CN116422224A - Spherical hollow powder and preparation method and application thereof - Google Patents
Spherical hollow powder and preparation method and application thereof Download PDFInfo
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- CN116422224A CN116422224A CN202310400113.XA CN202310400113A CN116422224A CN 116422224 A CN116422224 A CN 116422224A CN 202310400113 A CN202310400113 A CN 202310400113A CN 116422224 A CN116422224 A CN 116422224A
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- China
- Prior art keywords
- powder
- spherical hollow
- slurry
- hollow powder
- preparation
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- 239000000843 powder Substances 0.000 title claims abstract description 189
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 93
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 230000032683 aging Effects 0.000 claims abstract description 21
- 238000004321 preservation Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000009413 insulation Methods 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 7
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000889 atomisation Methods 0.000 claims abstract description 3
- 239000004566 building material Substances 0.000 claims abstract description 3
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- 239000010453 quartz Substances 0.000 claims description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- -1 aviation insulation Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
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- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011499 joint compound Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 4
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- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
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- 239000004005 microsphere Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
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- 239000004793 Polystyrene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000021120 animal protein Nutrition 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000000875 high-speed ball milling Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000005385 borate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 238000010073 coating (rubber) Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
- C01B21/0687—After-treatment, e.g. grinding, purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
- C01F7/025—Granulation or agglomeration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
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 1-180 μm, the surface aperture ratio is 0-50%, and the inside is provided with a single large cavity. The preparation method comprises the following steps: preparing powder raw materials and water into slurry, grinding the slurry to the powder granularity of 0.5-2 mu m, adding a binder and/or a surfactant into the slurry, stirring to form foam slurry, performing aging reaction in a closed reaction kettle, performing atomization molding to obtain a blank, sintering and cooling to obtain the composite material. The invention realizes the powder hollowing and the preparation of the internal large cavity structure and the accurate regulation and control of the wall thickness of hollow powder. 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
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
Compared with the common powder, the spherical powder has smaller particle size and uniform distribution, regular surface morphology and obviously increased bulk density, can greatly improve the fluidity and dispersibility of the powder, and maximally eliminate the influence of agglomeration, and in the field of thermal spraying, the spherical powder has more uniform and compact coating due to good fluidity, so that the coating has better wear resistance; in the field of powder metallurgy, a formed part prepared from spherical powder has high density, and the formed part is uniformly contracted in the sintering process, so that the obtained product has high precision and good performance, and has obvious advantages in advanced powder metallurgy forming technology applications such as injection forming, gel casting forming, additive manufacturing (such as 3D printing technology) and the like.
The spherical powder material is mainly solid spherical silica powder, spherical alumina powder and spherical metal powder, and in recent years, the spherical hollow powder material is gradually concerned by industry, is formed by important branches of the spherical powder material, and generally refers to a hollow inorganic nonmetallic spherical powder material with tiny dimensions (nano-scale and micron-scale), and has the advantages of light weight, low heat conduction, sound insulation, wear resistance, high dispersion, good electrical insulation, good thermal stability, low manufacturing cost and the like.
The spherical hollow powder material has the excellent performance, 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 And (3) regulating and controlling PTMS hydrolysis-polycondensation reaction by using an OH solution to form a layer of silicon oxide outside emulsion liquid drops, centrifuging, precipitating, washing with a solvent, washing with water, and drying to obtain the silicon oxide hollow spheres.
The processes for preparing the hollow powder by adopting the chemical synthesis method are also limited to the stage of small-scale and non-cost counting in a laboratory, and the prepared powder has the granularity more concentrated at the nanoscale below 1 micrometer, so that the preparation of the hollow powder with the internal large-cavity structure with a larger scale can not be realized.
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 1-180 mu m, a surface aperture ratio of 0-50% and a single large cavity inside.
Further, the pore wall structure of the spherical hollow powder comprises a thin-wall structure and/or a thick-wall structure, and when the pore wall structure is a thick-wall structure, the thick-wall structure is pore-free, pore-less or porous.
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 0.5-2 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 about 15-55%.
Preferably, the milling is carried out in a mill at a speed of 500-2000rpm for 24-48 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: and (2) adding a binder and/or a surfactant into the slurry in the step (S1), and stirring to form foam slurry.
Further, since the addition amount of the binder influences the rheological property of the slurry together with the grinding process, the addition amount of the binder is 0.1-4% by mass.
Further, since the addition amount of the surfactant, the stirring time and the stirring speed affect the diameter of the foam, the mass fraction of the surfactant added is 0.1-1.5%; the stirring time is 20-60min, and the stirring speed is 800-1500rpm.
Further, the foam diameter in the foam slurry is 0.01-0.2mm.
S3: and (3) carrying out aging reaction on the foam slurry in the step (S2) in a closed reaction kettle.
Further, the temperature of the closed reaction kettle is 5-45 ℃.
Preferably, the time of the aging reaction is 2-24 hours.
Preferably, the aging reaction is carried out with stirring; more preferably, the stirring is at a rate of 100-200rpm.
The combination growth of small bubbles and large bubbles can be realized by controlling the reaction conditions, so that the generation of an internal large cavity is realized, and the process combines the rheological property of the slurry in the steps S1 and S2 to determine whether and how much air holes exist under the condition of the thick wall of the final spherical hollow powder.
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 8000-15000rpm. 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 120 ℃. The inlet and outlet temperature of the forming tower influences the water content and the drying efficiency of the spherical hollow powder blank.
Further, the particle size of the spherical hollow powder body is controlled to be 1-200 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.
The ceramic material system is essentially different from the glass material system, the ceramic material system belongs to a crystal material, has a fixed melting point temperature, namely, the transition state from solid state to liquid state is not existed under the fixed temperature, the glass material system is not a crystal material, has no fixed melting point temperature, has a wider softening interval, namely, has a very long high viscosity state from solid state to liquid state, provides convenience for forming a hollow powder structure, and can perform hollowing treatment under the high-temperature softening state.
According to the invention, the higher the grinding rate of the slurry is, the longer the grinding time is, the smaller the granularity of the powder in the slurry is, the smaller the charge resistance is, the wall thickness of the final spherical hollow powder is more easily influenced by aggregation on the surface of the foam, the surface energy of inorganic powder particles in the process of small thinning can be greatly increased by high-speed ball milling, the activity of the particles is increased, the aggregation state of the particles on the surface of the foam is more easily controlled by combining the addition amount of the additive, and the accurate regulation and control of the wall thickness of the hollow powder are realized.
According to the invention, the aging treatment process of the slurry is realized by controlling conditions including bubble aging temperature, bubble aging pressure, bubble aging time and the like, so that the combination growth of small bubbles and large bubbles is realized, the generation of an internal large cavity is realized, and the process is combined with the rheological property of the slurry to determine whether and how much of air holes exist under the condition of the thick wall of the final spherical hollow powder.
Drawings
In order to more clearly illustrate the embodiments of the present invention 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 invention, 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 large cavity and a thin wall structure prepared in example 2;
FIG. 2 is a scanning electron microscope image of the spherical hollow powder of the large cavity, thick wall and non-porous structure prepared in example 5;
FIG. 3 is a scanning electron microscope image of the spherical hollow powder with large cavity, thick wall and small hole structure prepared in example 6;
FIG. 4 is a scanning electron microscope image of the spherical hollow powder of the large cavity, thick wall porous structure prepared in example 7;
FIG. 5 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 9;
FIG. 6 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 10;
fig. 7 is a graph showing the open pore ratio of the spherical hollow powder prepared in example 5.
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.
"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 15 μm and a surface aperture ratio of 23% and having a single insideThe surface of the large cavity is provided with a thin-wall structure, the average shell thickness is 1.5 mu m, and the bulk density is 0.53g/cm 3 The average diameter of the surface pores is 2.2 mu m, and the porosity is 35%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking Al with the mass ratio of 90:10 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 40%, the mass fraction of the water is about 60%, and the slurry is ground in a grinder at 1500rpm for 48 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: to the ground slurry, 2% PVA by mass and 0.2% AES by mass were added, and the slurry was stirred at a high speed of 1500rpm for 60 minutes to form a foam slurry, the average diameter of the foam being 0.03mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 10 hours at 40 ℃, and stirring at the stirring speed of 150rpm.
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 18.1 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 1400 ℃, the heat preservation time is 2h, 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 coating industry.
Example 2
A spherical hollow powder, as shown in figure 1, has an average particle diameter of 43 μm, a surface opening ratio of 1%, a single large cavity inside, a thin-wall structure on the surface, an average shell thickness of 0.7 μm, and a bulk density of 0.17g/cm 3 The average diameter of the surface pores is 0.4 μm, and the porosity is 92%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking kaolin powder and SiO with the mass ratio of 95:5 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 2000rpm for 48 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: 3% water glass by mass and 0.5% SDS by mass were added to the milled slurry, and the slurry was stirred at a high speed of 1500rpm for 60 minutes to form a foam slurry having an average foam diameter of 0.03mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 10 hours at 35 ℃, and stirring the reaction under stirring at a stirring speed of 150rpm.
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 11.3 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 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 plastic industry.
Example 3
A spherical hollow powder with average particle diameter of 21 μm, surface aperture ratio of 2%, large cavity, thick wall structure, average shell thickness of 3.5 μm, large number of closed pores on shell wall, and bulk density of 0.43g/cm 3 The average diameter of the surface pores is 0.3 μm, and the porosity is 83%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking SiC powder and Al with the mass ratio of 80:15:5 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 45%, waterThe mass fraction of (2) is about 55%, and the slurry is ground in a grinder at 800rpm for 24 hours to a powder particle size of between 0.5 μm and 2 μm.
S2: adding CMC with the mass fraction of 3% and animal protein with the mass fraction of 1% into the ground slurry, stirring at a high speed of 1500rpm for 60 minutes to form foam slurry, wherein the average diameter of the foam is 0.03mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 15 hours at 5 ℃, and stirring at the stirring speed of 200rpm.
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 24.2 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 aviation heat insulation industry.
Example 4
A spherical hollow powder with an average particle diameter of 38 μm, a surface aperture ratio of 11%, a single large cavity inside, a thick wall structure on the surface, an average shell thickness of 3.6 μm, a large number of closed pores on the shell wall, and a bulk density of 0.48g/cm 3 The average diameter of the surface pores is 0.8 mu m, and the porosity is 75%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking quartz powder and Al with the mass ratio of 60:20:20 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 40%, the mass fraction of the water is about 60%, 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 0.5 and 2 mu m.
S2: 4% water glass by mass and 0.8% SDS by mass were added to the ground slurry, and the slurry was stirred at a high speed of 2000rpm for 60 minutes to form a foam slurry having an average foam diameter of 0.05mm.
S3: the foam slurry was transferred to a closed reaction vessel and subjected to an aging reaction at 25℃for 12 hours with stirring at a stirring rate of 200rpm.
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 43.2 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 1400 ℃, 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 rubber industry.
Example 5
As shown in FIG. 2, the spherical hollow powder has an average particle diameter of 63 μm, a surface opening ratio of 29%, a single large cavity inside, a thick wall structure on the surface, an average shell thickness of 5.8 μm, no pores on the shell wall, and a bulk density of 0.47g/cm 3 The average diameter of the surface pores is 0.5 μm, and the porosity is 75%. It should be noted that, in this application, the hole is not an absolute hole, and any powder has a hole, but is a relative concept, and in this embodiment, the surface of the powder has a hole which is not easily observed in an electron microscope photograph and is obvious. The open pore ratio is shown in figure 7.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking Si with the mass ratio of 90:10 3 N 4 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 a rotating speed of 1000rpm for 40 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: adding PVA with the mass fraction of 2% and animal protein with the mass fraction of 1.5% into the ground slurry, stirring at a high speed of 1500rpm for 45 minutes to form foam slurry, wherein the average diameter of the foam is 0.08mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 45 ℃, and stirring at a stirring speed of 150rpm.
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 71.8 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 1500 ℃, 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 microorganism carrier industry.
Example 6
As shown in FIG. 3, the spherical hollow powder has an average particle diameter of 124 μm, a surface opening ratio of 7%, a single large cavity inside, a thick wall structure on the surface, an average shell thickness of 20.3 μm, a small number of pores on the shell wall, and a bulk density of 0.76g/cm 3 The average diameter of the surface pores is 0.7 μm, and the porosity is 75%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking quartz powder, mullite powder and Al with the mass ratio of 65:20:15 2 O 3 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 1500rpm for 45 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: 3% water glass by mass and 1.0% OEP by mass were added to the ground slurry, and the slurry was stirred at a high speed of 1500rpm for 30 minutes to form a foam slurry having an average foam diameter of 0.12mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 35 ℃, and stirring at a stirring speed of 150rpm.
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 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 146.7 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 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 petroleum exploitation industry.
Example 7
As shown in FIG. 4, the spherical hollow powder has an average particle diameter of 166 μm, a surface opening ratio of 4%, a single large cavity inside, a thick wall structure on the surface, an average shell thickness of 41.5 μm, a large number of pores on the shell wall, and a bulk density of 0.71g/cm 3 The average diameter of the surface pores is 3.9 mu m, and the porosity is 81%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking diatomite powder and Al with the mass ratio of 80:20 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 1500rpm for 30 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: 2% resin by mass and 1.0% AOS by mass were added to the ground slurry, and the slurry was stirred at a high speed of 1000rpm for 30 minutes to form a foam slurry having an average foam diameter of 0.22mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 35 ℃, and stirring at a stirring speed of 150rpm.
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 120 ℃, 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 173.4 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 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 preservation industry.
Example 8
A spherical hollow powder having an average particle diameter of 167 μm, a surface opening ratio of 29%, large cavities in the interior, a thick-wall structure on the surface, an average shell thickness of 10.3 μm, a small number of pores on the shell wall, and a bulk density of 0.64g/cm 3 The average diameter of the surface pores is 6.2 mu m, and the porosity is 93%.
The preparation method of the spherical hollow powder specifically comprises the following steps:
s1: taking zirconium silicate powder and Al with the mass ratio of 80:20 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 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 1500rpm for 40 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: 2% water glass by mass and 1.0% SDS by mass were added to the ground slurry, and the slurry was stirred at a high speed of 1000rpm for 30 minutes to form a foam slurry, wherein the average diameter of the foam was 0.22mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 35 ℃, and stirring at a stirring speed of 150rpm.
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 120 ℃, 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 189.3 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 1200 ℃, 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 preservation industry.
Example 9
A spherical hollow powder has an average particle diameter of 58 μm, a surface aperture ratio of 18%, a single large cavity inside, a thick-wall structure on the surface, an average shell thickness of 6.3 μm, a small number of pores on the shell wall, and a bulk density of 0.64g/cm 3 The average diameter of the surface pores is 4.2 mu m, and the porosity is 73%. The appearance of the aperture ratio is shown in figure 5.
The preparation method of the spherical hollow powder specifically comprises the following steps:
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 50%, the mass fraction of the water is about 50%, and the slurry is ground in a grinder at 1500rpm for 40 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: 3% water glass by mass and 1.0% SDS by mass were added to the milled slurry, and the slurry was stirred at a high speed of 1000rpm for 30 minutes to form a foam slurry, wherein the average diameter of the foam was 0.22mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 35 ℃, and stirring at a stirring speed of 150rpm.
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 120 ℃, 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 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 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 heat preservation industry.
Example 10
A spherical hollow powder having an average particle diameter of 151 μm, a surface opening ratio of 22%, large cavities in the interior, a thick-wall structure on the surface, an average shell thickness of 8.8 μm, a small number of pores in the shell wall, and a bulk density of 0.47g/cm 3 The average diameter of the surface pores is 16.5 mu m, and the porosity is 75%. The open pore ratio is shown in figure 6.
The preparation method of the spherical hollow powder specifically comprises the following steps:
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 40%, the mass fraction of the water is about 60%, and the slurry is ground in a grinder at a rotating speed of 1000rpm for 40 hours until the particle size of the powder is between 0.5 and 2 mu m.
S2: adding PVA with the mass fraction of 2% and animal protein with the mass fraction of 1.0% into the ground slurry, stirring at a high speed of 1500rpm for 45 minutes to form foam slurry, wherein the average diameter of the foam is 0.08mm.
S3: and conveying the foam slurry into a closed reaction kettle, carrying out aging reaction for 8 hours at 45 ℃, and stirring at a stirring speed of 150rpm.
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 173.8 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 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 microorganism carrier industry.
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 represent only a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (10)
1. The spherical hollow powder is characterized in that the average particle size of the spherical hollow powder is 1-180 mu m, the surface aperture ratio is 0-50%, and a single large cavity is formed inside the spherical hollow powder.
2. The spherical hollow powder according to claim 1, wherein the pore wall structure of the spherical hollow powder comprises a thin-walled structure and/or a thick-walled structure, and when the pore wall structure is a thick-walled structure, the thick-walled structure is non-porous, less porous or porous.
3. The preparation method of the spherical hollow powder is characterized by comprising the following steps:
s1: preparing a powder raw material and water into slurry, and grinding to a powder granularity of 0.5-2 mu m;
s2: adding a binder and/or a surfactant into the slurry in the step S1, and stirring to form foam slurry;
s3: carrying out aging reaction on the foam slurry in the step S2 in a closed reaction kettle;
s4: carrying out atomization molding on the product obtained in the step S3 in a molding tower to obtain a spherical hollow powder blank;
s5: and (3) sintering the spherical hollow powder blank obtained in the step (S4), and cooling to obtain the spherical hollow powder.
4. The method according to claim 3, wherein in step S1, 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 or fly ash.
5. The preparation method according to claim 3, wherein in the step S1, the mass fraction of the powder raw material in the slurry is 15-55%;
preferably, the milling is carried out in a mill at a speed of 500-2000rpm for 24-48 hours.
6. A method of preparation according to claim 3, wherein step S2 satisfies one or more of the following conditions:
a. the mass fraction of the binder is 0.1-4%;
b. the mass fraction of the surfactant is 0.1-1.5%;
c. the stirring time is 20-60min, and the stirring speed is 800-1500rpm;
d. the foam diameter in the foam slurry is 0.01-0.2mm.
7. A method of preparation according to claim 3, wherein step S3 fulfils one or more of the following conditions:
e. the temperature of the closed reaction kettle is 5-45 ℃;
f. the time of the aging reaction is 2-24 hours;
g. the aging reaction is carried out under stirring;
preferably, the stirring is at a rate of 100-200rpm.
8. A method of preparation according to claim 3, wherein step S4 satisfies one or more of the following conditions:
h. an atomizing disc is arranged in the forming tower, and the rotating speed of the atomizing disc is 8000-15000rpm;
i. the inlet temperature of the forming tower is 300-450 ℃;
j. the outlet temperature of the forming tower is not lower than 120 ℃;
k. the particle size of the spherical hollow powder body is 1-200 mu m, and the water content is 0.1-0.5%.
9. A method of preparation according to claim 3, wherein step S5 satisfies one or more of the following conditions:
the sintering device comprises one of a muffle furnace, a trolley furnace, a tunnel kiln, a rotary kiln or a shuttle kiln;
preferably, the spherical hollow powder blank is put into a sagger and then put into the sintering device for sintering;
m. the sintering temperature is 900-1600 ℃;
and n, the sintering heat preservation time is 0.5-2h.
10. Use of the spherical hollow powder according to claim 1 or 2 in the coating, plastic, aviation insulation, rubber, microbial carrier, oil exploitation, thermal insulation, fire resistance, paint, water treatment, slow release fertilizer, mortar filler, building materials, soil and water conservation, soil improvement, flue gas filtration or catalyst carrier industries.
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