CN117430335A - Preparation method of hollow glass microsphere with adjustable true density and compressive strength and high floating rate - Google Patents
Preparation method of hollow glass microsphere with adjustable true density and compressive strength and high floating rate Download PDFInfo
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- CN117430335A CN117430335A CN202311397788.XA CN202311397788A CN117430335A CN 117430335 A CN117430335 A CN 117430335A CN 202311397788 A CN202311397788 A CN 202311397788A CN 117430335 A CN117430335 A CN 117430335A
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- 239000011521 glass Substances 0.000 title claims abstract description 195
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011324 bead Substances 0.000 claims abstract description 102
- 239000002245 particle Substances 0.000 claims abstract description 71
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 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 12
- 239000002210 silicon-based material Substances 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 37
- 239000002699 waste material Substances 0.000 claims description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 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 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 239000006004 Quartz sand Substances 0.000 claims description 12
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 12
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 12
- 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 12
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000000227 grinding Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 229920001709 polysilazane Polymers 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 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
- 238000002156 mixing Methods 0.000 claims description 2
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 9
- 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
- 230000007547 defect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 208000034699 Vitreous floaters Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-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
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/107—Forming hollow beads
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 preparation method of hollow glass beads with adjustable true density and compressive strength and high floating rate, which comprises the steps of dispersing ground raw materials and associated hollow glass beads in water, adding water glass with the mass of 4-8% of the mixed solution under 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 pressurization and 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 99.5% 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 high-floating-rate hollow glass beads with a floating rate of more than 99.5% in an aqueous medium, and the prepared high-floating-rate 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.
In order to reduce the production cost, chinese patent application 201510177509.8 discloses a method for manufacturing hollow glass microspheres by using waste glass, which comprises the steps of cleaning and crushing the waste glass, adding feldspar accounting for 3-10% of the weight of the waste glass, talcum accounting for 0-6% of the weight of the waste glass, soda ash accounting for 1-3% of the weight of the waste glass, limestone accounting for 1-5% of the weight of the waste glass, water glass accounting for 1-3% of the waste glass, zinc sulfate accounting for 1-3% of the waste glass, calcium sulfate accounting for 1-3% of the waste glass, ball milling the mixed materials, adding sizing agent containing scoring and cellulose, and heating and spheroidizing at 1100-1200 ℃ by spray drying to obtain the hollow glass microspheres. However, the suspension rate of the hollow glass beads manufactured by the method in water is only 95%, and the breakage rate of the hollow glass beads under the compression strength test of 30Mpa is as high as 14% and 16%.
In order to further improve the floating rate of the hollow glass beads and effectively regulate and control the compressive strength and the true density of the hollow glass beads, chinese patent ZL201910972403.5 discloses a preparation method of the hollow glass beads with high floating rate, wherein the basic raw materials are a mixture of quartz, borax, calcium carbonate, sodium sulfate and sodium phosphate, and the sum of the mass of each component of the basic raw materials is calculated according to 100 percent: 60.30 to 61.15 percent of quartz, 14.00 to 14.90 percent of borax, 19.15 to 20.80 percent of calcium carbonate, 3.40 to 3.80 percent of sodium carbonate, 0.22 to 0.81 percent of sodium sulfate, 0.41 to 1.25 percent of sodium phosphate, and the like, and stabilizing dispersing agents, surfactants and the like are required to be added. However, the floating rate of the hollow glass beads prepared by the method is still less than 98.5%, and the raw material cost and the production cost are high.
Disclosure of Invention
The invention aims to provide the preparation method of the hollow glass microsphere with adjustable true density and compressive strength and high floatation rate, aiming at the defects of high production cost, low yield, difficult regulation and control of compressive strength and true density, uneven distribution of precursor particles and pores, difficult control of surface defects, serious ion precipitation phenomenon and the like in the existing preparation method of the hollow glass microsphere, so as to solve the problems of low floatation rate, poor strength and high ion precipitation of the hollow glass microsphere prepared from waste glass, and the preparation 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 high-end technical materials.
In order to achieve the aim, the invention relates to a preparation method of high-floating-rate hollow glass beads with adjustable true density and compressive strength, which takes waste glass powder as a main raw material, prepares microporous precursor particles by adding hollow glass bead accompaniment products, and simultaneously prepares the high-floating-rate hollow glass beads 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) Raw material pretreatment-preparation of microporous precursor particles
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: 74.5 to 84.5 percent of waste glass, 4.1 to 8.9 percent of quartz sand, 3.1 to 9.9 percent of anhydrous borax, 3.2 to 6.7 percent of calcium carbonate, 0.2 to 2.2 percent of sodium sulfate, 0.1 to 1.2 percent of lithium phosphate, 0.48 to 1.5 percent of zinc phosphate and 1.1 to 1.98 percent of hollow glass microsphere associated products; the true density of the hollow glass microsphere associated product is 1.0-1.8 g/cm 3 Hollow, porous glass bead particles having a particle size of less than 5 μm; wherein anhydrous borax can be converted intoAnhydrous borax pentahydrate and anhydrous borax decahydrate.
Grinding waste glass, quartz sand, anhydrous borax, calcium carbonate, sodium sulfate, lithium phosphate and zinc phosphate in raw materials until the particle size is smaller than 15 mu m, uniformly mixing, and uniformly dispersing the mixture 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 homogenization and particle refinement of the raw materials are realized through grinding, and the jet mill classifier or Raymond mill/ball milling-classifying system is adopted to synchronously finish the crushing and classifying, so that the generation of micro-subdivision is reduced, 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 hollow glass microspheres with high floatation rate and high strength is facilitated.
The total content of each compound in the waste glass is calculated as 100 percent:
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.
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, 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: pressurizing and ultrasonically buoyancy sorting the hollow glass beads prepared in the step 2) to obtain hollow glass beads with a floating rate of more than 99.3%; then dispersing the hollow glass beads subjected to pressurization and 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 99.5 percent.
The purpose of pressurization is to make water overcome resistance and enter into broken glass bead particles, increase the density of the broken particles, and make the broken particles settle down in the buoyancy separation process so as to improve the physical properties (improve compressive strength and improve floatation rate) of the hollow glass bead high-floaters.
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.
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.
Further, the pressurizing and ultrasonic buoyancy separation in the step 3) are carried out in a closed pressure container, the applied pressure is 0.5-1.6 MPa, and the ultrasonic frequency is 35-55 kHz.
Further, in the step 2), the content of each component is preferably as follows when the sum of the volume fractions of the combustion-supporting gas is calculated by 100 percent: 2-12% of oxygen, 2-5% of hydrogen and 85-94% of air.
As a preferred aspect of the present invention, in the step 1), a ball mill or a vibration mill is used for the grinding, and one of a multi-layer belt dryer, a drum dryer, and a fluidized bed dryer is used for the drying; 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; in the step 3), the buoyancy separation medium adopted by the ultrasonic buoyancy separation is water, ethanol or petroleum ether or other liquid substances with similar properties, which do not react with the hollow glass beads chemically and have no residue after drying, and the ultrasonic frequency adopted by the ultrasonic buoyancy separation is 40-50 kHz.
The method can produce hollow glass beads with different true densities, different compressive strengths and different floating rates according to market demands.
In order to prepare the material with compressive strength of several MPa and true density of less than or equal to 0.15g/cm 3 The hollow glass bead comprises the following components in percentage by mass when the sum of the mass of the raw material components is calculated according to 100 percent: 74.5 to 76.5 percent of waste glass, 4.1 to 7.1 percent of quartz sand, 5.7 to 9.7 percent of anhydrous borax, 3.2 to 6.6 percent of calcium carbonate, 1.2 to 2.2 percent of sodium sulfate, 0.26 to 1.2 percent of lithium phosphate, 0.48 to 1.4 percent of zinc phosphate and 1.68 to 1.97 percent of hollow glass microsphere associated product, wherein the true density of the adopted hollow glass microsphere associated product is 1.0～1.25g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.12-0.15 g/cm 3 The compressive strength is 5.0-6.0 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.70%.
In order to prepare the material with the compressive strength of 10 to 16MPa and the true density of 0.17 to 0.22g/cm 3 The hollow glass beads adopt the following raw material components in percentage by mass when the sum of the mass is calculated according to 100 percent: 75.3 to 79.8 percent of waste glass, 3.9 to 7.8 percent of quartz sand, 6.2 to 9.2 percent of anhydrous borax, 3.8 to 6.6 percent of calcium carbonate, 0.86 to 1.18 percent of sodium sulfate, 0.28 to 0.95 percent of lithium phosphate, 0.49 to 0.98 percent of zinc phosphate and 1.44 to 1.80 percent of hollow glass bead accompaniment, and the true density of the adopted hollow glass bead accompaniment is 1.21 to 1.54g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.17-0.22 g/cm 3 The compressive strength is 10-16 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.80%.
In order to prepare the hollow glass bead with the compressive strength of 30-40 MPa and the true density of 0.25-0.32, the mass content of each component is as follows when the sum of the mass of the adopted raw material components is calculated according to 100 percent: 77.8 to 81.8 percent of waste glass, 2.9 to 8.8 percent of quartz sand, 5.4 to 8.6 percent of anhydrous borax, 4.4 to 6.8 percent of calcium carbonate, 0.64 to 0.92 percent of sodium sulfate, 0.19 to 0.98 percent of lithium phosphate, 0.79 to 1.28 percent of zinc phosphate and 0.99 to 1.97 percent of hollow glass bead accompaniment, and the true density of the adopted hollow glass bead accompaniment is 1.52 to 1.76g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.25-0.32 g/cm 3 The compressive strength is 30-40 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.8%.
In order to prepare hollow glass beads with the compressive strength of 45-55 MPa and the true density of 0.34-0.40, the mass content of each component is as follows when the sum of the mass of the adopted raw material components is calculated according to 100 percent: 79.8 to 83.7 percent of waste glass, 3.9 to 9.8 percent of quartz sand, 3.9 to 7.8 percent of anhydrous borax, 2.9 to 6.8 percent of calcium carbonate, 0.19 to 0.68 percent of sodium sulfate, 0.19 to 0.78 percent of lithium phosphate, 0.99 to 1.57 percent of zinc phosphate and 0.99 to 1.97 percent of hollow glass bead accompaniment product, and the adopted hollow glass bead accompanimentThe true density of the product is 1.21-1.54 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.34-0.40 g/cm 3 The compressive strength is 45-55 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.75%.
The floating rate here means the floating rate of hollow glass beads in an aqueous medium; the hollow glass bead associated product is dust-removing ash or a small amount of micro-fine waste generated in the production process of the hollow glass bead.
Compared with the prior art, the preparation method of the hollow glass microsphere with adjustable true density and compressive strength and high floating rate 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 up to 74.5-84.5%, and the production cost of the hollow glass microspheres can be obviously reduced.
(2) According to the invention, the hollow glass beads dispersed in the solvent in the pressure vessel are pressurized to be applied with pressure of 0.5-1.6 MPa, and then subjected to ultrasonic buoyancy separation, wherein the ultrasonic frequency is 40-50 kHz, so that the defect particles such as solid, porous, through-hole, broken and the like can be removed efficiently.
(3) The hollow glass beads prepared in the step 2) are subjected to pressurization and ultrasonic buoyancy separation, and are separated by utilizing the difference of HGM particle densities, so that solid and thick-wall particles can be effectively removed. On the basis of buoyancy separation, the solvent is pressurized to overcome the actions of capillary force, surface tension, viscous resistance and the like to enter the HGM with micro-pore channels on the spherical shell wall, so that sedimentation of particles with through holes is promoted, and simultaneously, the micro-particles attached to the spherical shell surface of the HGM, fragments of the spherical shell of the HGM and the like are peeled off by mechanical force generated by ultrasound. Not only the floating rate of the prepared HGM is more than 99.5 percent, but also the compressive strength of the HGM is greatly improved due to the efficient removal of defective particles.
(4) The micropore precursor particles prepared by introducing the physical foaming agent 'hollow glass microsphere associated 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.
(5) 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 floating rate is more than 99.5% by combining buoyancy separation, so that the problem of low yield of the hollow glass beads prepared by taking waste glass powder as a raw material is solved.
(6) 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 invention, the following describes in further detail the preparation method of the hollow glass microsphere with adjustable true density and compressive strength and high floating rate. The invention is not limited to the examples.
The tests were carried out according to the raw material mass ratios given in Table 1, and the sum of the mass of each component in the raw material was 1000 g in each test.
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 bead accompaniment in water to obtain a mixed solution with 73% of solid content, wherein the true density of the adopted hollow glass bead accompaniment 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: the hollow glass beads prepared in the step (2) are subjected to buoyancy separation by pressurization (0.7 MPa) and ultrasonic waves (40 kHz), and the solvent is petroleum ether; then dispersing the hollow glass beads separated by buoyancy in a perhydro polysilazane solvent, stirring for 45min, drying, and treating at 200 ℃ for 50min to prepare the glass beads with the true density of 0.134g/cm 3 The hollow glass microsphere has the compressive strength of 5.2MPa, the floating rate of 99.77 percent, the free boron content of 403ppm and the sodium ion content of 79 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 71% of solid content, wherein the true density of the adopted hollow glass bead accompaniment 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: the hollow glass beads prepared in the step (2) are subjected to buoyancy separation by pressurization (1.0 MPa) and ultrasonic waves (45 kHz), and the solvent is ethanol; then buoyancy is carried outDispersing the separated hollow glass beads in silica sol solvent, stirring for 20min, drying, and treating at 450 deg.C for 35min to obtain a glass fiber with true density of 0.17g/cm 3 The hollow glass microsphere has the compressive strength of 15MPa, the floating rate of 99.88 percent, the free boron content of 354ppm and the sodium ion content of 87 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 true density of the adopted hollow glass bead accompaniment 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: the hollow glass beads prepared in the step (2) are subjected to buoyancy separation by pressurization (1.2 MPa) and ultrasonic waves (45 kHz), and the solvent is water; then dispersing the hollow glass beads separated by buoyancy in polypropylene siloxane solvent, stirring for 40min, drying, and treating at 230 deg.C for 45min to obtain a product with true density of 0.26g/cm 3 The hollow glass microsphere has the compression strength of 39MPa, the floating rate of 99.81 percent, the free boron content of 265ppm and the sodium ion content of 66 mg/L.
Example 4
The specific implementation process is as follows:
(1) The components of the raw materials are weighed according to the mixture ratio of the serial number 4 in the table 1, and the raw materials are ground to obtain the particles with the particle size smaller than 14.32 mu mMixing materials; uniformly dispersing the mixed material and the hollow glass bead accompaniment in water to obtain a mixed solution with 65% of solid content, wherein the true density of the adopted hollow glass bead accompaniment 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: the hollow glass beads prepared in the step (2) are subjected to buoyancy separation by pressurization (1.5 MPa) and ultrasonic waves (50 kHz), and the solvent is water; then dispersing the hollow glass beads separated by buoyancy 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 0.35g/cm 3 The hollow glass microsphere has the compression strength of 55MPa, the floating rate of 99.81 percent, the free boron content of 337ppm and the sodium ion content of 75 mg/L.
TABLE 1 examples 1-4 mass fraction tables of each component in raw materials
The invention can also prepare the material with the true density of 0.29-0.34 g/cm by regulating and controlling the raw material proportion and the technological parameters 3 The hollow glass microsphere has the compressive strength of 20-30 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 99.75 percent.
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. The preparation method of the hollow glass microsphere with adjustable true density and compressive strength and high floating rate is characterized by comprising the following steps:
1) Raw material pretreatment-preparation of microporous precursor particles
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: 74.5 to 84.5 percent of waste glass, 4.1 to 8.9 percent of quartz sand, 3.1 to 9.9 percent of anhydrous borax, 3.2 to 6.7 percent of calcium carbonate, 0.2 to 2.2 percent of sodium sulfate, 0.1 to 1.2 percent of lithium phosphate, 0.48 to 1.5 percent of zinc phosphate and 1.1 to 1.98 percent of hollow glass microsphere associated products; the true density of the hollow glass microsphere associated product is 1.0-1.8 g/cm 3 Hollow, porous glass bead particles having a particle size of less than 5 μm;
grinding waste glass, quartz sand, anhydrous borax, calcium carbonate, sodium sulfate, lithium phosphate and zinc phosphate in raw materials until the particle size is smaller than 15 mu m, uniformly mixing, and uniformly dispersing the mixture 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;
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: pressurizing and ultrasonically buoyancy sorting the hollow glass beads prepared in the step 2) to obtain hollow glass beads with a floating rate of more than 99.3%; then dispersing the hollow glass microspheres separated by pressurization and ultrasonic buoyancy in a solvent containing silicon compoundsStirring for 20-45 min to uniformly coat the surfaces of the hollow glass beads with silicon-containing 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 99.5 percent.
2. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, which is characterized in that: the pressurization and ultrasonic buoyancy separation are carried out in a closed pressure container, the applied pressure is 0.5-1.6 MPa, and the ultrasonic frequency is 35-55 kHz.
3. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, which is characterized in that: the total content of each compound in the waste glass is calculated as 100 percent:
4. the method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, which is characterized in that: 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: 2-12% of oxygen, 2-5% of hydrogen and 85-94% of air.
5. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, which is characterized in that: in the step 3), the silicon-containing compound is one or more than two of silica sol, polysiloxane and polysilazane.
6. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, which is characterized in that: in the step 1), a ball mill or a vibration grinder is adopted for grinding, and one of a multi-layer belt dryer, a rotary drum dryer and a fluidized bed dryer is adopted for drying; 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; in the step 3), the buoyancy separation medium adopted by 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, and the ultrasonic frequency adopted by the ultrasonic buoyancy separation is 40-50 kHz.
7. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, 2, 3, 4, 5 or 6, wherein the mass content of each component is as follows when the sum of the mass of the raw material components is calculated as 100 percent: 74.5 to 76.5 percent of waste glass, 4.1 to 7.1 percent of quartz sand, 5.7 to 9.7 percent of anhydrous borax, 3.2 to 6.6 percent of calcium carbonate, 1.2 to 2.2 percent of sodium sulfate, 0.26 to 1.2 percent of lithium phosphate, 0.48 to 1.4 percent of zinc phosphate and 1.68 to 1.97 percent of hollow glass bead accompaniment, and the true density of the adopted hollow glass bead accompaniment is 1.0 to 1.25g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.12-0.15 g/cm 3 The compressive strength is 5.0-6.0 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.70%.
8. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, 2, 3, 4, 5 or 6, wherein the mass content of each component is as follows when the sum of the mass of the raw material components is calculated as 100 percent: 75.3 to 79.8 percent of waste glass, 3.9 to 7.8 percent of quartz sand, 6.2 to 9.2 percent of anhydrous borax, 3.8 to 6.6 percent of calcium carbonate, 0.86 to 1.18 percent of sodium sulfate, 0.28 to 0.95 percent of lithium phosphate, 0.49 to 0.98 percent of zinc phosphate and 1.44 to 1.80 percent of hollow glass bead accompaniment, and the adopted hollow glass bead accompaniment is true and closeThe degree is 1.21-1.54 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.17-0.22 g/cm 3 The compressive strength is 10-16 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.80%.
9. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, 2, 3, 4, 5 or 6, wherein the mass content of each component is as follows when the sum of the mass of the raw material components is calculated as 100 percent: 77.8 to 81.8 percent of waste glass, 2.9 to 8.8 percent of quartz sand, 5.4 to 8.6 percent of anhydrous borax, 4.4 to 6.8 percent of calcium carbonate, 0.64 to 0.92 percent of sodium sulfate, 0.19 to 0.98 percent of lithium phosphate, 0.79 to 1.28 percent of zinc phosphate and 0.99 to 1.97 percent of hollow glass bead accompaniment, and the true density of the adopted hollow glass bead accompaniment is 1.52 to 1.76g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.25-0.32 g/cm 3 The compressive strength is 30-40 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.8%.
10. The method for preparing the hollow glass beads with adjustable true density and compressive strength and high floating rate according to claim 1, 2, 3, 4, 5 or 6, wherein the mass content of each component is as follows when the sum of the mass of the raw material components is calculated as 100 percent: 79.8 to 83.7 percent of waste glass, 3.9 to 9.8 percent of quartz sand, 3.9 to 7.8 percent of anhydrous borax, 2.9 to 6.8 percent of calcium carbonate, 0.19 to 0.68 percent of sodium sulfate, 0.19 to 0.78 percent of lithium phosphate, 0.99 to 1.57 percent of zinc phosphate and 0.99 to 1.97 percent of hollow glass bead accompaniment, and the true density of the adopted hollow glass bead accompaniment is 1.21 to 1.54g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The true density of the prepared hollow glass microsphere is 0.34-0.40 g/cm 3 The compressive strength is 45-55 MPa, the free boron content is less than 500ppm, the sodium ion content is less than 100mg/L, and the floating rate is more than 99.75%.
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