CN107417123B - Method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings - Google Patents

Method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings Download PDF

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CN107417123B
CN107417123B CN201710631368.1A CN201710631368A CN107417123B CN 107417123 B CN107417123 B CN 107417123B CN 201710631368 A CN201710631368 A CN 201710631368A CN 107417123 B CN107417123 B CN 107417123B
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stainless steel
steel slag
fluorite
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tailings
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CN107417123A (en
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国宏伟
陈剑啸
李洪玮
闫炳基
李鹏
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Suzhou University
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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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass

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Abstract

The invention discloses a method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings. The preparation raw materials of the method comprise: fluorite tailings and stainless steel slag; the preparation method comprises the following steps: (1) preparing raw materials: grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder; (2) uniformly mixing the ingredients: preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing; (3) high-temperature melting: melting the uniformly mixed mixture of the fine stainless steel slag powder and the fine fluorite tailing powder in a resistance furnace to obtain a high-temperature melt; (4) casting into blocks: pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling along with a furnace to obtain mother glass; (5) and (3) heat treatment: and (4) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain the microcrystalline glass. The invention greatly reduces the energy consumption in production and use, and finally obtains the microcrystalline glass with high crystallinity and good performance.

Description

Method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings
Technical Field
The invention relates to the field of metallurgy and inorganic non-metallic materials, in particular to a method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings.
Background
Stainless steel slag is a byproduct of stainless steel production, according to statistical data of the institute of special steel enterprises in China, the production amount of stainless steel in 2016 in China reaches 250 x 105t, and is estimated according to that 1t of stainless steel slag can be produced every 3t of stainless steel produced, and the production amount of stainless steel slag in China reaches about 83 x 105 t. The stainless steel slag contains chromium oxide and other heavy metals, and a simple stacking and disposal mode not only occupies a large amount of land resources, but also causes heavy metal pollution to the land. At present, in order to solve the problems, stainless steel slag is used for preparing cement, ceramics, bricks and the like in China, but the defects of environmental risk of leaching heavy metals and low product value still exist. Therefore, it is necessary to develop a technology for solidifying heavy metals from stainless steel slag and utilizing the heavy metals to a high value.
The fluorite tailings are the products after the fluorite ore is mined, namely, the ores with low calcium fluoride content. The tailings take a large amount of land, so that the tailings not only block traffic but also influence the life of residents, and can break a dam and pollute water sources and the environment after flowing into rivers after being washed by rainwater. Therefore, the treatment of dangerous waste fluorite tailings is urgent.
Most of fluorite tailings are silicate components, the main components of the stainless steel slag are silicate, aluminate and calcium magnesium oxide, and the silicate, the aluminate and the calcium magnesium oxide are good raw materials for preparing the microcrystalline glass. Meanwhile, calcium fluoride in fluorite tailings can reduce the melting temperature in the melting process in the preparation of the microcrystalline glass, and chromium in the stainless steel slag is an effective nucleating agent for preparing the microcrystalline glass. Therefore, the research on preparing the microcrystalline glass by using the stainless steel slag and the fluorite tailings has important significance for improving economic benefits, solving the problem of dangerous solid waste treatment and realizing circular economy.
In a published Chinese patent (application number: 201410345583.1, published: 2011, 10 and 12), a rolling process method for producing a microcrystalline glass plate by utilizing fluorite tailings is provided. The raw materials comprise fluorite tailings, modifiers (potassium feldspar, albite, calcite, clay, sodium nitrate and the like), clarifiers (white arsenic, antimony oxide, sodium nitrate, ammonium nitrate and cerium dioxide), colorants (one or more of Cr2O3, Cu2O, CoO, NiO, Fe2O3 and rare earth element oxides). The method mainly comprises the following steps: (1) batching, (2) melting, (3) clarifying and cooling, (4) pressing and forming, (5) carrying out heat treatment to obtain microcrystalline glass, and (6) cutting and polishing.
A microcrystalline glass and a preparation method thereof are disclosed in a published Chinese patent (application number: 201110119884.9, published: 10/1/2014). One or more of stainless steel dedusting ash, quartz sand, fly ash and waste glass are adopted, the stainless steel slag is adjusted to be in the range suitable for preparing the microcrystalline glass, and the microcrystalline glass comprises the following components in percentage by weight: 45-60% of SiO2, 20-28% of CaO, 10-15% of MgO, 2-9% of Al2O3, 0-8% of Na2O, 0.5-5% of Fe2O3, 0.4-2.5% of Cr2O3, 0.5-1.5% of F and 0.1-6% of TiO 2.
The above-mentioned patent discloses that fluorite tailings can be used for preparing microcrystalline glass, but the nucleation effect is poor, the obtained microcrystalline glass has low crystalline phase content, a crystal nucleus agent needs to be added to promote crystallization, and the melting temperature of microcrystalline glass prepared by using stainless steel slag in a large proportion is high, so that the invention of a method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings is necessary to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings.
In order to achieve the purpose, the invention designs a method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings,
the preparation raw materials comprise: fluorite tailings and stainless steel slag, wherein the fluorite tailings account for 60-80% of the total mass of the preparation raw materials, and the stainless steel slag accounts for 20-40% of the total mass of the preparation raw materials; the stainless steel slag comprises the following components in percentage by mass: SiO22：20-30%，CaO：30-40%，MgO：30-40%，Al2O3：5-10%，FeO：1-10%，MnO2：0-3%，Cr2O3：2-10%，K2O：0-3%，Na2O：0-1%，CaF2: 0-10%, other ingredients: 0 to 4 percent; the used fluorite tailings comprise the following components in percentage by mass of the total mass of the fluorite tailings: SiO22：70-85％，CaO：1-8％，MgO：0-7％，Al2O3：3-20％，FeO：1-5％，CaF2：0-10％，MnO2：0-3%，K2O: 0-3%, other ingredients: 0 to 4 percent;
the preparation method comprises the following steps:
(1) preparing raw materials: grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder;
(2) uniformly mixing the ingredients: preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing;
(3) high-temperature melting: melting the uniformly mixed mixture of the fine stainless steel slag powder and the fine fluorite tailing powder in a resistance furnace to obtain a high-temperature melt;
(4) casting into blocks: pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling along with a furnace to obtain mother glass;
(5) and (3) heat treatment: and (4) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain the microcrystalline glass.
Preferably: the particle size ranges of the stainless steel slag fine powder and the fluorite tailing fine powder in the step (1) are 100-200 meshes.
Preferably: in the step (3), the temperature rise rate of the resistance furnace is 10 ℃/min when the furnace temperature is below 1000 ℃, and the temperature rise rate is 5 ℃/min when the furnace temperature is above 1000 ℃.
Preferably: the melting temperature in the step (3) is 1400-1500 ℃, and the heat preservation time is 1-4 h.
Preferably: the preheating temperature of the steel plate in the step (4) is 500-600 ℃.
Preferably: the heat treatment system in the step (5) is as follows: and (4) putting the mother glass obtained in the step (4) into a heating furnace, heating the mother glass from room temperature to the temperature of 700-750 ℃, preserving the heat for 0.5-1h for nucleation, continuing heating to the temperature of 850-950 ℃, preserving the heat for 1-2h for crystallization, and then cooling along with the furnace.
Preferably: the microcrystalline glass obtained in the step (5) has pyroxene as a main crystal phase.
According to the invention, the microcrystalline glass is prepared by taking the fluorite tailings and the stainless steel slag as raw materials through a melting method, on one hand, the fluorite tailings and the stainless steel slag are subjected to harmless treatment and the resources are effectively utilized, heavy metals in the stainless steel slag can be solidified in a glass structure to obtain a practical microcrystalline glass product, on the other hand, calcium fluoride in the fluorite tailings can reduce the melting temperature of the raw materials, so that the production cost is reduced, chromium in the stainless steel slag can promote crystallization of the microcrystalline glass, the crystallization capacity is enhanced, and the microcrystalline glass product with better physical and chemical properties is obtained.
Drawings
FIG. 1 is a process flow diagram for preparing glass ceramics by using stainless steel slag and fluorite tailings.
Detailed description of the invention
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
the method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings provided by the embodiment comprises the following raw materials: fluorite tailings and stainless steel slag, wherein the fluorite tailings account for 60 percent of the total raw materials by mass, and the stainless steel slag accounts for 40 percent of the total raw materials by mass; the stainless steel slag comprises the following components in percentage by mass: SiO22：22.46%，CaO：34.87%，MgO：25.11%，Al2O3：6.46%，FeO：2.51%，MnO2：1.13%，Cr2O3：4.12%，K2O：0.14%，Na2O：0.08%，CaF2: 1.35 percent, and the content of other components is 1.77 percent; the percentage of each component of the fluorite tailings in the total mass of the fluorite tailings is as follows: SiO22：80.89％，CaO：4.94％，MgO：0.05％，Al2O3：5.82％，FeO：1.21％，MnO2：0.05%，K2O：2.49%，CaF2: 2.88 percent and the content of other components is 1.67 percent.
The method for preparing the microcrystalline glass by using the stainless steel slag and the fluorite tailings comprises the following steps:
(1) grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder, and screening the fine stainless steel slag powder and the fluorite tailings powder by a 100-mesh screen for later use;
(2) preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing, wherein the addition amount of the fluorite tailing fine powder is 75wt%, and the addition amount of the stainless steel slag fine powder is 25 wt%;
(3) melting the uniformly mixed mixture of the stainless steel slag fine powder and the fluorite tailing fine powder in a resistance furnace to obtain a high-temperature melt, wherein the melting temperature is 1400 ℃, the melting time is 2 hours, the heating rate of the resistance furnace is 10 ℃/min when the temperature of the resistance furnace is below 1000 ℃, and the heating rate is 5 ℃/min when the temperature of the resistance furnace is above 1000 ℃;
(4) pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling the high-temperature melt along with a furnace to obtain mother glass, wherein the preheating temperature of the steel plate is 600 ℃, and the furnace cooling temperature is 600 ℃;
(5) and (4) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain the microcrystalline glass, wherein the heat treatment process comprises the following steps: and (4) putting the mother glass obtained in the step (4) into a heating furnace, heating the mother glass from room temperature to 700 ℃, preserving heat for 0.5 to nucleate, continuing heating the mother glass to 850 ℃, preserving heat for 1 hour to crystallize, and then cooling the mother glass along with the furnace.
(6) And cutting and polishing.
As a result: the obtained microcrystalline glass product has pyroxene as the main crystalline phase, good crystallization degree, density of 260Kg/m and high breaking strength of 66.7MPa and water absorption rate of less than or equal to 0.5%.
Example two:
the method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings provided by the embodiment comprises the following raw materials: fluorite tailings and stainless steel slag, wherein the fluorite tailings account for 70 percent by mass of the total raw materials, and the stainless steel slag accounts for 30 percent by mass of the total raw materials; the stainless steel slag comprises the following components in percentage by mass: SiO22：20.46%，CaO：32.87%，MgO：26.11%，Al2O3：7.46%，FeO：3.51%，MnO2：2.13%，Cr2O3：4.12%，K2O：0.14%，Na2O：0.08%，CaF2: 1.35%, other ingredients: 1.77 percent; the used fluorite tailings comprise the following components in percentage by mass of the total mass of the fluorite tailings: SiO22：78.89％，CaO：5.94％，MgO：1.05％，Al2O3：5.82％，FeO：1.21％，MnO2：0.05%，K2O：2.49%，CaF2: 2.88%, other ingredients: 1.67 percent.
The method for preparing the microcrystalline glass by using the stainless steel slag and the fluorite tailings comprises the following steps:
(1) grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder, and screening the fine stainless steel slag powder and the fluorite tailings powder by a 100-mesh screen for later use;
(2) preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing, wherein the adding amount of fluorite tailing is 70wt%, and the adding amount of stainless steel slag is 30wt%
(3) Melting the uniformly mixed mixture of the stainless steel slag fine powder and the fluorite tailing fine powder in a resistance furnace to obtain a high-temperature melt, wherein the melting temperature is 1430 ℃, the melting time is 2 hours, the heating speed of the resistance furnace is 10 ℃/min when the furnace temperature is below 1000 ℃, and the heating speed is 5 ℃/min when the furnace temperature is above 1000 ℃;
(4) pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling the high-temperature melt along with a furnace to obtain mother glass, wherein the preheating temperature of the steel plate is 600 ℃, and the furnace cooling temperature is 600 ℃;
(5) and (4) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain the microcrystalline glass, wherein the heat treatment process comprises the following steps: and (4) putting the mother glass obtained in the step (4) into a heating furnace, heating the mother glass from room temperature to 730 ℃, preserving heat for 1h for nucleation, continuing heating the mother glass to 900 ℃, preserving heat for 1.5h for crystallization, and then cooling the mother glass along with the furnace.
(6) Performing cutting and polishing
As a result: the obtained microcrystalline glass product has pyroxene as main crystalline phase and higher crystallization degree than that of the first embodiment, wherein the density is 268Kg/m, the breaking strength is 70.1MPa, and the water absorption is less than or equal to 0.5 percent.
Example three:
the method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings provided by the embodiment comprises the following raw materials: fluorite tailings and stainless steel slag, wherein the fluorite tailings account for 80 percent of the total raw materials by mass, and the stainless steel slag accounts for 20 percent of the total raw materials by mass; the stainless steel slag comprises the following components in percentage by mass: SiO22：24.46%，CaO：32.87%，MgO：23.11%，Al2O3：7.46%，FeO：3.51%，MnO2：1.13%，Cr2O3：3.12%，K2O：0.14%，Na2O：0.08%，CaF2: 1.35%, other ingredients: 2.77 percent; the used fluorite tailings comprise the following components in percentage by mass of the total mass of the fluorite tailings: SiO22：80.89％，CaO：4.44％，MgO：0.1％，Al2O3：4.82％，FeO：2.21％，MnO2：0.1%，K2O：2.44%，CaF2：2.88％And other components: 1.67 percent.
The method for preparing the microcrystalline glass by using the stainless steel slag and the fluorite tailings comprises the following steps:
(1) grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder, and screening the fine stainless steel slag powder and the fluorite tailings powder by a 100-mesh screen for later use;
(2) preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing, wherein the addition amount of the fluorite tailing is 65wt%, and the addition amount of the stainless steel slag is 35 wt%;
(3) melting the uniformly mixed mixture of the stainless steel slag fine powder and the fluorite tailing fine powder in a resistance furnace to obtain a high-temperature melt, wherein the melting temperature is 1450 ℃, the melting time is 2 hours, the heating speed of the resistance furnace is 10 ℃/min when the furnace temperature is below 1000 ℃, and the heating speed is 5 ℃/min when the furnace temperature is above 1000 ℃;
(4) pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling the high-temperature melt along with a furnace to obtain mother glass, wherein the preheating temperature of the steel plate is 600 ℃, and the furnace cooling temperature is 600 ℃;
(5) and (4) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain the microcrystalline glass, wherein the heat treatment process comprises the steps of putting the mother glass obtained in the step (4) into a heating furnace, heating the mother glass to 750 ℃ from room temperature, preserving heat for 1h for nucleation, continuously heating to 950 ℃, preserving heat for 2h for crystallization, and then cooling along with the furnace. .
(6) And cutting and polishing.
As a result: the obtained microcrystalline glass product has pyroxene as main crystalline phase and higher crystallization degree than that of the second embodiment, wherein the density is 280Kg/m, the breaking strength is 73.2MPa, and the water absorption is less than or equal to 0.5 percent.
Comparative example one:
the method for preparing the microcrystalline glass by using the stainless steel slag and the pure reagent, which is provided by the comparative example, comprises the following raw materials: stainless steel slag and pure reagent; concrete composition of pure reagent CaF removal from Fluorite tailings of example III2Other components and their proportions. The stainless steel slag comprises the following components in percentage by mass: SiO22：24.46%，CaO：32.87%，MgO：23.11%，Al2O3：7.46%，FeO：3.51%，MnO2：1.13%，Cr2O3：3.12%，K2O：0.14%，Na2O：0.08%，CaF2: 1.35%, other ingredients: 2.77 percent. The method for preparing the microcrystalline glass by using the stainless steel slag and the pure reagent comprises the following steps:
(1) grinding and crushing the stainless steel slag to obtain fine stainless steel slag powder, and sieving the fine stainless steel slag powder by a 100-mesh sieve for later use;
(2) preparing stainless steel slag and a pure reagent according to a certain mass ratio, and uniformly mixing; wherein the addition amount of the stainless steel slag is 35 percent of the total mass;
(3) melting the uniformly mixed raw materials in a resistance furnace to obtain a high-temperature melt, wherein the melting temperature is 1550 ℃, the melting time is 2 hours, the heating speed of the resistance furnace is 10 ℃/min when the temperature of the resistance furnace is below 1000 ℃, and is 5 ℃/min when the temperature of the resistance furnace is above 1000 ℃;
(4) pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling the high-temperature melt along with a furnace to obtain mother glass, wherein the preheating temperature of the steel plate is 600 ℃, and the furnace cooling temperature is 600 ℃;
(5) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain microcrystalline glass, wherein the nucleation temperature is 750 ℃, and the nucleation time is 0.5 h; the crystallization temperature is 950 ℃, and the crystallization time is 1 h.
(6) And cutting and polishing.
As a result: the obtained microcrystalline glass product has pyroxene as main crystal phase, melting temperature higher than that of fluorine-containing examples I, II and III, and grain size higher than that of examples I, II and III, wherein density is 280Kg/m for carrying out heavy cultivation, flexural strength is 60.2MPa, and water absorption is less than or equal to 0.5%.
Comparative example two:
according to the method for preparing the microcrystalline glass by using the fluorite tailings and the pure reagents, the preparation raw materials comprise: fluorite tailings and pure reagents; the specific components of the pure reagent are prepared according to the components except the chromium oxide in the stainless steel slag of the third embodiment and the proportion thereof. The components of the fluorite tailingsThe percentage of the fluorite tailings in total mass is as follows: SiO22：80.89％，CaO：4.44％，MgO：0.1％，Al2O3：4.82％，FeO：2.21％，MnO2：0.1%，K2O：2.44%，CaF2: 2.88%, other ingredients: 1.67 percent.
The method for preparing the microcrystalline glass by using the fluorite tailings and the pure reagent specifically comprises the following steps:
(1) grinding and crushing fluorite tailings to obtain fluorite tailing fine powder, and screening the fluorite tailing fine powder by using a 100-mesh screen for later use;
(2) preparing fluorite tailings and pure reagents according to a certain mass ratio, and uniformly mixing; wherein the addition amount of the fluorite tailings accounts for 65 percent of the total mass;
(3) melting the uniformly mixed raw materials in a resistance furnace to obtain a high-temperature melt, wherein the melting temperature is 1410 ℃, the melting time is 2 hours, the heating rate of the resistance furnace is 10 ℃/min when the temperature of the resistance furnace is below 1000 ℃, and the heating rate is 5 ℃/min when the temperature of the resistance furnace is above 1000 ℃;
(4) pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling the high-temperature melt along with a furnace to obtain mother glass, wherein the preheating temperature of the steel plate is 600 ℃, and the furnace cooling temperature is 600 ℃;
(5) carrying out heat treatment on the mother glass block obtained in the step (4) to obtain microcrystalline glass, wherein the nucleation temperature is 700 ℃, and the nucleation time is 0.5 h; the crystallization temperature is 930 ℃, and the crystallization time is 1 h.
(6) And cutting and polishing.
As a result: the obtained product has no volume crystallization and only has surface crystallization.
The embodiment and the test result show that the fluorite tailings and the stainless steel slag are used as raw materials for preparing the microcrystalline glass, so that the lower melting temperature can be obtained, and meanwhile, chromium in the stainless steel slag enables the microcrystalline glass of the system to have good crystallization capacity, so that the nucleation temperature and the crystallization temperature are reduced, the energy consumption in production and use is greatly reduced, and the microcrystalline glass with high crystallinity and good performance is finally obtained.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (4)

1. A method for preparing microcrystalline glass by using stainless steel slag and fluorite tailings is characterized by comprising the following steps: the preparation raw materials comprise: fluorite tailings and stainless steel slag, wherein the fluorite tailings account for 60-80% of the total mass of the preparation raw materials, and the stainless steel slag accounts for 20-40% of the total mass of the preparation raw materials; the stainless steel slag comprises the following components in percentage by mass: SiO22：20-30%，CaO：30-40%，MgO：30-40%，Al2O3：5-10%，FeO：1-10%，MnO2：0-3%，Cr2O3：2-10%，K2O：0-3%，Na2O：0-1%，CaF2: 0-10%, other ingredients: 0 to 4 percent; the used fluorite tailings comprise the following components in percentage by mass of the total mass of the fluorite tailings: SiO22：70-85％，CaO：1-8％，MgO：0-7％，Al2O3：3-20％，FeO：1-5％，CaF2：0-10％，MnO2：0-3%，K2O: 0-3%, other ingredients: 0 to 4 percent; the preparation method comprises the following steps:
(1) preparing raw materials: grinding and crushing the stainless steel slag and the fluorite tailings to obtain fine stainless steel slag powder and fine fluorite tailings powder;
(2) uniformly mixing the ingredients: preparing stainless steel slag fine powder and fluorite tailing fine powder according to a certain mass ratio, and uniformly mixing;
(3) high-temperature melting: melting the uniformly mixed mixture of the fine stainless steel slag powder and the fine fluorite tailing powder in a resistance furnace to obtain a high-temperature melt; wherein the melting temperature is 1400-1500 ℃, the melting time is 2h, the heating speed of the resistance furnace is 10 ℃/min when the furnace temperature is below 1000 ℃, and is 5 ℃/min when the furnace temperature is above 1000 ℃;
(4) casting into blocks: pouring the high-temperature melt obtained in the step (3) onto a preheated steel plate, and cooling along with a furnace to obtain mother glass;
(5) and (3) heat treatment: and (3) carrying out heat treatment on the mother glass block obtained in the step (4), putting the mother glass obtained in the step (4) into a heating furnace, heating the mother glass to the temperature of 700-750 ℃, preserving the heat for 0.5-1h for nucleation, continuously heating the mother glass to the temperature of 850-950 ℃, preserving the heat for 1-2h for crystallization, and then cooling the mother glass along with the furnace to obtain the microcrystalline glass.
2. The method for preparing glass-ceramic by using stainless steel slag and fluorite tailings as claimed in claim 1, wherein the particle size of the stainless steel slag fine powder and the fluorite tailings fine powder in the step (1) is in the range of 100-200 meshes.
3. The method for preparing glass-ceramic by using stainless steel slag and fluorite tailings as claimed in claim 1, wherein the preheating temperature of the steel plate in the step (4) is 500-600 ℃.
4. The method for preparing the microcrystalline glass by using the stainless steel slag and the fluorite tailings as claimed in claim 1, wherein the microcrystalline glass obtained in the step (5) has a pyroxene-based main crystal phase.
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