CN113149024B - Preparation method of ultra-pure submicron silicon micropowder foam - Google Patents
Preparation method of ultra-pure submicron silicon micropowder foam Download PDFInfo
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- 239000006260 foam Substances 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 19
- 239000010703 silicon Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000006004 Quartz sand Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 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
- 239000000377 silicon dioxide 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
- 238000005201 scrubbing Methods 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000002612 dispersion medium Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 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 16
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing 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
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-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
- 230000009467 reduction Effects 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- 238000010902 jet-milling Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910021487 silica fume Inorganic materials 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
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to a preparation method of ultra-pure submicron silicon micropowder foam, which is characterized by comprising the following steps: (1) selecting high-purity quartz sand as a raw material; (2) Washing ores by using a scrubbing machine, dehydrating by using a filter, and obtaining high-purity quartz sand by using deionized water as a cleaning medium; (3) Wet grinding in a stirring mill, wherein a dispersion medium is deionized water, and adding 1-6% of silane coupling agent to obtain D 50 ≤0.8μm、D 100 Slurry with the thickness of less than or equal to 8 mu m; (4) Adding the slurry into a dispersing 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) And (3) adding the foamed slurry into a dryer, drying at a temperature less than or equal to 200 ℃, and then adding the foamed slurry into a jet mill for depolymerization and classification. The invention has the advantages that: the method effectively solves the industrial problem of powder agglomeration in the drying process, omits an indispensable scattering process, and has simple process and low cost; ultra-pure submicron silica powder D 50 ≤0.5μm、D 100 Can be used in the high-end electronic fields such as EMC, CCL and the like, and is less than or equal to 5 mu m.
Description
Technical Field
The invention belongs to the field of deep processing of nonmetallic minerals, relates to the field of high-end electronics such as EMC (epoxy film plastic package) and CCL (copper clad laminate) manufacturing, and particularly relates to a preparation method of ultra-pure submicron silicon micropowder foam.
Background
With the rapid development of the electronic industry, particularly the strict requirement of 5G communication chips, electronic devices are moving toward high frequency and high speed, high power density and portability. The resin has excellent insulating property, chemical corrosion resistance and high bonding strength, and is widely applied to electronic insulating materials. But the pure resin has poor mechanical strength, and the inorganic filler is added to improve the mechanical strength and thermal stability of the resin insulation composite material, so that the reduction of dielectric constant, dielectric loss and cost are necessary choices. In order to meet the above requirements, adding fillers such as silica micropowder is the preferred solution, and high purity, ultra-fine and low halogen are the development directions of silica micropowder.
Currently, the high-end electronic grade submicron silica powder market is mainly monopolized by Admatech and Denka company in Japan, and the development of high-purity superfine low-submicron silica powder is urgent. In order to meet the requirement of superfine scale production, a wet process is generally adopted, but the agglomeration in the drying process and the secondary pollution in the scattering process are all the time industry problems due to the structural crystal and surface property characteristics of quartz. In short, the dried powder generally generates soft agglomeration and hard agglomeration to a certain extent due to physical adsorption and chemical bonding, has compact and blocky appearance, generally needs to be scattered in a ball milling or crushing mode, and can be obtained into submicron-sized silicon powder through jet milling and classification. It is noted that the reduction of SiO due to the doping of impurity ions (Al, zr) into grinding media, equipment liners, conveying pipelines and the like is unavoidable during the breaking process 2 The content of the silicon powder finally influences the purity of the silicon powder. Taking ball milling and scattering, lining with alumina, and grinding with zirconia as examples (phi 3-phi 5mm, zrO 2 More than or equal to 95 percent) and 1.0 hour of breaking time, considering that the ore-to-dielectric ratio is 1:7 and SiO 2 The chemical quality of the silicon micropowder is finally reduced from 99.94% to 99.82%, which is not satisfactory.
Disclosure of Invention
The invention aims to solve the problems that the obtained agglomerated powder is required to be scattered again in the existing wet grinding, secondary pollution is easy to occur in the scattering process, and the purity of silicon micro-powder is affected, and provides a preparation method for ultra-pure submicron silicon micro-powder foaming.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the ultra-pure submicron silicon micropowder foam is characterized by comprising the following steps of:
(1) The high-purity quartz sand is selected as a raw material, and the chemical composition of the high-purity quartz sand is as follows: siO (SiO) 2 ≥99.9%，Al 2 O 3 ≤0.0020%，Fe 2 O 3 ≤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 requirement is less than or equal to 1 mu S/cm); the water extract liquid requires: conductivity is less than or equal to 1 mu S/cm, K + /Na + /Cl + ≤1ppm；
(3) Superfine grinding: grinding the product in the step (2) in a stirring mill, wherein the dispersion medium is deionized water (the conductivity requirement is 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 D 50 ≤0.8μm、D 100 Submicron silica powder slurry less than or equal to 8 mu m;
(4) Preparing foamed slurry: adding the product obtained in the step (3) into a dispersing machine, wherein the inner lining of the dispersing machine is polyurethane, the impeller is sprayed by zirconia, the impeller is double-layered, and a foaming agent accounting for 1-5% of the weight of the product, a foam stabilizer accounting for 0.25-1.0% of the weight of the product and a foam viscosity promoter accounting for 0.25-1.0% of the weight of the product are added, and stirring for 10-20 min to form stable foamed slurry;
(5) And (3) drying: adding the product obtained in the step (4) into a dryer, wherein a tray is sprayed by zirconia, and the drying temperature is less than or equal to 200 ℃;
(6) Depolymerization and fractionation: adding the product obtained in the step (5) into a jet mill to carry out depolymerization and classification to obtain D 50 ≤0.5μm、D 100 Submicron silicon micropowder of less than or equal to 5 mu m.
Further, the inner lining of the scrubbing machine in the cleaning process in the step (2) is polyurethane, and the impeller is double-layer stainless steel outer lining polyurethane.
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 maitugao new material (China Co.).
Further, the foaming agent in the step (4) is a quaternary ammonium salt type cationic surfactant, and the alkyl chain length is C14-C16 (for example, octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tridecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and the like); the foam stabilizer is sulfonic acid or carboxylic acid anionic surfactant, and the alkyl chain length is C12-C18 (such as sodium dodecyl sulfonate, sodium hexadecyl sulfonate, sodium oleate, etc.); the foam viscosity promoter is higher alkanol, and the chain length of the alkyl is C12-C16.
Furthermore, the classifying impeller of the jet mill for depolymerization and classification 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 stirring mill lining and the stirring rod outer lining in the step (3) are made of polyurethane, the milling medium is high-purity gangue particles, and the chemical components are controlled: siO (SiO) 2 ≥99.9%，Al 2 O 3 ≤0.0020%，Fe 2 O 3 Less than or equal to 0.0005%, and the particle size is 3-30 mm.
The foaming dispersion technology of the invention mainly adds the foaming agent, the foam stabilizer and the foam accelerator, and makes the foaming agent hydrophobic and dispersed under the synergistic effect of electrostatic repulsive force and steric hindrance, so as to effectively reduce hard agglomeration, and finally the foaming dispersion technology is loose and crushed when being touched.
The invention adopts the combination of modification and foam dispersion technology, adds a silane coupling agent in the grinding step, and prepares submicron-sized silica micropowder slurry; then, foaming agent, foam stabilizer and foam viscosity promoter are added into the silicon micro powder slurry, so that the problems of agglomeration and hardening in the wet preparation process of the ultra-fine powder are effectively solved, the dried product is in a loose foam shape, is slightly kneaded and crushed into particles with the size less than 1mm, and the submicron particle size requirement can be achieved after air flow crushing and classification, and the step of re-scattering the dried powder is reduced.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the silane coupling agent is introduced, so that the preparation step of the foamed slurry is added, the problem of hardening of ultrafine powder in the drying process can be solved, the scattering step after drying is omitted, and the preparation method has the advantages of simple process and low production cost;
2. the silicon micropowder D prepared by the invention 50 ≤0.5μm、D 100 Less than or equal to 5 mu m, and the chemical purity is SiO 2 ：99.94%，Al 2 O 3 ：13ppm，Fe 2 O 3 :4ppm; the purity of the raw material is SiO 2 ：99.96%，Al 2 O 3 ：18ppm，Fe 2 O 3 :2.5ppm, the product can be used in the high-end electronic fields such as EMC, ultrathin CCL and the like, and can realize domestic substitution of imported raw materials.
Drawings
FIG. 1 is a diagram of a foamed, loosely-shaped product of the present invention after drying;
FIG. 2 is a diagram of a hardened product after drying in a conventional process;
FIG. 3 is a foamed slurry product made in accordance with the present invention.
Detailed Description
The preparation method of the ultra-pure submicron silicon micropowder foam comprises the following specific implementation steps:
example 1
a. Raw materials: the high-purity quartz sand is selected as a raw material, and the chemical composition of the high-purity quartz sand is as follows: siO (SiO) 2 ：99.95%，Al 2 O 3 ：0.0022%，Fe 2 O 3 :0.00014% of a particle size composition of: +0.25 mm=0, 0.25-0.074mm is more than or equal to 80%;
b. cleaning: c, cleaning the high-purity quartz sand raw material in the step a by adopting a scrubbing machine, wherein a cleaning medium is deionized water (the conductivity is less than or equal to 0.074 mu S/cm), the inner lining of the scrubbing machine and the outer lining of the impeller are made of polyurethane, and the impeller is double-layer; filtering and dehydrating by adopting a vacuum filter after scrubbing to obtain high-purity quartz sand, wherein 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. Superfine grinding: grinding the high-purity quartz sand in the step b in a stirring mill, wherein the inner lining of the stirring mill and the outer lining of the stirring rod are made of polyurethane, adopting a 5mm high-purity vein quartz grinding medium, adopting deionized water (the conductivity is less than or equal to 0.084 mu S/cm) as a dispersion medium, adding a silane coupling agent of A-1387 and A-187 which account for 1% of the weight of slurry in the grinding process, and grinding for 3.5 hours to obtain D 50 =0.8μm、D 100 Submicron-sized silica fume slurry of 8 μm;
d. preparing foam slurry: c, adding the product obtained in the step c into a dispersing machine, wherein polyurethane is lined in the dispersing machine, the impeller is sprayed by zirconia, and the impeller is double-layer; firstly adding 3% of foaming agent cetyl trimethyl ammonium bromide by weight of the slurry, then adding 1.5% of foam stabilizer sodium dodecyl sulfonate by weight of the slurry, then adding 1.0% of foam viscosity promoter 1-cetyl alcohol, and stirring for 10min to obtain stable foam slurry;
e. and (3) drying: putting the product in the step d into a zirconia tray, and conveying the zirconia tray to a box-type dryer for drying at the drying temperature of 150 ℃;
f. depolymerizing: adding the product obtained in the step e into a jet mill to depolymerize and classify to obtain SiO 2 ：99.93%，Al 2 O 3 ：0.0025%，Fe 2 O 3 ：0.00045%，D 50 ≤0.5μm、D 100 Submicron ultra-pure silicon micropowder products with the diameter of less than or equal to 5 mu m.
Example 2
a. Raw materials: the high-purity quartz sand is selected as a raw material, and the chemical composition of the high-purity quartz sand is as follows: siO (SiO) 2 ：99.97%，Al 2 O 3 ：0.0020%，Fe 2 O 3 :0.00010% of a particle size composition of: 0.3 mm=0, 0.3-0.074 mm is more than or equal to 90%;
b. cleaning: as above, the scrubbing machine is used for scrubbing the high-purity quartz sand, the vacuum filter is used for dehydration, the medium is deionized water, and the high-purity quartz sand is obtained, and the water extract liquid requirements are as follows: conductivity is less than or equal to 1 mu S/cm, K + /Na + /Cl + ≤1ppm；
c. Superfine grinding: stirring mill for mixing high-purity quartz sand in step bGrinding with 3mm high purity gangue quartz ore block as grinding medium and deionized water as the dispersing medium (conductivity is less than or equal to 1 mu S/cm), adding oligomer of A-1387 and 3% of A-1877 silane coupling agent in 1.5 wt% of slurry, grinding for 4 hr to obtain D 50 ≤0.8μm、D 100 Submicron silica micropowder slurry less than or equal to 10 mu m;
d. preparing foam slurry: adding the product in the step c into the same disperser, adding 4% of foamer tridecyl trimethyl ammonium bromide by weight of the slurry, adding 2% of foam stabilizer sodium oleate by weight of the slurry, adding 1.0% of foam viscosity promoter 1-dodecanol, and stirring for 15min to obtain stable foam slurry;
e. and (3) drying: adding the product obtained in the step d into the box-type dryer, wherein the drying temperature is 180 ℃;
f. depolymerization and fractionation: adding the product obtained in the step e into a jet mill to depolymerize and classify to obtain SiO 2 ：99.95%，Al 2 O 3 ：0.0026%，Fe 2 O 3 ：0.00038%，D 50 ≤0.5μm、D 100 Submicron ultra-pure silicon micropowder with the diameter of less than or equal to 8 mu m.
Comparison of product indexes of the original process and the foaming process of the invention table 1:
the technical indexes of the ultra-pure submicron silicon micro powder prepared by the invention are shown in the following table 2:
the above embodiments are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the invention, which is defined in the claims and all changes that fall within the principles of the invention.
Claims (5)
1. The preparation method of the ultra-pure submicron silicon micropowder foam is characterized by comprising the following steps of:
(1) The high-purity quartz sand is selected as a raw material, and the chemical composition of the high-purity quartz sand is as follows: siO (SiO) 2 ≥99.9%，Al 2 O 3 ≤0.0020%，Fe 2 O 3 ≤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 water extract liquid requires: conductivity is less than or equal to 1 mu S/cm, K + /Na + /Cl + ≤1ppm；
(3) Superfine grinding: grinding the product in the step (2) in a stirring mill, wherein a dispersion medium is deionized water, and simultaneously adding a silane coupling agent accounting for 1-6% of the weight of the product to obtain D 50 ≤0.8μm、D 100 Submicron silica powder slurry less than or equal to 8 mu m; the silane coupling agent is formed by mixing A-1387 and A-187 according to the mass ratio of 1:1-1:4;
(4) Preparing foamed slurry: adding the product obtained in the step (3) into a dispersing machine, wherein the inner lining of the dispersing machine is polyurethane, the impeller is sprayed by zirconia, the impeller is double-layered, and a foaming agent accounting for 1-5% of the weight of the product, a foam stabilizer accounting for 0.25-1.0% of the weight of the product and a foam viscosity promoter accounting for 0.25-1.0% of the weight of the product are added, and stirring for 10-20 min to form stable foamed slurry; the foaming agent is a quaternary ammonium salt type 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 the alkyl is C12-C18; the foam viscosity promoter is higher alkanol, and the chain length of alkyl is C12-C16;
(5) And (3) drying: adding the product obtained in the step (4) into a dryer, wherein a tray is sprayed by zirconia, and the drying temperature is less than or equal to 200 ℃;
(6) Depolymerization and fractionation: adding the product obtained in the step (5) into a jet mill to carry out depolymerization and classification to obtain D 50 ≤0.5μm、D 100 Submicron silicon micropowder of less than or equal to 5 mu m.
2. The method for preparing the ultra-pure submicron silicon micro powder foam according to claim 1, which is characterized in that: the inner lining of the scrubbing machine in the cleaning process in the step (2) is polyurethane, and the impeller is double-layer stainless steel outer lining polyurethane.
3. The method for preparing the ultra-pure submicron silicon micro powder foam according to claim 1, which is characterized in that: the conductivity of deionized water in the step (3) is required to be less than or equal to 1 mu S/cm.
4. A process for the preparation of ultra-pure submicron grade silica micropowder foam according to any of claims 1-3, characterized in that: and (3) the classifying impeller of the jet mill for depolymerizing and classifying in the step (6) is made of zirconia integral ceramic, and zirconia or polyurethane protective materials are sprayed on the joints of the pipelines.
5. A process for the preparation of ultra-pure submicron grade silica micropowder foam according to any of claims 1-3, characterized in that: the stirring mill lining and the stirring rod outer lining in the step (3) are made of polyurethane, the grinding medium is high-purity gangue particles, and the chemical components are controlled: siO (SiO) 2 ≥99.9%，Al 2 O 3 ≤0.0020%，Fe 2 O 3 Less than or equal to 0.0005%, and the particle size is 3-30 mm.
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