CN112408802A - Method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass - Google Patents
Method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass Download PDFInfo
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- CN112408802A CN112408802A CN202011356357.5A CN202011356357A CN112408802A CN 112408802 A CN112408802 A CN 112408802A CN 202011356357 A CN202011356357 A CN 202011356357A CN 112408802 A CN112408802 A CN 112408802A
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- 239000011521 glass Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 44
- 239000011707 mineral Substances 0.000 claims abstract description 44
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 31
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 31
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 29
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000748 compression moulding Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052863 mullite Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010309 melting process Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000013081 microcrystal Substances 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 229910004762 CaSiO Inorganic materials 0.000 description 6
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 6
- 229910052637 diopside Inorganic materials 0.000 description 6
- 229910052656 albite Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052661 anorthite Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 229910020472 SiO7 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052907 leucite Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013080 microcrystalline material Substances 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical group [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass, belonging to the field of treatment and high-valued utilization of dangerous solid waste resources. The method of the invention comprises the following steps: vacuum melting is carried out on the mixture of CRT cone glass and minerals, lead oxide is removed, and residues are obtained; the mineral is red mud or kaolin; carrying out compression molding on the residue to obtain a blank; and sintering the blank at normal pressure to obtain the microcrystalline glass. The method for preparing the glass ceramics by using the CRT cone glass realizes the treatment of wastes with processes of wastes against one another and simultaneously realizes the reutilization of residual silicate in the vacuum melting process.
Description
Technical Field
The invention relates to the field of disposal and high-value utilization of dangerous solid waste resources, in particular to a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass.
Background
In recent years, glass display screens for CRTs (cathode ray tubes) containing lead have reached a peak of being discarded due to rapid development of electronic technology. It is statistical that over 2500 million CRT television products are scrapped each year, and the amount of CRT cone glass scrapped in the whole asia range will increase to around 1500 tons by 2020. The CRT cone glass mainly contains a large amount of silicon dioxide, lead oxide and other resources, wherein the silicon dioxide is about 50 wt%, and the lead oxide belongs to toxic substances and is about 20 wt%. The waste lead-containing CRT cone glass always belongs to dangerous electronic waste, wherein the recovery of lead resources and the high-value reuse of silicate are always problems to be solved urgently.
At present, the treatment method for recovering lead resources from waste CRT cone glass mainly adopts a pyrogenic process, and Chinese patent application No. 201910588641.6 discloses a method for removing lead from red mud reinforced CRT cone glass in vacuum, wherein the lead removal effect can reach more than 99%, but the residual silicate in the vacuum melting process is not researched for reutilization.
Disclosure of Invention
The invention aims to provide a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass, which realizes the treatment of wastes with processes of wastes against one another and realizes the reutilization of residual silicate in the vacuum melting process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass, which comprises the following steps of:
vacuum melting is carried out on the mixture of CRT cone glass and minerals, lead oxide is removed, and residues are obtained; the mineral is red mud or kaolin;
carrying out compression molding on the residue to obtain a blank;
and sintering the blank at normal pressure to obtain the microcrystalline glass.
Preferably, when the mineral is red mud, the mass ratio of the CRT cone glass to the mineral is (8:2) - (3: 7);
when the mineral is kaolin, the mass ratio of the CRT cone glass to the mineral is (5-0.5): 1.
Preferably, the pressure for press molding is 500MPa or more.
Preferably, the vacuum melting conditions include: the smelting temperature is 1000-1500 ℃, the pressure in the furnace is 1-100 Pa, and the heat preservation time is 0.5-4 h.
Preferably, when the mineral is red mud, the normal pressure sintering conditions include: heating the blank to 600-700 ℃, preserving heat for 1-3 h, and continuing heating to 850-950 ℃ after heat preservation is finished, and preserving heat for 0.5-4 h;
when the mineral is kaolin, the normal pressure sintering conditions comprise: and heating the blank to 800-1100 ℃, and preserving heat for 1-4 h.
Preferably, when the mineral is red mud or kaolin, the heating rate in the normal pressure sintering process is 5-20 ℃/min;
preferably, the atmospheric pressure sintering is performed in an air atmosphere.
Preferably, when the mineral is red mud, the obtained microcrystalline glass is CAS microcrystalline glass;
when the mineral is kaolin, the obtained microcrystalline glass is mullite microcrystalline glass.
Preferably, before compression molding, the method further comprises crushing the residue and grinding the crushed residue into powder of 200-400 meshes.
Preferably, the CRT cone glass contains 40-60 wt% of silicon dioxide and 15-30 wt% of lead oxide.
The invention provides a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass, which comprises the following steps of: vacuum melting is carried out on the mixture of CRT cone glass and minerals, lead oxide is removed, and residues are obtained; the mineral is red mud or kaolin; carrying out compression molding on the residue to obtain a blank; and sintering the blank at normal pressure to obtain the microcrystalline glass.
According to the invention, the mixture of CRT cone glass and red mud or the mixture of CRT cone glass and kaolin is subjected to vacuum melting, when the mineral is red mud, calcium ions in the red mud substitute lead ions in a-Pb-O-Si-O-network structure through migration in the melting process and release free lead oxide, and the lead oxide is volatilized in the vacuum melting process and recovered; when the mineral is kaolin, Al ions in the kaolin substitute lead and form a network structure with a silicon-oxygen tetrahedron in the smelting process, and lead oxide is volatilized and recovered; removing lead oxide after vacuum melting, and removing residual leadThe substance (mainly silicate) can be sintered under normal pressure to prepare CAS (CaO-Al)2O3-SiO2) Is a microcrystalline glass of mullite or mullite type.
The method prepares the microcrystalline material by cooperatively treating the waste CRT cone glass through the red mud or the kaolin, thereby realizing the resource utilization and high-value utilization of solid wastes.
The invention provides a solution for treating wastes with wastes by using the red mud, the kaolin and the waste CRT cone glass, and realizes the resource utilization of residual materials after vacuum melting of the mixture of the CRT cone glass and the red mud (or the kaolin).
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing glass ceramics by using CRT cone glass;
FIG. 2 is an SEM photograph of the product obtained in comparative example 1;
FIG. 3 is an SEM photograph of a crystallized glass obtained in example 1;
FIG. 4 is an SEM photograph of a crystallized glass obtained in example 2;
FIG. 5 is an SEM photograph of a crystallized glass obtained in example 3;
FIG. 6 is an SEM photograph of a crystallized glass obtained in example 4;
FIG. 7 is an SEM photograph of a crystallized glass obtained in example 5;
FIG. 8 is an XRD photograph of CAS series glass ceramics obtained by CRT cone glass and red mud at different mass ratios;
FIG. 9 is an SEM photograph of a mullite-based microcrystalline glass obtained in example 6;
FIG. 10 is an SEM photograph of a mullite-based microcrystalline glass obtained in example 7;
fig. 11 is an XRD photograph of the mullite-based microcrystalline glass obtained in example 6 and example 7.
Detailed Description
The invention provides a method for preparing microcrystalline glass by using CRT (cathode ray tube) cone glass, which comprises the following steps of:
vacuum melting is carried out on the mixture of CRT cone glass and minerals, lead oxide is removed, and residues are obtained; the mineral is red mud or kaolin;
carrying out compression molding on the residue to obtain a blank;
and sintering the blank at normal pressure to obtain the microcrystalline glass.
The invention carries out vacuum melting on the mixture of CRT cone glass and minerals, removes lead oxide and obtains residues.
The source of the CRT cone glass is not particularly required by the invention, and the CRT cone glass with the source well known in the field can be used. In the invention, the content of silicon dioxide in the CRT cone glass is preferably 40-60 wt.%, the content of lead oxide is preferably 15-30 wt.%, and the balance is potassium oxide, sodium oxide and trace amounts of calcium oxide, iron oxide and magnesium oxide. In the embodiment of the invention, the content of silicon dioxide in the CRT cone glass is 50.01 wt.%, and the content of lead oxide in the CRT cone glass is 19.05 wt.%. In the invention, the mineral is red mud or kaolin.
In the present invention, the particle size of the CRT cone glass and the minerals is preferably less than 100 mesh.
In the present invention, when the mineral is red mud, the mass ratio of the CRT cone glass to the mineral is preferably (8:2) to (3:7), and more preferably 7: 3.
In the invention, when the mineral is kaolin, the mass ratio of the CRT cone glass to the mineral is preferably (5-0.5): 1, and more preferably (2-0.5): 1.
The invention preferably mixes CRT cone glass and mineral directly to get the mixture of them.
In the present invention, the vacuum melting conditions preferably include: the smelting temperature is 1000-1500 ℃, the pressure in the furnace is 1-100 Pa, and the heat preservation time is 0.5-4 h. Further, the smelting temperature is preferably 1200-1400 ℃, and more preferably 1300 ℃; the heat preservation time is preferably 1-3 h, and more preferably 2 h; the pressure in the furnace is preferably 5 to 50Pa, and more preferably 10 Pa.
When the mineral is red mud, calcium ions in the red mud substitute lead ions in a-Pb-O-Si-O-network structure through migration and release free lead oxide in the smelting process, and the lead oxide is volatilized in the vacuum smelting process and is recovered; when the mineral is kaolin, Al ions in the kaolin substitute lead and form a network structure with a silicon-oxygen tetrahedron in the smelting process, and lead oxide is volatilized and recovered; lead oxide is removed after vacuum melting, and the main component of the residual residues is silicate.
After obtaining the residue, the invention carries out compression molding on the residue to obtain the blank.
The residues are preferably crushed, ground into powder of 200-400 meshes and then subjected to compression molding.
In the present invention, the pressure for the press molding is preferably 500MPa or more. The invention uses compression molding to perform the blank, and ensures that the glass block is obtained after normal pressure sintering.
After the blank is obtained, the blank is sintered under normal pressure to obtain the microcrystalline glass.
In the present invention, the atmospheric pressure sintering is preferably performed in an air atmosphere.
When the mineral is red mud, the conditions for the atmospheric sintering preferably include: heating the blank to 600-700 ℃, preserving heat for 1-3 h, and continuing heating to 850-950 ℃ after heat preservation is finished, and preserving heat for 0.5-4 h; further preferably: and heating the blank to 600-700 ℃, preserving heat for 1h, and continuing heating to 900 ℃ after heat preservation is finished, and preserving heat for 2-4 h. In the invention, the heating rate is preferably 5-20 ℃/min, and more preferably 10 ℃/min. After the sintering under normal pressure, the CAS series glass ceramics are preferably obtained by furnace cooling to room temperature.
When the mineral is kaolin, the conditions for the atmospheric sintering preferably include: heating the blank to 800-1100 ℃, and preserving heat for 1-4 h; further preferably: and heating the blank to 800-1000 ℃, and preserving heat for 2-3 h. In the invention, the heating rate is preferably 5-20 ℃/min, and more preferably 10 ℃/min. After the normal pressure sintering, the mullite microcrystalline glass is preferably obtained by furnace cooling to room temperature.
FIG. 1 is a process flow chart of the present invention for preparing glass ceramics by using CRT cone glass. As shown in figure 1, the invention carries out vacuum melting on the mixture of CRT cone glass and minerals to remove lead oxide and obtain residues; the mineral is red mud or kaolin; carrying out compression molding on the residue to obtain a blank; and sintering the blank at normal pressure to obtain the microcrystalline glass.
The following will explain the method for producing a glass-ceramic by using CRT cone glass according to the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
The CRT cone glasses used in the following examples and comparative examples had a silica content of 50.01 wt.% and a lead oxide content of 19.05 wt.%.
Example 1
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Red Mud (RM) in a mass ratio of 8:2 at a high temperature of 1300 ℃ in vacuum (the melting temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; heating the blank to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, continuing heating to 900 ℃ after heat preservation is finished, preserving heat for 2h, and naturally cooling the furnace body to room temperature after heat preservation is finished to obtain CAS (CaO-Al) with needle-shaped microcrystals of 100nm to 10 mu m2O3-SiO2) Is a microcrystalline glass, and has microcrystalline particles of 100nm to 10 μm and a microcrystalline phase mainly composed of wollastonite (CaSiO), as shown in FIG. 3 and FIG. 8 (b)3) Albite (NaAlSi)3O8) And orthoclase (KAlSi)3O8) And the crystallinity of the microcrystalline product is 19.11%.
Example 2
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Red Mud (RM) is 7: 3.
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Red Mud (RM) in a mass ratio of 7:3 at a high temperature of 1300 ℃ in vacuum (the melting temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; heating the blank to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and continuing heating to the temperature of the blank after heat preservation is finished900 ℃ and preserving heat for 2h, naturally cooling the furnace body to room temperature after the heat preservation is finished, and obtaining the CAS (CaO-Al) with needle-shaped microcrystal of 200nm to 20 mu m2O3-SiO2) Is a microcrystalline glass, and has microcrystalline particles of 200nm to 20 μm and a microcrystalline phase mainly composed of wollastonite (CaSiO), as shown in FIGS. 4 and 8 (c)3) Diopside (NaAlSi)3O8) And albite (NaAlSi)3O8) Etc., and the crystallinity of the microcrystalline product is 30.98%.
Example 3
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Red Mud (RM) is 6: 4.
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Red Mud (RM) in a mass ratio of 6:4 at a high temperature of 1300 ℃ in vacuum (the melting temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; heating the blank to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, continuing heating to 900 ℃ after heat preservation is finished, preserving heat for 2h, and naturally cooling the furnace body to room temperature after heat preservation is finished to obtain CAS (CaO-Al) with 300nm to 30 mu m needle-shaped microcrystal2O3-SiO2) The microcrystalline glass has microcrystalline particles of 300 nm-30 μm, and microcrystalline phase mainly composed of diopside (NaAlSi) as shown in FIG. 5 and FIG. 8 (d)3O8) Calpatite (CaSiO)3) And albite (NaAlSi)3O8) Etc., and the crystallinity of the microcrystalline product was 41.09%.
Example 4
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Red Mud (RM) is 5: 5.
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Red Mud (RM) in a mass ratio of 6:4 at a high temperature of 1300 ℃ in vacuum (the melting temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; the blank is first heated up at a heating rate of 10 ℃/minHeating to 700 deg.C and maintaining for 1h, continuing to raise to 900 deg.C and maintaining for 2h, naturally cooling to room temperature to obtain CAS (CaO-Al) with needle-like microcrystal of 400 nm-40 μm2O3-SiO2) The microcrystalline glass has microcrystalline particles of 400 nm-40 μm, and microcrystalline phase mainly composed of diopside (NaAlSi) as shown in FIG. 6 and FIG. 8 (e)3O8)、CaAl2Si2O8Albite (NaAlSi)3O8) And calpatite (CaSiO)3) And the like, and the crystallinity of the microcrystalline product is 53.09%.
Example 5
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Red Mud (RM) is 4: 6.
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Red Mud (RM) in a mass ratio of 6:4 at a high temperature of 1300 ℃ in vacuum (the melting temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; heating the blank to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, continuing heating to 900 ℃ after heat preservation is finished, preserving heat for 2h, and naturally cooling the furnace body to room temperature after heat preservation is finished to obtain CAS (CaO-Al) with needle-shaped microcrystals of 500nm to 50 mu m2O3-SiO2) The microcrystalline glass has microcrystalline particles of 500 nm-50 μm, and microcrystalline phase mainly composed of diopside (NaAlSi) as shown in FIG. 7 and FIG. 8 (f)3O8) Calpatite (CaSiO)3)、CaAl2Si2O8 and albite (NaAlSi)3O8) Etc., and the crystallinity of the microcrystalline product was 74.71%.
Comparative example 1
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Red Mud (RM) is 10: 0.
SEM pictures of the products prepared in examples 1-5 and comparative example 1 are shown in figures 2-7, and XRD patterns are shown in figure 8. As can be seen from fig. 2 to 8, when FG: RM is 10:0, i.e., no red mud is added, the sintered product is completely in an amorphous-glassy state, and the product is not microcrystalline glass; when in useFG: RM values of 8:2, 7:3, 6:4, 5:5 or 4:6, calcipatite (CaSiO) appeared in the product3) And diopside (Ca)2Al2SiO7) CAS (CaO-Al) as a predominant phase, acicular microcrystals with a particle size of 50nm to 50 μm2O3-SiO2) Is a microcrystalline glass, and the crystallinity of the prepared microcrystalline glass product gradually increases as the FG: RM value decreases.
Example 6
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Kaolin (KL) at a mass ratio of 2:1 at high temperature in vacuum (the melting temperature is 1300 ℃, the temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and performing compression molding (the pressure is 500MPa) to obtain a blank; and heating the blank to 800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2 hours, and naturally cooling the furnace body to room temperature after the heat preservation is finished to obtain the spheroidal mullite microcrystalline glass with the particle size of 30nm to 10 mu m. As shown in FIG. 9 and FIG. 11(a), the microcrystalline particles of the product are 30nm to 10 μm, and the microcrystalline phase is mainly mullite (Al)6Si2O13)。
Example 7
The difference from example 1 is that the mass ratio of CRT cone glass (FG) to Kaolin (KL) is 1: 1.
Removing lead oxide in the cone glass by melting the mixture of CRT cone glass (FG) and Kaolin (KL) at a mass ratio of 1:1 at high temperature in vacuum (the melting temperature is 1300 ℃, the temperature is kept for 2h, and the pressure in the furnace is 10 Pa); crushing and grinding the residue after lead removal into powder of 200-400 meshes, and carrying out compression molding (the pressure is 500MPa) to obtain a blank; heating the blank to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, naturally cooling the furnace body to room temperature after the heat preservation is finished, and obtaining the mullite microcrystalline glass with 30nm to 30 mu m chain-shaped microcrystals, wherein as shown in figures 10 and 11(b), the microcrystalline particles of the product are 30nm to 30 mu m, and the microcrystalline phase is mainly mullite (Al)6Si2O13) Diopside (KAlSi)3O8) Leucite (KAl (SiO)3)2) And CaAl2Si2O8。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing microcrystalline glass by using CRT cone glass comprises the following steps:
vacuum melting is carried out on the mixture of CRT cone glass and minerals, lead oxide is removed, and residues are obtained; the mineral is red mud or kaolin;
carrying out compression molding on the residue to obtain a blank;
and sintering the blank at normal pressure to obtain the microcrystalline glass.
2. The method according to claim 1, wherein when the mineral is red mud, the mass ratio of the CRT cone glass to the mineral is (8:2) - (3: 7);
when the mineral is kaolin, the mass ratio of the CRT cone glass to the mineral is (5-0.5): 1.
3. The method according to claim 1, wherein the pressure for the press molding is 500MPa or more.
4. The method of claim 1, wherein the conditions of the vacuum melting comprise: the smelting temperature is 1000-1500 ℃, the pressure in the furnace is 1-100 Pa, and the heat preservation time is 0.5-4 h.
5. The method according to claim 1, wherein when the mineral is red mud, the atmospheric sintering conditions comprise: heating the blank to 600-700 ℃, preserving heat for 1-3 h, and continuing heating to 850-950 ℃ after heat preservation is finished, and preserving heat for 0.5-4 h;
when the mineral is kaolin, the normal pressure sintering conditions comprise: and heating the blank to 800-1100 ℃, and preserving heat for 1-4 h.
6. The method according to claim 5, wherein when the mineral is red mud or kaolin, the temperature rise rate in the normal pressure sintering process is 5-20 ℃/min.
7. The method of claim 1, 5 or 6, wherein the atmospheric sintering is performed in an air atmosphere.
8. The method according to claim 1, wherein when the mineral is red mud, the obtained glass ceramics is CAS-series glass ceramics;
when the mineral is kaolin, the obtained microcrystalline glass is mullite microcrystalline glass.
9. The method according to claim 1, further comprising crushing the residue and grinding the crushed residue into 200-400 mesh powder before the compression molding.
10. The method of claim 1, wherein the CRT cone glass contains 40 to 60 wt.% silica and 15 to 30 wt.% lead oxide.
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| CN110316957A (en) * | 2019-07-02 | 2019-10-11 | 昆明理工大学 | A kind of method of red mud collaboration cone glass removing lead oxide |
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| US20160122232A1 (en) * | 2014-11-03 | 2016-05-05 | Nazim Muhammad | Ceramic frits incorporating crt glass |
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