CN117185663B - Method for preparing microcrystalline glass from pyroxene tailings - Google Patents
Method for preparing microcrystalline glass from pyroxene tailings Download PDFInfo
- Publication number
- CN117185663B CN117185663B CN202311262929.7A CN202311262929A CN117185663B CN 117185663 B CN117185663 B CN 117185663B CN 202311262929 A CN202311262929 A CN 202311262929A CN 117185663 B CN117185663 B CN 117185663B
- Authority
- CN
- China
- Prior art keywords
- parts
- glass
- tailings
- heating
- pyroxene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 54
- 229910052611 pyroxene Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 6
- 239000010459 dolomite Substances 0.000 claims abstract description 6
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 6
- 239000000156 glass melt Substances 0.000 claims abstract description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 6
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052582 BN Inorganic materials 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 11
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002223 garnet Substances 0.000 claims description 11
- 229910052642 spodumene Inorganic materials 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005401 pressed glass Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910017976 MgO 4 Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000218228 Humulus Species 0.000 description 1
- 241000208672 Lobelia Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- -1 calcium magnesium aluminum Chemical compound 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a method for preparing microcrystalline glass from pyroxene tailings, which belongs to the field of microcrystalline glass preparation, and comprises the steps of weighing raw materials of 50-60 parts of pyroxene tailings, 5-7 parts of rutile, 20-30 parts of quartz, 20-30 parts of dolomite, 1-2 parts of antimony oxide and 2-3 parts of sodium nitrate, uniformly mixing, heating to 1480-1550 ℃, and preserving heat for 60-180 minutes to prepare a glass melt; carrying out water quenching and grinding on the glass melt to obtain glass powder; adding 3% -5% of liquid binder into glass powder, uniformly stirring, pressing and forming under the pressure of 20-40 MPa, placing the pressed and formed glass plate into a special fixture, heating to 300-350 ℃ at 10 ℃/min, and preserving heat for 30min; pressurizing to 10-20 mpa, continuously heating to 600-650 ℃ at 10 ℃/min, and preserving heat for 1-2 h; and (3) maintaining the pressure, heating to 850-900 ℃ at 5-8 ℃/min, crystallizing for 1-2 h, cooling the sample along with a furnace after crystallization, removing the pressure when the temperature is reduced to below 600 ℃, and taking out the sample after recovering the normal temperature to obtain the microcrystalline glass. The problem that the durite tailings are accumulated in a large quantity and the utilization rate is not high is solved; the microcrystalline glass prepared by the method is compact in structure and has high bending strength.
Description
Technical Field
The invention belongs to the field of preparation of microcrystalline glass, solves the technical problems of large accumulation of tailings and low utilization rate after garnet and spodumene are separated from pyroxene, and provides a preparation method of microcrystalline glass with compact structure and high bending strength.
Background
The spodumene is metamorphic rock formed in high-pressure environment, and is the rock with the largest specific gravity in metamorphic rock. It is generally formed by the deterioration of basic and super basic rock under the condition of extremely high pressure, but the temperature condition is not limited, and the formation can be realized in the range from low temperature to high temperature. The main mineral components are light red garnet and green spodumene, and the main mineral components are a medium-coarse grain unequal grain crystal-changing structure and a block-shaped structure, and have deep color.
Glass ceramics are composite materials with uniformly distributed microcrystals and glass phases, and are also called ceramic glass, which are glass with special components and high requirements for chemical composition and melting, and are heat treated at a certain temperature. It has many precious properties such as low expansion coefficient, high mechanical strength, good chemical stability and thermal stability, high use temperature, hardness and wear resistance. Because the glass composition can be adjusted in a large range, the precipitated crystal phase is fine and uniformly distributed, and therefore, the microcrystalline glass material has a plurality of superior properties which cannot be replaced by other materials. The glass ceramics can be used as the exterior wall of the building and the indoor high-grade decoration, and can be used as the insulating material of the mechanical structure, such as the electronic and electrical engineering, the base plate material of the large-scale integrated circuit, the heat-resistant vessel of the microwave oven, the chemical and anti-corrosion material, the mine wear-resistant material and the like, and the application is very wide.
In combination with the description of the prior art, the pyroxene is usually lenticular or a small rock mass is produced in the gneiss, after the pyroxene is beneficiated to separate useful minerals, the tailings components are mainly calcium magnesium aluminum silicate, and the mineral components contain basic components such as Al2O3, siO2, caO, mgO and the like required for preparing microcrystalline glass, so that the pyroxene tailings are utilized to prepare the microcrystalline glass, thereby not only realizing the full utilization of resources, but also solving the problems of environmental and economic cost caused by the stockpiling of the tailings.
Disclosure of Invention
The preparation method of the microcrystalline glass comprises the following raw materials of 50-60 parts of pyroxene tailings, 5-7 parts of rutile, 20-30 parts of quartz, 20-30 parts of dolomite, 1-2 parts of antimony oxide and 2-3 parts of sodium nitrate. The garnet tailings are tailings obtained by separating garnet, spodumene and rutile from the durite tailings, and comprise the main components of 42% -50% of SiO2, 10% -14% of Al2O3, 10% -13% of TFe, 4% -6% of MgO, 6% -10% of CaO, 1% -5% of Na2O, 0% -2% of K2O, 2 1% -3% of TiO and 0% -0.5% of P2O5
The preparation method of the microcrystalline glass comprises the following steps:
firstly, weighing raw materials according to the weight portion ratio, drying and grinding to below 0.074mm respectively.
And step two, uniformly mixing all the raw materials in the step one, heating to 1480-1550 ℃, and preserving heat for 60-180 min to obtain the glass melt.
And thirdly, pouring the glass melt obtained in the second step into cold water at 20 ℃ for water quenching, taking out and drying glass particles, grinding and sieving by a ball mill, and obtaining glass powder with the granularity smaller than 0.074 mm.
And step four, adding 3% -5% of liquid binder, uniformly stirring, and then pressing and forming under the pressure of 20-40 MPa.
Placing the pressed glass plate in a boron nitride clamp, placing the boron nitride clamp in an induction hot press furnace, vacuumizing, introducing N2, heating to 300-350 ℃ at 10 ℃/min, and preserving heat for 30min; pressurizing to 10-20 mpa, continuously heating to 600-650 ℃ at 10 ℃/min, and preserving heat for 1-2 h; and (3) maintaining the pressure, heating to 850-900 ℃ at 5-8 ℃/min, crystallizing for 1-2 h, cooling the sample along with a furnace after crystallization, removing the pressure when the temperature is reduced to below 600 ℃, and taking out the sample after recovering the normal temperature to obtain the microcrystalline glass.
The fixture is made of boron nitride, tungsten strips distributed at equal intervals are embedded in the upper and lower parts contacted with the sample, and the width of the tungsten strips is 1-2 cm, and the interval is 2-5 cm. The tungsten bar in the graphite mould of the induction furnace is induced to generate high temperature, and the tungsten bar is overlapped with the thermal field of the graphite mould to lead the temperature of the surface of the sample to be unevenly distributed, thereby promoting the directional growth of the crystallized glass on the surface of the glass ceramics after the crystallization, and improving the bending strength of the product.
In the sintering and crystallization processes of the glass ceramics, pressure of 20-30 MPa is applied in the vertical direction, the structure densification of the glass ceramics is promoted, and the deformation of the glass ceramics caused by an uneven thermal field is avoided.
The technical contribution advantage of this application for prior art is:
1. is different from the raw materials of the microcrystalline glass in the prior art: in general, as a raw material for producing glass ceramics, there are many common chemical raw materials, minerals and the like, and there are also used tailings (iron tailings, gold tailings, molybdenum tailings and the like), metallurgical slag (blast furnace slag, open hearth furnace slag) and ash slag (fly ash and the like) and the like as a raw material for glass ceramics. The utility model adopts the pyroxene tailing as the main raw materials, can also realize high value recycle when having solved the tailing and stacked the problem, and more specifically, after the present conventional mineral processing technique that this application adopted selected out garnet, pyroxene, the proportion of components such as SiO2, al2O3 in the tailing not only satisfied the proportion requirement of microcrystalline glass goods, can also remain the original mineral structure relation of pyroxene to a certain extent for other tailings such as iron, gold, molybdenum can have higher compressive strength and hardness under lower fusing temperature, thereby promote microcrystalline glass material performance.
2. Unlike the binders of the prior art (polyvinyl alcohol, carboxymethyl cellulose, water glass, etc.), the binders employed in this application have good compatibility with glass and can be decomposed and converted into TiO2 and B2O3 at relatively low temperatures. TiO2 generated by the decomposition of n-butyl titanate is an important crystal nucleus agent of microcrystalline glass, and B2O3 generated by the decomposition of tributyl borate can reduce the sintering temperature of the glass. The binder adopted by the application can promote the rapid formation of the sintering-crystallization behavior of the glass ceramics at a relatively low temperature through functional conversion.
3. Different from the sintering crystallization process in the prior art, the application of pressure in the heating and heat preservation stages can avoid deformation in the binder decomposition, sintering, crystallization and other stages, and improve the compactness of the glass ceramics. On the other hand, tungsten bars which are arranged at intervals are embedded in the specially-made boron nitride clamp, the periodically and regularly arranged tungsten bars generate heat in an induction furnace in an induction way, an uneven thermal field is provided, and directional growth of microcrystalline glass crystal nuclei is promoted, so that improvement of mechanical properties in the design direction is realized.
Drawings
FIG. 1 is a cross-sectional view of a boron nitride-tungsten clamp according to the present invention.
FIG. 2 is a schematic view of a boron nitride-tungsten fixture according to the present invention; a represents a tungsten bar width of 1cm, and B represents a boron nitride clamp width of 2cm.
FIG. 3 is a schematic diagram showing the distribution structure of tungsten strips of the boron nitride-tungsten clamp in the invention; a represents a tungsten bar width of 1cm, and B represents a boron nitride clamp width of 2cm.
Wherein 1 is a boron nitride clamp, 2 is microcrystalline glass, and 3 is a tungsten bar.
Detailed Description
Example 1, garnet tailings after garnet and spodumene are separated from Humulus lobelia in Jiangsu Donghai, the main components are 45.95% of SiO2, 13.09% of Al2O3, 12.50% of TFe, 5.66% of MgO, 7.54% of CaO, 2.45% of Na2O, 0.72% of K2O, 1.71% of TiO2 and 0.082% of P
50 parts of pyroxene tailings, 7 parts of rutile, 30 parts of quartz, 30 parts of dolomite, 2 parts of antimony oxide and 3 parts of sodium nitrate are weighed. Drying at 105deg.C, and grinding and sieving to below 0.074mm with a vibration mill. And (3) uniformly mixing the raw materials, placing the mixture into a crucible, heating to 1480 ℃ by adopting a resistance furnace at 10 ℃/min, and preserving heat for 60min to obtain glass in a molten state. And rapidly pouring the molten glass into cold water at 20 ℃ for water quenching to obtain glass particles. And (3) drying the glass particles, and grinding and sieving the dried glass particles by using a ceramic ball mill to obtain glass powder with the granularity smaller than 0.074 mm. Uniformly stirring glass powder and 5 parts of binder (the volume ratio of n-butyl titanate to tributyl borate is 4:1), placing into a mould, and pressing into a plate shape by a press under the pressure of 40 MPa. Placing the formed glass between an upper clamp and a lower clamp of boron nitride, placing the glass into a graphite crucible of an induction hot pressing furnace, vacuumizing, introducing N2 to micro positive pressure, heating to 350 ℃ at 10 ℃/min, and preserving heat for 30min; pressurizing to 20Mpa, continuously heating to 650 ℃ at 10 ℃/min, and preserving heat for 1h; and (3) maintaining the pressure, heating to 900 ℃ at 8 ℃/min, crystallizing for 1h, cooling the sample along with a furnace after crystallization, removing the pressure when the temperature is reduced to below 600 ℃, and taking out the sample after recovering the normal temperature to obtain the microcrystalline glass. Flexural strength 76MPa and compressive strength 192MPa.
Example 2, garnet tailings after garnet and spodumene are separated from the spodumene in the eastern China, wherein the main components of the garnet tailings are 42.57% of SiO2, 13.54% of Al2O3, 13.19% of TFe, 5.97% of MgO, 9.74% of CaO, 2.09% of Na2O, 0.15% of K2O, 3.38% of TiO2 and 0.12% of P205.
60 parts of pyroxene tailings, 5 parts of rutile, 20 parts of quartz, 20 parts of dolomite, 1 part of antimony oxide and 2 parts of sodium nitrate are weighed. Drying at 105deg.C, and grinding and sieving to below 0.074mm with a vibration mill. And (3) uniformly mixing the raw materials, placing the mixture into a crucible, heating to 1550 ℃ by adopting a resistance furnace at 10 ℃/min, and preserving heat for 180min to obtain glass in a molten state. And rapidly pouring the molten glass into cold water at 20 ℃ for water quenching to obtain glass particles. And (3) drying the glass particles, and grinding and sieving the dried glass particles by using a ceramic ball mill to obtain glass powder with the granularity smaller than 0.074 mm. Uniformly stirring glass powder and 3 parts of binder (the volume ratio of n-butyl titanate to tributyl borate is 2:1), placing into a mould, and pressing into a plate shape by a press under the pressure of 20 MPa. Placing the formed glass between an upper clamp and a lower clamp of boron nitride, placing the glass into a graphite crucible of an induction hot pressing furnace, vacuumizing, introducing N2 to micro positive pressure, heating to 300 ℃ at 10 ℃/min, and preserving heat for 30min; pressurizing to 10Mpa, continuously heating to 600 ℃ at 10 ℃/min, and preserving heat for 2h; and (3) maintaining the pressure, heating to 850 ℃ at 8 ℃/min, crystallizing for 2 hours, cooling the sample along with a furnace after crystallization, removing the pressure when the temperature is reduced to below 600 ℃, and taking out the sample after recovering the normal temperature to obtain the microcrystalline glass. The flexural strength was measured at 72MPa and the compressive strength at 177MPa.
In comparative example 1, iron tailings are adopted as main raw materials, and the main chemical components are SiO2 47.36%, al2O3 8.70%, TFe 9.88%, mgO 12.16% and CaO 15.17%. 50 parts of iron tailings, 7 parts of rutile, 30 parts of quartz, 20 parts of dolomite, 2 parts of antimony oxide and 3 parts of sodium nitrate are weighed. After obtaining glass ceramics by the same method as in example 1, the flexural strength was measured at 64MPa and the compressive strength was measured at 168MPa.
Comparative example 2 using the same raw materials and preparation method as in example 2, 3 parts of polyvinyl alcohol as a binder gave a glass ceramic, and after that, a flexural strength of 69MPa and a compressive strength of 154MPa were measured.
Comparative example 3, using the same raw materials and preparation method as in example 1, the sintering and crystallization process is as follows, the glass powder is pressed into a plate and then put into a common resistance furnace, and the temperature is raised to 350 ℃ at 10 ℃/min and is kept for 30min; continuously heating to 650 ℃ at 10 ℃/min, and preserving heat for 1h; and (3) heating to 900 ℃ at 8 ℃/min for crystallization for 1h, cooling the sample along with a furnace after crystallization, and taking out the sample after recovering the normal temperature to obtain the microcrystalline glass. Flexural strength 58MPa and compressive strength 172MPa.
Claims (6)
1. The glass ceramic prepared from the pyroxene tailings is characterized by being prepared from the pyroxene tailings serving as a main raw material in parts by weight: 50-60 parts of pyroxene tailings, 5-7 parts of rutile, 20-30 parts of quartz, 20-30 parts of dolomite, 1-2 parts of antimony oxide and 2-3 parts of sodium nitrate; the durite tailings are tailings obtained by separating garnet, spodumene and rutile from durite, and mainly comprise SiO 2 42%~50%，Al 2 O 3 10%~14%，TFe 10%~13%，MgO 4%~6%，CaO 6%~10%，Na 2 O 1%~5%，K 2 O 0~2%，TiO 2 1%~3%，P 2 O 5 0~0.5%。
2. The method for preparing glass ceramics from the spodumene tailings according to claim 1, comprising the following steps:
firstly, weighing raw materials according to the weight parts of the raw materials, drying and respectively grinding to below 0.074 mm;
step two, uniformly mixing all the raw materials in the step one, heating to 1480-1550 ℃, and preserving heat for 60-180 min to obtain a glass melt;
pouring the glass melt obtained in the step two into cold water at 20 ℃ for water quenching, taking out and drying glass particles, grinding and sieving by a ball mill to obtain glass powder with the granularity smaller than 0.074 mm;
adding 3% -5% of liquid binder, uniformly stirring, and then compacting and forming under the pressure of 20-40 MPa;
fifthly, placing the pressed glass plate into a boron nitride clamp (1), placing into an induction hot pressing furnace, vacuumizing, and introducing N 2 And (3) crystallizing, cooling the crystallized sample along with a furnace, removing pressure when the temperature is reduced to below 600 ℃, and taking out the sample after recovering the normal temperature to obtain the glass ceramics (2).
3. The preparation method of glass ceramics from durite tailings according to claim 2, wherein the liquid binder in the fourth step is a mixture of n-butyl titanate and tributyl borate in a volume ratio of 2-4:1.
4. The method for preparing glass ceramics from the dumene tailings according to claim 2, wherein the equipment adopted in the fifth step is an induction hot press furnace, the heating mode is medium frequency induction heating, a working area is positioned in a graphite mold, and nitrogen is filled for test protection.
5. The method for preparing glass ceramics from the spodumene tailings according to claim 2, wherein the five-purpose clamp is made of boron nitride, the upper part and the lower part are respectively embedded with tungsten strips (3) which are distributed at equal intervals and are in contact with the sample, and the width of each tungsten strip (3) is 1-2 cm, and the interval is 2-5 cm.
6. The method for preparing glass ceramics from the spodumene tailings according to claim 2, wherein the sintering crystallization conditions in the fifth step are as follows: pumping the induction hot-pressing furnace to vacuum and then introducing N 2 Heating to 300-350 ℃ at 10 ℃/min, and preserving heat for 30min, pressurizing by 10-20 mpa, continuously heating to 600-650 ℃ at 10 ℃/min, preserving heat for 1-2 h, keeping the pressure, heating to 850-900 ℃ at 5-8 ℃/min, crystallizing for 1-2 h, cooling the sample along with the furnace, and discharging the pressure when the temperature is reduced to below 600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311262929.7A CN117185663B (en) | 2023-09-27 | 2023-09-27 | Method for preparing microcrystalline glass from pyroxene tailings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311262929.7A CN117185663B (en) | 2023-09-27 | 2023-09-27 | Method for preparing microcrystalline glass from pyroxene tailings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117185663A CN117185663A (en) | 2023-12-08 |
| CN117185663B true CN117185663B (en) | 2024-03-08 |
Family
ID=88994199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311262929.7A Active CN117185663B (en) | 2023-09-27 | 2023-09-27 | Method for preparing microcrystalline glass from pyroxene tailings |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117185663B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2237016A (en) * | 1989-09-07 | 1991-04-24 | Dennis Roy Prosser | Glass-ceramic material and production thereof |
| CN1613806A (en) * | 2004-11-24 | 2005-05-11 | 沈阳建筑大学 | Microcrystallizing glass for construction and produced from metal flume and its production |
| CN106316134A (en) * | 2016-08-24 | 2017-01-11 | 中国地质大学（武汉） | Diopside and feldspar main crystal phase microcrystalline glass and preparing method thereof |
| CN110818266A (en) * | 2019-11-26 | 2020-02-21 | 西南科技大学 | Preparation method of basalt microcrystalline glass |
| CN113277737A (en) * | 2021-05-27 | 2021-08-20 | 凯盛石墨碳材料有限公司 | Method for preparing microcrystalline glass from graphite tailings |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7704907B2 (en) * | 2005-08-25 | 2010-04-27 | Ceramext, Llc | Synthesized hybrid rock composition, method, and article formed by the method |
-
2023
- 2023-09-27 CN CN202311262929.7A patent/CN117185663B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2237016A (en) * | 1989-09-07 | 1991-04-24 | Dennis Roy Prosser | Glass-ceramic material and production thereof |
| CN1613806A (en) * | 2004-11-24 | 2005-05-11 | 沈阳建筑大学 | Microcrystallizing glass for construction and produced from metal flume and its production |
| CN106316134A (en) * | 2016-08-24 | 2017-01-11 | 中国地质大学（武汉） | Diopside and feldspar main crystal phase microcrystalline glass and preparing method thereof |
| CN110818266A (en) * | 2019-11-26 | 2020-02-21 | 西南科技大学 | Preparation method of basalt microcrystalline glass |
| CN113277737A (en) * | 2021-05-27 | 2021-08-20 | 凯盛石墨碳材料有限公司 | Method for preparing microcrystalline glass from graphite tailings |
Non-Patent Citations (1)
| Title |
|---|
| 鲁东榴辉岩矿地质特征及开发利用;李光明等;中国非金属矿工业导刊;20041231(第第6期期);56-57 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117185663A (en) | 2023-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6508546B2 (en) | Pyroxene ceramics and method for manufacturing the same | |
| CN101555143B (en) | Preparation method of normal pressure-sintered silicon carbide ceramics | |
| CN104496438B (en) | A kind of quartz sand ore mine tailing or silica sand ore deposit mine tailing base high-strength ceramic plate and preparation method thereof | |
| CN103395996A (en) | Preparation method of low melting point aluminum-boron-silicon glass ceramic bond for CBN (Cubic Boron Nitride) grinding tool | |
| CN103030415A (en) | High-performance forsterite refractory raw material and preparation method thereof | |
| CN103011870B (en) | Forsterite refractory and production method thereof | |
| CN101381240A (en) | Method for preparing dichroite heat proof/refractory materials | |
| CN101921130A (en) | Corundum-mullite crucible | |
| CN113321487B (en) | Lithium-free heat-resistant domestic ceramic and preparation method thereof | |
| CN110683851A (en) | Environment-friendly acid furnace lining dry type vibration material | |
| CN107089835A (en) | Carbon calciner andalusite mullite composite brick and preparation method thereof | |
| CN102219530B (en) | Silicon mullite brick and preparation method thereof | |
| CN113213887A (en) | Ceramic vessel with high thermal shock resistance and preparation method thereof | |
| CN113061021A (en) | High thermal shock brick for top combustion type hot blast stove and preparation method thereof | |
| CN101767984B (en) | Fused silica ceramic material containing holmium oxide and preparation method thereof | |
| CN117185663B (en) | Method for preparing microcrystalline glass from pyroxene tailings | |
| CN111548171B (en) | Silica refractory mortar with excellent high-temperature performance | |
| CN106830690B (en) | A kind of silicon nitride/aluminium nitride of self-reinforcing toughening/lanthanum barium Aluminous Silicate Glass-Ceramics trielement composite material and preparation method thereof | |
| CN104072160B (en) | Ultralow pore mullite brick | |
| CN101851107A (en) | Compact zircon brick with low alkali content, hole fusion rate and stress and manufacturing method thereof | |
| CN113213905B (en) | Cordierite-based microcrystalline glass combined Al 2 O 3 -SiO 2 System ceramic material and preparation method thereof | |
| CN107935556B (en) | Preparation method of nano ceramic binder | |
| CN102432305A (en) | Zirconium-corundum composite fireproof ball and preparation method thereof | |
| CN113526946B (en) | High-toughness modified silicon corundum brick | |
| CN109231961B (en) | Deformation-resistant rapid-fired fine pottery blank and preparation and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |