CN115893846A - Production method of photovoltaic silicon slag microcrystalline thin plate - Google Patents
Production method of photovoltaic silicon slag microcrystalline thin plate Download PDFInfo
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- CN115893846A CN115893846A CN202211428684.6A CN202211428684A CN115893846A CN 115893846 A CN115893846 A CN 115893846A CN 202211428684 A CN202211428684 A CN 202211428684A CN 115893846 A CN115893846 A CN 115893846A
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- calcium
- silicon slag
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- photovoltaic silicon
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 239000002893 slag Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 56
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011575 calcium Substances 0.000 claims abstract description 49
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000008395 clarifying agent Substances 0.000 claims abstract description 11
- 238000005352 clarification Methods 0.000 claims abstract description 5
- 238000000265 homogenisation Methods 0.000 claims abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000010436 fluorite Substances 0.000 claims description 5
- 239000013081 microcrystal Substances 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000004579 marble Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000003490 calendering Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000002210 silicon-based material Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000005034 decoration Methods 0.000 abstract description 3
- 239000002969 artificial stone Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004575 stone Substances 0.000 abstract 2
- 239000000919 ceramic Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 239000003245 coal Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 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 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 229910052907 leucite Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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Abstract
The invention relates to a production method of a microcrystalline thin plate, and relates to the technical field of silicon slag recycling and artificial stone production in the photovoltaic silicon material industry. Mixing the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw materials and the fluxing clarifying agent, then carrying out hot melting, carrying out homogenization and clarification to form a high-temperature melt, carrying out calendering or pouring on the high-temperature melt to prepare a basic amorphous sheet, and carrying out crystallization treatment to form a microcrystalline sheet. The invention comprehensively utilizes the silicon slag solid waste in the photovoltaic silicon material industry, provides the microcrystalline thin plate which has good physical and mechanical properties and excellent processing performance, can replace natural stone or partial engineering materials, has better physical and mechanical properties and chemical stability than the natural stone or partial engineering materials, and can be widely applied to the fields of chemical industry, metallurgy, architectural decoration, petroleum, power electronics and the like.
Description
Technical Field
The invention relates to the technical field of silicon slag recycling in photovoltaic silicon material industry and artificial stone production, and also relates to the technical fields of chemical industry, metallurgy, architectural decoration, petroleum, power electronics and the like.
Background
The photovoltaic industry presents a rapid development trend, and the demand of silicon materials is greatly increased, however, the yield of the associated silicon slag in the industrial silicon production process is increased, and the silicon slag is accumulated for a long time, so that the environmental protection is greatly challenged, and a certain economic burden is caused to enterprises. The metallurgical silicon slag contains rich metal resources and SiO 2 、Na 2 O、CaO、Al 2 O 3 、FeO x And the like, and a certain amount of elemental silicon. At present, the silicon slag is often used as common waste materials for paving, building filling materials and the like, which is undoubtedly waste of resources; in addition, part of the silicon slag is subjected to residual elemental silicon extraction treatment, the process is long, secondary pollution is serious, economic benefits are not obvious, and the silicon slag cannot be completely consumed. Therefore, an economical and effective utilization technology of metallurgical silicon slag is needed.
With the stricter national regulations on pollution-type enterprises, metallurgical enterprises as major manufacturers of solid wastes urgently need to find ways to effectively utilize metallurgical silicon slag to consume waste slag accumulated in production over the years, and hope that the metallurgical waste slag is used in the field of generating high value-added products to increase the economic benefits of the enterprises.
In recent years, with the increasing popularity of domestic high-rise buildings and super high-rise buildings, the ceramic tile industry for domestic building curtain walls has been developed at a high speed, the total project value of 3500 hundred million yuan has been completed in 2016, and domestic leading construction companies have actively expanded business overseas. With the excessive consumption of ceramic resources, energy shortage, environmental pollution and the like, the production cost and environmental protection pressure of ceramic building enterprises are increasing day by day. The thinning and reduction production of ceramics is the future development direction of the architectural ceramics industry. Due to the size requirement of the ceramic sheet, higher requirements are put on the requirements of raw materials and the preparation process of the ceramic sheet, and the technologies of formula, strength improvement, surface decoration and the like of the ceramic sheet also need continuous research and innovation. In 2012, the content of the polycrystalline ceramic sheet applied to curtain wall dry hanging is added to revised technical rules for application of building ceramic sheets (JGJ/T172-2012) and is published and implemented, so that a road is paved for the ceramic sheet in the use of the curtain wall, and the ceramic sheet has a good market prospect in the project of the curtain wall.
Because the ceramic thin plate has large specification and thin thickness, the problems of low strength, poor toughness and the like of green bodies and finished products are easy to occur in the production process, the thinning production of the ceramic tile must firstly consider the reinforcing and toughening technology of the ceramic tile in the selection of raw materials and the design of a formula. The technology takes the silicon slag as a raw material, designs the raw material and a formula through auxiliary raw materials, fluxing clarifying agents and the like, provides a production method of a high-strength wear-resistant microcrystal sheet through the control of crystal growth, and solves the problems of strength and toughness of the sheet.
Disclosure of Invention
The invention aims to provide a production method of a complex phase microcrystal engineering material which has high strength, wear resistance, corrosion resistance and no radioactive hazard to a human body by comprehensively utilizing solid wastes.
The technical scheme of the invention is as follows:
uniformly mixing photovoltaic silicon slag, calcium-based waste, auxiliary raw materials, a fluxing clarifying agent and water, then putting the mixture into a melting furnace, homogenizing and clarifying the mixture to form a high-temperature melt, then calendering or pouring the high-temperature melt to form a basic amorphous sheet, and crystallizing the basic amorphous sheet to form a complex-phase polycrystalline engineering sheet blank plate; the photovoltaic silicon slag is silicon slag generated in the industrial silicon smelting process; the calcium-based waste is limestone waste or marble waste or calcite waste; the auxiliary raw materials are at least four materials of aluminum oxide, zinc oxide, sodium carbonate, potassium carbonate, magnesium oxide, fluorite or sodium nitrate; the fluxing clarifying agent is CeO 2 ，Na 2 O，Al 2 O 3 ，SiO 2 ， CaO，Li 2 O，NH 4 NO 3 ，Na 2 SO 4 At least any one of them.
The invention uses photovoltaic silicon slag and calcium-based waste as raw materials to produce high-strength wear-resistant complex phase polycrystalline engineering boards with high added value, building decorative boards with different colors and specifications can be manufactured by adopting the method after the blank boards of the complex phase polycrystalline engineering boards are discharged from a furnace, and the building decorative boards have unique high-temperature wear resistance, strong high-temperature impact resistance, strong corrosion resistance, burst impact resistance and other performances, are manufactured into water slag ditch linings, wear-resistant pipeline products, material distribution chutes and various wear-resistant lining boards, and can be widely applied to industries such as coal, steel, ore dressing, electric power and the like. And (4) performing fixed thickness, coarse grinding, fine polishing, cutting and chamfering on the prepared product to obtain finished products with different specifications and sizes and glossiness.
Compared with the existing common microcrystal plate, the invention has the following beneficial effects:
1. high strength, abrasion resistance, excellent physical and mechanical properties and chemical stability:
the microcrystalline thin plate has excellent physical and mechanical properties and the density of the microcrystalline thin plate is 2.5-2.8g/cm 3 Mohs hardness of 6-8, breaking strength of 30.0-103.5 MP, compression strength of 70.0-903.0 MPa and wear resistance of 0.063-0.15g/cm 2 o
2. The grain size in the structure is small, the crystal content is high:
the tissue structure of the microcrystalline sheet material of the photovoltaic silicon slag and the calcium-based waste material consists of a glass phase and a crystal phase, wherein the crystal phase consists of one or more than one crystal of kyanite, gehlenite, wollastonite, fluorapatite, anorthite, wollastonite, forsterite, diopside, mullite, leucite and quartz, has excellent high-strength wear resistance, and simultaneously regulates and controls the crystal content (crystallization rate) and the crystal grain size in the multiphase polycrystalline material by regulating production process parameters, and simultaneously ensures that trace elements in the photovoltaic silicon slag and the calcium-based waste material play a key role in regulating and controlling the crystallization rate, the crystal grain size, the physical and mechanical properties and the chemical stability of the multiphase polycrystalline material.
3. High-value comprehensive utilization of calcium-based waste materials:
not only can reduce the production cost of the microcrystal material, but also can reduce the pollution of solid waste to the environment.
The photovoltaic silicon slag accounts for 20.0-35.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, the calcium-based waste accounts for 10.0-25.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, the auxiliary raw material accounts for 35.0-43.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, and the fluxing clarifier accounts for 2.0-10.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water.
The production method is characterized in that SiO in the photovoltaic silicon slag 2 55.0 to 65 percent of the total mass of the photovoltaic silicon slag and Fe 2 O 3 Accounting for 0.5 to 1.0 percent of the total mass of the photovoltaic silicon slag and Al 2 O 3 Accounting for 5.0-15.0 percent of the total mass of the photovoltaic silicon slag, and accounting for 10.0-25.0 percent of the total mass of the photovoltaic silicon slag.
The production method is characterized in that CaO in the calcium-based waste accounts for 45.0-55% of the total mass of the calcium-based waste, and SiO 2 0.01 to 1.5 percent of Al in the total mass of the calcium-based waste 2 O 3 0.01-2.0% of the total mass of the calcium-based waste, 0.01-2.0% of MgO in the total mass of the calcium-based waste, and Fe 2 O 3 Accounting for 0.01 to 2.0 percent of the total mass of the calcium-based waste.
The production method is characterized in that CeO in the fluxing clarifying agent 2 ，Na 2 O，Al 2 O 3 ， SiO 2 ，CaO，Li 2 O，NH 4 NO 3 ，Na 2 SO 4 The mass ratio of the components is 0-5:0-28.
The production method is characterized in that the mass ratio of soda ash, alumina, zinc oxide, sodium carbonate, potassium carbonate, magnesium oxide, fluorite and sodium nitrate in the auxiliary raw materials is 8-35, namely 0-5:0-4:0-5: 5-7:7-14.
In addition, the particle sizes of the photovoltaic silicon slag, the calcium-based waste and the auxiliary raw materials are less than 2mm.
The production method is characterized in that the temperature of the melting furnace is 1400-1560 ℃, and the melting time in the melting furnace is 1.0-10.0 h.
The production method is characterized in that high-temperature melt with the temperature of 1100-1200 ℃ is rolled into the amorphous base sheet by a pair-roller calender.
The crystallization method of the invention is as follows:
annealing the amorphous base sheet at 400-650 ℃ for 2.0-8.0 h, then crystallizing at 650-950 ℃ for 1.0-9.0 h, and finally annealing at 25-600 ℃ for 2.0-8.0 h to prepare the high-strength wear-resistant microcrystalline sheet.
Drawings
FIG. 1 is a schematic diagram of a microcrystalline sheet manufacturing process according to embodiments 1, 2 and 3 of the present invention
Detailed Description
The present invention will now be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention.
The following examples: siO in photovoltaic silicon slag 2 55.0-65% of the total mass of the photovoltaic silicon slag and Fe 2 O 3 Accounting for 0.5 to 1.0 percent of the total mass of the photovoltaic silicon slag and Al 2 O 3 Accounting for 5.0-15.0% of the total mass of the photovoltaic silicon slag, and accounting for 10.0-25.0% of the total mass of the photovoltaic silicon slag; caO in the calcium-based waste accounts for 45.0-55% of the total mass of the calcium-based waste, and SiO 2 0.01 to 1.5 percent of Al in the total mass of the calcium-based waste 2 O 3 0.01-2.0% of the total mass of the calcium-based waste, 0.01-2.0% of MgO in the total mass of the calcium-based waste, and Fe 2 O 3 Accounting for 0.01 to 2.0 percent of the total mass of the calcium-based waste.
Example 1:
crushing the photovoltaic silicon slag, the calcium-based waste and various mineral auxiliary materials, sieving the crushed materials by a 40-mesh sieve, and weighing 45.0 to 55.0 kg of photovoltaic silicon slag, 10.0 to 25.0 kg of calcium-based waste and 0 to 14.0 kg of sodium carbonate (Na) 2 CO 3 ) 0 to 3.0 kg of zinc oxide (ZnO), 9.0 to 16.0 kg of potassium carbonate (K) 2 CO 3 ) 9.0 to 15.0 kg of fluorite (CaF) 2 )， 3.0～5.0Kilogram sodium nitrate (NaNO) 3 ) 1.0 to 3.0 kg of ammonium Nitrate (NH) 4 NO 3 ). Fully mixing the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw materials and the fluxing clarifying agent, adding water accounting for 4.0 percent of the total weight of the raw materials in the mixing process, stirring for 10min, and uniformly mixing to form a basic batch.
The basic batch is sent into a melting furnace through a conveyer belt or a unit charging bucket, the melting temperature is controlled to be 1460-1490 ℃, the melting is carried out for 2.0-6.0 h, and the qualified high-temperature melt is prepared through homogenization and clarification. The clarified high-temperature melt enters the working part of the melting furnace through a throat, the temperature is reduced to 1120-1180 ℃, and the high-temperature melt is pressed into a basic amorphous sheet through a pair-roller calender (the calendering and molding speed is 12.0-25.0 m/h).
The formed basic amorphous plate enters a roller kiln, firstly enters an annealing temperature area of the basic amorphous plate, is annealed for 2.0-3.0 h in the temperature area of 450-650 ℃, then enters a temperature area of 650-850 ℃, is crystallized for 5.0-7.0 h, finally enters a temperature area of 600-25 ℃, and is annealed for 4.0-6.0 h.
And after the high-strength wear-resistant microcrystalline thin plate blank is discharged from the furnace, performing fixed thickness, coarse grinding, fine polishing, cutting and chamfering on the high-strength wear-resistant microcrystalline thin plate blank to obtain finished products with different specifications and sizes and glossiness. The process route is shown in figure 1.
Example 2
Crushing the photovoltaic silicon slag, the calcium-based waste and various mineral auxiliary materials, sieving the crushed materials by a 40-mesh sieve, and weighing 40.0 to 50.0 kg of photovoltaic silicon slag, 10.0 to 25.0 kg of calcium-based waste and 8.0 to 14.0 kg of sodium carbonate (Na) 2 CO 3 ) 0 to 4.0 kg of alumina (Al) 2 O 3 ) 5.0 to 10.0 kg of potassium carbonate (K) 2 CO 3 ) 4.0 to 8.0 kg of lithium oxide (Li) 2 O), 3.0 to 5.0 kg of sodium sulfate (Na) 2 SO 4 ) 1.0 to 3.0 kg of ammonium Nitrate (NH) 4 NO 3 ). Fully mixing the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw materials and the fluxing clarifying agent, adding water accounting for 3-4.0% of the total weight of the raw materials in the mixing process, stirring for 10-15 min, and uniformly mixing to form a basic batch.
The basic batch is sent into a melting furnace through a conveyer belt or a unit charging bucket, the melting temperature is controlled to be 1470-1530 ℃, the melting is carried out for 2.0-6.0 h, and the qualified high-temperature melt is prepared through homogenization and clarification. And (3) feeding the clarified high-temperature melt into a working part of a melting furnace through a throat, reducing the temperature to 1250-1300 ℃, and pouring the high-temperature melt into a preheated mold for molding to obtain the basic amorphous sheet.
The cast basic amorphous sheet block is sent into a shuttle kiln or a tunnel kiln or a roller kiln, the temperature is raised to 650-950 ℃ at the speed of 5 ℃/min in the shuttle kiln, the heat preservation is carried out for 6.0h for crystallization, then the temperature is lowered to 200-700 ℃ at the speed of 3 ℃/min, the heat preservation is carried out for 6.0h for annealing, various stresses generated in the heat treatment process of the microcrystalline sheet are eliminated, and the microcrystalline sheet block is cooled along with the furnace.
And after the high-strength wear-resistant microcrystalline thin plate blank is discharged from the furnace, performing fixed thickness, coarse grinding, fine polishing, cutting and chamfering on the high-strength wear-resistant microcrystalline thin plate blank to obtain finished products with different specifications and sizes and glossiness. The process route is shown in figure 1.
Example 3
Crushing the photovoltaic silicon slag, the calcium-based waste and various mineral auxiliary materials, sieving the crushed materials by a 40-mesh sieve, and weighing 30.0 to 40.0 kg of photovoltaic silicon slag, 15.0 to 28.0 kg of calcium-based waste and 8.0 to 14.0 kg of sodium carbonate (Na) 2 CO 3 ) 10.0 to 15.0 kg of silicon dioxide (SiO) 2 ) 0 to 2.0 kg of cerium oxide (CeO) 2 ) 4.0-8.0 kg of magnesium oxide (MgO), 2.0-4.0 kg of zinc oxide (ZnO), 2.0-4.0 kg of sodium sulfate (Na) 2 SO 4 ) 1.0 to 3.0 kg of sodium nitrate (NaNO) 3 ). Fully mixing the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw materials and the fluxing clarifying agent, adding water accounting for 3.0-4.0% of the total weight of the raw materials in the mixing process, stirring for 10-15 min, and uniformly mixing to form a basic batch.
The basic batch is sent into a melting furnace through a conveyer belt or a unit charging bucket, the melting temperature is controlled to be 1460-1490 ℃, the melting is carried out for 2.0-6.0 h, and the qualified high-temperature melt is prepared through homogenization and clarification. The clarified high-temperature melt enters a working part of a melting furnace through a throat, the temperature is reduced to 1120-1180 ℃, and the high-temperature melt is pressed into a basic amorphous sheet through a double-roll calender (the calendering speed is 12.0-25.0 m/h).
The formed basic amorphous plate enters a roller kiln, firstly enters an annealing temperature area of the basic amorphous plate, is annealed for 2.0-3.0 h in the temperature area of 450-650 ℃, then enters a temperature area of 650-850 ℃, is crystallized for 5.0-7.0 h, finally enters a temperature area of 600-25 ℃, and is annealed for 4.0-6.0 h. The process route is shown in figure 1.
Claims (9)
1. A production method of a photovoltaic silicon slag microcrystalline sheet is characterized in that photovoltaic silicon slag, calcium-based waste materials, auxiliary raw materials, a fluxing clarifying agent and water are uniformly mixed and then are put into a melting furnace, a high-temperature melt is formed after homogenization and clarification, then a basic amorphous sheet is manufactured by rolling or pouring of the high-temperature melt, and a microcrystalline sheet blank plate is formed by crystallizing the basic amorphous sheet; the photovoltaic silicon slag is silicon slag generated in the industrial silicon smelting process; the calcium-based waste is limestone waste, marble waste or calcite waste; the auxiliary raw materials are at least four materials of aluminum oxide or zinc oxide or sodium carbonate or potassium carbonate or magnesium oxide or fluorite or sodium nitrate; the fluxing clarifying agent is CeO 2 ，Na 2 O，Al 2 O 3 ，SiO 2 ，CaO，Li 2 O，NH 4 NO 3 ，NaNO 3 And Na 2 SO 4 At least any one of them.
2. The production method according to claim 1, wherein the photovoltaic silicon slag accounts for 20.0-35.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, the calcium-based waste accounts for 10.0-25.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, the auxiliary raw material accounts for 35.0-43.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water, and the fluxing clarifier accounts for 2.0-10.0 wt% of the total mass of the photovoltaic silicon slag, the calcium-based waste, the auxiliary raw material, the fluxing clarifier and the water.
3. The production method according to claim 1, wherein SiO in the photovoltaic silicon slag 2 55.0-65% of the total mass of the photovoltaic silicon slag and Fe 2 O 3 Accounting for 0.5 to 1.0 percent of the total mass of the photovoltaic silicon slag, Al 2 O 3 Accounting for 5.0-15.0% of the total mass of the photovoltaic silicon slag, and accounting for 10.0-25.0% of the total mass of the photovoltaic silicon slag.
4. The production method according to claim 1, wherein CaO in the calcium-based scrap accounts for 45.0 to 55% of the total mass of the calcium-based scrap, and SiO is contained in the calcium-based scrap 2 0.01 to 1.5 percent of Al in the total mass of the calcium-based waste 2 O 3 0.01-2.0% of the total mass of the calcium-based waste, 0.01-2.0% of MgO in the total mass of the calcium-based waste, and Fe 2 O 3 Accounting for 0.01 to 2.0 percent of the total mass of the calcium-based waste.
5. The production method according to claim 1, characterized in that CeO in the fluxing and clarifying agent 2 ，Na 2 O，Al 2 O 3 ，SiO 2 ，CaO，Li 2 O，NH 4 NO 3 ，Na 2 SO 4 The mass ratio of (A) is 0-5:0-28.
6. The production method according to claim 1, wherein the mass ratio of soda ash, alumina, zinc oxide, sodium carbonate, potassium carbonate, magnesium oxide, fluorite and sodium nitrate in the auxiliary raw materials is 8-35.
7. The production method according to claim 1, wherein the photovoltaic silica slag, the calcium-based waste material and the auxiliary raw material have a particle size of less than 2mm.
8. The production method according to claim 1, wherein the melting temperature of the melting furnace is 1300 to 1600 ℃ and the melting time in the melting furnace is 1.0 to 10.0 hours.
9. The production method according to claim 1, characterized in that the high-temperature melt with the temperature of 1100-1200 ℃ is made into amorphous base sheet by rolling through a double-roll calender; then the amorphous base thin plate is annealed for 2.0 to 8.0 hours at the temperature of 400 to 650 ℃, then crystallized for 1.0 to 9.0 hours at the temperature of 650 to 950 ℃, and finally annealed for 2.0 to 8.0 hours at the temperature of 25 to 600 ℃ to prepare the microcrystal thin plate.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0222145A (en) * | 1988-07-12 | 1990-01-25 | Central Glass Co Ltd | Crystalline foam glass and production thereof |
| CN103539357A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon-slag microcrystalline glass and preparation method thereof |
| CN103539360A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon smelting waste residue foam microcrystalline glass and preparation method thereof |
| CN103864308A (en) * | 2014-03-31 | 2014-06-18 | 南通大明玉新材料科技有限公司 | Method for producing high-tenacity semi-transparent glass crystal duplex engineering board |
| CN103936285A (en) * | 2014-03-31 | 2014-07-23 | 南通大明玉新材料科技有限公司 | Production method of high-strength wear-resistant complex-phase poly-crystal engineering plate |
| WO2016095180A1 (en) * | 2014-12-16 | 2016-06-23 | 北京科技大学 | Microcrystalline glass prepared from hazardous solid wastes, and preparation method therefor |
-
2022
- 2022-11-15 CN CN202211428684.6A patent/CN115893846A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0222145A (en) * | 1988-07-12 | 1990-01-25 | Central Glass Co Ltd | Crystalline foam glass and production thereof |
| CN103539357A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon-slag microcrystalline glass and preparation method thereof |
| CN103539360A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon smelting waste residue foam microcrystalline glass and preparation method thereof |
| CN103864308A (en) * | 2014-03-31 | 2014-06-18 | 南通大明玉新材料科技有限公司 | Method for producing high-tenacity semi-transparent glass crystal duplex engineering board |
| CN103936285A (en) * | 2014-03-31 | 2014-07-23 | 南通大明玉新材料科技有限公司 | Production method of high-strength wear-resistant complex-phase poly-crystal engineering plate |
| WO2016095180A1 (en) * | 2014-12-16 | 2016-06-23 | 北京科技大学 | Microcrystalline glass prepared from hazardous solid wastes, and preparation method therefor |
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