CN113233774B - Method for preparing microcrystalline glass by utilizing gasified slag, microcrystalline glass and application thereof - Google Patents
Method for preparing microcrystalline glass by utilizing gasified slag, microcrystalline glass and application thereof Download PDFInfo
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- CN113233774B CN113233774B CN202110534964.4A CN202110534964A CN113233774B CN 113233774 B CN113233774 B CN 113233774B CN 202110534964 A CN202110534964 A CN 202110534964A CN 113233774 B CN113233774 B CN 113233774B
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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
- C03C10/0063—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 waste materials, e.g. slags
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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
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
Abstract
The invention provides a method for preparing microcrystalline glass by utilizing gasified slag, microcrystalline glass and application thereof, wherein the method comprises the following steps: (1) screening the gasified slag to obtain low-carbon slag; (2) grinding the low-carbon slag obtained in the step (1) to obtain base glass powder; (3) carrying out compression molding on the base glass powder obtained in the step (2) to obtain a molded sample; (4) and (4) crystallizing the molded sample obtained in the step (3), and cooling to obtain the microcrystalline glass. The microcrystalline glass integrates the advantages of ceramic and glass, has low thermal expansion coefficient, high mechanical strength and excellent corrosion resistance and weathering resistance, can be widely applied to the fields of national defense, industry, civilian use and the like, and has huge development prospect. The preparation method provided by the invention has the advantages of short flow, low energy consumption and easy large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, relates to a method for preparing microcrystalline glass, and particularly relates to a method for preparing microcrystalline glass by utilizing gasified slag, microcrystalline glass and application of the microcrystalline glass.
Background
The gasified slag is formed by incomplete combustion of coal and oxygen or oxygen-enriched air to generate CO and H 2 The inorganic minerals in the coal undergo various physicochemical transformations accompanied by solid residues formed by residual carbon particles in the coal. With the large-scale popularization of the coal gasification technology, the gasification slag is produced in large quantityThe gasification slag produced in the year is more than 3300 ten thousand t. At present, the gasified slag is mainly stockpiled and buried, is not applied industrially in a large scale, causes serious environmental pollution and land resource waste, and has adverse effect on the sustainable development of coal chemical enterprises. Therefore, the treatment of the gasified slag is imminent.
The microcrystalline glass is also called glass ceramic or microcrystalline ceramic, and is a polycrystalline solid material containing a large amount of microcrystalline phases and glass phases, which is prepared by controlling crystallization of base glass with a specific composition. The microcrystalline glass integrates the advantages of ceramic and glass, has low thermal expansion coefficient, high mechanical strength and excellent corrosion resistance and weathering resistance, is widely applied to the fields of national defense, industry, civilian use and the like, and has huge development prospect.
The existing microcrystalline glass preparation method mostly takes metallurgical waste residues, thermal power plant fly ash, tailings under various working conditions or pure reagents as raw materials and adopts a melting method, a sintering method, a sol-gel method, a secondary forming process, a strengthening and toughening technology and the like for preparation.
CN108314324A discloses a method for preparing a new microcrystalline glass material by using iron tailings and steel slag as main raw materials, and various series of microcrystalline glasses can be prepared by adjusting the mixing ratio of the iron tailings and the steel slag. CN110217995A discloses a method for preparing microcrystalline glass by the cooperation of molten blast furnace slag and fly ash, which can improve the utilization rate and additional value of blast furnace slag in iron works. CN108483927A discloses a method for producing nepheline glass ceramics by using aluminum ash as a main raw material, the utilization rate can reach about 35 percent, and the environmental hazard brought by the aluminum ash is effectively solved. However, the method still has the problems of long flow and high energy consumption, and at the same time, the technology for preparing the glass ceramics by utilizing the gasified slag is not available at present.
Therefore, how to develop a method for preparing microcrystalline glass by utilizing gasification slag with short flow and low energy consumption becomes a problem which needs to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a method for preparing microcrystalline glass by utilizing gasified slag, the microcrystalline glass and application thereof, and the method has the advantages of short flow, low energy consumption and easy large-scale popularization and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing glass ceramics by using gasified slag, which comprises the following steps:
(1) screening the gasified slag to obtain low-carbon slag;
(2) grinding the low-carbon slag obtained in the step (1) to obtain base glass powder;
(3) carrying out compression molding on the base glass powder obtained in the step (2) to obtain a molded sample;
(4) and (4) crystallizing the molded sample obtained in the step (3), and cooling to obtain the microcrystalline glass.
The microcrystalline glass is prepared by taking the gasified slag as a single raw material, so that the reduction and resource utilization of the gasified slag are realized, and the environmental hazard caused by the gasified slag is effectively solved; in addition, the invention makes full use of the characteristic of high content of amorphous aluminosilicate in the gasification slag, adopts the ground low-carbon slag as the basic glass raw material for preparing the glass ceramics, omits the melting, clarifying, homogenizing and water quenching processes required by the traditional sintering method for preparing the basic glass powder, has the advantages of low energy consumption and low cost, and simultaneously avoids secondary pollution caused by the water quenching process.
Preferably, the sieving of step (1) is performed in a vibrating sieving machine.
Preferably, the carbon content of the low-carbon slag in step (1) is less than or equal to 3wt%, and may be, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3wt%, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the invention, the carbon content of the low-carbon slag in the step (1) has a significant influence on the structure and the performance of the glass ceramics. When the carbon content of the low-carbon slag is higher than 3wt%, the microcrystalline glass is difficult to mold and form, and the crystallized microcrystalline glass has poor mineral phase crystal development, large porosity and easy pulverization, so that the product has low volume density and low compressive and bending strength.
Preferably, the mesh number of the low-carbon residue in the step (1) is less than or equal to 20 meshes, for example, 2 meshes, 4 meshes, 6 meshes, 8 meshes, 10 meshes, 15 meshes or 20 meshes, but the mesh number is not limited to the listed values, and other values not listed in the numerical range are also applicable.
In the present invention, the carbon distribution/occurrence of the low carbon slag is closely related to the particle size, and specifically, the carbon content is reduced as the mesh number is reduced. Therefore, the invention controls the carbon content of the low-carbon slag by controlling the mesh number of the screen in the screening process.
Preferably, the low-carbon slag in the step (1) comprises the following components:
wherein, SiO 2 The proportion in the low-carbon slag is, for example, 30 to 50 wt%, and may be, for example, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, or 50 wt%, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Al 2 O 3 The proportion in the low-carbon slag is, for example, 10 to 20 wt%, and may be, for example, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The CaO content in the low-carbon slag is 10 to 30 wt%, and may be, for example, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, or 30 wt%, but is not limited to the recited values, and other values not recited in the above range are also applicable.
Fe 2 O 3 The proportion of the carbon-containing slag is 5 to 20 wt%, and may be, for example, 5wt%, 7.5 wt%, 10 wt%, 12.5 wt%, 15 wt%, 17.5 wt%, or 20 wt%, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the low-carbon slag in the step (1) further comprisesMgO、Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 Any one or a combination of at least two of the above, typical but not limiting combinations include MgO and Na 2 Combination of O, Na 2 O and K 2 Combination of O, K 2 O and TiO 2 Combinations of (A) and (B), TiO 2 With SO 3 In combination with (A), (B) 3 And P 2 O 5 Combination of (A), MgO, Na 2 O and K 2 Combination of O, Na 2 O、K 2 O and TiO 2 Combination of (1), K 2 O、TiO 2 With SO 3 Combinations of (A) and (B), TiO 2 、SO 3 And P 2 O 5 Combination of (A), MgO, Na 2 O、K 2 O and TiO 2 Combination of (A) and (B), Na 2 O、K 2 O、TiO 2 With SO 3 Combination of (1), K 2 O、TiO 2 、SO 3 And P 2 O 5 Combination of (1), MgO, Na 2 O、K 2 O、TiO 2 With SO 3 Combination of (A) and (B), Na 2 O、K 2 O、TiO 2 、SO 3 And P 2 O 5 Combinations of (A) or MgO, Na 2 O、K 2 O、TiO 2 、SO 3 And P 2 O 5 Combinations of (a) and (b).
Preferably, the MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 The proportion in the low-carbon slag is, independently of one another, 0 to 5 wt.%, but does not contain 0, and may be, for example, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.% or 5 wt.%, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the grinding of step (2) is carried out in a ball mill.
Preferably, the mesh size of the base glass powder in step (2) is 150 mesh or more, such as 150 mesh, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh or 500 mesh, but not limited to the listed values, and other values not listed in the range of the values are also applicable.
Preferably, the absolute pressure for the press molding in step (3) is 50 to 100MPa, and may be, for example, 50MPa, 55MPa, 60MPa, 65MPa, 70MPa, 75MPa, 80MPa, 85MPa, 90MPa, 95MPa or 100MPa, but it is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the crystallization process of step (4) is performed in a muffle furnace.
Preferably, the temperature increase rate of the crystallization treatment in step (4) is 3-5 ℃/min, and may be, for example, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min, 4 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min, or 5 ℃/min, but is not limited to the values listed, and other values not listed within the range of values are also applicable.
In the invention, the temperature rise rate of the crystallization treatment in the step (4) has a significant influence on the structure and performance of the glass ceramics. When the heating rate is lower than 3 ℃/min, the heating time is long, the energy consumption is high, and the production efficiency is low; when the temperature rise rate is higher than 5 ℃/min, the microcrystalline glass after crystallization is poor in crystal growth, large in space dislocation defect, low in volume density and prone to product deformation and cracking.
Preferably, the crystallization temperature of the crystallization treatment in step (4) is 950-.
In the invention, the crystallization temperature of the crystallization treatment in the step (4) has a significant influence on the structure and performance of the glass ceramics. When the crystallization temperature is lower than 950 ℃, the phase transformation of the microcrystalline glass is incomplete, the crystal growth is slow, the volume density of the product after crystallization treatment is low, and the bending resistance and compression strength are low; when the crystallization temperature is higher than 1100 ℃, the crystallization treatment temperature exceeds the melting point of the base glass powder, which causes the microcrystalline glass product to be softened and deformed, even collapsed.
Preferably, the crystallization time of the crystallization treatment in step (4) is 1 to 3 hours, and may be, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The invention adopts a one-step crystallization method to prepare the microcrystalline glass, and has the advantages of short flow and simple process.
As a preferred technical solution of the first aspect of the present invention, the method comprises the steps of:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of less than or equal to 3wt% and the mesh number of less than or equal to 20 meshes; the low-carbon slag comprises the following components:
the low-carbon slag also comprises MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 Any one or a combination of at least two of; and the MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 The proportion in the low-carbon slag is 0-5wt% respectively and independently, but 0 is not included;
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number not less than 150;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the absolute pressure of 50-100MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 3-5 ℃/min, the crystallization temperature is 950-.
In a second aspect, the present invention provides a glass-ceramic obtained by the method according to the first aspect.
In the invention, the microcrystalline glass is mainly composed of red aluminum diopside and secondarily composed of fayalite and calcuite, and has a bulk density of 2.78-2.86g/cm 3 Bending strength of 101-138MPa, compressive strengthThe alloy has the advantages of 508-533MPa degree, 96-128GPa elastic modulus, 5-6 Mohs hardness, 99.5% acid resistance, 99.7% alkali resistance and 0.02% water absorption, integrates the advantages of ceramics and glass, has low thermal expansion coefficient, high mechanical strength, excellent corrosion resistance and weathering resistance, can be widely applied to the fields of national defense, industry, civil use and the like, and has huge development prospect.
In a third aspect, the invention provides a use of the glass ceramics according to the second aspect in national defense, industrial and civil fields.
Compared with the prior art, the invention has the following beneficial effects:
(1) the microcrystalline glass is prepared by taking the gasified slag as a single raw material, so that the reduction and resource utilization of the gasified slag are realized, and the environmental hazard caused by the gasified slag is effectively solved;
(2) the method fully utilizes the characteristic of high content of amorphous aluminosilicate in the gasification slag, adopts the ground low-carbon slag as the raw material of the base glass for preparing the microcrystalline glass, omits the melting, clarifying, homogenizing and water quenching processes required by preparing the base glass powder by the traditional sintering method, has the advantages of low energy consumption and low cost, and avoids secondary pollution caused by the water quenching process;
(3) the invention adopts Fe in the gasified slag 2 O 3 The iron-rich phase is used as a nucleating agent and a fluxing agent for preparing the microcrystalline glass, and the iron-rich phase is formed to induce the nucleation of the basic glass, so that the grain refinement is promoted;
(4) the invention adopts a one-step crystallization method to prepare the microcrystalline glass, and has the advantages of short flow and simple process;
(5) the microcrystalline glass prepared by the invention has the main crystal phase of red aluminum diopside and the secondary crystal phases of fayalite and calcerite, and the volume density can reach 2.86g/cm at most 3 The bending strength can reach 138MPa, the compression strength can reach 533MPa, the elastic modulus can reach 128GPa, the Mohs hardness can reach 6 grades, the acid resistance can reach more than 99.5%, the alkali resistance can reach more than 99.7%, the water absorption rate is lower than 0.02%, the advantages of ceramic and glass are integrated, and the ceramic and glass composite material has the advantages of low thermal expansion coefficient, high mechanical strength, excellent corrosion resistance and weather resistanceThe method can be widely applied to the fields of national defense, industry, civilian use and the like, and has huge development prospect.
Drawings
FIG. 1 is a flow chart of a method for preparing glass ceramics by using gasified slag according to the invention;
FIG. 2 is an X-ray diffraction chart of the base glass powder obtained in example 1;
FIG. 3 is a DSC chart of the molded sample obtained in example 1 during the crystallization treatment;
FIG. 4 is an X-ray diffraction chart of a crystallized glass obtained in examples 1 to 10;
FIG. 5 is an X-ray diffraction chart of a crystallized glass obtained in examples 11 to 14.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 0.92 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number not less than 150 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 3 ℃/min, the crystallization temperature is 950 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
FIG. 2 is an X-ray diffraction chart of the base glass powder obtained in step (2) of this example, and it can be seen from FIG. 2 that: the main crystalline phase of the base glass powder is quartz, the 20-30 DEG bulge peak in the spectrogram is amorphous aluminosilicate in the base glass powder, and the part of amorphous phase is the main mineral phase of the base glass powder.
FIG. 3 is a DSC chart of the molded sample obtained in step (3) of this example during crystallization, which is shown in FIG. 3: the formed sample has an exothermic peak at 580 ℃ which is the decomposition exothermic peak of carbon in the sample, and the formed sample has three obvious exothermic peaks at 820 ℃, 880 ℃ and 1050 ℃ which are crystallization exothermic peaks.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 2
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 0.22 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 200 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 4 ℃/min, the crystallization temperature is 1000 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 3
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 0.24 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 200 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 4 ℃/min, the crystallization temperature is 1050 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 4
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) screening the gasified slag in a vibrating screen machine to obtain low-carbon slag with the carbon content of 1.66 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number not less than 250;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 5
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) screening the gasified slag in a vibrating screen machine to obtain low-carbon slag with the carbon content of 2.73 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 250 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 1h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 6
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 0.76 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number not less than 150 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 3h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 7
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 0.28 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 250 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 8
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) screening the gasified slag in a vibrating screen machine to obtain low-carbon slag with the carbon content of 2.16 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 250 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the absolute pressure of 50MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 9
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of 1.84 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 300 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the absolute pressure of 100MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 10
The embodiment provides a method for preparing microcrystalline glass by using gasified slag, which comprises the following steps as shown in figure 1:
(1) screening the gasified slag in a vibrating screen machine to obtain low-carbon slag with the carbon content of 1.58 wt% and the mesh number of less than or equal to 20 meshes; analyzing the mass percentage of each component of the obtained low-carbon slag by adopting an X-ray fluorescence spectrum, wherein the low-carbon slag comprises the following components:
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number of more than or equal to 300 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the condition that the absolute pressure is 80MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 5 ℃/min, the crystallization temperature is 1100 ℃, the crystallization time is 2h, and cooling to obtain the microcrystalline glass.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 4.
Example 11
This embodiment provides a method for preparing microcrystalline glass using gasified slag, which is the same as embodiment 1 except that the temperature increase rate in step (4) is reduced to 2 ℃/min, and therefore, the details are not repeated herein.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 5.
Example 12
This embodiment provides a method for preparing microcrystalline glass using gasified slag, which is the same as embodiment 1 except that the temperature increase rate in step (4) is increased to 6 ℃/min, and therefore, the details are not repeated herein.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 5.
Example 13
This embodiment provides a method for preparing microcrystalline glass using gasified slag, which is the same as embodiment 1 except that the crystallization temperature in step (4) is reduced to 900 ℃, and therefore, the details are not repeated herein.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 5.
Example 14
This embodiment provides a method for preparing microcrystalline glass using gasified slag, which is the same as embodiment 1 except that the crystallization temperature in step (4) is raised to 1150 ℃, and therefore, the details are not repeated herein.
In this embodiment, the X-ray diffraction pattern of the base glass powder obtained in step (2) and the DSC curve of the molded sample obtained in step (3) during crystallization are both similar to those of embodiment 1, and therefore, no further description is provided herein.
The X-ray diffraction pattern of the crystallized glass obtained in this example is shown in FIG. 5.
Comparative example 1
The comparative example provides a method for preparing microcrystalline glass by using gasification slag, which is the same as that in example 1 except that the step (1) of screening the gasification slag is removed, namely the gasification slag is directly ground to obtain base glass powder with the carbon content of 17.73 wt% and the mesh number of more than or equal to 150, and other conditions are the same as those in example 1, so that details are not repeated herein.
The base glass powder of the present comparative example cannot be press-molded in the step (3) due to excessively high carbon content, and cannot be subsequently crystallized, so that glass ceramics cannot be produced under such conditions.
Comparative example 2
The comparative example provides a method for preparing microcrystalline glass by using gasification slag, which is the same as that in example 1 except that the grinding of the low-carbon slag in the step (2) is removed, that is, the low-carbon slag is directly subjected to compression molding, and therefore, the detailed description is omitted.
The base glass powder of the present comparative example cannot prepare glass ceramics under such conditions because the low carbon slag is not ground and the particles are coarse, and thus compression molding cannot be performed during the step (3) and crystallization cannot be performed subsequently.
The physicochemical properties of the crystallized glass obtained in examples 1 to 14 are shown in Table 1.
TABLE 1
As can be seen from Table 1: examples 1 to 10 all produced bulk densities of 2.78 to 2.86g/cm 3 The microcrystalline glass has the bending strength of 101-138MPa, the compressive strength of 508-533MPa, the elastic modulus of 96-128GPa, the Mohs hardness of 5-6 grade, the acid resistance of more than or equal to 99.5 percent, the alkali resistance of more than or equal to 99.7 percent and the water absorption of less than or equal to 0.02 percent; in example 11, although the microcrystalline glass with the same performance as that of example 1 can be prepared, compared with example 1, the energy consumption is higher, and the production efficiency is reduced due to the excessively slow temperature rising rate; in examples 12 to 13, due to the excessively high temperature rise rate and the excessively low crystallization temperature, the microcrystalline glass with excellent physicochemical properties cannot be prepared, the mineral phase transformation is incomplete, and the volume density and the bending and compression strength of the product are both significantly reduced; in example 14, since the crystallization temperature was too high to exceed the melting point, the microcrystalline glass was softened and deformed, and even collapsed, and thus it was not practically used, the performance was not examined.
As can be seen from FIG. 4, the microcrystalline glasses obtained in examples 1 to 10 had a main crystal phase of red aluminum diopside and secondary crystal phases of fayalite and calcuite; as can be seen from FIG. 5, the microcrystalline glasses obtained in examples 11-14 have a main crystal phase of red aluminum diopside and secondary crystal phases of fayalite and calcium iron garnet, and although the crystal phase of example 11 develops well, the temperature rise rate is slow, the energy consumption is high, and the peak intensities of the corresponding crystal phases of examples 12-13 are low, and the crystal phase conversion is incomplete; in example 14, the crystal phase developed well, but the corresponding glass ceramics softened and deformed, and thus it was not practically used.
Therefore, the invention adopts the gasified slag as the single raw material to prepare the glass ceramics, realizes the reduction and resource utilization of the gasified slag, and effectively solves the environmental hazard brought by the gasified slag(ii) a The method fully utilizes the characteristic of high content of amorphous aluminosilicate in the gasification slag, adopts the ground low-carbon slag as the raw material of the base glass for preparing the microcrystalline glass, omits the melting, clarifying, homogenizing and water quenching processes required by preparing the base glass powder by the traditional sintering method, has the advantages of low energy consumption and low cost, and avoids secondary pollution caused by the water quenching process; the invention adopts Fe in the gasified slag 2 O 3 The iron-rich phase is used as a nucleating agent and a fluxing agent for preparing the microcrystalline glass, and the iron-rich phase is formed to induce the nucleation of the basic glass, so that the grain refinement is promoted; the invention adopts a one-step crystallization method to prepare the microcrystalline glass, and has the advantages of short flow and simple process; the microcrystalline glass prepared by the invention has the main crystal phase of red aluminum diopside and the secondary crystal phases of fayalite and calcerite, and the volume density can reach 2.86g/cm at most 3 The bending strength can reach 138MPa, the compression strength can reach 533MPa, the elastic modulus can reach 128GPa, the Mohs hardness can reach 6 grades, the acid resistance can reach more than 99.5%, the alkali resistance can reach more than 99.7%, and the water absorption rate is lower than 0.02%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The method for preparing the microcrystalline glass by using the gasified slag is characterized by comprising the following steps of:
(1) sieving the gasified slag to obtain low-carbon slag with the carbon content of less than or equal to 3wt% and the mesh number of less than or equal to 20 meshes;
(2) grinding the low-carbon slag obtained in the step (1) to obtain base glass powder;
(3) carrying out compression molding on the base glass powder obtained in the step (2) to obtain a molded sample;
(4) crystallizing the molded sample obtained in the step (3), wherein the heating rate is 3-5 ℃/min, the crystallization temperature is 950-;
the main crystalline phase of the microcrystalline glass is red aluminum diopside, and the secondary crystalline phase of the microcrystalline glass is fayalite and calcium iron garnet;
the method omits the melting, clarifying, homogenizing and water quenching processes required by the traditional sintering method for preparing the base glass powder.
2. The method of claim 1, wherein said screening of step (1) is performed in a shaker.
3. The method according to claim 1, wherein the low-carbon slag of step (1) comprises the following components:
SiO 2 30-50wt%
Al 2 O 3 10-20wt%
CaO 10-30wt%
Fe 2 O 3 5-20wt%。
4. the method according to claim 1, wherein the low-carbon slag of step (1) further comprises MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 Any one or a combination of at least two of them.
5. The method according to claim 4, wherein the MgO, Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 The ratio in the low carbon slag is 0 to 5wt% independently, but 0 is not included.
6. The method of claim 1, wherein said grinding of step (2) is performed in a ball mill.
7. The method according to claim 1, wherein the mesh size of the base glass powder in the step (2) is 150 meshes or more.
8. The method according to claim 1, wherein the absolute pressure for the compression molding in step (3) is 50 to 100 MPa.
9. The method according to claim 1, wherein the crystallization of step (4) is performed in a muffle furnace.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) sieving the gasified slag in a vibrating sieving machine to obtain low-carbon slag with the carbon content of less than or equal to 3wt% and the mesh number of less than or equal to 20 meshes; the low-carbon slag comprises the following components:
SiO 2 30-50wt%
Al 2 O 3 10-20wt%
CaO 10-30wt%
Fe 2 O 3 5-20wt%；
the low-carbon slag also comprises MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 Any one or a combination of at least two of; and the MgO and Na 2 O、K 2 O、TiO 2 、SO 3 Or P 2 O 5 The proportion in the low-carbon slag is 0-5wt% respectively and independently, but 0 is not included;
(2) grinding the low-carbon slag obtained in the step (1) in a ball mill to obtain base glass powder with the mesh number not less than 150 meshes;
(3) carrying out compression molding on the base glass powder obtained in the step (2) under the absolute pressure of 50-100MPa to obtain a molded sample;
(4) and (4) carrying out crystallization treatment on the molded sample obtained in the step (3) in a muffle furnace, wherein the heating rate is 3-5 ℃/min, the crystallization temperature is 950-.
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