CN116285426A - Composite ceramic microsphere and preparation method thereof - Google Patents
Composite ceramic microsphere and preparation method thereof Download PDFInfo
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- CN116285426A CN116285426A CN202310195628.0A CN202310195628A CN116285426A CN 116285426 A CN116285426 A CN 116285426A CN 202310195628 A CN202310195628 A CN 202310195628A CN 116285426 A CN116285426 A CN 116285426A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 74
- 239000000919 ceramic Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010881 fly ash Substances 0.000 claims abstract description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000007667 floating Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 17
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 17
- 239000000084 colloidal system Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- URAZVWXGWMBUGJ-UHFFFAOYSA-N di(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[NH2+]C(C)C URAZVWXGWMBUGJ-UHFFFAOYSA-N 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 239000011324 bead Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000012767 functional filler Substances 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000011325 microbead Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000012634 fragment Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002864 coal component Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 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 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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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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- 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)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the field of inorganic composite materials, and particularly relates to a composite ceramic microsphere and a preparation method thereof. Fly ash is industrial waste residue rich in aluminosilicate, and floating beads and sinking beads contained in the fly ash can be used as light fireproof materials, filling materials and the like. But the dispersion degree is high, the material is non-uniform, and the added value is low. The invention uses fly ash as raw material to prepare a uniform feed liquid system of solution or sol, and the uniform feed liquid system is directly prepared into ceramic microspheres. The invention has low energy consumption, short process period, no need of fusion sintering and high yield, and can be used for the production of various composite materials. The invention aims to provide a preparation scheme of composite ceramic microspheres by using fly ash, which is prepared by firstly selecting hollow microspheres and then preparing zeolite seed crystals. The product is suitable for reinforcing materials and filling materials of various media and functional fillers of various conducting media, and improves certain properties of matrix materials, such as reinforcement, wear resistance, corrosion resistance, weather resistance and the like.
Description
Technical Field
The invention belongs to the field of inorganic composite materials, and particularly relates to a composite ceramic microsphere and a preparation method thereof.
Background
Fly ash is fine powder industrial waste residue containing a small amount of carbon, crystals (quartz stone, mullite) and a large amount of aluminosilicate glass body, and is prepared from SiO 2 And Al 2 O 3 Mainly. The comprehensive treatment of fly ash is a problem to be solved urgently at present. The ceramic microsphere is synthesized by using aluminosilicate as main component in fly ash as raw material, adding a certain additive for treatment and adopting special steps.
The formation of the fly ash microspheres is related to the combustion process of the coal components, the microstructure and the coal powder particles. Generally, the coal ash generated after the combustion of the bituminous coal with high heat and low sulfur content has more hollow microspheres and the anthracite coal has less hollow microspheres, and the coal ash generated after the combustion of the lignite coal hardly contains ceramic microspheres.
The ceramic microsphere has extremely wide application, is suitable for reinforcing materials and filling materials of various media, can improve certain properties of matrix materials, such as reinforcing, wear resistance, abrasion resistance, hardness, chemical corrosion resistance, weather resistance and the like, and has very wide application prospect. Because the ceramic microspheres have isotropic spherical geometric shapes, the ceramic microspheres can not generate stress concentration on the matrix under the action of external stress, so that the casting performance and plastic fluidity of the matrix are greatly improved, and the secondary molding of the composite material is facilitated.
The ceramic microsphere prepared by using bauxite as raw material can be produced by using conventional process and equipment, and its cost is low, sphericity is good, and the aluminium-base and plastic-base composite material reinforced by using said ceramic microsphere can be extensively used for manufacturing wear-resisting parts of civil industry, such as machining, automobile and bearing, etc..
The main methods for producing and preparing ceramic microspheres at present are basically classified into one type although they are different, namely: the solid phase powder method, the liquid phase atomization method and the soft chemistry method have advantages and disadvantages.
The main technical route of the solid phase powder method is as follows: and uniformly mixing the glass powder with a foaming agent, and then carrying out high-temperature treatment, wherein the foaming agent is decomposed to release gas so as to expand and foam the softened glass powder, and finally forming a finished product. The process has the outstanding disadvantages of high energy consumption, high product density and difficult control of particle size distribution. The most important energy consumption is that the high temperature of more than 1200 ℃ is needed in the process of producing glass powder, and grinding and crushing are needed, and the main flow of the process can be summarized as follows: batching-high temperature expansion.
The main technical route of the liquid phase atomization method is as follows: the method is characterized in that a strong-alkalinity low-density ceramic microsphere product is obtained by taking sodium silicate aqueous solution or sodium silicate aqueous solution added with boric acid, salts thereof, lithium ions and the like as raw materials through spray drying. The process technology has the outstanding disadvantages of low strength and easy water absorption. The main flow of the process can be summarized as follows: dosing-spray drying.
The main technical route of the soft chemistry method is as follows: synthesizing an aqueous slurry system of silicate solution, sol or slurry, inorganic salt material, stable dispersing agent and water containing silicon dioxide and/or alkali metal or alkaline earth metal containing silicon dioxide, preparing solid precursor materials after spray drying, and then performing vitrification sintering on the solid precursor materials to obtain ceramic microspheres. The process has the defects of complex components and fine grinding and crushing when the aqueous slurry is mixed, and the stability of the product quality is at risk. The main flow of the process can be summarized as follows: dosing-spray drying (solid precursor) -high temperature sintering (hollow).
Disclosure of Invention
The solid phase powder method has high energy consumption, high product density and difficult control of particle size distribution; the product of the liquid phase atomization method has low strength and is easy to absorb water; the water-based slurry prepared by the soft chemistry method has complex components, needs fine grinding and crushing, and has risks in stability of product quality.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of composite ceramic microspheres, which comprises the following steps:
s11: preparing fly ash microsphere and zeolite colloid solution respectively;
the fly ash microspheres are obtained by a method of floating the fly ash by boiling water after sieving; the zeolite colloid solution is obtained by dispersing nano X-type molecular sieve (LSX) in water after impurity removal and adding ammonia water;
s12: sequentially adding the fly ash microspheres into a polydimethyl diisopropyl ammonium chloride (PDDA) aqueous solution and a polystyrene sulfonic acid (PSS) aqueous solution to alternately adsorb for 30min, and repeating for 4-6 times to obtain treated fly ash microspheres;
s13: adding the treated fly ash microspheres into zeolite colloid solution for adsorption to obtain seed crystal modified microspheres;
s14: adding the seed crystal modified microsphere into the mixed solution, and reacting to obtain the composite ceramic microsphere; the mixed solution comprises NaOH and NaAlO 2 And water.
Further, in the step S12, the fly ash microbeads are immersed into the cationic polydimethyl diisopropylammonium chloride with the mass fraction of 0.2% and the anionic poly-p-sulfostyrene with the mass fraction of 0.1% in sequence according to the alternating sequence of PDDA/PSS/PDDA for 10min, so that the surfaces of the microbeads are provided with uniformly distributed positive charges, and the process is repeated for 4-6 times, thereby obtaining the treated fly ash microbeads.
Principle of electrostatic seed adsorption-induced transformation technique:
the surface of the fly ash microbead modified by PDDA/PSS/PDDA alternately can adsorb a layer of uniform zeolite seed crystal (induce crystallization) to modify uniform positive charges. The fly ash microbeads uniformly adsorbed by the seed crystal can form a relatively compact zeolite layer after hydrothermal treatment. And after proper crystallization temperature and time, the active components in the spherical shell of the fly ash microsphere are completely pumped out and converted into the composite ceramic microsphere.
PDDA and PSS are alternately adsorbed, so that the surface of the microbead is provided with positive charges uniformly distributed, and uniform electropositivity is obtained. PSS is polyanion, PDDA is polycation and is alternately modified and deposited on the substrate, even if zeolite seed crystals are excellent in adsorption quantity on the surface of the fly ash microbeads, only a small amount of zeolite seed crystals can be adsorbed on the surface of the fly ash microbeads modified by the cationic PDDA only once. In an alkaline solution containing or not containing aluminum: an alkaline environment (pH=10) is provided, so that the active silicon-aluminum component in the coal ash hollow microsphere is crystallized into zeolite, the zeolite presents electronegativity and is easy to adsorb on the surface of the microsphere, and the driving force is electrostatic force and hydrogen bond.
Preferably, the fly ash comprises 55-60% by mass of SiO 2 25-30% of Al 2 O 3 3-4% Fe 2 O 3 1-2% of CaO,0.5-1% of MgO and the balance of other unavoidable impurities. In the fly ash microsphere, the inevitable impurities are the partially broken spherical shell fragments, and the components are approximately the same as the microsphere.
Preferably, in the step S11, a fine sieve of 100-300 mesh is used for sieving.
Preferably, in the step S11, the diameter of the fly ash microsphere is 50-80 μm, and the thickness is 2-4 μm.
Preferably, in the step S11, the nano X-type molecular sieve (LSX) is prepared by the following steps:
s21: adding sodium aluminate into an alkaline aqueous solution, and mixing to obtain a sodium aluminate aqueous solution;
s22: adding silica sol into the sodium aluminate aqueous solution, aging at 25-60 ℃ for 12-36h, and crystallizing at 80-120 ℃ for 2-9h to obtain the nano X-type molecular sieve.
Specifically, in the step S11, the nano X-type molecular sieve is prepared by a method comprising the steps of mixing the substances of the reactants in a ratio of Na 2 O：K 2 O：SiO 2 ：Al 2 O 3 ：H 2 O=4: 1:2:2:90, first, desired NaAlO is prepared 2 Adding KOH, naOH and water into the mixed solution to form solution A; then adding the needed silicic acid into a mixed solution of a proper amount of NaOH and water to form a solution B; finally, the mixed solution A and the mixed solution B are stirred uniformly, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, aged for 12-36h at 25-60 ℃, crystallized for 2-9h at 80-120 ℃, cooled, filtered, washed and dried to obtain the nano X-type molecular sieve.
Preferably, in the step S11, the impurity removing method is water washing after centrifugation.
Preferably, in the step S11, the pH of the zeolite colloid solution is 9 to 11.
Preferably, the solid content in the zeolite colloid solution is 0.1-0.2wt%.
Preferably, in the polydimethyl diisopropyl ammonium chloride aqueous solution, the concentration of the polydimethyl diisopropyl ammonium chloride is 0.1-0.3wt%.
Preferably, in the aqueous solution of polystyrene sulfonic acid, the concentration of polystyrene sulfonic acid is 0.1 to 0.2 weight percent.
Preferably, in the mixed aqueous solution, naOH and NaAlO 2 And water in a molar ratio of 8 to 10:1:250.
preferably, in the step S14, the reaction temperature is 100-200 ℃ and the reaction time is 24-48h.
Preferably, in the step S14, the reaction mixture is washed with water and dried.
The invention also provides the composite ceramic microsphere prepared by the preparation method.
The invention aims to provide a preparation scheme of composite ceramic microspheres by using fly ash, which is prepared by firstly selecting hollow microspheres and then preparing zeolite seed crystals. The fly ash is used for resource development and application in the preparation of the microspheres, so that the increasingly prominent problems of land and environmental pollution can be solved, and the ceramic production cost can be reduced. The product is suitable for reinforcing materials and filling materials of various media and functional filling materials of various conductive media, and improves certain properties of matrix materials, such as reinforcement, wear resistance, corrosion resistance, weather resistance and the like.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) The product has the characteristics of hollow microsphere structure, zeolite thin layer covered on the surface, good thermal stability, light weight and the like, the macroscopic morphology of the product enables the material to be easily separated in practical application, and the fly ash microsphere raw material is cheap and easily obtained, so that the product can be developed into a practical zeolite material.
2) The method is simple and convenient in operation and provides an environment-friendly approach for treating the industrial waste fly ash.
3) The method avoids a large amount of high polymer as a template, reduces the cost, and avoids the environmental resistance in the process of removing the high polymer spherical template in the traditional method because the silica spheres are completely consumed at the same time of forming the compact zeolite spherical shell.
Drawings
FIG. 1 is a SEM image of fly ash microbeads.
Fig. 2 is a schematic diagram of an electrostatic alternating deposition technique.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Step one, microsphere selection: sieving the fly ash with a 200-mesh sieve, and removing fragments by floatation with boiling water; obtaining the fly ash microsphere with the spherical shell thickness of between 5 and 80um and the diameter of between 2 and 4 um. Second step zeolite seed crystal preparation: preparing a nano X-type molecular sieve LSX: the ratio of the amounts of reactant substances is Na 2 O：K 2 O：SiO 2 ：Al 2 O 3 ：H 2 O=4: 1:2:2:90, first, desired NaAlO is prepared 2 Adding the mixture into a mixed solution of a proper amount of KOH, naOH and water to form a solution A; then adding the needed silicic acid into a mixed solution of a proper amount of NaOH and water to form a solution B; finally, after the mixed solution A and the mixed solution B are stirred uniformly, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, aged for 12 hours at 25 ℃, crystallized for 2 hours at 80 ℃, cooled, filtered, washed and dried to obtain a crystallized product. The product was washed with water by centrifugation, dispersed as a zeolite colloid solution with a mass fraction of about 0.1%, and adjusted to pH 10 with aqueous ammonia for use. And thirdly, preparing composite ceramic microspheres: the fly ash microsphere is respectively and alternately adsorbed on PDDA with the mass fraction of 0.2 percent and PSS with the mass fraction of 0.1 percent according to the sequence of PDDA/PSS, then is adsorbed in zeolite colloid solution, is washed by deionized water, and is dried to obtain the seed crystal modified microsphereA ball. Then mixing 0.4g of zeolite modified fly ash microsphere with 5mL of NaOH with molar ratio: naAlO (NaAlO) 2 ：H 2 O=9: 1:250, mixing the solutions in the generation of the solution, placing the mixture into a sealed reaction kettle, reacting for 48 hours at 100 ℃, washing the reaction product with deionized water, and drying to obtain the composite microsphere.
Example 2
Step one, microsphere selection: sieving the fly ash with a 200-mesh sieve, and removing fragments by floatation with boiling water; the fly ash microsphere with the spherical shell thickness of between 5 and 80 mu m and the diameter of between 2 and 4 mu m is obtained. Second step zeolite seed crystal preparation: preparation of the nano-X molecular sieve LSX-ratio of the amount of reactant substances Na 2 O：K 2 O：SiO 2 ：Al 2 O 3 ：H 2 O=4: 1:2:2:90, first, desired NaAlO is prepared 2 Adding the mixture into a mixed solution of a proper amount of KOH, naOH and water to form a solution A; then adding the needed silicic acid into a mixed solution of a proper amount of NaOH and water to form a solution B; finally, the mixed solution A and the mixed solution B are stirred uniformly, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, aged for 36 hours at 60 ℃, crystallized for 9 hours at 120 ℃, cooled, filtered, washed and dried to obtain a crystallized product. The product was repeatedly centrifuged and washed with water, dispersed as a zeolite colloid solution with a mass fraction of about 0.1%, and adjusted to pH 10 with aqueous ammonia for further use. And step three, preparation of composite microspheres: and (3) respectively alternately adsorbing the fly ash microspheres with the mass fraction of 0.2% PDDA and 0.1% PSS according to the PDDA/PSS sequence, adsorbing a layer of zeolite in a zeolite colloid solution, washing with deionized water, and drying to obtain the seed crystal modified microspheres. Then mixing 0.4g of zeolite modified fly ash microsphere with 5mL of NaOH with molar ratio: naAlO (NaAlO) 2 ：H 2 O=9: 1:250, mixing the solutions in the generation of the solution, placing the mixture into a sealed reaction kettle, reacting for 2 days at 150 ℃, washing the reaction product with deionized water, and drying to obtain the composite microsphere.
Example 3
Step one, microsphere selection: sieving the fly ash with a 200-mesh sieve, and removing fragments by floatation with boiling water; the fly ash microsphere with the spherical shell thickness of between 5 and 80 mu m and the diameter of between 2 and 4 mu m is obtained. Second step zeolite seed crystal preparation: preparation of nano-X molecular sieves LSX-ratio of the amount of reactant materialsIs Na (Na) 2 O：K 2 O：SiO 2 ：Al 2 O 3 ：H 2 O=4: 1:2:2:90, first, desired NaAlO is prepared 2 Adding the mixture into a mixed solution of a proper amount of KOH, naOH and water to form a solution A; then adding the needed silicic acid into a mixed solution of a proper amount of NaOH and water to form a solution B; finally, after the mixed solution A and the mixed solution B are stirred uniformly, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, aged for 24 hours at 40 ℃, crystallized for 6 hours at 100 ℃, cooled, filtered, washed and dried to obtain a crystallized product. The product was repeatedly centrifuged and washed with water, dispersed as a zeolite colloid solution with a mass fraction of about 0.1%, and adjusted to pH 10 with aqueous ammonia for further use. And step three, preparation of composite microspheres: and (3) respectively alternately adsorbing the fly ash microspheres with PDDA (polymer dispersed drug) with the mass fraction of 0.2% and PSS with the mass fraction of 0.1% according to the sequence of PDDA/PSS, adsorbing a layer of zeolite in a zeolite colloid solution, washing with deionized water, and drying to obtain the seed crystal modified microspheres. Then mixing 0.4g of zeolite modified fly ash microsphere with 5mL of NaOH with molar ratio: naAlO (NaAlO) 2 ：H 2 O=9: 1:250, mixing the solutions in the generation of the solution, placing the mixture into a sealed reaction kettle, reacting for 1 day at 100 ℃, washing the reaction product with deionized water, and drying to obtain the composite microsphere.
Table 1 specific example results and comparative example results
As shown in Table 1, al in the product 2 O 3 The content of (2) is 55-65%, siO 2 The content of Fe is about 10% 2 O 3 7-15% (in mass fraction) and a surface area of 1.0-2.5m 2 The 100% passing particle diameter is the maximum particle diameter of the product detected by the instrument.
Table 2 physical Properties of fly ash used
As shown in table 2, the physical properties of the fly ash raw materials used in the present invention for preparing the composite ceramic microspheres.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the composite ceramic microsphere is characterized by comprising the following steps:
s11: preparing fly ash microsphere and zeolite colloid solution respectively;
the fly ash microspheres are obtained by a method of floating the fly ash by boiling water after sieving; the zeolite colloid solution is obtained by dispersing nano X-type molecular sieve after impurity removal in water and adding ammonia water;
s12: sequentially adding the fly ash microspheres into a polydimethyl diisopropyl ammonium chloride aqueous solution and a polystyrene sulfonic acid aqueous solution to alternately adsorb for 30min, and repeating for 4-6 times to obtain treated fly ash microspheres;
s13: adding the treated fly ash microspheres into zeolite colloid solution for adsorption to obtain seed crystal modified microspheres;
s14: adding the seed crystal modified microsphere into the mixed solution, and reacting to obtain the composite ceramic microsphere; the mixed solution comprises NaOH and NaAlO 2 And water.
2. The preparation method according to claim 1, wherein the fly ash comprises 55 to 60% by mass of SiO 2 25-30% of Al 2 O 3 3-4% Fe 2 O 3 1-2% of CaO,0.5-1% of MgO and the balance of other unavoidable impurities.
3. The method according to claim 1, wherein in the step S11, the fly ash microspheres have a diameter of 50 to 80 μm and a thickness of 2 to 4 μm.
4. The preparation method according to claim 1, wherein in the step S11, the nano X-type molecular sieve is prepared by the following steps:
s21: adding sodium aluminate into an alkaline aqueous solution, and mixing to obtain a sodium aluminate aqueous solution;
s22: adding silica sol into the sodium aluminate aqueous solution, aging at 25-60 ℃ for 12-36h, and crystallizing at 80-120 ℃ for 2-9h to obtain the nano X-type molecular sieve.
5. The method according to claim 1, wherein the zeolite colloid solution has a pH of 9 to 11 in step S11.
6. The method according to claim 1, wherein the concentration of the polydimethyl diisopropyl ammonium chloride in the polydimethyl diisopropyl ammonium chloride aqueous solution is 0.1 to 0.3wt%.
7. The method according to claim 1, wherein the concentration of the polystyrene sulfonic acid in the aqueous solution of polystyrene sulfonic acid is 0.1 to 0.2wt%.
8. The process according to claim 1, wherein the aqueous mixture comprises NaOH and NaAlO 2 And water in a molar ratio of 8 to 10:1:250.
9. the method according to claim 1, wherein the reaction temperature is 100-200 ℃ and the reaction time is 24-48 hours in step S14.
10. A composite ceramic microsphere prepared by the method of any one of claims 1-9.
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