CN114835397B - Batch and method for preparing lithium-containing high-zirconium aluminum silicate glass by using spodumene and zirconite - Google Patents
Batch and method for preparing lithium-containing high-zirconium aluminum silicate glass by using spodumene and zirconite Download PDFInfo
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- CN114835397B CN114835397B CN202210673091.XA CN202210673091A CN114835397B CN 114835397 B CN114835397 B CN 114835397B CN 202210673091 A CN202210673091 A CN 202210673091A CN 114835397 B CN114835397 B CN 114835397B
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 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 title claims abstract description 43
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 16
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 title description 2
- 239000005368 silicate glass Substances 0.000 title description 2
- 239000011521 glass Substances 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 42
- 230000008018 melting Effects 0.000 claims abstract description 42
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 29
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 20
- 235000010755 mineral Nutrition 0.000 claims abstract description 20
- 239000011707 mineral Substances 0.000 claims abstract description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 16
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 16
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 16
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 12
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 10
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 8
- 239000005354 aluminosilicate glass Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 229910021646 siderite Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006066 glass batch Substances 0.000 abstract description 8
- 238000005352 clarification Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 19
- 230000006872 improvement Effects 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 5
- 239000011819 refractory material Substances 0.000 description 4
- 239000013064 chemical raw material Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate 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
- 239000006060 molten glass Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method 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
- 238000003860 storage Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
-
- 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
- C03B5/225—Refining
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a batch and a method for preparing lithium-containing high-zirconium aluminum silicon glass by using spodumene and zirconite, wherein the batch comprises the following components in parts by mass: 62 to 74 portions of spodumene, 3.1 to 8.71 portions of zircon and 20 to 37.91 portions of fluxing agent; wherein, the granularity of mineral raw materials of spodumene and zirconite is 325-1000 meshes, the granularity of fluxing agent is 20-80 meshes, and the fluxing agent comprises 0-5 parts of anhydrous borax, 0-4 parts of sodium phosphate, 7.5-27.41 parts of sodium silicate, 1-2 parts of potassium carbonate, 0-5 parts of magnesite and 0-6 parts of magnesite according to parts by weight. According to the invention, the characteristics of raw materials and the reaction rule of silicate are combined, refractory raw materials and fluxing raw materials are organically combined, in addition, the granularity of the raw materials is synergistically optimized, the melting chemical reaction of glass batch is promoted, the clarification quality of glass liquid is improved, high-quality uniform glass liquid is obtained, and meanwhile, the energy consumption of the batch melting stage is reduced.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to a batch and a method for preparing lithium-containing high-zirconium aluminum silicon glass by using spodumene and zirconite.
Background
Aluminosilicate glass was developed in the early 30 th 20 th century, but is limited by the technology that the melting point of alumina is as high as 2050 ℃, which naturally leads to the increase of glass melting temperature, the increase of glass viscosity, the increase of surface tension, and the easy generation of stripes, which are unfavorable for glass clarification and homogenization, so that the production of aluminosilicate glass presents serious challenges for the moment; the melting temperature of the glass melting furnace is difficult to exceed 1550 ℃ under the limitation of traditional energy sources mainly comprising coal at the time, so that the aluminum silicon glass is not fully applied and popularized before the 21 st century.
In recent years, as electronic information display products have been increasingly demanded for scratch resistance of glass surfaces, oxides capable of improving hardness of glass have been mainly composed of zirconium oxide (ZrO 2 ) And alumina (Al) 2 O 3 ) Mainly, the Mohs hardness of the glass is basically 9 or more, and is inferior to the diamond with the highest hardness (Mohs hardness is 10), and the Mohs hardness of the common glass is only 6 to 7. However, zirconia (ZrO 2 ) The melting point is higher, up to 2715 ℃, and the melting point of alumina is 2050 ℃, so that if it is used as a glass raw material directly, the melting difficulty of the glass batch is very great.
At present, although glass melting technology has advanced to a certain extent, the flame space of a glass melting furnace can bear a temperature of only 1650 ℃ generally, if a higher melting temperature is adopted, the corrosion of refractory materials of the glass melting furnace is accelerated, the service life of the furnace is affected, and molten materials corroded by the refractory materials drop into the glass melt, so that defects of glass stripes are increased, and the quality of glass is affected.
The invention discovers that when the alumina and the zirconia are used cooperatively, the invention has good performance on improving the hardness of the glass surface, improving the scratch resistance of the glass surface and reducing the impact breakage rate of the glass; however, how to introduce alumina and zirconia components from the aspects of raw materials and ingredients can improve and promote the glass performance, and can realize high-quality melting of the lithium-containing high-zirconium aluminum silicon glass batch on the premise of the existing glass melting technology, so that the obtained glass liquid with good homogenization and sufficient clarification creates conditions for glass molding preparation, and the glass is the difficult problem to be overcome and solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a batch and a method for preparing lithium-containing high-zirconium aluminum silicon glass by using superfine spodumene and zirconite mineral raw materials.
The invention discloses a batch for preparing lithium-containing high-zirconium aluminum silicon glass by using spodumene and zirconite, which comprises the following components in parts by weight:
62-74 parts of spodumene;
3.1 to 8.71 portions of zircon;
20-37.91 parts of fluxing agent;
wherein,
the granularity of mineral raw materials of spodumene and zirconite is 325-1000 meshes;
the granularity of the fluxing agent is 20-80 meshes, and the fluxing agent comprises, by mass, 0-5 parts of anhydrous borax, 0-4 parts of sodium phosphate, 7.5-27.41 parts of sodium silicate, 1-2 parts of potassium carbonate, 0-5 parts of magnesite and 0-6 parts of magnesite.
As a further improvement of the invention, the mass ratio of spodumene to zircon is (8.5-20): 1.
As a further improvement of the invention, the particle size of the mineral raw materials of spodumene and zircon is 800-1000 meshes.
As a further improvement of the invention, the content of iron oxide in the mineral raw materials of spodumene and zircon is less than 0.1%.
As a further improvement of the invention, the spodumene comprises the following components: siO (SiO) 2 65.6±1.0wt％，Al 2 O 3 26.4±0.5wt％，Li 2 O7.4 + -0.2 wt% and the balance impurities.
As a further improvement of the invention, the zircon comprises the following components in percentage by weight: zrO (ZrO) 2 68.5±1.5wt％，SiO 2 31+ -1.0 wt% and the balance of impurities.
As a further improvement of the invention, the sodium silicate has a modulus n of 3, i.e. a molecular formula Na 2 O·3SiO 2 。
As a further improvement of the invention, the fluxing agent comprises, by mass, 1-5 parts of anhydrous borax, 1-1.5 parts of sodium phosphate, 7.5-27.41 parts of sodium silicate, 1-2 parts of potassium carbonate, 1-5 parts of magnesite and 1-6 parts of magnesite.
The invention also discloses a method for preparing the lithium-containing high-zirconium aluminum silicon glass based on the batch, which comprises the following steps:
weighing spodumene and zircon according to parts by weight, and premixing to form a mixture A;
weighing anhydrous borax, sodium phosphate, sodium silicate, potassium carbonate, magnesite and zincite according to parts by weight, and premixing to form a mixture B;
mixing the mixture A with the mixture B to form a mixture of the lithium-containing high-zirconium aluminum silicon glass;
putting the batch into a kiln, melting and clarifying the batch, and providing qualified glass liquid for preparing lithium-containing high-zirconium aluminum silicon glass; wherein the melting and clarifying process comprises the following steps: the temperature of the inlet in the kiln is 1200-1350 ℃, the temperature is continuously increased along the length direction of the kiln, the highest temperature of 1650 ℃ is reached at the position of 75-80% of the length of the kiln, and then the temperature is reduced to the temperature corresponding to 600-800 poise, the temperature is maintained for 15-30min, the whole melting time is not less than 18h, and the bubbles in the glass liquid are completely removed and absorbed.
As a further improvement of the invention, zrO in the obtained lithium-containing high-zirconium aluminum silicon glass 2 2.08 to 5.85 weight percent of Al 2 O 3 16.37 to 19.57wt% and Al 2 O 3 With ZrO 2 The mass ratio of (3.3, 3.9, 5.9 or 7.9) is 1.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the refractory raw materials and the fluxing raw materials are organically combined by combining the characteristics of the raw materials and the reaction rule of silicate, the granularity of the raw materials is synergistically optimized, the melting chemical reaction of glass batch is promoted, the clarifying quality of glass liquid is improved, and high-quality uniform glass liquid is obtained; meanwhile, the silicate reaction temperature and the glass phase forming temperature of the batch can be effectively reduced, the energy consumption of the batch in the melting stage can be reduced, and ZrO can be obtained 2 2.08 to 5.85 weight percent of Al 2 O 3 16.37 to 19.57 weight percent of lithium-containing high-zirconium aluminosilicate glass.
Drawings
FIG. 1 is a sintering experimental XRD phase analysis diagram of chemical raw materials 2-1# and superfine mineral raw materials 1-1#; wherein, (a) is chemical raw material 2-1#, and (b) is superfine mineral raw material 1-1#;
FIG. 2 is a high temperature video photograph of a chemical material and an ultra fine mineral material; wherein, (a) is 1300 ℃ for a 2-1# sample, (b) is 1300 ℃ for a 1-1# sample, (c) is 1650 ℃ for 4 hours for a 2-1# sample, (d) is 1650 ℃ for a 1-1# sample, and (e) is a change curve of the number of heat-insulating bubbles of the 2-1# and 1-1# samples at 1650 ℃;
FIG. 3 is a graph comparing DSC analysis curves of chemical raw material 2-1# and superfine mineral raw material 1-1#;
FIG. 4 is a chart showing statistics of the number of bubbles in glass gobs for different samples.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is described in further detail below with reference to the attached drawing figures:
the invention provides a batch for preparing lithium-containing high-zirconium aluminum silicon glass by using spodumene and zircon mineral raw materials, which comprises the following components in parts by weight:
62-74 parts of spodumene;
3.1 to 8.71 portions of zircon;
20-37.91 parts of fluxing agent.
Wherein,
the spodumene selected in the invention is not only rich in alumina (Al 2 O 3 ) And silicon oxide (SiO) 2 ) Also contains a small amount of lithium oxide (Li 2 O) andhas a relatively low melting point range of 1520-1564 ℃; compared with silicon oxide (SiO) 2 ) Melting point 1730 ℃ and alumina (Al 2 O 3 ) Melting point 2050 ℃ is reduced by several hundred degrees celsius. Further, the spodumene comprises the following components in percentage by weight: siO (SiO) 2 65.6±1.0wt％，Al 2 O 3 26.4±0.5wt％，Li 2 O7.4 + -0.2 wt% and the balance impurities.
The zircon selected by the invention is not only rich in zirconia (ZrO 2 ) And silicon oxide (SiO) 2 ) And has a relatively low melting point of 2550 ℃ compared with zirconia (ZrO 2 ) Melting point 2715 ℃ is reduced by 165 ℃. Further, the zircon comprises the following components in percentage by weight: zrO (ZrO) 2 68.5±1.5wt％，SiO 2 31+ -1.0 wt% and the balance of impurities.
In order to promote silicate reaction and the melting and clarifying process of glass liquid, the particle size range of spodumene and zirconite minerals used for preparing the lithium-containing high-zirconium aluminum silicon glass is 325-1000 meshes, preferably 800-1000 meshes; wherein, the granularity of the raw materials can increase the specific surface area of the raw materials, increase the reactivity of the glass batch, promote the reaction and shorten the melting reaction time; if the raw material particle size is too small, for example, the particle size exceeds 1000 meshes, not only is the raw material preparation difficulty increased, but also the raw material cost is increased intangibly, and two fatal problems are caused: firstly, the mixing of raw materials is unfavorable, after all, the cosolvent is a coarse raw material (20-80 meshes), spodumene and zirconite belong to a fine raw material (325-1000 meshes), the granularity difference of the spodumene and zirconite is large, and the homogenization of mixed convection and diffusion is difficult, so that the proper reaction can be generated when the particle size is larger than 1000 meshes. The particle size of the raw materials is reduced (more than 1000 meshes), the specific surface is increased, hydroxyl or organic matters are adsorbed on the surface of the raw materials in the production, processing, storage and transportation processes, and air inclusion among particles can generate poor clarification when the raw materials are melted.
In order to make spodumene and zirconite more favorable for silicate reaction, an optimal batch scheme of the lithium-containing high-zirconium aluminosilicate glass is obtained; the best mass ratio of spodumene to zircon is 8.5-20, namely, the spodumene is zircon= (8.5-20) 1 in mass portion. If the ratio of spodumene to zircon is less than 8.5:1, the zircon is brought into the high zirconia content, and the refractory and difficult-to-clarify glass batch materials are necessarily caused because the melting point of the zirconia is 2715 ℃; if the ratio of spodumene to zircon is larger than 20:1, the content of zirconia carried by zircon is too low, and the aim of improving glass mechanics by depending on zirconia cannot be achieved; therefore, the ratio of spodumene to zircon is preferably in the range of (8.5 to 20): 1, in order to achieve both the glass batch melting quality and the glass properties.
In order to obtain the lithium-containing high-zirconium aluminum silicon glass with good transparency, the content of iron oxide in mineral raw materials of spodumene and zirconite is less than 0.1 percent, so that the glass is prevented from being colored, and the visible light transmittance of the glass is prevented from being influenced.
The fluxing agent of 20 to 37.91 parts by mass comprises 0 to 5 parts of anhydrous borax, 0 to 4 parts of sodium phosphate, 7.5 to 27.41 parts of sodium silicate, 1 to 2 parts of potassium carbonate, 0 to 5 parts of magnesite, 0 to 6 parts of magnesite, preferably 1 to 5 parts of anhydrous borax, 1 to 1.5 parts of sodium phosphate, 7.5 to 27.41 parts of sodium silicate, 1 to 2 parts of potassium carbonate, 1 to 5 parts of magnesite and 1 to 6 parts of magnesite. Further, sodium silicate has a modulus n of 3, i.e. a molecular formula Na 2 O·3SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the selection basis of the fluxing agent is as follows: the cosolvent selection and use mainly takes three points into consideration: firstly, the fluxing agent acts in stages, such as sodium phosphate, anhydrous borax and potassium carbonate act as fluxing before 600 ℃, sodium silicate acts at 600-800 ℃, and magnesite and zincite act at 800-1000 ℃; secondly, the cosolvent is designed according to monovalent alkali metal oxide and divalent alkali metal oxide, wherein the monovalent alkali metal oxide mainly comprises sodium phosphate, anhydrous borax and sodium silicate which can be introduced with sodium oxide and potassium oxide, and the monovalent alkali metal oxide has strong screen breaking effect but can cause glass performance degradation; the divalent alkali metal oxide is prepared by introducing magnesium oxide and zinc oxide into magnesite and calamine, and has the effect of reducing the high-temperature melting temperature, so that the chemical stability and the thermal stability can be relatively improved; thirdly, the glass network structure is further supplemented and perfected through sodium phosphate,The anhydrous borax being incorporated into network formers, e.g. [ BO ] 3 ]、[BO 4 ]、[PO 4 ]The practicability and the functionality of the glass are combined.
The granularity of each raw material in the fluxing agent is 20-80 meshes, and the granularity can avoid the separation of the fluxing agent raw material from refractory materials caused by rapid melting, promote the combination of the fluxing agent raw material and the refractory materials to form silicate reaction and glass melt, enable the batch to be sufficiently melted, reduce the defects of bubbles and stones, and realize the high-quality preparation of glass; wherein, if the flux particle size is smaller than 20 mesh (the particle size is larger), the specific surface area is relatively reduced, the contact probability with the refractory spodumene and zircon is reduced, and the mixing uniformity is also deteriorated, so that it is not preferable to be smaller than 20 mesh; if the flux particle size is less than 80 mesh (smaller particle size), the heat conduction rate increases as the flux particle size decreases under heated conditions in the furnace, and the risk of premature reaction occurs under the action of heat, which in combination with refractory spodumene and zircon cannot cooperate in the optimal silicate reaction zone of 1000-1450 ℃, thus not being more than 80 mesh.
The invention also provides a method for preparing the lithium-containing high-zirconium aluminum silicon glass based on the batch, which comprises the following steps:
weighing spodumene and zircon according to parts by weight, and premixing to form a mixture A;
weighing anhydrous borax, sodium phosphate, sodium silicate, potassium carbonate, magnesite and zincite according to parts by weight, and premixing to form a mixture B;
mixing the mixture A with the mixture B to form a mixture of the lithium-containing high-zirconium aluminum silicon glass;
putting the batch into a kiln, melting and clarifying the batch, and providing qualified glass liquid for preparing lithium-containing high-zirconium aluminum silicon glass; wherein the melting and clarifying process comprises the following steps: the temperature of the inlet in the kiln is 1200-1350 ℃, the temperature is continuously increased along the length direction of the kiln, the highest temperature of 1650 ℃ is reached at the position of 75-80% of the length of the kiln, and then the temperature is reduced to the temperature corresponding to 600-800 poise, the temperature is maintained for 15-30min, the whole melting time is not less than 18h, and the bubbles in the glass liquid are completely removed and absorbed.
ZrO in the lithium-containing high-zirconium aluminum silicon glass prepared by the invention 2 2.08 to 5.85 weight percent of Al 2 O 3 16.37 to 19.57wt% and Al 2 O 3 With ZrO 2 The mass ratio of (3.3, 3.9, 5.9 or 7.9) is 1.
Examples 1 to 8:
the invention provides a batch for preparing lithium-containing high-zirconium aluminum silicon glass by using spodumene and zircon mineral raw materials, wherein the proportion and the granularity range of each component in the corresponding batch 1-1# to 1-8# are shown in tables 1 and 2.
TABLE 1
Units: parts by weight
TABLE 2
Units: order of (A)
Note that: the unit "mesh" is the number of holes of 25.4mm length.
Comparative examples 2-1# to 2-8# the oxide composition achievable in table 1 was changed to 80 mesh to 140 mesh zirconium dioxide and quartz sand according to the conventional raw material scheme, spodumene was changed to 80 mesh to 140 mesh quartz sand, alumina, lithium carbonate, and a table 3 batch inventory table was formed, wherein 1-1# in table 1 and 2-1# in table 3 were compared, and the rest were analogized in turn, i.e., 1-2# and 2-2#, 1-3# and 2-3#, etc.
TABLE 3 Table 3
Units: parts by weight
Experiment:
500 g of batch is prepared by weighing the raw materials according to the proportion in table 1, each raw material is weighed and placed into a clean container and mixed uniformly, and the batch preparation is completed. Grinding a small amount of batch materials to 200-400 meshes for differential thermal analysis; dividing 100 g of the batch into four parts uniformly, and carrying out sintering experiment and phase analysis; 100 g of batch was subjected to a high Wen Shixiang experiment; in addition, the rest batch is used for high-temperature melting experiments, a platinum-rhodium alloy crucible is adopted, the melting temperature of the batch is 1650 ℃, and the batch is kept for 6 hours; and then pouring and forming the molten glass, carrying out annealing treatment to eliminate stress, and then carrying out bubble observation under the room temperature condition.
The batch was prepared by weighing the raw materials in the proportions shown in Table 3, and a high Wen Shixiang experiment and a high temperature melting experiment were performed in the same manner as described above.
The feed schemes of table 1 of the present invention versus comparative example 3 were found by comparison:
as shown in fig. 1 (a) and 1 (b), the samples in the feed schemes in table 1 all underwent silicate reactions at relatively low temperatures.
As shown in fig. 2 (a) and 2 (b), the glass liquid phase in the feed scheme in table 1 appears and flows faster; when the temperature of the batch material adopting the superfine powder is raised to 1300 ℃, obvious liquid phase flow can be observed through high-temperature vision; wherein, the white part in the figure is a clear area of the black part, which is a light transmission deterioration caused by bubbles;
as shown in fig. 2 (c) -2 (e), the glass batch materials in the raw material schemes in table 1 are clarified earlier and more fully; after the temperature is kept at 1650 ℃ for 4 hours, the air bubbles are basically discharged out of the batch material adopting the superfine mineral raw material, and the batch material adopting the chemical raw material still contains a large number of air bubbles.
As shown in FIG. 3, the result of differential thermal analysis of the batch showed a 18% reduction in energy consumption during batch melting of the ultra-fine mineral feedstock.
As shown in fig. 4, the glass sample block produced by the raw material scheme of table 1 was more fully bubble-free, indicating that the ultra-fine mineral raw material scheme was able to reduce silicate reaction steps and courses, and to promote the melting and bubble-free process of the entire batch on the basis of reduced energy consumption.
Based on the above, the invention adopts the proposal of superfine spodumene and zirconite mineral raw materials, and can realize the preparation of lithium-containing high-zirconium aluminosilicate glass which is difficult to prepare by single oxide raw materials.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the lithium-containing high-zirconium aluminosilicate glass batch by using spodumene and zircon is characterized by comprising the following steps of:
62-74 parts of spodumene;
3.1 to 8.71 portions of zircon;
20-37.91 parts of fluxing agent;
wherein,
the mass ratio of spodumene to zircon is (8.5-20): 1;
the granularity of mineral raw materials of spodumene and zirconite is 325-1000 meshes;
the granularity of the fluxing agent is 20-80 meshes, and the fluxing agent comprises, by mass, 1-5 parts of anhydrous borax, 1-1.5 parts of sodium phosphate, 7.5-27.41 parts of sodium silicate, 1-2 parts of potassium carbonate, 1-5 parts of magnesite and 1-6 parts of siderite.
2. The batch according to claim 1, wherein the spodumene and zircon mineral raw materials have a particle size of 800 mesh to 1000 mesh.
3. The batch according to claim 1, wherein the spodumene and zircon mineral raw materials have a ferric oxide content of less than 0.1%.
4. The batch as claimed in claim 1, wherein the spodumene comprises the following components: siO (SiO) 2 65.6±1.0wt％，Al 2 O 3 26.4±0.5wt％，Li 2 O7.4 + -0.2 wt% and the balance impurities.
5. The batch according to claim 1, wherein the zircon comprises the following components: zrO (ZrO) 2 68.5±1.5wt％，SiO 2 31+ -1.0 wt% and the balance of impurities.
6. The batch according to claim 1, wherein the sodium silicate has a modulus n of 3, i.e. a formula Na 2 O·3SiO 2 。
7. A method for preparing a lithium-containing high zirconium aluminosilicate glass based on a batch according to any one of claims 1 to 6, comprising:
weighing spodumene and zircon according to parts by weight, and premixing to form a mixture A;
weighing anhydrous borax, sodium phosphate, sodium silicate, potassium carbonate, magnesite and zincite according to parts by weight, and premixing to form a mixture B;
re-mixing the mixture A and the mixture B to form a mixture of the lithium-containing high-zirconium aluminum silicon glass;
putting the batch into a kiln, melting and clarifying the batch, and providing qualified glass liquid for preparing lithium-containing high-zirconium aluminum silicon glass; wherein the melting and clarifying process comprises the following steps: the temperature of the inlet in the kiln is 1200-1350 ℃, the temperature is continuously increased along the length direction of the kiln, the highest temperature of 1650 ℃ is reached at the position of 75-80% of the length of the kiln, and then the temperature is reduced to the temperature corresponding to 600-800 poise, the temperature is maintained for 15-30min, the whole melting time is not less than 18h, and the bubbles in the glass liquid are completely removed and absorbed.
8. The method according to claim 7, wherein ZrO in the obtained lithium-containing high-zirconium aluminum silicon glass 2 2.08 to 5.85 weight percent of Al 2 O 3 16.37 to 19.57wt% and Al 2 O 3 With ZrO 2 The mass ratio of (3.3, 3.9, 5.9 or 7.9) is 1.
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