CN116422225B

CN116422225B - Spherical hollow powder and preparation method and application thereof

Info

Publication number: CN116422225B
Application number: CN202310400117.8A
Authority: CN
Inventors: 李阳; 徐星星; 张建军; 陈杰
Original assignee: Beijing Huaqi Ecological Technology Co ltd
Current assignee: Beijing Huaqi Ecological Technology Co ltd
Priority date: 2023-04-14
Filing date: 2023-04-14
Publication date: 2023-11-28
Anticipated expiration: 2043-04-14
Also published as: CN116422225A

Abstract

The invention discloses spherical hollow powder and a preparation method and application thereof, and belongs to the technical field of powder preparation. The average grain diameter is 20-500 μm, the surface aperture ratio is 10-80%, and a plurality of small cavities are arranged inside. The preparation method comprises the following steps: preparing powder raw materials and water into slurry, and grinding the slurry until the granularity of the powder is 3-10 mu m, so that the accurate regulation and control of the wall thickness of the hollow powder is realized; the method comprises the steps of dividing into two parts of slurry A and slurry B, respectively adding different binders and surfactants, uniformly stirring, then mixing and uniformly stirring, carrying out atomization forming in a forming tower to obtain spherical hollow powder blanks, sintering, and cooling to form multi-cavity spherical hollow powder which are mutually communicated or not communicated. The powder can be applied to industries such as coating, plastic, aviation heat insulation, rubber, microorganism carrier, petroleum exploitation, heat preservation, heat insulation, fire resistance, paint, water treatment, slow release fertilizer, mortar filler, building materials, water and soil conservation, soil improvement, flue gas filtration or catalyst carrier.

Description

Spherical hollow powder and preparation method and application thereof

Technical Field

The invention belongs to the technical field of powder preparation, and particularly relates to spherical hollow powder, and a preparation method and application thereof.

Background

The spherical hollow powder material has various excellent performances, can be applied to various fields such as light materials, heat insulation materials, refractory materials, sound absorption materials, fillers of plastic rubber coatings, desert control, soil improvement, medicine slow release, chemical fertilizer slow release, sewage treatment, smoke treatment and the like, can meet the requirements of organic fillers such as petroleum well cementation, automobile chassis shock resistance, hull decks, resins and the like, emulsion explosives, high-grade fireproof coatings, heat insulation and energy conservation of building outer walls, retroreflective materials, carriers of biopharmaceutical slow release medicines and the like, and has potential application in the aspects of light packaging materials, wave absorption materials, deep water buoyancy materials, low-density adhesives, light high-strength concrete and the like in the electronic industry.

In the prior art, the fly ash hollow microsphere is a naturally-formed hollow powder material which is found earliest, and the phase composition of the fly ash hollow microsphere is as follows: 80-85% of silicate glass phase, 10-15% of mullite phase and 5% of other minerals. Many scholars do investigation and research on the formation process, the formation mechanism and the influence factors of the hollow microspheres in the fly ash, and a unified conclusion cannot be formed at present. It is considered that the formation of hollow micro-beads in fly ash is a dynamic process, and the critical state exists among combustion temperature, oxygen, gas and cooling, and the formation and yield of hollow micro-beads can be directly influenced by the design of coal and boiler. Because of this, the appearance characteristics (color, particle size, sphericity), density (true density, apparent density), optical properties, acoustic properties, thermal properties, electrical properties, mechanical properties, chemical composition, etc. of the fly ash hollow microspheres cannot be manually preset and controlled, which results in that the fly ash hollow microspheres cannot be widely and largely applied, especially in the field of high-end process application.

The hollow glass bead is a novel material with wide application and excellent performance, the hollow sphere with the granularity of 10-250 micrometers and the wall thickness of 1-2 micrometers is developed in recent years, and the main components of the hollow glass bead are alkali silicate glass, borosilicate glass, lead borate glass and the like, and the hollow glass bead has plasticity and simpler process, but the hollow glass bead mainly depends on glass materials, other materials have no plasticity, and ceramic spherical hollow powder materials with large cavity structures inside cannot be formed through common processes.

In addition, the nano hollow sphere is a method for preparing nano hollow powder by adopting a chemical synthesis method, and the hundred-nano hollow structure not only has the characteristics of low density and high specific surface area, but also can contain a large amount of guest molecules or large-size guests in a cavity part, so that a plurality of peculiar properties based on microcosmic wrapping effect can be generated; the method has extremely important research value and wide application prospect in various fields of electromagnetism, optics, chemistry, pharmacology, biology and the like.

Fowler et al use an O/W (oil in water) system in which tetraethyl orthosilicate (TEOS) is the dispersed phase and silicon source, H ₂ O is a continuous phase, naOH is used as a catalyst, CTAB is used as a surfactant and also is used as a mesoporous template agent, and hydrolysis polycondensation reaction of TEOS is utilized to prepare silica hollow spheres; adopting a W/O system by Buchold and the like, mixing a certain amount of dodecane, CTAB and n-hexanol to form an oil phase, forming a stable water-in-oil microemulsion system, reacting for 12 hours, hydrolyzing and polycondensing aluminum tert-butoxide to generate aluminum boehmite, adding diethylene glycol to break emulsion, and stopping the reaction to prepare the nano-scale aluminum boehmite hollow spheres; GQi and the like take Polystyrene Spheres (PS) as templates, the surfaces of the polystyrene spheres adsorb CTAB, the CTAB is used as a mesoporous template agent under the electrostatic action of CTAB cations and TEOS hydrolyzed silicon anions, and finally the templates are removed by roasting, so that monodisperse silica hollow spheres with different particle diameters are successfully synthesized; in an O/W system with n-heptane as a disperse phase (O), silicon source TEOS, deionized water as a continuous phase (W) CTAB as an emulsifier, zhao et al found that compressed CO under certain pressure was added ₂ Can form nano-scale emulsion without adding cosurfactant and simultaneously utilize the generated H ⁺ Initiating TEOS hydrolysis to form nano-scale hollow silicon spheres; q. Wang et al use Phenyltrimethoxysilane (PTMS) as a self-sacrificial template, add Phenyltrimethoxysilane (PTMS) to aqueous nitric acid to promote dissolution of PTMS, use emulsion formed by hydrolysis of trimethoxysilane as a self-template, add NH ₄ OH solution for regulating and controlling hydrolysis-polycondensation reaction of PTMSAnd forming a layer of silicon oxide outside the emulsion liquid drops, centrifuging, precipitating, washing with a solvent, washing with water, and drying to obtain the silicon oxide hollow spheres.

The hollow powder prepared by the chemical synthesis method cannot realize preparation of the hollow powder with larger scale, and cannot prepare the hollow powder with a plurality of small cavities inside and accurately control the hollow powder, and the hollow powder has a structure with a plurality of small cavities inside, has larger specific surface area and is more suitable for the fields of carrier, adsorption, water treatment and the like.

Particularly, the adsorbent for trapping VOCs gas is mainly porous materials such as active carbon, active carbon fiber, diatomite, mesoporous silica, metal Organic Frameworks (MOFs), molecular sieves and the like, but the materials are consumable materials, frequently need replacement, are high in price and need specific material preparation. The activated carbon and the activated carbon fiber belong to carbon-based porous materials, have large adsorption capacity and are the adsorbent materials which are most widely applied, but abundant surface groups of the activated carbon and the activated carbon fiber are easy to chemically adsorb with VOCs molecules or form stable hydrogen bonds, desorption/desorption is not thorough, and the carbon-based material is not resistant to high temperature, so that regeneration is difficult; diatomite has poor hydrothermal stability and mainly has a macroporous structure, which is unfavorable for VOC under low concentration _S Gas adsorption, mesoporous silica is also limited by mesoporous channels with larger self, has relatively weak adsorption binding force on VOCs molecules with smaller kinetic diameters, and enriches low-concentration VOC _S Poor gas capability; metal organic framework compounds (MOFs) _S ) The porous material is an emerging porous material which has higher adsorption capacity to VOCs molecules, but the precursor preparation cost is high, a large amount of organic solvents are needed during synthesis, and the thermal stability is poor, so that the porous material is still in the basic research and development stage at present.

In view of this, the present invention has been made.

Disclosure of Invention

In order to solve the technical problems, the invention provides spherical hollow powder and a preparation method and application thereof, and the technical scheme is as follows:

the invention provides spherical hollow powder, which has an average particle diameter of 20-500 mu m, a surface aperture ratio of 10-80% and a plurality of small cavities inside.

Further, the plurality of small cavities are closed or communicated, and the diameter of the small cavities is 1-50 mu m.

The invention also provides a preparation method of the spherical hollow powder, which comprises the following steps:

s1: preparing the powder raw material and water into slurry, and grinding to the powder granularity of 3-10 mu m.

Further, the powder raw material comprises Al ₂ O ₃ 、ZrO ₂ Kaolin, siO ₂ SiC, quartz, si ₃ N ₄ Mullite, diatomite, zirconium silicate, bauxite, red mud, dolomite, potassium feldspar, cordierite, iron tailings, silica micropowder, attapulgite, coal gangue, molybdenum tailings, feldspar and Y ₂ O ₃ 、ZnO、TiO ₂ One or more of MgO, zeolite, borax, fly ash, etc.

Further, the mass fraction of the powder raw material in the slurry is 25-65%.

Preferably, the milling is carried out in a mill at a speed of 50-1000rpm for 12-36 hours.

The grinding rate and time of the slurry influence the granularity of powder in the slurry, the smaller the granularity is, the smaller the charge resistance is, the more easily the charge resistance is accumulated on the surface of foam, the wall thickness of the final spherical hollow powder is influenced, and the surface energy of inorganic powder particles in the process of small thinning can be greatly increased by high-speed ball milling, so that the rheological property of the slurry is influenced.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B, adding a first binder and a first surfactant into the slurry A, and uniformly stirring to obtain foam slurry C with the diameter of 0.05-0.3 mm; and adding a second binder and a second surfactant into the slurry B, and uniformly stirring to obtain foam slurry D with the diameter of 5-50 mu m.

Further, the mass fraction of the first binder is 0.1-3%, and the mass fraction of the first surfactant is 0.1-2%; the mass fraction of the second binder is 0.5-3%, and the mass fraction of the second surfactant is 0.5-2%.

Further, the mass ratio of the slurry A to the slurry B is 1:8-15.

S3: and (3) mixing and uniformly stirring the foam slurry C and the foam slurry D obtained in the step S2.

Further, the stirring time is 20-60min; the stirring rate was 100-900rpm.

Two kinds of foam slurry with different foam sizes are prepared respectively through the step S2, and different binders and surfactants are added respectively, so that the foam with large diameter has small surface energy and the foam with small diameter has large surface energy. In step S3, the two foams are mixed together, and the small foam having a large surface energy is made to enter the inside of the large foam having a small surface energy by stirring.

S4: and (3) carrying out atomization molding on the product obtained in the step (S3) in a molding tower to obtain a spherical hollow powder blank.

Further, an atomizing disc is arranged in the forming tower, and the rotating speed of the atomizing disc is 6000-12000. The rotational speed of the atomizing disk in combination with the slurry rheology in steps S1 and S2 affects the particle size of the final powder.

Further, the inlet temperature of the forming tower is 300-450 ℃; the outlet temperature of the forming tower is not lower than 90 ℃. The inlet and outlet temperature of the forming tower influences the water content and the drying efficiency of the spherical hollow powder blank.

Further, based on the mixing process of the foam slurry C and the foam slurry D in the step S3, the particle size of the spherical hollow powder blank is controlled to be 50-600 mu m, and the water content is controlled to be 0.1-0.5% by controlling the inlet and outlet temperatures of the forming tower.

S5: and (3) sintering the spherical hollow powder blank obtained in the step (S4), and cooling to obtain the spherical hollow powder.

Preferably, the means for sintering comprises one of a muffle furnace, a trolley furnace, a tunnel kiln, a rotary kiln or a shuttle kiln.

More preferably, the spherical hollow powder body is put into a sagger and then put into the sintering device for sintering.

Further, the sintering temperature is 900-1600 ℃, and the sintering heat preservation time is 0.5-2h.

The invention also provides application of the spherical hollow powder in industries such as coating, plastics, aviation heat insulation, rubber, microorganism carriers, petroleum exploitation, heat preservation, heat insulation, fire resistance, paint, water treatment, slow release fertilizer, mortar filler, building materials, water and soil conservation, soil improvement, flue gas filtration or catalyst carriers and the like.

According to the application, firstly, accurate regulation and control of the wall thickness of the hollow powder is realized through grinding and adding of additives, then, two kinds of foam slurry with different foam sizes are prepared respectively, and different surfactants are added respectively, so that the surface energy of the foam with large diameter is small, the surface energy of the foam with small diameter is large, the two kinds of foam are mixed together, and the small foam with large surface energy enters the interior of the large foam with small surface energy through stirring action to form the multi-cavity spherical hollow powder which is mutually communicated or not communicated.

The spherical hollow powder provided by the application is an artificially synthesized multi-cavity spherical hollow powder, has a structure with a plurality of small cavities, has larger specific surface area, is suitable for the fields of carrier, adsorption, water treatment and the like, has microporous channels or multi-cavity structures with ordered height and adjustable aperture on molecular size, has rich skeleton structure, can be selectively adsorbed according to the size of VOCs molecules and the like, has good thermal stability and is easy to regenerate. In particular for the adsorption and trapping of industrial adsorption/separation processes and industrial emission VOCs gases.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

FIG. 1 is a scanning electron microscope image of a spherical hollow powder with a plurality of independent small cavity structures, which is internally sealed, prepared in example 11;

FIG. 2 is a scanning electron microscope image of the spherical hollow powder with a plurality of independent small cavity structures, which are internally sealed, prepared in example 10;

FIG. 3 is a scanning electron microscope image of the spherical hollow powder with a plurality of independent small cavity structures with internal communication prepared in example 14;

FIG. 4 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 9;

FIG. 5 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 12;

fig. 6 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 11.

Detailed Description

The term as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. If the ratio of the components is not specified, it means that the components can be combined in any ratio.

"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).

Example 1

A spherical hollow powder having an average particle diameter of 26 μm, a surface opening ratio of 13%, a plurality of small cavities in the interior thereof, which are mutually communicated, an average diameter of the small cavities in the interior of 3.7 μm, an average shell thickness of 1.8 μm, and a bulk density of 0.24g/cm ³ The average diameter of the surface pores is 1.4 mu m, and the porosity is 42%.

The preparation method of the spherical hollow powder specifically comprises the following steps:

s1: taking ZrO with the mass ratio of 70:30 ₂ Powder and Al ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 30%, the mass fraction of the water is about 70%, and the slurry is ground in a grinder at a rotating speed of 1000rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 3% into the slurry A, adding SAS with a mass fraction of 0.3%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding PVA with the mass fraction of 3% into the slurry B, adding AES with the mass fraction of 1%, stirring at a high speed for 60 minutes at a stirring speed of 1500rpm to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S3: and mixing and uniformly stirring the foam slurry C and the foam slurry D for 40min at a stirring speed of 800rpm.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 12000rpm, and a spherical hollow powder blank body with the diameter (D50) of 29.4 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1500 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the microorganism carrier industry.

Example 2

A spherical hollow powder with an average particle diameter of 34 μm, a surface aperture ratio of 8%, a plurality of small cavities inside, which are independent and closed and not communicated with each other, an average diameter of the small cavities inside of 2.3 μm, an average shell thickness of 1.4 μm, and a bulk density of 0.18g/cm ³ The average diameter of the surface pores is 0.6 μm, and the porosity is 88%.

s1: taking bauxite powder and Al with the mass ratio of 80:10:10 ₂ O ₃ Mixing with fly ash powder uniformly, and preparing into slurry with water; the mass fraction of the powder raw material is about 25%, the mass fraction of the water is about 75%, and the slurry is ground in a grinder at a rotating speed of 1000rpm for 36 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding resin with a mass fraction of 1% into the slurry A, adding SAS with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.8%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S3: and mixing and uniformly stirring the foam slurry C and the foam slurry D for 50min at a stirring speed of 800rpm.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 12000rpm, and a spherical hollow powder blank body with the diameter (D50) of 39.5 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the plastic industry.

Example 3

A spherical hollow powder having an average particle diameter of 40 μm, a surface opening ratio of 53%, a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 7.5 μm, the average shell thickness being 1.5 μm, and the bulk density being 0.57g/cm ³ The average diameter of the surface pores is 3.5 mu m, and the porosity is 93%.

S1: taking fly ash powder with the mass ratio of 70:10:20 and Y ₂ O ₃ Powder and TiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 35%, the mass fraction of the water is about 65%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 2% into the slurry A, adding AES with a mass fraction of 0.2%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C with a foam diameter of 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.8%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 12000rpm, and a spherical hollow powder blank body with the diameter (D50) of 48.6 mu m and the water content of 0.2% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1100 ℃, the heat preservation time is 0.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the paint industry.

Example 4

A spherical hollow powder having an average particle diameter of 45 μm, a surface opening ratio of 21% and a plurality of small cavities inside, which are not communicated with each other, and having an average diameter of 5.6 μm, an average shell thickness of 2.4 μm and a bulk density of 0.46g/cm ³ The average diameter of the surface pores is 2.6 mu m, and the porosity is 46%.

s1: taking mullite powder and Al with the mass ratio of 60:30:10 ₂ O ₃ Powder and SiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 40%, the mass fraction of the water is about 60%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:8, adding water glass with a mass fraction of 2% into the slurry A, adding animal protein with a mass fraction of 1%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass percent of 1% into the slurry B, adding SDS with the mass percent of 0.3%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 10000rpm, and a spherical hollow powder blank body with the diameter (D50) of 49.3 mu m and the water content of 0.1% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1200 ℃, the heat preservation time is 0.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat preservation industry.

Example 5

A spherical hollow powder having an average particle diameter of 49 μm, a surface opening ratio of 4%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 4.8 μm, an average shell thickness of 10.4 μm, and a bulk density of 0.63g/cm ³ The average diameter of the surface pores is 0.7 μm, and the porosity is 44%.

S1: uniformly mixing coal gangue powder, diatomite powder, attapulgite powder and feldspar powder with the mass ratio of 45:25:25:5, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 36 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:8, adding resin with a mass fraction of 2% into the slurry A, adding SDS with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 1.5% into the slurry B, adding SDS with the mass fraction of 0.2%, stirring at a high speed for 60 minutes at a stirring speed of 1500rpm to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 10000rpm, and a spherical hollow powder blank body with the diameter (D50) of 53.4 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1050 ℃, the heat preservation time is 0.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat insulation industry.

Example 6

A spherical hollow powder having an average particle diameter of 53 μm, a surface opening ratio of 37% and a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 4.8 μm, the average shell thickness being 3.2 μm, and the bulk density being 0.21g/cm ³ The average diameter of the surface pores is 2.9 mu m, and the porosity is 75%.

s1: taking Al with the mass ratio of 80:15:5 ₂ O ₃ Uniformly mixing the powder, mullite powder and ZnO powder, and preparing slurry with water; the mass fraction of the powder raw material is about 25%, the mass fraction of the water is about 75%, and the slurry is ground in a grinder at 800rpm for 12 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to the mass ratio of 1:12, adding PVA with the mass fraction of 3% into the slurry A, adding SAS with the mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and AES with the mass fraction of 0.2% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 300 ℃, the outlet temperature of the forming tower is 150 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 10000rpm, and a spherical hollow powder blank body with the diameter (D50) of 56.7 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1450 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the fire-resistant industry.

Example 7

A spherical hollow powder having an average particle diameter of 66 μm, a surface opening ratio of 43% and a plurality of small cavities inside, which are not communicated with each other, and having an average diameter of 7.7 μm, an average shell thickness of 5.7 μm and a bulk density of 0.67g/cm ³ The average diameter of the surface pores is 6.2 mu m, and the porosity is 66%.

S1: mixing kaolin powder, feldspar powder and dolomite powder with the mass ratio of 80:10:10 uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 12 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 3% into the slurry A, adding SDS with a mass fraction of 1%, and stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, so as to form foam slurry C, and the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and AES with the mass fraction of 0.3% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 320 ℃, the outlet temperature of the forming tower is 120 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 10000rpm, and a spherical hollow powder blank body with the diameter (D50) of 72.3 mu m and the water content of 0.2% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1150 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the water treatment industry.

Example 8

A spherical hollow powder having an average particle diameter of 71 μm, a surface opening ratio of 17%, a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 5.7 μm, the average shell thickness being 4.7 μm, and the bulk density being 0.59g/cm ³ The average diameter of the surface pores is 2.4 mu m, and the porosity is 48%.

s1: taking red mud powder and SiO with the mass ratio of 60:15:15 ₂ Powder and Al ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 40%, the mass fraction of the water is about 60%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 2% into the slurry A, adding AOS with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding PVA with the mass fraction of 2% into the slurry B, adding AES with the mass fraction of 0.3%, stirring at a high speed of 1500rpm for 45 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 320 ℃, the outlet temperature of the forming tower is 120 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 78.8 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the heat preservation time is 1h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the rubber industry.

Example 9

A spherical hollow powder, as shown in FIG. 4, has an average particle diameter of 95 μm, a surface opening ratio of 26%, a plurality of small cavities inside, and is mutually communicated, the average diameter of the small cavities inside is 9.7 μm, the average shell thickness is 3.9 μm, and the bulk density is 0.42g/cm ³ The average diameter of the surface pores is 3.3 mu m, and the porosity is 53%.

S1: taking SiC powder and Y with the mass ratio of 90:5:5 ₂ O ₃ Powder and Al ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 35%, the mass fraction of the water is about 65%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 1% into the slurry A, adding AES with a mass fraction of 0.3%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C with a foam diameter of 0.05-0.3mm; PVA in the amount of 1.5% by mass and AES in the amount of 0.2% by mass are added to the slurry B, and the mixture is stirred at a high speed for 60 minutes at a stirring speed of 1500rpm to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 320 ℃, the outlet temperature of the forming tower is 120 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 102 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1350 ℃, the heat preservation time is 1h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the slow-release fertilizer industry.

Example 10

A spherical hollow powder, as shown in figure 2, has an average particle diameter of 106 μm, a surface aperture ratio of 12%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of 8.8 μm, an average shell thickness of 7.9 μm, and a bulk density of 0.36g/cm ³ The average diameter of the surface pores is 1.6 mu m, and the porosity is 56%.

s1: taking Al with the mass ratio of 60:20:10:10 ₂ O ₃ Uniformly mixing powder, dolomite powder, potassium feldspar powder and MgO powder, and preparing slurry with water; the mass fraction of the powder raw material is about 35%, the mass fraction of the water is about 65%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to the mass ratio of 1:10, adding 1% of resin by mass into the slurry A, adding 1% of AOS by mass, and stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, so as to form foam slurry C, and the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and AES with the mass fraction of 0.2% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 320 ℃, the outlet temperature of the forming tower is 120 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 124.6 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 1h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the plastic industry.

Example 11

A spherical hollow powder, as shown in FIGS. 1 and 6, has an average particle diameter of 122 μm, a surface opening ratio of 22%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of 10.3 μm, an average shell thickness of 4.3 μm, and a bulk density of 0.25g/cm ³ The average diameter of the surface pores is 5.4 mu m, and the porosity is 67%.

S1: taking coal gangue powder and Al with the mass ratio of 60:20:20 ₂ O ₃ Uniformly mixing the powder and mullite powder, and preparing slurry with water; the mass fraction of the powder raw material is about 30%, the mass fraction of the water is about 70%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 2% into the slurry A, adding SAS with a mass fraction of 1%, stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, and forming foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and AES with the mass fraction of 0.1% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 138.4 mu m and the water content of 0.5% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the heat preservation time is 1h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat preservation industry.

Example 12

As shown in FIG. 5, the spherical hollow powder has an average particle diameter of 132 μm, a surface opening ratio of 32%, a plurality of small cavities inside, which are mutually communicated, an average diameter of the internal small cavities of 9.2 μm, an average shell thickness of 8.6 μm, and a bulk density of 0.63g/cm ³ The average diameter of the surface pores is 5.3 mu m, and the porosity is 65%.

s1: taking kaolin powder, quartz powder and Al with the mass ratio of 60:20:15:5 ₂ O ₃ Uniformly mixing the powder and zeolite powder, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 800rpm for 36 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 3% into the slurry A, adding SDS with a mass fraction of 1%, and stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, so as to form foam slurry C, and the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding AES with the mass fraction of 0.2%, stirring at a high speed for 60 minutes at a stirring speed of 1500rpm to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 152.1 mu m and the water content of 0.1% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1250 ℃, the heat preservation time is 1h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the slow-release fertilizer industry.

Example 13

A spherical hollow powder having an average particle diameter of 135 μm, a surface opening ratio of 17%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 8.4 μm, an average shell thickness of 11.4 μm, and a bulk density of 0.78g/cm ³ The average diameter of the surface pores is 3.5 mu m, and the porosity is 55%.

S1: taking cordierite powder, mullite powder and Al with the mass ratio of 70:20:10 ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, the slurry is ground for 24 hours in a grinder at a rotating speed of 800rpm until the particle size of the powder is between 3 mu m and 10 mu m。

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 3% into the slurry A, adding AOS with a mass fraction of 1%, and stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, so as to form foam slurry C, and the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and AES with the mass fraction of 0.1% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 9500rpm, and a spherical hollow powder blank body with the diameter (D50) of 148.2 mu m and the water content of 0.2% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat preservation industry.

Example 14

A spherical hollow powder, as shown in FIG. 3, has an average particle diameter of 137 μm, a surface opening ratio of 43%, a plurality of small cavities in the interior, the small cavities being mutually communicated, the average diameter of the small cavities in the interior being 23.7 μm, the average shell thickness being 5.1 μm, and the bulk density being 0.49g/cm ³ The average diameter of the surface pores is 7.6 mu m, and the porosity is 85%.

s1: taking fly ash powder, quartz powder and diatomite powder with the mass ratio of 75:15:10, uniformly mixing, and preparing slurry with water; the mass fraction of the powder raw material is about 60%, the mass fraction of the water is about 40%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 1% into the slurry A, adding SDS with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 1.5% and SDS with the mass fraction of 0.2% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 8000rpm, and a spherical hollow powder blank body with the diameter (D50) of 151.9 mu m and the water content of 0.2% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the mortar filler industry.

Example 15

A spherical hollow powder having an average particle diameter of 142 μm, a surface opening ratio of 21%, a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 18.7 μm, the average shell thickness being 7.6 μm, and the bulk density being 0.36g/cm ³ The average diameter of the surface pores is 6.5 mu m, and the porosity is 69%.

S1: taking iron tailing powder and Al with the mass ratio of 90:5:5 ₂ O ₃ Powder and SiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 35%, the mass fraction of the water is about 65%, and the slurry is preparedGrinding in a grinder at 800rpm for 12h to powder particle size of 3-10 μm.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 3% into the slurry A, adding SDS with a mass fraction of 1.5%, and stirring at a high speed for 30 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 2% and SDS with the mass fraction of 0.2% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 8000rpm, and a spherical hollow powder blank body with the diameter (D50) of 161.3 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1050 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the water treatment industry.

Example 16

A spherical hollow powder having an average particle diameter of 148 μm, a surface opening ratio of 3%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 13.8 μm, an average shell thickness of 12.5 μm, and a bulk density of 0.53g/cm ³ The average diameter of the surface pores is 0.6 μm, and the porosity is 74%.

s1: taking silicon micro powder, mullite powder and Al with the mass ratio of 80:10:10 ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about45% water, about 55% by mass, and grinding the slurry in a grinder at 800rpm for 12 hours to a powder particle size of between 3 μm and 10 μm.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 2% into the slurry A, adding AES with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.3%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 8000rpm, and a spherical hollow powder blank body with the diameter (D50) of 167.4 mu m and the water content of 0.2% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the petroleum exploitation industry.

Example 17

A spherical hollow powder having an average particle diameter of 153 [ mu ] m, a surface aperture ratio of 38%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 18.3 [ mu ] m, an average shell thickness of 15.6 [ mu ] m, and a bulk density of 0.91g/cm ³ The average diameter of the surface pores is 6.9 mu m, and the porosity is 72%.

S1: taking ZrO with the mass ratio of 50:30:15:5 ₂ Powder, al ₂ O ₃ Powder, siO ₂ Powder and TiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 55%, the mass fraction of the water is about 45%, and the slurry is ground in a grinder at 800rpm for 36 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 2% into the slurry A, adding animal protein with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 8000rpm, and a spherical hollow powder blank body with the diameter (D50) of 172.6 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1450 ℃, the heat preservation time is 1.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the building material industry.

Example 18

A spherical hollow powder having an average particle diameter of 178 μm, a surface opening ratio of 46%, a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 28.5 μm, the average shell thickness being 6.7 μm, and the bulk density being 0.53g/cm ³ The average diameter of the surface pores is 7.8 mu m, and the porosity is 78%.

s1: the mass ratio is 70:10:20Fly ash powder of (Y) ₂ O ₃ Powder and TiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 2% into the slurry A, adding OEP with a mass fraction of 2%, and stirring at a high speed for 20 minutes, wherein the stirring speed is 1000rpm, so as to form foam slurry C, and the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 350 ℃, the outlet temperature of the forming tower is 100 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 8000rpm, and a spherical hollow powder blank body with the diameter (D50) of 188.2 mu m and the water content of 0.5% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 900 ℃, the heat preservation time is 1.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the water and soil conservation industry.

Example 19

A spherical hollow powder having an average particle diameter of 185 μm, a surface opening ratio of 6%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 14.3 μm, an average shell thickness of 18.5 μm, and a bulk density of 0.65g/cm ³ The average diameter of the surface pores is 1.1 mu m, and the porosity is 85%.

S1: uniformly mixing coal gangue powder, diatomite powder, attapulgite powder and feldspar powder with the mass ratio of 45:25:25:5, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 3% into the slurry A, adding AES with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C with a foam diameter of 0.05-0.3mm; adding CMC with the mass fraction of 1.5% and SDS with the mass fraction of 0.3% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 204.5 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 950 ℃, the heat preservation time is 1.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat insulation industry.

Example 20

A spherical hollow powder having an average particle diameter of 192 μm, a surface opening ratio of 26% and a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 38.4 μm, the average shell thickness being 9.5 μm, and the bulk density being 0.54g/cm ³ The average diameter of the surface pores is 5.3 mu m, and the porosity is 75%.

s1: taking zeolite powder, kaolin powder, mgO powder and Al in a mass ratio of 50:30:10:10 ₂ O ₃ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 3% into the slurry A, adding animal protein with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 1.5% and SDS with the mass fraction of 0.3% into the slurry B, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 228.4 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the heat preservation time is 1.5h, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the soil improvement industry.

Example 21

A spherical hollow powder having an average particle diameter of 203 [ mu ] m, a surface aperture ratio of 28%, a plurality of small cavities in the interior thereof, the small cavities being communicated with each other, the average diameter of the small cavities in the interior being 27.5 [ mu ] m, the average shell thickness being 27.5 [ mu ] m, and the bulk density being 0.86g/cm ³ The average diameter of the surface pores is 4.9 mu m, and the porosity is 65%.

S1: taking quartz powder and Al with the mass ratio of 70:20:10 ₂ O ₃ Powder and ZrO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 1.5% into the slurry A, adding SAS with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 1.5% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed for 60 minutes at a stirring speed of 1500rpm to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 225.6 mu m and the water content of 0.4% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1100 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the flue gas filtering industry.

Example 22

A spherical hollow powder having an average particle diameter of 214 μm, a surface opening ratio of 32%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 31.2 μm, an average shell thickness of 21.8 μm, and a bulk density of 0.61g/cm ³ The average diameter of the surface pores is 3.6 mu m, and the porosity is 57%.

s1: uniformly mixing molybdenum tailing powder, fly ash powder, mullite powder and borax powder in a mass ratio of 50:30:10:10, and preparing slurry with water; the mass fraction of the powder raw material is about 40%, the mass fraction of the water is about 60%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding water glass with a mass fraction of 3% into the slurry A, adding SDS with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 236.7 mu m and the water content of 0.5% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the heat preservation industry.

Example 23

A spherical hollow powder has an average particle diameter of 236 μm, a surface aperture ratio of 19%, a plurality of small cavities in the interior, and an average shell diameter of 25.6 μmLayer thickness 12.4 μm, bulk density 0.73g/cm ³ The average diameter of the surface pores is 3.5 mu m, and the porosity is 78%.

S1: taking Al with the mass ratio of 50:30:15:5 ₂ O ₃ Uniformly mixing the powder, feldspar powder, znO powder and borax powder, and preparing slurry with water; the mass fraction of the powder raw material is about 45%, the mass fraction of the water is about 55%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 1.5% into the slurry A, adding OEP with a mass fraction of 1%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C with a foam diameter of 0.05-0.3mm; adding water glass with the mass fraction of 2% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 258.4 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the soil improvement industry.

Example 24

A spherical hollow powder with an average particle diameter of 248 μm and a surface aperture ratio of 26% has a plurality of small cavities therein, and the cavities are mutually separatedThe average diameter of the communicated small internal cavity is 37.3 mu m, the average shell thickness is 25.6 mu m, and the stacking density is 0.57g/cm ³ The average diameter of the surface pores is 4.8 mu m, and the porosity is 86%.

s1: taking ZrO with the mass ratio of 50:30:10:10 ₂ Powder, al ₂ O ₃ Powder, siO ₂ Powder and TiO ₂ Mixing the powder uniformly, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding PVA with a mass fraction of 2% into the slurry A, adding AES with a mass fraction of 0.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C with a foam diameter of 0.05-0.3mm; adding CMC with the mass fraction of 1.5% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 279.3 mu m and the water content of 0.3% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1350 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the catalyst carrier industry.

Example 25

Spherical hollow powder, wherein the average particle size of the spherical hollow powderThe diameter is 253 mu m, the surface aperture ratio is 37%, a plurality of small cavities are arranged in the hollow cavity and are communicated with each other, the average diameter of the internal small cavity is 28.3 mu m, the average shell thickness is 8.5 mu m, and the bulk density is 0.68g/cm ³ The average diameter of the surface pores is 7.3 μm, and the porosity is 74%.

S1: uniformly mixing fly ash powder, diatomite powder, zeolite powder and borax powder in a mass ratio of 40:30:25:5, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding CMC with a mass fraction of 3% into the slurry A, adding SAS with a mass fraction of 1.5%, and stirring at a high speed for 20 minutes at a stirring speed of 1000rpm to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 1.5% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 286.5 mu m and the water content of 0.5% is obtained.

S5: and (3) loading the spherical hollow powder blank obtained in the step (S4) into a sagger, placing the sagger into a muffle furnace for sintering, wherein the sintering temperature is 1050 ℃, the heat preservation time is 2 hours, and cooling the sagger to room temperature along with the furnace to obtain the spherical hollow powder. The spherical hollow powder can be applied to the water-retaining industry.

Example 26

Spherical hollow powder bodyThe spherical hollow powder has an average particle diameter of 266 μm, a surface aperture ratio of 12%, a plurality of small cavities inside, which are not communicated with each other, an average diameter of the small cavities inside of 17.3 μm, an average shell thickness of 7.4 μm, and a bulk density of 0.32g/cm ³ The average diameter of the surface pores is 2.3 mu m, and the porosity is 83%.

s1: taking quartz powder and Al with the mass ratio of 55:30:10:5 ₂ O ₃ Uniformly mixing the powder, mgO powder and SiC powder, and preparing slurry with water; the mass fraction of the powder raw material is about 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 800rpm for 24 hours until the particle size of the powder is between 3 and 10 mu m.

S2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B according to a mass ratio of 1:10, adding 3% of resin into the slurry A, adding 1.5% of animal protein into the slurry A, and stirring at a high speed of 1000rpm for 20 minutes to form foam slurry C, wherein the diameter of foam is 0.05-0.3mm; adding CMC with the mass fraction of 1.5% into the slurry B, adding SDS with the mass fraction of 0.1%, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry D, wherein the diameter of foam is 5-50 mu m.

S4: and (3) conveying the foam slurry into a forming tower by using a diaphragm pump, wherein the inlet temperature of the forming tower is 370 ℃, the outlet temperature of the forming tower is 90 ℃, an atomizing disk is arranged in the forming tower, the rotating speed of the atomizing disk is 7000rpm, and a spherical hollow powder blank body with the diameter (D50) of 293.1 mu m and the water content of 0.4% is obtained.

Note that the technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be regarded as the scope of the description. The foregoing examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims

1. The preparation method of the spherical hollow powder is characterized by comprising the following steps:

s1: preparing a ceramic powder raw material and water into slurry, and grinding to a powder granularity of 3-10 mu m;

s2: dividing the ground slurry in the step S1 into two parts of slurry A and slurry B, adding a first binder and a first surfactant into the slurry A, and uniformly stirring to obtain foam slurry C with the foam diameter of 0.05-0.3 mm; adding a second binder and a second surfactant into the slurry B, and uniformly stirring to obtain foam slurry D with the foam diameter of 5-50 mu m;

s3: mixing and uniformly stirring the foam slurry C and the foam slurry D obtained in the step S2;

s4: carrying out atomization molding on the product obtained in the step S3 in a molding tower to obtain a spherical hollow powder blank;

and S5, sintering the spherical hollow powder blank obtained in the step S4, and cooling to obtain the spherical hollow powder.

2. The method according to claim 1, wherein in step S1, the powder raw material includes Al ₂ O ₃ 、ZrO ₂ Kaolin, siO ₂ SiC, quartz, si ₃ N ₄ Mullite, diatomite, zirconium silicate, bauxite, red mud, dolomite, potassium feldspar, cordierite, iron tailings, silica micropowder, attapulgite, coal gangue, molybdenum tailings, feldspar and Y ₂ O ₃ 、ZnO、TiO ₂ One or more of MgO, zeolite, borax or fly ash.

3. The preparation method according to claim 1, wherein in the step S1, the mass fraction of the powder raw material in the slurry is 25-65%.

4. A method of preparation according to claim 3, wherein in step S1 the milling is carried out in a mill at a speed of 50-1000rpm, in the range of 12-36 h.

5. The method of claim 1, wherein step S2 satisfies one or more of the following conditions:

a. the mass fraction of the first binder is 0.1-3%;

b. the mass fraction of the first surfactant is 0.1-2%;

c. the mass fraction of the second binder is 0.5-3%;

d. the mass fraction of the second surfactant is 0.5-2%.

6. The method according to claim 1, wherein in step S3, the stirring time is 20 to 60 minutes; the stirring rate was 100-900rpm.

7. The method of claim 1, wherein step S4 satisfies one or more of the following conditions:

e. an atomizing disc is arranged in the forming tower, and the rotating speed of the atomizing disc is 6000-12000rpm;

f. The inlet temperature of the forming tower is 300-450 ℃;

g. the outlet temperature of the forming tower is not lower than 90 ℃;

h. the particle size of the spherical hollow powder body is 50-600 mu m, and the water content is 0.1-0.5%.

8. The method of claim 1, wherein step S5 satisfies one or more of the following conditions:

i. the sintering device comprises one of a muffle furnace, a trolley furnace, a tunnel kiln, a rotary kiln or a shuttle kiln;

j. the sintering temperature is 900-1600 ℃;

k. the sintering heat preservation time is 0.5-2 h.

9. The method according to claim 8, wherein in step S5, the spherical hollow powder body is put into a sagger and then put into the sintering device for sintering.