CN113149024A - Preparation method of ultra-pure submicron silicon micro-powder through foaming - Google Patents
Preparation method of ultra-pure submicron silicon micro-powder through foaming Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005187 foaming Methods 0.000 title claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000006260 foam Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000006004 Quartz sand Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000002609 medium Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 238000005201 scrubbing Methods 0.000 claims abstract description 8
- 239000002612 dispersion medium Substances 0.000 claims abstract description 6
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 18
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 210000003462 vein Anatomy 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000001238 wet grinding Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- AICNZRYBCUSVMO-UHFFFAOYSA-M trimethyl(tridecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCC[N+](C)(C)C AICNZRYBCUSVMO-UHFFFAOYSA-M 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007003 mineral medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
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- 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
- 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
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C01P2004/51—Particles with a specific particle size distribution
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a preparation method of ultra-pure submicron silicon micro powder foam, which is characterized by comprising the following steps: (1) selecting high-purity quartz sand as a raw material; (2) washing the ore by a scrubbing machine, dehydrating by a filter, and obtaining high-purity quartz sand by using deionized water as a cleaning medium; (3) wet grinding in a stirring mill, adding 1-6% of silane coupling agent into deionized water as a dispersion medium to obtain D50≤0.8μm、D100Slurry with the particle size less than or equal to 8 mu m; (4) adding the slurry into a dispersion machine, adding 1-5% of foaming agent, 0.25-1.0% of foam stabilizer and 0.25-1.0% of foam viscosity promoter, and stirring to form stable foamed slurry; (5) adding the foamed slurry into a dryer at the drying temperature of less than or equal to 200 ℃, and then adding the foamed slurry into a jet mill for depolymerizationAnd (4) grading. The invention has the advantages that: the industrial problem of powder agglomeration in the drying process is effectively solved, the essential scattering process is omitted, the process is simple, and the cost is low; ultra-pure submicron silicon powder D50≤0.5μm、D100Less than or equal to 5 mu m, can be used in high-end electronic fields such as EMC and CCL.
Description
Technical Field
The invention belongs to the field of nonmetal mineral deep processing, relates to the high-end electronic field of EMC (epoxy film plastic package) and CCL (copper clad laminate) manufacturing and the like, and particularly relates to a preparation method for foaming ultra-pure submicron silicon micro powder.
Background
With the rapid development of the electronic industry, especially the strict requirements of 5G communication chips, electronic devices are developing towards high frequency, high speed, high power density and light weight. Because of its excellent insulating property, chemical resistance and high adhesive strength, the resin is widely used in electronic insulating materials. However, pure resin has poor mechanical strength, and the addition of inorganic filler improves the mechanical strength and thermal stability of the resin insulation composite material, and the reduction of dielectric constant, dielectric loss and cost is the inevitable choice. In order to meet the above requirements, adding fillers such as silica powder is the preferred solution, and high purity, ultra-fine and low halogen are the development directions of silica powder.
At present, the market of high-end electronic grade submicron silicon powder is mainly monopolized by Japan Admatech and Denka company, and the development of high-purity superfine low-submicron grade silicon powder is urgent. In order to meet the requirement of superfine scale production, a wet process is generally adopted, but secondary pollution in the process of agglomeration and scattering in the drying process is always an industrial problem due to the structural crystal and surface property characteristics of quartz. In brief, the dried powder generally generates a certain degree of soft agglomeration and hard agglomeration due to physical adsorption and chemical bonding, is hardened and compact in appearance, and generally needs a ball milling or crushing modeThe silicon micro powder with submicron level can be obtained after the dispersion and the air flow crushing and classification. It is noted that the reduction of SiO by the doping of impurity ions (Al, Zr) into the grinding media, the lining of the equipment, the conveying pipelines, etc. cannot be avoided during the scattering process2The content of the silicon micro powder finally influences the purity of the silicon micro powder. Taking ball milling and scattering, lining with alumina, and milling medium zirconia as an example (phi 3-phi 5mm, ZrO)2Not less than 95 percent) and 1.0 hour of break-up time, considering the mineral-medium ratio of 1:7 and SiO2The reduction from 99.94% to 99.82% finally results in the chemical quality of the silica micropowder being unsatisfactory.
Disclosure of Invention
The invention aims to solve the problems that the obtained agglomerated and hardened powder needs to be scattered again in the existing wet grinding process, secondary pollution is easily caused in the scattering process, and the purity of silicon micropowder is influenced, and provides a preparation method for foaming ultra-pure submicron silicon micropowder.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of ultra-pure submicron silicon micro powder foam is characterized by comprising the following steps:
(1) selecting high-purity quartz sand as a raw material, wherein the chemical composition of the high-purity quartz sand is as follows: SiO 22≥99.9%，Al2O3≤0.0020%，Fe2O3≤0.0005%；
(2) Cleaning: washing the high-purity quartz sand by using a scrubbing machine, dehydrating by using a filter, and obtaining the high-purity quartz sand by using deionized water as a cleaning medium (the conductivity is required to be less than or equal to 1 mu S/cm); the requirements of the water extract liquid are as follows: conductivity is less than or equal to 1 mu S/cm, K+/Na+/Cl+≤1ppm；
(3) Ultra-fine grinding: grinding the product obtained in the step (2) in a stirring mill, wherein a dispersion medium is deionized water (the conductivity is required to be less than or equal to 1 mu S/cm), and simultaneously adding a silane coupling agent accounting for 1-6% of the weight of the product to obtain D50≤0.8μm、D100Submicron silicon micropowder slurry with the particle size less than or equal to 8 mu m;
(4) preparing foamed slurry: adding the product obtained in the step (3) into a dispersion machine, wherein the lining of the dispersion machine is polyurethane, an impeller is formed by spraying zirconia, the impeller is double-layer, 1-5% of foaming agent, 0.25-1.0% of foam stabilizer and 0.25-1.0% of foam viscosity promoter by weight of the product are added, and stirring for 10-20 min to form stable foamed slurry;
(5) drying: adding the product obtained in the step (4) into a dryer, spraying zirconia on a tray, and drying at the temperature of less than or equal to 200 ℃;
(6) depolymerization and classification: adding the product obtained in the step (5) into a jet mill for depolymerization and classification to obtain D50≤0.5μm、D100Submicron silicon powder end product with the particle size less than or equal to 5 mu m.
Further, the lining of the scrubbing machine in the cleaning process in the step (2) is made of polyurethane, and the impeller is made of double-layer stainless steel polyurethane with an outer lining.
Further, the silane coupling agent in the step (3) is formed by mixing A-1387 and A-187 according to a mass ratio of 1: 1-1: 4 (the source is Mitigo advanced materials (China) Co., Ltd.).
Further, the foaming agent in the step (4) is a quaternary ammonium salt cationic surfactant, and the alkyl chain length is C14-C16 (such as octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tridecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and the like); the foam stabilizer is a sulfonic acid or carboxylic acid anionic surfactant, and the alkyl chain length is C12-C18 (such as sodium dodecyl sulfate, sodium hexadecyl sulfonate, sodium oleate and the like); the foam viscosity promoter is higher alkanol, and the chain length of alkyl is C12-C16.
Further, the grading impeller of the jet mill for depolymerization and grading in the step (6) is made of zirconia integral ceramic, and zirconia or polyurethane protective materials are sprayed on the pipeline and the joint.
Further, the material of the stirring mill lining and the stirring rod outer lining in the step (3) is polyurethane, the milling medium is high-purity vein quartz particles, and the chemical components are controlled as follows: SiO 22≥99.9%，Al2O3≤0.0020%，Fe2O3Less than or equal to 0.0005 percent and the particle size of 3-30 mm.
The foam dispersion technology of the invention mainly adds a foaming agent, a foam stabilizer and a foam promoter, and makes the foam stabilizer hydrophobic and dispersed under the synergistic action of electrostatic repulsion and steric hindrance, thereby effectively reducing hard agglomeration, and finally the foam stabilizer is loose and can be crushed by touch.
The invention adopts the combination of modification and foam dispersion technology, adds silane coupling agent in the step of grinding ore, and firstly, the submicron silicon micropowder slurry is prepared; and then, a foaming agent, a foam stabilizer and a foam viscosity promoter are added into the silicon micro powder slurry, so that the difficult problems of agglomeration and hardening in the wet preparation process of the superfine powder are effectively solved, the dried product is in a foam loose shape and is crushed into particles with the particle size of less than 1mm by slight kneading, and the submicron particle size requirement can be met after airflow crushing and grading, thereby reducing the step of re-scattering the dried powder.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, by introducing the silane coupling agent and adding the preparation step of the foamed slurry, the problem of hardening of the ultrafine powder in the drying process can be solved, the scattering step after drying is omitted, and the method has the advantages of simple process and low production cost;
2. the silicon micropowder D prepared by the invention50≤0.5μm、D100Less than or equal to 5 microns and chemical purity of SiO2：99.94%，Al2O3：13ppm，Fe2O3:4 ppm; the purity of the raw material is SiO2：99.96%，Al2O3：18ppm，Fe2O3: 2.5ppm, the product can be used in high-end electronic fields such as EMC and ultrathin CCL, and domestic substitution of imported raw materials can be realized.
Drawings
FIG. 1 is a diagram of a foamed, fluffed product after drying in accordance with the present invention;
FIG. 2 is a diagram of a plate-shaped product after being dried by a conventional process;
FIG. 3 is a foamed slurry product made according to the present invention.
Detailed Description
A preparation method of ultra-pure submicron silicon micro powder foam comprises the following specific implementation steps:
example 1
a. Raw materials: selecting high-purity quartz sand asIs taken as a raw material, and comprises the following chemical components: SiO 22：99.95%，Al2O3：0.0022%，Fe2O3: 0.00014%, the particle size composition is: +0.25mm =0, 0.25-0.074 mm is more than or equal to 80%;
b. cleaning: b, cleaning the high-purity quartz sand raw material in the step a by using a scrubbing machine, wherein a cleaning medium is deionized water (the conductivity is less than or equal to 0.074 mu S/cm), the lining of the scrubbing machine and the outer lining of the impeller are made of polyurethane, and the impeller is double-layer; after scrubbing, a vacuum filter is adopted for filtering and dehydrating to obtain high-purity quartz sand, and the water extract liquid of the high-purity quartz sand requires: conductivity is less than or equal to 1 mu S/cm, K+/Na+/Cl+≤1ppm；
c. Ultra-fine grinding: grinding the high-purity quartz sand in the step b in a stirring mill, wherein the lining of the stirring mill and the outer lining of a stirring rod are made of polyurethane, a 5mm high-purity vein quartz grinding medium is adopted, a dispersion medium is deionized water (the conductivity is less than or equal to 0.084 mu S/cm), 1% of A-1387 and 3% of A-187 by weight of slurry are added in the grinding process, and D is obtained after grinding for 3.5 hours50=0.8μm、D100Silica micropowder slurry of sub-micron grade of =8 μm;
d. preparing foam slurry: c, adding the product obtained in the step c into a dispersion machine, wherein the dispersion machine is lined with polyurethane, an impeller is sprayed with zirconia, and the impeller is double-layer; firstly, adding 3% of foaming agent cetyl trimethyl ammonium bromide based on the weight of the slurry, then adding 1.5% of foam stabilizer sodium dodecyl sulfate based on the weight of the slurry, then adding 1.0% of foam viscosity promoter 1-hexadecanol, and stirring for 10min to obtain stable foamed slurry;
e. and (3) drying: d, putting the product in the step d into a zirconia tray, and conveying the zirconia tray to a box type dryer for drying, wherein the drying temperature is 150 ℃;
f. depolymerization: e, adding the product obtained in the step e into a jet mill for depolymerization and classification to obtain SiO2：99.93%，Al2O3：0.0025%，Fe2O3：0.00045%，D50≤0.5μm、D100Submicron ultra-pure silicon micropowder product with the particle size less than or equal to 5 mu m.
Example 2
a. Raw materials: high-purity quartz sand is selected as a raw material, and the chemical composition of the high-purity quartz sand is as follows: SiO 22：99.97%，Al2O3：0.0020%，Fe2O3: 0.00010%, the particle size composition is: 0.3mm =0, 0.3-0.074 mm is more than or equal to 90%;
b. cleaning: and in the same way, the high-purity quartz sand is scrubbed by using a scrubber, the vacuum filter is used for dewatering, the medium is deionized water, the high-purity quartz sand is obtained, and the water extract liquid of the high-purity quartz sand is as follows: conductivity is less than or equal to 1 mu S/cm, K+/Na+/Cl+≤1ppm；
c. Ultra-fine grinding: grinding the high-purity quartz sand obtained in the step b in a stirring mill configured in the same way, grinding the high-purity quartz sand into high-purity vein quartz ore blocks with the grinding medium of 3mm, adding an A-1387 and a 3% A-1877 oligomer of silane coupling agent into the high-purity vein quartz ore blocks with the grinding dispersion medium of deionized water (the conductivity is required to be less than or equal to 1 mu S/cm), wherein the weight of the grinding dispersion medium is 1.5% of the weight of the slurry, and grinding the high-purity quartz sand for 4 hours to obtain a D product50≤0.8μm、D100Submicron silicon micropowder slurry with the particle size less than or equal to 10 mu m;
d. preparing foam slurry: c, adding the product obtained in the step c into the same dispersion machine, adding a foaming agent tridecyl trimethyl ammonium bromide accounting for 4% of the weight of the slurry, adding a foam stabilizer sodium oleate accounting for 2% of the weight of the slurry, adding 1.0% of a foam viscosity promoter 1-dodecanol, and stirring for 15min to obtain stable foamed slurry;
e. drying: d, adding the product obtained in the step d into the box type dryer, wherein the drying temperature is 180 ℃;
f. depolymerization and classification: e, adding the product obtained in the step e into a jet mill for depolymerization and classification to obtain SiO2：99.95%，Al2O3：0.0026%，Fe2O3：0.00038%，D50≤0.5μm、D100Submicron ultra-pure silicon micropowder with the particle size less than or equal to 8 mu m.
The product indexes of the original process and the foaming process of the invention are compared in table 1:
the technical indexes of the ultra-pure submicron silicon powder prepared by the invention are as follows:
the above embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and all changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (7)
1. A preparation method of foaming ultra-pure submicron silica powder is characterized by comprising the following steps:
(1) selecting high-purity quartz sand as a raw material, wherein the chemical composition of the high-purity quartz sand is as follows: SiO 22≥99.9%，Al2O3≤0.0020%，Fe2O3≤0.0005%；
(2) Cleaning: washing the high-purity quartz sand by using a scrubbing machine, dehydrating by using a filter, and obtaining the high-purity quartz sand by using deionized water as a cleaning medium; the requirements of the water extract liquid are as follows: conductivity is less than or equal to 1 mu S/cm, K+/Na+/Cl+≤1ppm；
(3) Ultra-fine grinding: grinding the product obtained in the step (2) in a stirring mill, wherein the dispersion medium is deionized water, and meanwhile, a silane coupling agent with the weight of 1-6% of that of the product is added to obtain D50≤0.8μm、D100Submicron silicon micropowder slurry with the particle size less than or equal to 8 mu m;
(4) preparing foamed slurry: adding the product obtained in the step (3) into a dispersion machine, wherein the lining of the dispersion machine is polyurethane, an impeller is formed by spraying zirconia, the impeller is double-layer, 1-5% of foaming agent, 0.25-1.0% of foam stabilizer and 0.25-1.0% of foam viscosity promoter by weight of the product are added, and stirring for 10-20 min to form stable foamed slurry;
(5) drying: adding the product obtained in the step (4) into a dryer, spraying zirconia on a tray, and drying at the temperature of less than or equal to 200 ℃;
(6) depolymerization and classification: adding the product obtained in the step (5) into a jet mill for depolymerization and classification to obtain D50≤0.5μm、D100Submicron silicon powder end product with the particle size less than or equal to 5 mu m.
2. The method for preparing the ultra-pure submicron-sized silicon micropowder by foaming according to claim 1, wherein the method comprises the following steps: the inner lining of the scrubbing machine in the cleaning process in the step (2) is made of polyurethane, and the impeller is made of double-layer stainless steel and polyurethane lined outside.
3. The method for preparing the ultra-pure submicron-sized silicon micropowder by foaming according to claim 1, wherein the method comprises the following steps: the silane coupling agent in the step (3) is formed by mixing A-1387 and A-187 according to a mass ratio of 1: 1-1: 4.
4. The method for preparing the ultra-pure submicron-sized silicon micropowder by foaming according to claim 1, wherein the method comprises the following steps: the conductivity of the deionized water in the step (2) and the step (3) is required to be less than or equal to 1 mu S/cm.
5. The method for preparing the ultra-pure submicron-sized silicon micropowder by foaming according to claim 1, wherein the method comprises the following steps: the foaming agent in the step (4) is a quaternary ammonium salt cationic surfactant, and the chain length of an alkyl group is C12-C16; the foam stabilizer is a sulfonic acid or carboxylic acid anionic surfactant, and the chain length of alkyl is C12-C18; the foam viscosity promoter is higher alkanol, and the chain length of alkyl is C12-C16.
6. The process for the foam production of ultra-pure submicron sized fine silica powder according to any one of claims 1 to 5, wherein: and (3) a grading impeller of the jet mill for depolymerization and grading in the step (6) is made of zirconia integral ceramic, and zirconia or polyurethane protective materials are sprayed on the pipeline and the joint.
7. The process for the foam production of ultra-pure submicron sized fine silica powder according to any one of claims 1 to 5, wherein: the material of the stirring mill lining and the stirring rod outer lining in the step (3) is polyurethane, the milling medium is high-purity vein quartz particles, and the chemical components are controlled as follows: SiO 22≥99.9%，Al2O3≤0.0020%，Fe2O3Less than or equal to 0.0005 percent and the particle size of 3-30 mm.
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