CN117447053A - Method for preparing hollow glass beads with high floating rate by using waste glass as raw material - Google Patents
Method for preparing hollow glass beads with high floating rate by using waste glass as raw material Download PDFInfo
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- CN117447053A CN117447053A CN202311397966.9A CN202311397966A CN117447053A CN 117447053 A CN117447053 A CN 117447053A CN 202311397966 A CN202311397966 A CN 202311397966A CN 117447053 A CN117447053 A CN 117447053A
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- 239000011521 glass Substances 0.000 title claims abstract description 152
- 239000011324 bead Substances 0.000 title claims abstract description 70
- 239000002994 raw material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000004005 microsphere Substances 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002210 silicon-based material Substances 0.000 claims abstract description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001709 polysilazane Polymers 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000005373 porous glass Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 8
- 238000002679 ablation Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/107—Forming hollow beads
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/27—Oxides by oxidation of a coating previously applied
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a method for preparing hollow glass beads with high floating rate by taking waste glass as a raw material, dispersing ground raw materials and hollow glass bead associated products in water, adding water glass with the mass of 4-8% of the mixed solution in a stirring state, and aging at room temperature, drying, crushing and grading to prepare microporous precursor particles; hollow spheroidization is carried out on the microporous precursor particles in a reducing atmosphere to prepare hollow glass microspheres with a floating rate of more than 97%; the hollow glass beads are subjected to ultrasonic buoyancy separation to obtain hollow glass beads with the floating rate of more than 99%, the surfaces of the hollow glass beads are uniformly coated with silicon-containing compounds in a solvent containing the silicon-containing compounds, and the hollow glass beads with the high floating rate of more than 99.3% are finally prepared after drying. The hollow glass microsphere prepared by the invention has the excellent characteristics of low density, high compressive strength, high floatation rate, low ion precipitation and low cost, and can be used in the fields of aerospace ablation-resistant materials, deep sea floating body materials, automobile adhesives and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of functional inorganic filling materials, and particularly relates to a preparation method of hollow glass beads, and the prepared hollow glass beads can be widely applied to the fields of military industry, building materials, petroleum, chemical industry and the like, and are particularly suitable for the fields of deep sea floating bodies, aerospace, rail transit, automobile manufacturing, 5G base stations and the like.
Background
Hollow glass beads (HGM) are hollow, thin-walled, high-strength and light micron-sized vitreous spheres, and have excellent characteristics which are incomparable with other fillers such as low density, high strength, high temperature resistance, low heat conduction, low dielectric constant, excellent dispersibility and the like, and the hollow glass beads (HGM) can be used as a filling material, so that the cost of products can be reduced, and can endow the products with new functions, so that the hollow glass beads become the main stream of novel filling materials in the 21 st century.
A large amount of waste glass is produced in China every year, but the recycling rate of the waste glass is lower due to the different sources, uses and production mechanisms of raw materials of the waste glass. And the glass is a non-degradable substance, and with the increase of accumulation, huge pressure is brought to environmental protection and resource utilization. U.S. 3M company patent CN103415481A, CN102811965AD and the like disclose a method for preparing hollow glass microspheres by using waste glass as a raw material, but the prepared HGM has high true density and low compressive strength, and cannot meet application requirements.
With the continuous expansion of the application field of the HGM, higher requirements are put on the performance of the HGM, mainly including true density, compressive strength and floating rate. The true density and the compressive strength of the HGM belong to the mutually restricted relation, the compressive strength of the HGM is determined by factors such as material strength, shape factor/aspect ratio (ratio of radius to wall thickness), surface condition, floating rate and the like, and the HGM has a negative correlation with the aspect ratio, so that the lower the true density of the HGM is, the thinner the wall thickness of the spherical shell is, and the lower the compressive strength is. The lower the true density of the HGM is, the lighter the product is, the lower the cost is, and the more obvious the special functional performance is given by the HGM is, but the high compressive strength is required to be maintained to meet the requirements of the process and the product performance, so the preparation of the hollow glass microsphere with low density, high compressive strength and high floating rate becomes a great key problem to be solved at present. In special fields, such as aerospace ablation-resistant materials, deep sea floats and other fields, and international regulations (such as European Union REACH regulations) of some application fields, strict requirements are imposed on HGM ion precipitation.
In addition, the hollow glass beads prepared by using waste glass as raw materials at present have the defects of surface defects, ion precipitation and the like.
Disclosure of Invention
The invention aims to provide a method for preparing hollow glass beads with high floatation rate by using waste glass as a raw material, so as to solve the problems of low floatation rate, poor strength and high ion precipitation of the hollow glass beads prepared by using waste glass, and the method can be applied to the fields of aerospace ablation-resistant materials, deep sea floating body materials, automobile adhesives and the like, and has important significance for realizing localization of technical materials in high-end fields.
In order to achieve the above purpose, the method for preparing the hollow glass beads with high floating rate by taking waste glass as a raw material uses waste glass powder as a main raw material, prepares microporous precursor particles by adding hollow glass bead accompaniment products, and simultaneously prepares the hollow glass beads with high floating rate by matching with the control of the hollow spheroidization process conditions; the silica layer is coated on the surfaces of the hollow glass beads, so that the repair of surface defects and the control of ion precipitation are realized, and meanwhile, the compressive strength of the hollow glass beads can be improved. The method specifically comprises the following process steps:
1) Preparation of microporous precursor particles
Uniformly dispersing the ground and uniformly mixed raw materials and hollow glass microsphere associated products in water to prepare a mixed solution with the solid content of 65-73%; then adding water glass with the mass of 4-8% of the mixed solution in a stirring state, and solidifying gel into a block structure; the block structure is aged at room temperature, dried, crushed and graded to prepare microporous precursor particles with the particle diameter of 10-35 mu m and the average pore diameter of less than 2.6 mu m.
The sum of the mass of the raw material components is calculated according to 100 percent, and the contents of the components are as follows: 76-85% of waste glass, 4-9% of quartz sand, 3-10% of anhydrous borax, 3-7% of calcium carbonate, 0.2-2.3% of sodium sulfate, 0-1.3% of lithium phosphate and 0.5-1.6% of zinc phosphate; wherein, the anhydrous borax can be converted into borax pentahydrate and borax decahydrate in the same proportion.
The true density of the hollow glass microsphere associated product is 1.0-1.8 g/cm 3 Hollow and porous glass bead particles with the particle diameter smaller than 5 mu m are added in an amount of 1.0-2.0% of the total mass of the raw materials, and preferably 1.3-2.0%. The purpose of adding the hollow glass microsphere associated product is to form pore nuclear points by utilizing physical pores of the hollow glass microsphere associated product, so that the hollow glass microsphere is easier to foam. As a physical foaming agent and a nuclear bubble in the microporous precursor particles, the activation energy of bubble formation is reduced, and the hollow spheroidization proportion of the hollow glass beads is improved.
The water glass is sodium silicate water solution with unlimited modulus.
In this step, the raw materials are mixed and ground to a particle size of less than 15 μm, preferably by a ball mill or a vibration mill, and the raw materials are homogenized and refined by grinding.
2) Hollow spheroidization of microporous precursor particles
The microporous precursor particles prepared in the step 1) are pre-dispersed in combustion-supporting gas at 220-300 ℃, are conveyed into a high-temperature spheroidizing furnace, are subjected to hollow spheroidization in a reducing atmosphere, and are rapidly solidified and shaped through a cooling device to prepare the hollow glass microspheres with the floating rate of more than 97%.
In the step, the sum of the volume fractions of the combustion-supporting gas is calculated according to 100 percent, and the contents of the components are as follows: 0-13% of oxygen, 2-5% of hydrogen and 83-96% of air; the preferable content of each component is as follows: 4-10% of oxygen, 2-5% of hydrogen and 87-94% of air.
In the step, microporous precursor particles are uniformly dispersed in combustion-supporting gas with an initial temperature of 220-300 ℃ at first, so that after the particles are conveyed to high-temperature spheroidizing equipment, the liquefying speed of the surfaces of the particles is improved, the energy consumption is reduced, the particles are heated more uniformly, and the gas coating is realized more efficiently; and simultaneously, hollow spheroidization is carried out in a reducing atmosphere, the glass liquid on the surface of the particles still has lower surface tension at a lower temperature, the energy consumption is reduced, the bubble coalescence and the expansion resistance are reduced, and finally the hollow glass microsphere with the floating rate more than 97% is prepared.
3) Strengthening the hollow glass beads: the hollow glass beads prepared in the step 2) are subjected to ultrasonic buoyancy separation to obtain hollow glass beads with the floating rate more than 99%; then dispersing the hollow glass beads subjected to ultrasonic buoyancy separation in a solvent containing silicon compounds, and stirring for 20-45 min to uniformly coat the surfaces of the hollow glass beads with the silicon compounds; after drying, the hollow glass beads coated with the silicon-containing compound are heat treated for 35 to 50 minutes at the temperature of between 200 and 450 ℃ to convert the coated silicon-containing compound into a silicon oxide layer, and finally the true density is between 0.12 and 0.40g/cm 3 The high-floating rate hollow glass microsphere has the compressive strength of 4.5-55 MPa, the free boron content of less than 500ppm, the sodium ion content of less than 100mg/L and the floating rate of more than 99.3 percent.
In the step 3), the silicon-containing compound is one or two or more compounds of silica sol, polysiloxane and polysilazane, and the like, after high-temperature treatment, no other residues are left except the coated silicon dioxide layer, the silicon-containing compound is coated on the surfaces of the hollow glass beads, and a silicon dioxide layer is formed by heating, wherein the heating temperature is lower than the softening point of the hollow glass beads. The curing temperature is low, the time is short, the bonding is firm, the surface defects are repaired, the ion precipitation of the hollow glass beads is effectively prevented, and the prepared hollow glass beads have the excellent characteristics of high strength and low ion precipitation. The buoyancy separation efficiency and the optimal quality can be effectively improved by adopting the ultrasonic buoyancy separation, and the ultrasonic wave promotes broken particles, micro powder particles and the like to separate from the attached hollow glass particles through physical acting force so as to sink into the bottom of the solvent.
As the preference of the invention, the sum of the mass of the raw material components is calculated according to 100 percent, and the content of each component is as follows: 76 to 84 percent of waste glass, 5 to 9 percent of quartz sand, 4 to 10 percent of anhydrous borax, 3 to 7 percent of calcium carbonate, 0.2 to 2.2 percent of sodium sulfate, 0.2 to 1.3 percent of lithium phosphate and 0.5 to 1.5 percent of zinc phosphate.
As a preferred aspect of the present invention, the waste glass has the following contents, calculated as 100%, of the total of the contents of the respective compounds:
further, in the step 1), the drying adopts one of a multi-layer belt dryer, a rotary drum dryer and a fluidized bed dryer; and the jet mill classifier or the Raymond mill/ball milling-classifying system is adopted to synchronously finish the crushing and classifying so as to reduce the generation of micro-subdivision, the particle size span of the prepared microporous precursor particles is narrower, the thermodynamic consistency in the hollow spheroidization process of the particles is improved, and the preparation of the high-floating-rate and high-strength hollow glass microspheres is facilitated.
In the step 3), the buoyancy separation medium adopted in the ultrasonic buoyancy separation is water, ethanol, petroleum ether or other substances with similar properties, which do not react with the hollow glass microspheres chemically and do not remain after drying; the ultrasonic frequency of the ultrasonic buoyancy separation is 35-55 kHz, and is preferably 40-50 kHz.
The floating rate here means the floating rate of hollow glass beads in an aqueous medium; the hollow glass bead accompanying product is dust-removing ash or a small amount of waste products generated in the production process of the hollow glass bead.
Compared with the prior art, the method for preparing the hollow glass microsphere with high floating rate by using the waste glass as the raw material has the following beneficial effects:
(1) The waste glass is used as the main raw material, so that the high added value utilization of the waste glass is realized, the raw material cost is low, the adding amount of the waste glass is 76-85%, and the production cost of the hollow glass beads can be obviously reduced.
(2) The micropore precursor particles prepared by introducing the physical foaming agent-hollow glass microsphere concomitant product have uniform pore distribution and easily controlled pore size. Hollow glass microsphere accompaniment products have a hollow or porous closed-pore structure with the particle size smaller than 5 mu m, and air holes are always covered by spherical shells and keep independent distribution.
(3) The micro air holes in the microporous precursor particles are used as nuclear bubbles, so that the formation and growth activation energy of the air bubbles are greatly reduced, meanwhile, the surface tension is lower under a reducing atmosphere, the viscous resistance and the surface tension which need to be overcome by gas coalescence and expansion are reduced, the precursor particles are easier to form a hollow structure, and the hollow glass beads with the floating rate more than 99% are finally prepared by combining flotation, so that the problem of low yield of the hollow glass beads prepared by taking waste glass powder as a raw material is solved.
(4) The silicon compound is evenly coated on the surfaces of the hollow glass beads, a silicon dioxide layer can be formed at a lower temperature, the method is residue-free, safe and environment-friendly, the defects of spherical shells on the surfaces of the hollow glass beads are repaired, the compressive strength is improved, and meanwhile, the silicon dioxide layer effectively blocks ion precipitation in the spherical shells.
Detailed Description
In order to describe the present invention, the method for preparing hollow glass beads with high floating rate using waste glass as a raw material according to the present invention will be described in further detail with reference to examples. The invention is not limited to the examples.
Example 1
The specific implementation process is as follows:
(1) Preparation of microporous precursor particles: weighing the components in the raw materials according to the proportion of the serial number 1 in the table 1, and grinding to obtain a mixed material with the particle size smaller than 10.15 mu m; uniformly dispersing the mixed material and the hollow glass microsphere associated product in water to obtain a mixed solution with 73% of solid content, whereinThe hollow glass microsphere accompaniment is 1.85% of the total mass of the raw materials, and the true density is 1.16g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Adding water glass with the mass of 7.4% and the modulus of 2.45 into the mixed solution under stirring, and solidifying the gel into a block structure; the microporous precursor particles with the particle diameter D50 of 18 mu m and the average pore diameter of 1.125 mu m are prepared by ageing at room temperature, drying, crushing and grading.
(2) Hollow spheroidization of microporous precursor particles: pre-dispersing the microporous precursor particles prepared in the step (1) in 260 ℃ combustion-supporting gas with an atmosphere composition of 6% of oxygen, 5% of hydrogen and 89% of air; then the hollow glass microspheres are conveyed into a high-temperature spheroidizing furnace to be subjected to hollow spheroidization under a reducing atmosphere, and finally the hollow glass microspheres with the floating rate of 97.8% are prepared by rapidly solidifying and shaping through a cooling device.
(3) Strengthening the hollow glass beads: carrying out ultrasonic buoyancy separation on the hollow glass beads prepared in the step (2), wherein the solvent is petroleum ether; then dispersing the floating hollow glass beads in a perhydro polysilazane solvent, stirring for 45min, drying, and treating at 200 ℃ for 50min to prepare the glass with the true density of 0.135g/cm 3 The hollow glass microsphere has the compressive strength of 5MPa, the floating rate of 99.75 percent, the free boron content of 410ppm and the sodium ion content of 82 mg/L.
Example 2
The specific implementation process is as follows:
(1) Preparation of microporous precursor particles: weighing the components in the raw materials according to the serial number 2 in the table 1, and grinding to obtain a mixed material with the particle size smaller than 13.62 mu m; uniformly dispersing the mixed material and the hollow glass bead accompaniment in water to obtain a mixed solution with the solid content of 71%, wherein the hollow glass bead accompaniment is 1.8% of the total mass of the raw materials, and the true density is 1.47g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then adding water glass with the mass of 5.6% and the modulus of 3.1 into the mixed solution in a stirring state, and solidifying the gel into a block structure; the microporous precursor particles with the particle diameter D50 of 21 mu m and the average pore diameter of 1.837 mu m are prepared by ageing at room temperature, drying, crushing and grading.
(2) Hollow spheroidization of microporous precursor particles: pre-dispersing microporous precursor particles prepared in the step (1) in a combustion-supporting gas with an atmosphere composition of 10% of oxygen, 2% of hydrogen and 88% of air at 300 ℃; then the hollow glass microspheres are conveyed into a high-temperature spheroidizing furnace to be subjected to hollow spheroidization under a reducing atmosphere, and finally the hollow glass microspheres with the floatation rate of 98.5% are prepared by rapidly solidifying and shaping through a cooling device.
(3) Strengthening the hollow glass beads: carrying out ultrasonic buoyancy separation on the hollow glass beads prepared in the step (2), wherein the solvent is ethanol; then dispersing the floating hollow glass beads in a silica sol solvent, stirring for 20min, drying, and treating at 450 ℃ for 35min to prepare the glass with the true density of 0.18g/cm 3 The hollow glass microsphere has the compressive strength of 14MPa, the floating rate of 99.86 percent, the free boron content of 360ppm and the sodium ion content of 90 mg/L.
Example 3
The specific implementation process is as follows:
(1) Preparation of microporous precursor particles: weighing the components in the raw materials according to the ratio of the serial number 3 in the table 1, and grinding to obtain a mixed material with the particle size smaller than 8.96 mu m; uniformly dispersing the mixed material and the hollow glass bead accompaniment in water to obtain a mixed solution with the solid content of 68%, wherein the hollow glass bead accompaniment is 2.0% of the total mass of the raw materials, and the true density is 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then adding water glass with the mass of the mixed solution of 6.1 percent and the modulus of 2.1 in a stirring state, and solidifying the gel into a block structure; the microporous precursor particles with the particle diameter D50 of 16 mu m and the average pore diameter of 2.546 are prepared by ageing at room temperature, drying, crushing and grading.
(2) Hollow spheroidization of microporous precursor particles: pre-dispersing the microporous precursor particles prepared in the step (1) in 220 ℃ combustion-supporting gas with an atmosphere composition of 4% oxygen, 2% hydrogen and 94% air; then the hollow glass microspheres are conveyed into a high-temperature spheroidizing furnace to be subjected to hollow spheroidization under a reducing atmosphere, and finally the hollow glass microspheres with the floating rate of 97.6% are prepared by rapidly solidifying and shaping through a cooling device.
(3) Strengthening the hollow glass beads: carrying out ultrasonic buoyancy separation on the hollow glass beads prepared in the step (2), wherein the solvent is water; then dispersing the floating hollow glass beads in polypropylene siloxane solvent, stirring for 40min, drying, and treating at 230 deg.C for 45min to obtain a product with a true density of 0.27g/cm 3 Compressive strength of 38The hollow glass microsphere has the advantages of MPa, 99.76 percent of floating rate, 270ppm of free boron and 69mg/L of sodium ion.
Example 4
The specific implementation process is as follows:
(1) Weighing the components in the raw materials according to the serial number 4 ratio in the table 1, and grinding to obtain a mixed material with the particle size smaller than 14.32 mu m; uniformly dispersing the mixed material and the hollow glass bead accompaniment in water to obtain a mixed solution with the solid content of 65%, wherein the hollow glass bead accompaniment is 1.4% of the total mass of the raw materials, and the true density is 1.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then adding water glass with the mass of 4.5% and the modulus of 3.3 into the mixed solution in a stirring state, and solidifying the gel into a block structure; the microporous precursor particles with the particle diameter D50 of 23 mu m and the average pore diameter of 1.390 mu m are prepared by ageing at room temperature, drying, crushing and grading.
(2) Hollow spheroidization of microporous precursor particles: pre-dispersing the microporous precursor particles prepared in the step (1) in 280 ℃ combustion-supporting gas with an atmosphere composition of 9% of oxygen, 4% of hydrogen and 87% of air; then the hollow glass microspheres are conveyed into a high-temperature spheroidizing furnace to be subjected to hollow spheroidization under a reducing atmosphere, and finally the hollow glass microspheres with the floatation rate of 98.1% are prepared by rapidly solidifying and shaping through a cooling device.
(3) Strengthening the hollow glass beads: carrying out ultrasonic buoyancy separation on the hollow glass beads prepared in the step (2), wherein the solvent is water; then dispersing the floated hollow glass beads in a perhydro polysilazane vinyl polysilazane solvent, stirring for 37min, drying, and treating at 250 ℃ for 30min to prepare the glass with a true density of 0.37g/cm 3 The hollow glass microsphere has the compressive strength of 52MPa, the floating rate of 99.77 percent, the free boron content of 345ppm and the sodium ion content of 78 mg/L.
TABLE 1 examples 1-4 mass fraction tables of each component in raw materials
The present invention can be realized by the upper and lower limit values and interval values of the raw materials and the process parameters, and are not limited to this.
Claims (10)
1. A method for preparing hollow glass beads with high floating rate by using waste glass as a raw material is characterized by comprising the following steps:
1) Preparation of microporous precursor particles
Uniformly dispersing the ground and uniformly mixed raw materials and hollow glass microsphere associated products in water to prepare a mixed solution with the solid content of 65-73%; then adding water glass with the mass of 4-8% of the mixed solution in a stirring state, and solidifying gel into a block structure; aging, drying, crushing and grading the block structure at room temperature to obtain microporous precursor particles with the particle diameter of 10-35 mu m and the average pore diameter of less than 2.6 mu m;
the sum of the mass of the raw material components is calculated according to 100 percent, and the contents of the components are as follows: 76-85% of waste glass, 4-9% of quartz sand, 3-10% of anhydrous borax, 3-7% of calcium carbonate, 0.2-2.3% of sodium sulfate, 0-1.3% of lithium phosphate and 0.5-1.6% of zinc phosphate;
the true density of the hollow glass microsphere associated product is 1.0-1.8 g/cm 3 Hollow porous glass bead particles with the particle diameter smaller than 5 mu m, wherein the addition amount is 1.0-2.0% of the total mass of the raw materials;
2) Hollow spheroidization of microporous precursor particles
Pre-dispersing the microporous precursor particles prepared in the step 1) in combustion-supporting gas at 220-300 ℃, conveying the pre-dispersed microporous precursor particles into a high-temperature spheroidizing furnace, carrying out hollow spheroidization in a reducing atmosphere, and rapidly solidifying and shaping the pre-dispersed microporous precursor particles by a cooling device to prepare hollow glass microspheres with a floating rate of more than 97%;
3) Strengthening the hollow glass beads: the hollow glass beads prepared in the step 2) are subjected to ultrasonic buoyancy separation to obtain hollow glass beads with the floating rate more than 99%; then dispersing the hollow glass beads subjected to ultrasonic buoyancy separation in a solvent containing silicon compounds, and stirring for 20-45 min to uniformly coat the surfaces of the hollow glass beads with the silicon compounds; after drying, the hollow glass beads coated with the silicon-containing compound are heat treated for 35 to 50 minutes at the temperature of between 200 and 450 ℃ to convert the coated silicon-containing compound into a silicon oxide layer, and finally the true density is between 0.12 and 0.40g/cm 3 The high-floating rate hollow glass microsphere has the compressive strength of 5.0-55 MPa, the free boron content of less than 500ppm, the sodium ion content of less than 100mg/L and the floating rate of more than 99.3 percent.
2. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 1, wherein the method comprises the following steps: the sum of the mass of the raw material components is calculated according to 100 percent, and the contents of the components are as follows: 76 to 84 percent of waste glass, 5 to 9 percent of quartz sand, 4 to 10 percent of anhydrous borax, 3 to 7 percent of calcium carbonate, 0.2 to 2.2 percent of sodium sulfate, 0.2 to 1.3 percent of lithium phosphate and 0.5 to 1.5 percent of zinc phosphate.
3. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 1, wherein the method comprises the following steps: the total content of each compound in the waste glass is calculated as 100 percent:
4. the method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 1, wherein the method comprises the following steps: in the step 1), the grinding and uniformly mixing are to grind the raw materials until the particle size is smaller than 15 mu m, wherein a ball mill or a vibration grinder is adopted for grinding.
5. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 1, 2, 3 or 4, wherein the method comprises the following steps: in the step 1), the accompanying addition amount of the hollow glass beads is 1.3-2.0% of the total mass of the raw materials.
6. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 5, wherein the method comprises the following steps: in the step 2), the sum of the volume fractions of the combustion-supporting gas is calculated according to 100 percent, and the contents of the components are as follows: 0-13% of oxygen, 2-5% of hydrogen and 83-96% of air.
7. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 6, wherein the method comprises the following steps: in the step 3), the silicon-containing compound is one or more than two of silica sol, polysiloxane and polysilazane.
8. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 7, wherein the method comprises the following steps: in the step 3), the buoyancy separation medium adopted in the ultrasonic buoyancy separation is water, ethanol or petroleum ether which does not react with the hollow glass beads chemically and does not remain after drying; ultrasonic frequency adopted by ultrasonic buoyancy separation is 35-55 khz.
9. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 8, wherein the method comprises the following steps: in the step 2), the sum of the volume fractions of the combustion-supporting gas is calculated according to 100 percent, and the contents of the components are as follows: 4-10% of oxygen, 2-5% of hydrogen and 87-94% of air.
10. The method for preparing the hollow glass microsphere with high floating rate by using waste glass as a raw material according to claim 9, wherein the method comprises the following steps: in the step 1), the drying adopts one of a multi-layer belt dryer, a rotary drum dryer and a fluidized bed dryer, and adopts an air current crushing classifier or a Raymond mill/ball milling-classifying system to synchronously finish crushing and classifying; in the step 3), the ultrasonic frequency adopted by the ultrasonic buoyancy separation is 40-50 kHz.
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