temperature of drying termination is 180 ℃.

Example 7

20L of mixed solution of water and ethanol (wherein the volume ratio of the water to the ethanol is 3:1) is added into a reaction kettle, 1.2kg of aluminum nitrate is added, 7L of strong ammonia water is added, 7g of ethyl cellulose and nitroglycerin are added with 2kg, 5kg of TEOS is added, and the mixture is stirred uniformly and ground to obtain dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 700 ℃, and the air outlet temperature of drying termination is 160 ℃.

Example 8

20L of mixed solution of water and ethanol (wherein the volume ratio of the water to the ethanol is 4:1) is added into a reaction kettle, 0.3kg of zirconium nitrate is added into the reaction kettle, 3L of strong ammonia water is added into the reaction kettle, 0.5kg of PEG4000 and 6g of picric acid are added into the reaction kettle, and finally 2.6kg of TEOS is added into the reaction kettle, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 660 ℃, and the air outlet temperature of drying termination is 140 ℃.

Example 9

30kg of water was added to a reaction kettle, 1.2kg of zirconium nitrate was added thereto, 2.5kg of PEG4000 was added thereto, and finally 7kg of zirconium hydroxide was added thereto, and the mixture was stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 45 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 110 ℃.

A photomicrograph of raspberry-type oxide microspheres is shown in FIG. 7.

Example 10

30kg of water is added into a reaction kettle, 0.7kg of zirconium nitrate is added into the reaction kettle, then 2L of concentrated ammonia water is added, 1.5kg of PEG4000 and 8g of picric acid are added, finally 7kg of zirconium hydroxide is added, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 2 hours with stirring.

Example 11

30kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 2L of concentrated ammonia water is added, 2kg of PEG4000 and 2g of trinitrotoluene are added, and finally 7kg of zirconium hydroxide is added, stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 620 ℃, and the air outlet temperature of drying termination is 141 ℃.

Example 12

30kg of water is added into a reaction kettle, 0.5kg of magnesium nitrate is added into the reaction kettle, then 2.5L of concentrated ammonia water is added, 1kg of methyl cellulose and 6g of nitroglycerin are added, finally 7.5kg of zirconium hydroxide is added, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Example 13

30kg of water is added into a reaction kettle, 1.2kg of titanium nitrate is added into the reaction kettle, 2.5kg of PEG4000 and 3g of digested cotton are added into the reaction kettle, and finally 500g of concentrated nitric acid and 6kg of titanium dioxide are stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 55 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 480 ℃, and the air outlet temperature of drying termination is 120 ℃.

A photomicrograph of raspberry-type oxide microspheres is shown in FIG. 8.

Example 14

30kg of water is added into a reaction kettle, 0.7kg of titanium nitrate is added into the reaction kettle, then 2.6L of concentrated ammonia water is added, 1.5kg of PEG4000 and 6g of picric acid are added, and finally 500g of concentrated nitric acid and 7kg of titanium nitrate are added, stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 2 hours with stirring.

Example 15

30kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, then 2.1L of concentrated ammonia water is added, 2kg of PEG4000 and 2g of trinitrotoluene are added, finally 400g of concentrated nitric acid and 7kg of titanium tetrachloride are added, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 620 ℃, and the air outlet temperature of drying termination is 150 ℃.

Example 16

30kg of water is added into a reaction kettle, 0.5kg of magnesium nitrate is added into the reaction kettle, then 2.4L of concentrated ammonia water is added, 1kg of methylcellulose and 6g of nitroglycerin are added, finally 400g of concentrated nitric acid and 7kg of titanium tetrachloride are added, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Comparative example 1

Adding 20kg of water into a reaction kettle, adding 4.5kg of pseudo-boehmite powder, and stirring and mixing uniformly; adding 200g of concentrated hydrochloric acid, mixing and grinding; adding 2.3kg of PEG4000, continuing pulping, stirring and aging at 25 ℃ for 1 hour, and drying and forming by a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in the tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 145 ℃.

The microphotograph of the obtained oxide microspheres is shown in fig. 9, which shows that the oxide microspheres are substantially solid, and a hollow structure communicating with the outside rarely exists in the central part.

Comparative example 2

Adding 30kg of water and 5.5kg of sodium silicate into a reaction kettle, and stirring and mixing uniformly; adding 200g of concentrated hydrochloric acid; the resulting dispersion was filtered and the precipitate was washed 2 times with ethanol and deionized water, respectively, to remove unreacted inorganic and organic impurities.

Adding water 20kg and PEG4000 of 2.0kg, continuing pulping, stirring at 25 ℃ and aging for 1 hour, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in the tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 450 ℃, and the air outlet temperature of drying termination is 120 ℃.

When observed under a microscope, the structure of the material is similar to that of comparative example 1, and the material is basically solid, and a hollow structure communicated with the outside rarely exists in the central part.

Comparative example 3

30kg of water and 7kg of zirconium hydroxide were added to the reaction vessel, stirred vigorously at 30 ℃ until complete mixing, and the dispersion was ground for 30 minutes by means of a mill.

After mixing and grinding, adding concentrated ammonia water as a regulator until the pH value is about 10, reacting for 2 hours to obtain a dispersion system, stirring and aging for 1 hour at 25 ℃, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 650 ℃, and the air outlet temperature of drying termination is 150 ℃.

Comparative example 4

30kg of water, 6kg of titanium dioxide and 500g of concentrated hydrochloric acid were added to the reaction vessel, stirred vigorously at 30 ℃ until complete mixing, and the dispersion was ground for 30 minutes by means of a grinder.

After mixing, reacting and grinding, adding concentrated ammonia water as a regulator until the pH value is about 9, after reacting for 2 hours, adding 2.5kg of PEG4000 to obtain a dispersion system, stirring and aging at 45 ℃ for 1 hour, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 520 ℃, and the air outlet temperature of drying termination is 170 ℃.

When observed under a microscope, the structure of the material is similar to that of the comparative example 1, and the material is basically solid, and a hollow structure communicated with the outside rarely exists in the central part.

Comparative example 5

5.5kg of HZSM-5 molecular sieve with the grain size of 300-350 nm, 3kg of kaolin, 1kg of cement and 0.5kg of ammonium carbonate are added into 20kg of deionized water, and shearing emulsification is carried out for 2 hours at 2000rpm by a homogenizing emulsifier to form uniform colloidal slurry, wherein the solid content of the colloidal slurry is 31.7%.

And adding 300g of P123 surfactant into the colloidal slurry, and continuously stirring for 1h to obtain the microsphere slurry.

And (3) conveying the microsphere slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.8Mpa, the inlet temperature of the spray dryer is 280 ℃, the outlet temperature of the spray dryer is 120 ℃, and the microsphere slurry flows out of the outlet of the spray dryer for 2-5 seconds to obtain microsphere particles.

Comparative example 6

And (3) conveying the microsphere slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.8Mpa, the inlet temperature of the spray dryer is 560 ℃, the outlet temperature of the spray dryer is 140 ℃, and the microsphere slurry flows out of the outlet of the spray dryer for 2-5 seconds to obtain microsphere particles.

The microphotograph of the microspheroidal particles is shown in FIG. 10, in which most of the microspheroidal particles have irregular shapes and the central portion rarely has a hollow structure communicating with the outside.

Comparative example 7

5.5kg of pseudo-boehmite powder, 3kg of kaolin, 1kg of cement and 0.5kg of ammonium carbonate are added into 20kg of deionized water, and shearing emulsification is carried out for 2 hours at 2000rpm by a homogenizing emulsifier to form uniform colloidal slurry, wherein the solid content of the colloidal slurry is 31.7%.

And adding 300g of P123 surfactant into the colloidal slurry, and continuing stirring for 1h to obtain the microsphere slurry.

The microphotograph of the microspheroidal particle is shown in FIG. 11, in which the microspheroidal particle is substantially solid and has a hollow structure communicating with the outside rarely at the central part.

The effect of the oxide microspheres of the examples of the present invention and the comparative examples as a carrier on the performance of a catalyst was tested by the following application examples.

Application example

The oxide microspheres obtained in examples 1, 5, 9, 13 and comparative examples 1 to 5 were calcined at 600 ℃ for 3 hours to obtain a support. The physical properties of the carrier are shown in table 1.

The carrier is impregnated with cobalt nitrate solution, dried at 120 ℃ and calcined at 420 ℃ to obtain the catalyst with the Co content of 16wt%, and the physical properties of the catalyst are shown in Table 2.

The pressure drop of the catalyst bed layer is measured by communicating a precise standard pressure gauge at the inlet end of the bed layer, and the gas space velocity is 24000h ^-1 The gas medium is nitrogen.

In a fixed bed reactionThe performance of the catalyst in the Fischer-Tropsch (FT) synthesis reaction was evaluated in a pilot plant. The FT synthesis catalyst needs to be reduced to a metallic state before use. Catalyst reduction reaction conditions: the pressure is normal pressure, the heating rate is 5 ℃/min, and the airspeed of hydrogen is 600h ^-1 The reduction temperature was 400 ℃ and the reduction time was 5 hours. After the reduction, a reaction performance test was conducted,

the reaction conditions were as follows: feed gas composition H ₂ /CO/N ₂ Pressure of 45%/45%/10% (volume percentage) 2.5MPa, temperature of 200 deg.C, 210 deg.C and 220 deg.C, synthetic gas (raw gas) space velocity of 24000h ^-1 . Gas samples were taken for chromatography after 12 hours for each reaction temperature point. The results of the reaction performance test are shown in table 3.

TABLE 1 physical Properties of the vectors

As can be seen from table 1, when the raspberry-type oxide microspheres of the present invention are used as a carrier, the specific surface, pore volume, and average pore diameter are similar to those of the comparative example, but the sphericity and strength are greatly improved, which is significantly better than those of the oxide microspheres of the comparative example. The possibility is provided for the use of these vectors.

TABLE 2 physical Properties of the catalysts

As can be seen from table 2, the catalyst prepared by using the raspberry type oxide microspheres of the present invention as a carrier is significantly superior to the oxide microspheres of the comparative example in strength and bed pressure drop.

TABLE 3 results of reaction Performance test of catalyst

The test results in table 3 show that the catalyst prepared by using the raspberry-type oxide microspheres of the present invention as a carrier has significantly better CO conversion, methane selectivity, and C5+ hydrocarbon selectivity in the FT synthesis reaction than the comparative oxide microspheres.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. A raspberry type oxide microsphere is characterized in that the raspberry type oxide microsphere is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, and the large pore and the hollow structure are communicated to form a cavity with one open end;

wherein the oxide in the raspberry type oxide microspheres is selected from one or more of alumina, silica, zirconia, magnesia, calcium oxide and titanium oxide;

the preparation method of the raspberry type oxide microsphere comprises the following steps:

adding nitrate, peptizing agent, pore-forming agent, oxide and/or precursor thereof into a dispersing agent and stirring to obtain dispersed slurry;

aging the dispersed slurry;

and (3) feeding the aged dispersed slurry into a drying device, and drying and forming under the conditions that the air inlet temperature is 400-1200 ℃ and the air outlet temperature is 50-300 ℃ to obtain the raspberry type oxide microspheres.

2. The raspberry-type oxide microsphere of claim 1, wherein the raspberry-type oxide microsphere has a particle size of 3 to 2500 μm.

3. The raspberry-type oxide microsphere of claim 2, wherein the raspberry-type oxide microsphere has a particle size of 10 to 500 μm.

4. The raspberry-type oxide microsphere of claim 1, wherein the diameter of the hollow structure is 1-2000 μm.

5. The raspberry-type oxide microsphere of claim 4, wherein the diameter of the hollow structure is 1-400 μm.

6. The raspberry-type oxide microsphere of claim 1, wherein the macropores have a pore size of 0.2-1000 μm.

7. The raspberry-type oxide microsphere of claim 6, wherein the macropores have a pore size of 0.5-200 μm.

8. The raspberry-type oxide microsphere of claim 1, wherein the shell layer of the hollow microsphere is 0.2-1000 μm thick.

9. The raspberry-type oxide microsphere of claim 8, wherein the shell layer thickness of the hollow microsphere is 0.5-200 μm.

10. The raspberry-type oxide microsphere of claim 1, wherein the raspberry-type oxide microsphere has a sphericity of 0.50-0.99.

11. The raspberry type oxide microsphere of any one of claims 1 to 10, wherein the breakage of the raspberry type oxide microsphere is 0-1%.

12. The raspberry type oxide microsphere of claim 1, wherein the inlet air temperature is 450-700 ℃ and the outlet air temperature is 120-200 ℃.

13. Raspberry-type oxide microspheres according to claim 1, wherein the nitrate is selected from one or more of aluminium nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate.

14. The raspberry-type oxide microsphere of claim 1, wherein the peptizing agent is selected from one or more of acids, bases and salts.

15. The raspberry-type oxide microsphere of claim 1, wherein the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactants.

16. Raspberry-type oxide microspheres according to claim 1, wherein the oxide and/or its precursors are selected from one or more of the group consisting of an aluminium source selected from one or more of pseudo-boehmite, aluminium alkoxide, aluminium nitrate, aluminium sulphate, aluminium chloride and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, waterglass and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulphate, zirconium phosphate, zirconium oxynitrate, zirconium nitrate, zirconium hydroxycarbonate and zirconium tetrabutoxide, a titanium source selected from one or more of titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulphate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminide chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate and tetra-isopropyl titanate.

17. The raspberry-type oxide microsphere of claim 1, wherein the dispersant is selected from one or more of water, alcohols, ketones, and acids.

18. The raspberry-type oxide microsphere of claim 1, wherein the mass ratio of the nitrate, the peptizing agent, the pore former and the oxide and/or its precursor is (10-500): (1-10): (10-500): (10-1000).

19. The raspberry-type oxide microsphere of claim 1, further comprising adding a blasting agent to the dispersing agent, wherein the blasting agent is selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, dana explosives, hexogen, and C4 plastic explosives.

20. The raspberry-type oxide microsphere of claim 1, wherein the blasting agent is added in an amount of 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent, and the oxide and/or its precursor.

21. The raspberry-type oxide microsphere of any one of claims 1 to 20, wherein the drying device is a flash drying device or a spray drying device.

22. The raspberry-type oxide microsphere of any one of claims 1 to 20, wherein the temperature of the aging treatment is 0 to 90 ℃.

23. The raspberry-type oxide microsphere of claim 22, wherein the temperature of the aging treatment is 20-60 ℃.

24. Use of raspberry-type oxide microspheres according to any one of claims 1 to 23 as a support in the field of catalysts.