CN111635140A - Method for preparing high-scattering opaque hollow glass microspheres by using sodium fluoride-containing silica slag - Google Patents
Method for preparing high-scattering opaque hollow glass microspheres by using sodium fluoride-containing silica slag Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/08—Other methods of shaping glass by foaming
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- 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
- C03B19/1075—Forming hollow beads by blowing, pressing, centrifuging, rolling or dripping
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- 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
- C03B19/108—Forming porous, sintered or foamed beads
- C03B19/1085—Forming porous, sintered or foamed beads by blowing, pressing, centrifuging, rolling or dripping
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- 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
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- 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
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- 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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
Abstract
The invention discloses a method for preparing high-scattering opaque hollow glass microspheres by using silicon slag containing sodium fluoride, which comprises the steps of mixing and pulping silicon slag with adjusted sodium fluoride content and raw material powder of alkali metal oxide, alkaline earth metal oxide, aluminum oxide, boron trioxide, tin dioxide, titanium dioxide and sulfate by using water, grinding and spray drying, feeding the obtained powder into a high-temperature spheroidizing furnace for fusion vitrification and hollow spheroidizing, and carrying out hydraulic flotation and drying on the spheroidized powder to obtain the high-scattering opaque hollow glass microspheres with the refractive index of 1.92-2.21. The method solves the problem of utilization of the sodium fluoride-containing silica slag, improves the performance of the hollow glass microspheres, improves the scattering ability and the opaqueness of the microspheres, improves the ultraviolet resistance and the aging resistance of applied products such as rubber, plastic and the like, and provides a material choice for developing the ultra-light, high-heat-resistance and strong-scattering wave-absorbing coating.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a method for preparing high-scattering opaque hollow glass microspheres by using sodium fluoride-containing silica slag.
Background
The hollow glass bead is an inorganic hollow particle powder material, and each particle is hollowSpherical, the cavity contains a trace amount of inert gas or is in a micro-vacuum state. The hollow glass microsphere has a particle size range of 2-250 um and a true density of 0.12-0.8 g/cm3The bulk density is 0.07 to 0.7g/cm3The wall thickness is 8-10% (1-2 um) of the diameter. The hollow glass beads are resistant to high temperature, the softening point is more than or equal to 615 ℃, the thermal expansion coefficient is 8.8-108.8 (60-440 ℃), the dielectric constant is 1.2-8.6 MHz, and the thermal conductivity is 0.030-0.035 w/m.k. The hollow glass microspheres have the characteristics of small specific gravity, large stacking coefficient, high compressive strength, good isotropy, low oil absorption rate, heat insulation, sound insulation, electric insulation, corrosion resistance, high chemical stability, good fluidity and the like, are used as functional fillers to be applied to products such as plastic products, electric wires and cables, rubber products, heat-insulating coatings, heat-insulating ceramics, light concrete, light high polymer materials and the like, can improve the strength of the products, improve the service performance of the products, reduce the weight of the products and save the energy consumption, and have wide application prospects in the industrial fields of building materials, machinery, electronics, light industry, automobiles, ships, aerospace, oil exploitation and the like.
The hollow glass microspheres can be obtained by two methods, one method is that flotation fly ash contains a small amount of hollow glass microspheres, the product has more impurities, heavy chromaticity, large particle size, poor uniformity of particle size, low compressive strength, single variety, narrow application range, a large amount of waste residues can be discharged in production, and the pollution is serious. The other is artificial synthesis, which is white hollow particles artificially synthesized by using inorganic mineral substances and inorganic salt with higher purity, the appearance is regular and uniform, the granularity range is small, the compressive strength is high, and process parameters can be changed to prepare various functional differentiated varieties so as to meet different requirements of various industries.
The hollow glass microspheres floated from the fly ash or artificially synthesized by the conventional method have strong light transmittance and small refractive index, generally between 1.50 and 1.58, are used as light fillers to be applied to products such as rubber, plastics, coatings, furniture plates and the like, and have unsatisfactory ultraviolet resistance and aging resistance.
The hollow glass beads are in an amorphous glass phase, and the main component of the hollow glass beads is silicon dioxide and accounts for 55-80% of the total components. The silicon dioxide can adopt crystalline silicon dioxide as raw materials, such as: quartz sand; amorphous silica or silicon compounds may also be used as starting materials, such as: white carbon black, silica gel and sodium silicate. The requirements of artificially synthesized hollow glass beads on a silicon source are the same as those of ordinary glass production, both the adoption of crystalline silica and the adoption of amorphous silica have higher requirements on the purity of silica, the purity of the silica cannot be less than 98.5 percent, and otherwise, the quality index stability and the production control difficulty of the hollow glass beads are seriously influenced.
The method comprises the steps of adopting quartz sand type crystalline silica as a silicon source for producing hollow glass beads, generally adopting a powder method process form, sending a raw material complex into a melting furnace, melting at 1350-1600 ℃, then cooling and carrying out ultrafine grinding to obtain micron-sized amorphous glass powder, sending the micron-sized amorphous glass powder into a high-temperature spheroidizing furnace to carry out secondary melting, balling and puffing on irregular powder particles, and carrying out hydraulic flotation to obtain closed hollow spherical micron-sized particles. Chinese patent CN102320743B discloses an aluminosilicate high-strength hollow glass bead and a preparation method thereof, which is a typical method for producing hollow glass beads by taking crystalline quartz sand as a silicon source, wherein a batch containing 60-75% of quartz sand is put into an electric melting crucible for melting at 1400-1600 ℃, then the melted glass liquid is quenched with water, dried and ground to obtain powder with required particle size, then the powder is sent into a spheroidizing furnace for spheroidization at 1250-1450 ℃, and the spheroidized powder is subjected to hydraulic flotation to obtain the closed hollow glass bead.
Amorphous silicon dioxide such as white carbon black, silica gel and the like or water-soluble compound sodium silicate of silicon dioxide are used as a silicon source for producing the hollow glass microspheres, generally, the silicon dioxide is dispersed and reduced to nanoscale original particles in water, other raw materials are added for mixing and pulping, slurry is centrifugally sprayed and dried to obtain micron-sized round particle powder, namely a precursor for producing the hollow glass microspheres, and then the micron-sized round particle powder is sent into a high-temperature spheroidizing furnace to instantly complete the melting, vitrification and hollow spheroidizing of powder particles by a one-step method, and the closed hollow glass microspheres are obtained by hydraulic flotation. Chinese patent CN103979796B discloses a high-strength hollow glass bead and a preparation method thereof, Ba, Al, Si, Li, S, Ca, P, Na and B oxide gel is prepared by a sol-gel method of multi-alkoxide hydrolysis, silicon dioxide nano powder is prepared by an alkoxide hydrolysis precipitation method, the Ba, Al, Si, Li, S, Ca, P, Na and B oxide gel and the silicon dioxide nano powder are mixed and homogenized, and after the mixture is atomized and dried, spherical precursor powder is obtained, and the hollow glass bead is obtained through a vitrification sintering process at 600-650 ℃.
The sodium fluosilicate byproduct of wet-process phosphoric acid and phosphate fertilizer is used for producing sodium fluoride by a soda decomposition method, the device investment is small, the production cost is low, meanwhile, the contradiction between the excess of the sodium fluosilicate productivity and the small market demand can be solved, the sodium fluoride production method is a main production mode of the sodium fluoride industry in China, but a large amount of silicon dioxide slag can be produced as a byproduct in the production process, the main chemical components of the silicon dioxide slag are 35-50% of silicon dioxide, 4-15% of sodium fluoride, 40-50% of water and less other impurity components. The silicon dioxide of the silicon slag is amorphous silicon dioxide, the particle size is less than 60um, the particle surface is porous, 80% of the pore diameter is less than 5nm, and although the silicon dioxide has certain adsorption and activity, the adsorption capacity is weak because the pore diameter belongs to micropores, and the silicon dioxide cannot be processed into active silicon dioxide for use. And because of the existence of the microporous pore path, the silica gel is easy to absorb water and expand, and cannot be used as crystalline silica. Therefore, even though sodium fluoride is thoroughly separated out at a high cost, the silicon slag has no direct use value, becomes solid waste which troubles the sodium fluoride industry, restrains the development of the sodium fluoride industry, and can meet the environmental protection requirement of 'using slag for fixed production' only by searching a way for the silicon slag.
Fluoride is commonly used as a fluxing agent in melting glass, if the content of fluorine exceeds 3 wt%, the precipitation of fluoride can cause the glass to have an opacification phenomenon, along with the increase of the content of fluorine, the opacification degree can also be improved, the corresponding reflection and diffraction capabilities are stronger, namely, the scattering capability to light and electromagnetic waves is stronger, and the fluoride has important significance for improving the aging resistance of rubber, plastics, coatings and high polymer materials and preparing high-temperature-resistant wave-absorbing materials. The high-scattering opaque hollow glass bead is prepared by utilizing the silica slag containing sodium fluoride, amorphous silicon dioxide with higher purity in the silica slag can be utilized, and sodium fluoride in the amorphous silicon dioxide can be fully utilized to improve the performance of the hollow glass bead and expand the application of the hollow glass bead.
Disclosure of Invention
The invention aims to provide a method for preparing high-scattering opaque hollow glass microspheres by using silica slag containing sodium fluoride, which solves the problem of utilization of the silica slag containing sodium fluoride in the sodium fluoride industry, turns harm into benefit, provides a silicon dioxide raw material for producing the hollow glass microspheres, improves the performance of the hollow glass microspheres, and improves the scattering ability and the opacity of the microspheres, thereby improving the ultraviolet resistance and the aging resistance of application products such as rubber, plastic, paint, high polymer material and the like, and also provides a material choice for developing ultra-light, high-heat-resistance and strong-scattering wave-absorbing paint.
The high-scattering opaque hollow glass bead prepared by the invention has a refractive index of 1.92-2.21, and the main components playing roles in scattering and opacifying are sodium fluoride (NaF) and stannic oxide (SnO)2) And titanium dioxide (TiO)2)。
According to the invention, the high-scattering opaque hollow glass beads are prepared from the silica slag containing sodium fluoride, wherein the fluorine content in the raw material composition is required to be 3-7 wt%, and the corresponding sodium fluoride content is required to be 6.6-15.5 wt%.
The invention uses silica slag containing sodium fluoride to prepare high-scattering opaque hollow glass beads, and the chemical components of the raw material composition are as follows:
silicon dioxide (SiO)2) 65～78wt％；
5-12 wt% of alkaline earth metal oxide (RO);
alkali metal oxide (R)2O) 3～8wt％；
Aluminum oxide (Al)2O3) 1～4wt％；
Boron trioxide (B)2O3) 2～7wt％；
6.6-15.5 wt% of sodium fluoride (NaF);
tin dioxide (SnO)2) 1～5wt％；
Titanium dioxide (TiO)2) 1～5wt％；
Sulfate (R)2SO4、RSO4) 0.3～1.0wt％。
The silicon dioxide refers to solid silicon dioxide in the silicon slag containing sodium fluoride.
One or two of the alkaline earth metal oxide, calcium oxide (CaO) and magnesium oxide (MgO). The raw material for providing the calcium oxide component is quicklime (CaO) powder, and the raw material for providing the magnesium oxide component is magnesia (MgO) powder.
The alkali metal oxide, sodium oxide (Na)2O) and potassium oxide (K)2O), one or two of them. The raw material for providing sodium oxide component is sodium carbonate (Na)2CO3) Powder, potassium carbonate (K) as the raw material for providing potassium oxide2CO3) And (3) powder.
The aluminum oxide (Al)2O3) The raw material may be alumina (Al)2O3) Powder and aluminum hydroxide [ Al (OH) ]3]Powder, one of them.
The boron trioxide (B)2O3) Boric acid (H) can be used as the raw material3BO3) Powder, anhydrous borax (Na)2B4O7) Powder, borax pentahydrate (Na)2B4O7·5H2O) powder, one of them.
The sodium fluoride refers to the total amount of solid sodium fluoride contained in the silicon slag and supplemented sodium fluoride.
The tin dioxide adopts tin dioxide (SnO)2) White powder.
The titanium dioxide adopts titanium dioxide (TiO)2) White powder, type A and type R.
The sulfate (R)2SO4、RSO4) The raw material can adopt anhydrous sodium sulfate (Na)2SO4) Powder, potassium sulfate (K)2SO4) Powder, calcium sulfate (CaSO)4) Powder, one of them.
The method for preparing the high-scattering opaque hollow glass microspheres by using the silica slag containing sodium fluoride comprises the following steps:
(1) adjusting the amount of sodium fluoride in the raw material complex, if the amount of sodium fluoride in the silicon slag is 6.6-15.5 wt% higher than that of the sodium fluoride required by the raw material complex, adopting a method of washing the silicon slag with water to remove redundant sodium fluoride by water, collecting an aqueous solution of sodium fluoride, and concentrating and crystallizing to obtain a sodium fluoride byproduct; and if the sodium fluoride contained in the silicon slag is 6.6-15.5 wt% lower than the required sodium fluoride of the raw material complex, supplementing the deficient sodium fluoride into the silicon slag.
(2) According to the mass ratio of water to solid materials of 1: 0.4-1: 1, firstly injecting water into a mixing tank, then adding all complex solid materials into the mixing tank, stirring and pulping, and then feeding into a ball mill lined with zirconia-corundum and graded zirconia-corundum balls for grinding, wherein the particle size of the solid slurry is controlled to be 1-5 um.
(3) And conveying the ground slurry to a spray dryer by a pump for atomization and drying to obtain fine powder with the moisture content of not more than 10%, namely the precursor for producing the hollow glass microspheres.
(4) And carrying out multistage airflow classification or screening on the dried precursor to obtain precursors with multiple particle size ranges so as to prepare the hollow glass microspheres with multiple particle size ranges.
(5) The precursors with different particle size ranges are respectively sent into a spheroidizing furnace, powder particles are instantly melted into glass droplets, the surfaces of the droplets are automatically arranged into spheres under the action of hot flue gas, the spherical droplets are expanded into hollows by gas generated by particle melting, and then the hollow glass microspheres are obtained by air instant cooling. The temperature of the spheroidizing furnace is controlled to be 1200-1550 ℃.
(6) Respectively collecting hollow glass microspheres with different particle size ranges, feeding the hollow glass microspheres into a water tank for flotation, taking out powder floating on the upper part of the water tank, and feeding the powder into a dryer for drying until the moisture content is less than 3%, so as to obtain high-scattering opacified hollow glass microspheres with target particle size ranges; taking out a small amount of wet powder settled at the lower part of the water tank, sending the wet powder into the step (2), and pulping and grinding the wet powder together with new ingredients.
Detailed Description
In order to further illustrate the present invention, the method for preparing the high scattering opaque hollow glass microspheres by using the silica slag containing sodium fluoride according to the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
The method for preparing the high-scattering opaque hollow glass microspheres by using the silica slag containing sodium fluoride is implemented by the following ingredients:
sodium fluoride-containing silica slag-reduced Silica (SiO)2) The proportion of the ingredients is 71 wt%;
the alkaline earth metal oxide raw material adopts quicklime (CaO), and the proportion of the ingredients is 7 wt%;
the alkali metal oxide is sodium carbonate (Na)2CO3) Reduced sodium oxide (Na)2O), the proportion of ingredients is 5 wt%;
the aluminum oxide raw material adopts aluminum oxide (Al)2O3) The proportion of the ingredients is 1.5 wt%;
the boron trioxide adopts anhydrous borax (Na) as a raw material2B4O7) Reduced diboron trioxide (B)2O3) The proportion of the ingredients is 4.5 wt%;
sodium fluoride (NaF) with the proportion of 7.2 wt%;
tin dioxide (SnO)2) The proportion of the ingredients is 1.5 wt%;
titanium dioxide (TiO)2) The proportion of the ingredients is 1.8 wt%;
the sulfate raw material adopts calcium sulfate (CaSO)4) The proportion of the ingredients is 0.5 wt%.
The method for preparing the high-scattering opaque hollow glass beads by using the silica slag containing sodium fluoride comprises the following production steps:
(1) adjusting the amount of sodium fluoride in the raw material complex, if the amount of sodium fluoride in the silicon slag is 7.2 wt% higher than that of the sodium fluoride required by the raw material complex, adopting a method of washing the silicon slag with water to dissolve and remove redundant sodium fluoride, collecting an aqueous solution of sodium fluoride, and concentrating and crystallizing to obtain a sodium fluoride byproduct; and if the sodium fluoride contained in the silicon slag is 7.2 wt% lower than the required sodium fluoride of the raw material complex, supplementing the deficient sodium fluoride into the silicon slag.
(2) According to the mass ratio of water to solid materials of 1: 0.6, firstly injecting water into a mixing tank, then adding all complex solid materials into the mixing tank, stirring and pulping, then sending into a ball mill for grinding, and controlling the particle size of solid materials of the slurry to be 1-3 um.
(3) And conveying the ground slurry to a spray dryer for atomization and drying to obtain fine powder with the moisture content of not more than 10%, namely a precursor for producing the hollow glass beads, wherein the particle size is 1-50 microns.
(4) And performing multi-stage airflow classification or screening on the dried precursor to obtain the precursor with the particle sizes of 1.0-20.0 um, 20.0-35.0 um and 35.0-50.0 um.
(5) And respectively feeding the precursors with three particle size ranges into a spheroidizing furnace, and carrying out instant fusion vitrification, spheroidizing and mesocavitation on powder particles to obtain the hollow glass microspheres. The temperature of the spheroidizing furnace is controlled to be 1400 +/-5 ℃.
(6) Respectively collecting hollow glass microspheres with different particle size ranges, feeding the hollow glass microspheres into a water tank for flotation, taking out powder floating on the upper part of the water tank, and feeding the powder into a dryer for drying until the moisture content is less than 3%, so as to obtain high-scattering opacified hollow glass microspheres with target particle size ranges; taking out a small amount of wet powder settled at the lower part of the water tank, sending the wet powder into the step (2), and pulping and grinding the wet powder together with new ingredients.
The high-scattering opaque hollow glass beads prepared by the method have the vitrification rate of 99.5 percent, the closed pore rate of 97 percent, the floating rate of 95 percent and the refractive index of 2.05, and respectively obtain products with three particle size ranges. Varieties with the grain diameter of 1.0-20.0 um and the true density of 0.5g/cm3The compressive strength is 57.2 MPa; the variety with the grain diameter of 20.0-35.0 um and the true density of 0.35g/cm3The compressive strength is 24.7 MPa; the variety with the grain diameter of 35.0-50.0 um and the true density of 0.22g/cm3And the compressive strength is 11.5 MPa.
Example 2
The method for preparing the high-scattering opaque hollow glass microspheres by using the silica slag containing sodium fluoride is implemented by the following ingredients:
sodium fluoride-containing silica slag-reduced Silica (SiO)2) The proportion of the ingredients is 68 wt%;
the alkaline earth metal oxide raw material adopts quicklime (CaO), and the proportion of the ingredients is 7.4 wt%;
the alkali metal oxide is sodium carbonate (Na)2CO3) Reduced sodium oxide (Na)2O), the proportion of ingredients is 5 wt%;
the aluminum oxide raw material adopts aluminum oxide (Al)2O3) The proportion of the ingredients is 2.2 wt%;
the boron trioxide adopts anhydrous borax (Na) as a raw material2B4O7) Reduced diboron trioxide (B)2O3) The proportion of the ingredients is 4.3 wt%;
sodium fluoride (NaF) with the proportion of 8.4 wt%;
tin dioxide (SnO)2) The proportion of the ingredients is 1.6 wt%;
titanium dioxide (TiO)2) The proportion of the ingredients is 2.4 wt%;
the sulfate raw material adopts calcium sulfate (CaSO)4) The proportion of the ingredients is 0.7 wt%.
The method for preparing the high-scattering opaque hollow glass beads by using the silica slag containing sodium fluoride comprises the following production steps:
(1) adjusting the amount of sodium fluoride in the raw material complex, if the amount of the sodium fluoride in the silicon slag is 8.4 wt% higher than the amount of the sodium fluoride required by the raw material complex, adopting a method of washing the silicon slag with water to remove redundant sodium fluoride by water, collecting an aqueous solution of the sodium fluoride, and concentrating and crystallizing to obtain a sodium fluoride byproduct; and if the sodium fluoride contained in the silicon slag is 8.4 wt% lower than the required sodium fluoride of the raw material complex, supplementing the deficient sodium fluoride into the silicon slag.
(2) According to the mass ratio of water to solid materials of 1: 0.7, firstly injecting water into a mixing tank, then adding all complex solid materials into the mixing tank, stirring and pulping, then sending into a ball mill for grinding, and controlling the particle size of solid materials in the slurry to be 1-3 um.
(3) And conveying the ground slurry to a spray dryer for atomization and drying to obtain fine powder with the moisture content of not more than 10%, namely a precursor for producing the hollow glass beads, wherein the particle size is 1-50 microns.
(4) And performing multi-stage airflow classification or screening on the dried precursor to obtain the precursor with the particle sizes of 1.0-20.0 um, 20.0-35.0 um and 35.0-50.0 um.
(5) And respectively feeding the precursors with three particle size ranges into a spheroidizing furnace, and carrying out instant fusion vitrification, spheroidizing and mesocavitation on powder particles to obtain the hollow glass microspheres. The temperature of the spheroidizing furnace is controlled to 1450 +/-5 ℃.
(6) Respectively collecting hollow glass microspheres with different particle size ranges, feeding the hollow glass microspheres into a water tank for flotation, taking out powder floating on the upper part of the water tank, and feeding the powder into a dryer for drying until the moisture content is less than 3%, so as to obtain high-scattering opacified hollow glass microspheres with target particle size ranges; taking out a small amount of wet powder settled at the lower part of the water tank, sending the wet powder into the step (2), and pulping and grinding the wet powder together with new ingredients.
The high-scattering opaque hollow glass beads prepared by the method have the vitrification rate of 99.2 percent, the closed pore rate of 96 percent, the floating rate of 95 percent and the refractive index of 2.17, and respectively obtain products with three particle size ranges. Varieties with the grain diameter of 1.0-20.0 um and the true density of 0.5g/cm3The compressive strength is 65.7 MPa; the variety with the grain diameter of 20.0-35.0 um and the true density of 0.35g/cm3The compressive strength is 31.6 MPa; the variety with the grain diameter of 35.0-50.0 um and the true density of 0.22g/cm3And the compressive strength is 19.2 MPa.
The above examples are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and any simple modifications and equivalent changes and modifications made to the above examples according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (2)
1. The method for preparing the high-scattering opaque hollow glass bead by using the silica slag containing sodium fluoride comprises the following chemical components:
silicon dioxide (SiO)2)65～78wt％；
5-12 wt% of alkaline earth metal oxide (RO);
alkali metal oxide (R)2O)3～8wt％；
Aluminum oxide (Al)2O3)1～4wt％；
Boron trioxide (B)2O3)2～7wt％；
6.6-15.5 wt% of sodium fluoride (NaF);
tin dioxide (SnO)2)1～5wt％；
Titanium dioxide (TiO)2)1～5wt％；
Sulfate (R)2SO4、RSO4)0.3～1.0wt％。
2. The method for preparing the high-scattering opaque hollow glass beads by using the silica slag containing sodium fluoride comprises the following preparation steps:
(1) adjusting the content of sodium fluoride in the raw material complex, if the content of the sodium fluoride in the silicon slag is 6.6-15.5 wt% higher than the required content of the sodium fluoride in the raw material complex, adopting a method of washing the silicon slag with water to remove redundant sodium fluoride by water, collecting an aqueous solution of the sodium fluoride, and concentrating and crystallizing to obtain a sodium fluoride byproduct; if the sodium fluoride contained in the silicon slag is 6.6-15.5 wt% lower than the sodium fluoride required by the raw material complex, supplementing the deficient sodium fluoride into the silicon slag;
(2) according to the mass ratio of water to solid materials of 1: 0.4-1: 1, firstly injecting water into a mixing tank, then adding all complex solid materials into the mixing tank, stirring and pulping, then feeding into a ball mill lined with zirconia-corundum and graded zirconia-corundum balls for grinding, and controlling the particle size of slurry solid matters to be 1-5 um;
(3) conveying the ground slurry to a spray dryer by a pump for atomization and drying to obtain fine powder with the moisture content of not more than 10%, namely a precursor for producing the hollow glass beads;
(4) performing multi-stage airflow classification or screening on the dried precursor to obtain precursors with multiple particle size ranges for producing hollow glass microspheres with multiple particle size ranges;
(5) the precursors with different particle size ranges are respectively sent into a spheroidizing furnace, powder particles are instantly melted into glass droplets, the surfaces of the droplets are automatically arranged into spheres under the action of hot flue gas, the spherical droplets are expanded into hollows by gas generated by particle melting, and then the hollow glass microspheres are obtained by air instant cooling. Controlling the temperature of the spheroidizing furnace kiln at 1200-1550 ℃;
(6) respectively collecting hollow glass microspheres with different particle size ranges, feeding the hollow glass microspheres into a water tank for flotation, taking out powder floating on the upper part of the water tank, and feeding the powder into a dryer for drying until the moisture content is less than 3%, so as to obtain high-scattering opacified hollow glass microspheres with target particle size ranges; taking out a small amount of wet powder settled at the lower part of the water tank, sending the wet powder into the step (2), and pulping and grinding the wet powder together with new ingredients.
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| CN110818271A (en) * | 2019-12-03 | 2020-02-21 | 陈保军 | Preparation method of high-refractive-index glass beads |
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| CN104961344A (en) * | 2015-07-01 | 2015-10-07 | 合肥鼎亮光学科技有限公司 | High-performance glass micro-bead for reflective film and preparation method thereof |
| CN106957151A (en) * | 2016-01-11 | 2017-07-18 | 沈兰 | Soda lime borosilicate hollow glass micropearl and its production method containing rare earth |
| CN110818271A (en) * | 2019-12-03 | 2020-02-21 | 陈保军 | Preparation method of high-refractive-index glass beads |
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