CN109336380B - Super white glass and its production method and special equipment - Google Patents
Super white glass and its production method and special equipment Download PDFInfo
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- CN109336380B CN109336380B CN201811473203.7A CN201811473203A CN109336380B CN 109336380 B CN109336380 B CN 109336380B CN 201811473203 A CN201811473203 A CN 201811473203A CN 109336380 B CN109336380 B CN 109336380B
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- 239000011521 glass Substances 0.000 title claims abstract description 290
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 53
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims description 38
- 238000002844 melting Methods 0.000 claims description 36
- 230000008018 melting Effects 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000006060 molten glass Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005352 clarification Methods 0.000 claims description 8
- 238000000265 homogenisation Methods 0.000 claims description 8
- 238000005192 partition Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims 1
- 229910018071 Li 2 O 2 Inorganic materials 0.000 abstract description 5
- 239000005329 float glass Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 46
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 43
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 38
- 239000000292 calcium oxide Substances 0.000 description 22
- 239000000395 magnesium oxide Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 19
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000008395 clarifying agent Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000005496 tempering Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- -1 tempering Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003258 bubble free glass Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007495 chemical tempering process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 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
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
- C03B13/04—Rolling non-patterned sheets continuously
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
- C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
-
- 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
- C03B5/04—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in tank furnaces
-
- 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
- C03B5/18—Stirring devices; Homogenisation
-
- 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
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 ultra-white glass, a production method and special equipment thereof, wherein the ultra-white glass comprises the following raw materials: siO (SiO) 2 43％‑65％，Al 2 O 3 5％‑11％，CaO 14％‑17％，MgO 2％‑4％，Na 2 O 5％‑10％，K 2 O 1％‑3％，B 2 O 3 2％‑5％，ZnO 0.2％‑2％，Li 2 O 2％‑3％,MnO 0.1％‑0.5％,CeO 2 0.7％‑1.8％，Na 2 Sb 2 O 7 0.9% -2.3%. The ultra-white glass has higher strength after being chemically tempered compared with the common float glass, is suitable for products with thin requirements and high strength, can keep high-level strength, has good mechanical processing performance, and can be widely applied to liquid crystal displays, and product windows of watches, mobile phones, flat panel displays, cameras and the like.
Description
Technical Field
The invention relates to the technical field of glass processing, in particular to ultra-white glass, a method for producing the ultra-white glass and special equipment for producing the ultra-white glass.
Background
The super white glass is super transparent low-iron glass, the basic components of the super white glass are shown in table 1, the super white glass is a novel high-grade glass with high quality and multiple functions, the light transmittance is generally more than 91%, the super white glass has the characteristics of crystal clear, noble and elegant, and the super white glass is called as a glass family 'crystal prince'. The main characteristic of the ultra-white glass is Fe 2 O 3 The content is lower and is less than 0.01 percent (100 ppm), so the preparation has strict requirements on the types of raw materials, chemical components, particle composition, moisture, weighing precision and the like, for example, the sandstone powder in the raw materials has the requirements on the components: siO (SiO) 2 ≥99.10±0.3％，Al 2 O 3 ≤0.6±0.1％，Fe 2 O 3 ≤0.01±0.001％，TiO 2 Less than or equal to 0.1+/-0.001%; the granularity is as follows:>the particle size of the particles above 20 meshes is 0,<the particle size of 150 meshes is less than or equal to 10; the water content is less than or equal to 5 percent; and the introduction of mechanical iron needs to be tightly controlled in the process. The ultra-white glass has excellent physical, mechanical and optical properties, and can be subjected to various deep processing like other high-quality float glass, such as tempering, coating, colored glaze, hot bending, laminating, hollowing and the like.
TABLE 1 basic ingredients of ultrawhite glass
| Composition of the components | SiO 2 | Al 2 O 3 | CaO | MgO | Na 2 O+K 2 O | Fe 2 O 3 |
| Content (wt%) | 71-73 | 0.1-2.0 | 8.0-10.0 | 1.5-5.0 | 13.0-15.0 | ≤0.01 |
At present, the preparation method of the ultra-white glass comprises the following steps: the float method and the calendaring method respectively comprise the following process flows:
the float process flow comprises the following steps: batching, smelting, clarifying, forming in a tin bath, annealing, defect detection, transverse cutting and longitudinal cutting, glass original plate detection, packaging and warehousing;
the calendaring process comprises the following steps: batching, smelting, clarifying, compression molding, annealing, cutting, checking, packaging and warehousing.
The ultra-white glass produced by the two methods at present has the following problems:
(1) clarification of ultrawhite glass
Because the iron content in the ultra-white glass is low, the heat conductivity coefficient is 3-4 times that of the common glass, so that the heat permeability is good, the viscosity is low, the upper and lower temperature difference is relatively small, the convection is reduced, and bubbles are not easy to discharge during clarification, so that clarification is difficult. In addition, the temperature of the reflux glass liquid below the forming ring flow is continuously increased in the advancing process, so that micro bubbles are extremely easy to rise into surface flow, the number of bubbles in the glass liquid is obviously increased, the qualification rate is reduced, and the production efficiency is seriously reduced.
(2) Mildew of ultrawhite glass
Glass mildew is an alkali metal ion (Na + And K + ) As a result of the exchange of diffusion of the alkali metal (Na + And K + ) The higher the content, the more severe the tendency to mold. Because the content of alkali metal ions in the ultra-white glass is high, the glass is easy to mould. In addition, the ultra-white glass has less content of divalent metal oxides (CaO and MgO) and weakens the alkali metal ions (Na + And K + ) And the pressing action of the glass is more liable to mold.
(3) Density of ultra-white glass
The ultra-white glass has the advantages that the radiation transmission is high, the heat absorption quantity of the body is less, the heating area at the front section of the annealing kiln cannot absorb the same heat as that of the common float glass, so that the glass body is relatively cool, the annealing cooling process is shortened, more stress residues of the internal structure of the glass can be caused (the cold state stress value of the ultra-white glass is 18% higher than that of the common float glass), the compactness of the glass structure is influenced, the strength of the glass is reduced, the glass is fragile and easy to crack, and the subsequent processing is difficult.
Disclosure of Invention
The invention aims at overcoming the technical defects existing in the prior art, and in a first aspect, provides bubble-free and low-stress ultra-white glass, which comprises the following raw materials in parts by weight: siO (SiO) 2 43％-65％，Al 2 O 3 5％-11％，CaO 14％-17％，MgO 2％-4％，Na 2 O 5％-10％，K 2 O 1％-3％，B 2 O 3 2％-5％，ZnO 0.2％-2％，Li 2 O 2％-3％,MnO 0.1％-0.5％,CeO 2 0.7％-1.8％，Na 2 Sb 2 O 7 0.9％-2.3％。
The raw materials of the composition comprise: siO (SiO) 2 50％-58％，Al 2 O 3 6％-10％，CaO 15％-16％，MgO 2.5％-3.5％，Na 2 O 6％-9％，K 2 O 1.5％-2.5％，B 2 O 3 3％-4％，ZnO 0.4％-1.6％，Li 2 O 2.2％-2.8％,MnO 0.2％-0.4％,CeO 2 0.9％-1.5％，Na 2 Sb 2 O 7 1.1% -2.0%; preferably comprises: siO (SiO) 2 53.5％，Al 2 O 3 8％，CaO 15.6％，MgO 3％，Na 2 O 7.5％，K 2 O 2％，B 2 O 3 3.5％，ZnO 1.0％，Li 2 O 2.5％,MnO 0.3％,CeO 2 1.2％，Na 2 Sb 2 O 7 1.5％。
The raw materials are tantalum-niobium tailings and SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 、ZnO、Li 2 One or more of O and MnO.
The adding mass of the tantalum-niobium tailings is 32.7-72.0 percent, preferably 39.3-65.5 percent, and more preferably 52.4 percent of the total mass of the raw materials.
In a second aspect, the invention provides a special device for producing the ultra-white glass, which comprises a glass melting furnace, a cooling tank, a forming area, a primary annealing furnace and a secondary annealing furnace which are connected in sequence.
The glass melting furnace is used for mixing and melting glass raw materials to prepare glass liquid, and clarifying the glass liquid to remove visible bubbles in the glass liquid;
the cooling pool is used for homogenizing and cooling the clarified glass liquid so as to ensure that the glass raw materials are uniformly mixed and cooled to the forming temperature;
the forming area is used for hydraulically forming molten glass uniformly mixed into a glass ribbon with a certain thickness, and comprises two forming pairs of rollers which are symmetrically arranged up and down, a gap is reserved between the forming pairs of rollers, and the glass ribbon is formed by pressing glass liquid through the gap between the forming pairs of rollers.
The primary annealing kiln is a cold air annealing kiln and comprises a porous partition plate arranged above the glass ribbon, and the porous partition plate is connected with an air duct for introducing cold air so as to enable the cold air to be uniformly blown on the surface of the glass ribbon; the secondary annealing kiln is a natural convection air kiln for reducing the temperature of the glass ribbon to 100-120 ℃.
In a third aspect, the invention provides a production method of the ultra-white glass, and the special equipment is used, and the production method comprises the steps of pretreatment of tantalum-niobium tailings, mixing of raw materials, melting and clarifying of molten glass, homogenization and cooling of the molten glass, forming, primary annealing, secondary annealing and the like.
The pretreatment of the tantalum-niobium tailings is specifically as follows: sequentially carrying out procedures such as grading, scrubbing, magnetic separation, acid washing and the like on the tantalum-niobium tailings to obtain Fe 2 O 3 A tantalum niobium tailings sample having a content of less than 0.01% (100 ppm), a particle size of 0.1-1.5mm, and a water content of less than 5%; or (b)
Preferably, the mixing of the raw materials specifically comprises:
SiO is made of 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 、ZnO、Li 2 Mixing one or more of O and MnO with a tantalum-niobium tailing sample obtained by pretreatment of the tantalum-niobium tailing to obtain a mixture containing SiO 2 43％-65％，Al 2 O 3 5％-11％，CaO 14％-17％，MgO 2％-4％，Na 2 O 5％-10％，K 2 O 1％-3％，B 2 O 3 2％-5％，ZnO 0.2％-2％，Li 2 O 2％-3％,MnO 0.1％-0.5％,CeO 2 0.7％-1.8％，Na 2 Sb 2 O 7 0.9% -2.3% of glass raw material; the glass raw material preferably contains SiO 2 50％-58％，Al 2 O 3 6％-10％，CaO 15％-16％，MgO 2.5％-3.5％，Na 2 O 6％-9％，K 2 O 1.5％-2.5％，B 2 O 3 3％-4％，ZnO 0.4％-1.6％，Li 2 O 2.2％-2.8％,MnO 0.2％-0.4％,CeO 2 0.9％-1.5％，Na 2 Sb 2 O 7 1.1% -2.0%; more preferably comprises SiO 2 53.9％，Al 2 O 3 8％，CaO 15.6％，MgO 3％，Na 2 O 7.5％，K 2 O 2％，B 2 O 3 3.5％，ZnO 1.0％，Li 2 O 2.5％,MnO 0.3％,CeO 2 1.2％，Na 2 Sb 2 O 7 1.5%; or (b)
Preferably, the melting and clarifying of the molten glass specifically comprises:
melting the mixed glass raw materials into glass liquid at 1580-1620 ℃, and keeping the temperature of the glass liquid at 1600-1650 ℃ until no bubbles emerge; or (b)
Preferably, the homogenization and cooling of the molten glass is specifically:
maintaining the temperature of the clarified glass liquid at 1570-1605 ℃ until the glass liquid is uniformly mixed, and then reducing the temperature of the glass liquid to 1020-1280 ℃; or (b)
Preferably, the molding specifically includes:
the cooled glass liquid is hydraulically pressed into glass belts with required thickness and size through forming paired rollers at the temperature of 1020-1280 ℃.
The primary annealing specifically comprises the following steps:
carrying out primary annealing on the formed glass ribbon at 630-720 ℃ by using cold air for 1.5-4 hours; the cold air temperature is-10-20deg.C, air pressure is 20-50Pa, and flow is 130-280Nm 3 /h；
The secondary annealing specifically comprises the following steps:
carrying out secondary annealing on the glass ribbon subjected to primary annealing at 580-650 ℃ by natural convection air for 3-6 hours until the temperature of the glass ribbon is 100-120 ℃ to obtain the ultrawhite glass; the natural convection air temperature is 15-40 ℃, the air pressure is 7-18Pa, and the flow is 200-350Nm 3 /h；
Preferably, the total time of the primary annealing and the secondary annealing is not less than 5 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) The ultra-white glass provided by the invention has higher alumina content and Al 2 O 3 Belongs to intermediate oxide of glass, can reduce crystallization tendency of glass and improve chemical stability, thermal stability, mechanical strength, hardness and refractive index of glass.
(2) The components of the ultra-white glass are very suitable for chemical tempering (the chemical tempering is to put the glass in high-temperature molten salt, sodium ions on the surface of the glass and potassium ions in the molten salt are exchanged with each other, and large-radius ion potassium ions (K + A kind of electronic device) Displacing sodium ions (Na + Is->). The large ions occupy smaller gaps to generate a phenomenon of 'crowding' on the surface, so that compressive stress is generated on the surface of the glass, and tensile stress is generated in the center, thereby achieving the enhancement effect, namely ion tempering. Al (Al) 2 O 3 Acceleration in ion exchange is due to [ AlO 4 ]Has a molecular volume of 41cm 3 Mol/mol, and [ SiO ] 4 ]Is 27.24cm 3 /mol，Al 2 O 3 Substituted SiO 2 After that, the molecular volume is increased, and the gaps of the structural network are enlarged, which is beneficial to the diffusion of alkali ions; on the other hand, the volume is increased, which is favorable for absorbing K with large volume + Ions promote ion exchange.
(3) The glass raw material contains potassium oxide, sodium oxide, lithium oxide and boron oxide, so that the melting of glass can be promoted, the viscosity of the glass can be reduced, and the elimination of tiny bubbles in glass liquid can be accelerated; the glass raw material has high alumina content, and the boron oxide and manganese oxide contained in the glass raw material can enable the structure of the glass to be more compact and the strength to be higher.
(4) In order to reduce the thermal stress problem of the glass, the invention adopts secondary annealing, solves the problem of over-high stress in the production of the ultra-white glass, can reduce the burst of the glass in the cutting and application processes, improves the yield and reduces the cost. The special equipment provided by the invention can stably produce the ultra-white glass, and the produced ultra-white glass is beneficial to the chemical tempering process of the glass.
Drawings
FIG. 1 is a schematic diagram showing the structure of a special apparatus for producing ultra-white glass according to the present invention;
1 glass melting furnace, 2 glass liquid, 3 cooling tank, 4 forming area, 5 glass belt, 6 forming pair roller, 7 primary annealing furnace, 8 secondary annealing furnace, 9 porous baffle and 10 dryer.
Detailed Description
The Jiangxi Yichun tantalum-niobium tailings are tailings sand which is remained after carefully selecting tantalum-niobium from lithium feldspar minerals containing rare metals of tantalum and niobium. If not reasonably utilized, the tantalum-niobium tailings will become more and more serious in environmental pollution in the future, and are a serious problem for the local government. The requirements for the development of the recycling economy are pointed out from the energy saving method, the environmental impact evaluation method, the renewable energy method and the like.
The preparation of the ultra-white glass by using the tantalum-niobium tailings can fully utilize the local raw materials and the geographic advantages, and form a new productivity growth point for enterprises and local governments. Ore dressing analysis of Al in tantalum-niobium tailing sample 2 O 3 Higher, and therefore, al is required for incorporation into the ultrawhite glass 2 O 3 At the same time, a small part of Na can be introduced 2 O is used for reducing the consumption of sodium carbonate, which is beneficial to reducing the production cost of glass, and the chemical composition of the tantalum-niobium tailings is determined after a mineral separation test and is shown in table 2.
TABLE 2 chemical composition of tantalum-niobium tailings after beneficiation test
| Oxide compound | SiO 2 | Al 2 O 3 | Fe 2 O 3 | CaO | MgO | K 2 O | Na 2 O | Li 2 O | MnO | IL |
| Content (wt%) | 75.12 | 15.27 | 0.010 | 0.39 | 0.040 | 1.75 | 5.33 | 0.20 | 0.070 | 0.13 |
The ultra-white glass has high elastic modulus, low thermal expansion coefficient, high chemical stability and strain point, and is high-quality float plate glass with nearly no color and high permeability. Therefore, it is required to have a high alumina content and to improve the chemical stability, thermal stability, mechanical strength, etc. of the glass. Meanwhile, in the tempering process, al 2 O 3 Accelerating in ion exchange process, al 2 O 3 Substituted SiO 2 After that, the molecular volume is increased, and the gaps of the structural network are enlarged, which is beneficial to the diffusion of alkali ions; on the other hand, the volume is increased, which is favorable for absorbing K with large volume + Ions promote ion exchange. Based on the physical and chemical properties of the glass, siO is selected 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 And ZnO and the like as raw materials for the ultrawhite glass of the present invention. The main composition of the glass and the function of the glass in the high-strength ultra-white glass are as follows:
silicon dioxide SiO 2 Is the main body of the framework formed by glass,SiO in soda lime silicate glass 2 Can reduce the thermal expansion coefficient of the glass and improve the thermal stability, chemical stability, softening temperature, hardness and mechanical strength of the glass.
Alumina Al 2 O 3 Belongs to intermediate oxide of glass, can reduce crystallization tendency of glass, improve chemical stability, thermal stability, mechanical strength, hardness and refractive index of glass, and reduce corrosion of glass to refractory materials. Al in the ultra-white glass of the invention 2 O 3 The content of Al in the common ultra-white glass is 5-11 percent 2 O 3 The content of the aluminum oxide is not more than 4%, and the aluminum oxide is high, so that the ultra-white glass product is not easy to mildew, the requirements on environmental parameters are low when the glass product is directly applied and deeply processed, the chemical tempering of the glass is facilitated, and the large-area popularization of the product is facilitated.
Sodium oxide Na 2 O is an external oxide of a glass network, can reduce the viscosity of glass, enables the glass to be easily melted, and is a good fluxing agent for the glass. Na (Na) 2 O can increase the thermal expansion coefficient of the glass and reduce the thermal stability, chemical stability and mechanical strength of the glass.
Potassium oxide K 2 O is also an external oxide of the glass network, its role in the glass and Na 2 O is similar. Potassium ion (K) + ) Radius ratio of sodium ion (Na) + ) The viscosity of the potassium glass is higher than that of the sodium glass, the crystallization tendency of the glass can be reduced, and the transparency, the luster and the like of the glass are improved.
Calcium oxide CaO is a divalent glass network exosome oxide. The main function of the glass is a stabilizer, namely to increase the chemical stability and the mechanical strength of the glass. When the content is high, the crystallization tendency of the glass increases.
Magnesium oxide MgO is a network exo-oxide in soda lime silicate glass. The MgO with the content of less than 3.5 percent is used for replacing part of CaO in the glass, so that the hardening speed of the glass can be reduced, the crystallization tendency of the glass is reduced, and the chemical stability and the mechanical strength of the glass are improved.
Boron oxide B 2 O 3 Also glass forming oxides. Can reduce the expansion coefficient of glassHigh thermal stability and chemical stability of glass, increased refractive index of glass, improved luster of glass, and improved mechanical properties of glass.
Zinc oxide ZnO is a glass intermediate oxide. Can reduce the thermal expansion coefficient of the glass, improve the thermal stability and chemical stability of the glass and increase the refractive index of the glass.
B in the ultra-white glass of the invention 2 O 3 ZnO is a glass intermediate, so that the glass structure is more compact, meanwhile, the melting of the glass at high temperature can be accelerated, mnO can promote the melting of the glass, and manganous oxide is generated at high temperature, and the glass belongs to a spinel structure, so that the glass structure is compact.
In the glass melting process, a large amount of gas can be separated out due to the decomposition of each component of the batch, the volatilization of volatile components and the like. Until the glass forming process is completed, a small portion of the gas cannot escape completely from the glass liquid and remains in the glass liquid in the form of bubbles. Therefore, ceO is added into the glass batch to obtain pure, uniform and consistent high-quality glass liquid 2 And Na (Na) 2 Sb 2 O 7 As a fining agent to promote the removal of bubbles from the glass. CeO is selected in the invention 2 And Na (Na) 2 Sb 2 O 7 As a clarifying agent, the two clarifying agents can not generate sulfate secondary bubbles compared with sulfate clarifying agents, and can not generate pollutant SO in flue gas 2 Is beneficial to reducing the load of flue gas desulfurization and denitrification and reducing the production cost of the ultra-white glass.
CeO 2 And Na (Na) 2 Sb 2 O 7 As a clarifying agent, in effect an oxidizing agent, the working principle is as follows: ceO (CeO) 2 Decomposing at high temperature (above 1400 ℃) to obtain Ce 2 O 3 And oxygen, na 2 Sb 2 O 7 Decomposing at high temperature to obtain Sb 2 O 3 And oxygen generated by decomposition of the clarifying agent can bring out gas which does not completely escape from the glass liquid, thereby achieving the purpose of clarifying the glass liquid. However, the ultrawhite glass is specific to Fe 2+ Is very sensitive because of Fe 2+ High colouring power, fe 2+ The existence of (C) can lead to superWhite glass is bluish, and the requirement of color consistency cannot be met. After adding the clarifier of the invention, even if Fe exists in the glass liquid 2+ Exist and are also oxidized into Fe 3+ ，Fe 3+ Poor coloring ability, and does not affect the color consistency of the ultra-white glass.
The clarifying agent in the existing preparation process of the ultra-white glass is antimony oxide and sodium nitrate, and the working principle is as follows: antimony oxide Sb 2 O 3 Oxidized into Sb under the action of sodium nitrate at about 800-900 DEG C 2 O 5 With the temperature rising to 1500-1600 ℃, sb 2 O 5 Decomposing to obtain Sb 2 O 3 And oxygen, thereby acting to clarify the molten glass. However, the problem is that the melting temperature of the ultrawhite glass can reach 1600 ℃ or higher, that is to say, sb is not reached before the glass melting temperature is reached 2 O 5 The generated oxygen is discharged in the early stage of melting, and the generated oxygen can not be left to carry out the gas which does not completely escape from the molten glass in the later stage of melting, so that the generated oxygen has no clarifying effect.
According to the invention, the tantalum-niobium tailings are used as raw materials to prepare the high-strength ultra-white glass, so that the prepared glass sample has stable performance, the tantalum-niobium tailings can be comprehensively utilized, and the pollution to the environment is reduced.
The ultra-white glass prepared by the invention has high strength, however, the strength is high, which means that Al in the glass component 2 O 3 The content is higher, so that two technical problems exist in the production: firstly, the glass melting temperature is higher, the common fuel oil melting furnace is not easy to reach, and secondly, the clarification and homogenization are difficult. When the oxy-fuel combustion technology is adopted, the viscosity of the glass is reduced, meanwhile, the oxy-fuel combustion flame is stable, no reversing exists, the residence time of combustion gas in the kiln is long, the pressure in the kiln is stable and low, the melting and clarification of the glass are facilitated, bubbles, gray bubbles and stripes in the glass are reduced, and the quality of the glass is improved.
The present invention will be described more specifically with reference to the following examples, which are not intended to limit the present invention in any way.
The process of heating the batch material at high temperature to form uniform bubble-free glass liquid meeting the forming requirements is called melting of glass. The glass melting process is an important link in glass production. Many defects in glass (e.g., bubbles, stones, streaks, etc.) are caused by non-uniformity of the glass melt during the melting process. The yield, quality, qualification rate, production cost, fuel consumption, tank furnace life for melting and the like of the glass are closely related to the melting of the glass. Therefore, reasonable glass melting is an important guarantee that the whole production process is smoothly carried out and high-quality glass products are produced efficiently.
The invention has determined through a large number of researches that the tantalum-niobium tailings are used for producing the ultra-white glass used as the high-strength display and the fireproof glass, and the ultra-white glass comprises the following raw materials: siO (SiO) 2 43％-65％，Al 2 O 3 5％-11％，CaO 14％-17％，MgO 2％-4％，Na 2 O 5％-10％，K 2 O 1％-3％，B 2 O 3 2％-5％，ZnO 0.2％-2％，Li 2 O 2％-3％,MnO 0.1％-0.5％,CeO 2 0.7％-1.8％，Na 2 Sb 2 O 7 0.9％-2.3％；
Preferably:
SiO 2 50％-58％，Al 2 O 3 6％-10％，CaO 15％-16％，MgO 2.5％-3.5％，Na 2 O 6％-9％，K 2 O 1.5％-2.5％，B 2 O 3 3％-4％，ZnO 0.4％-1.6％，Li 2 O 2.2％-2.8％,MnO 0.2％-0.4％,CeO 2 0.9％-1.5％，Na 2 Sb 2 O 7 1.1％-2.0％；
more preferably:
SiO 2 53.5％，Al 2 O 3 8％，CaO 15.6％，MgO 3％，Na 2 O 7.5％，K 2 O 2％，B 2 O 3 3.5％，ZnO 1.0％，Li 2 O 2.5％,MnO 0.3％,CeO 2 1.2％，Na 2 Sb 2 O 7 1.5％。
the optimal introduced mass percentage of the tantalum-niobium tailings in the raw material for producing the ultra-white glass is 32.7% -72.0%, preferably 39.3% -65.5%, and more preferably 52.4% of the total mass of the glass raw material.
The invention also provides special equipment for producing the ultra-white glass, which is an improvement of equipment based on a calendaring method, and has a structure shown in figure 1 and comprises a glass melting furnace 1, a cooling tank 3, a forming area 4, a primary annealing furnace 7 and a secondary annealing furnace 8 which are connected in sequence. Wherein:
the glass melting furnace 1 is used for melting the mixed glass raw materials into glass liquid 2 and removing visible bubbles in the glass liquid. The process of removing visible bubbles is called refining of glass liquid, namely melting of glass raw materials and refining of glass liquid are carried out in the glass melting furnace 1.
The cooling pool 3 is used for homogenizing and cooling the clarified glass liquid, adjusting the viscosity of the glass liquid, even if the molten glass raw materials are uniformly mixed, adjusting the viscosity of the glass liquid and cooling to the forming temperature, and providing guarantee for the subsequent forming of the glass liquid;
the forming zone 4 is used for pressing molten and uniformly mixed glass liquid into glass products with fixed geometric shapes, the forming zone 4 comprises an upper forming pair roller 6 and a lower forming pair roller 6, the glass liquid is pressed into glass strips 5 when passing through the forming pair roller 6, forming is completed, and the glass strips 5 with different thicknesses can be obtained through adjusting the clearance between the forming pair rollers 6 for pressing forming.
In the annealing step, in order to eliminate stress in the formed glass ribbon 5 having a certain thickness, two anneals are used, the first annealing being rough annealing and the second annealing being finish annealing. The first annealing uses a first annealing kiln 7, and adopts cold air annealing, the cold air temperature is-10-20 ℃, the air pressure is 20-50Pa, and the flow is 130-280Nm 3 And/h. The primary annealing kiln 7 is provided with a porous partition plate 9 above the glass ribbon, the porous partition plate 9 is connected with an air duct 10, and cold air is introduced through the air duct 10 and then is beaten on the porous partition plate 9, so that uneven cold impact of cold air on the glass ribbon is reduced, and the cold air uniformly falls on the surface of the glass ribbon. The glass ribbon after primary annealing enters a secondary annealing furnace 8 for secondary annealing, the secondary annealing furnace 8 adopts natural convection air for annealing, the temperature of the natural convection air is 15-40 ℃, the wind pressure is 7-18Pa, and the flow is 200-350Nm 3 And/h. And when the temperature of the glass ribbon is reduced to 100-120 ℃, the second annealing is finished.
The invention also provides a production method of the ultra-white glass, which comprises the steps of pretreatment of tantalum-niobium tailings, mixing of raw materials, melting and clarifying of glass liquid, homogenization and cooling of the glass liquid, molding, primary annealing, secondary annealing and the like; all the steps are carried out in the special equipment for producing the ultra-white glass, and specifically the steps are as follows:
1) Pretreatment of tantalum-niobium tailings:
sequentially carrying out procedures such as grading, scrubbing, magnetic separation, acid washing and the like on the tantalum-niobium tailings to obtain a tantalum-niobium tailings sample suitable for producing ultra-white glass, wherein Fe is contained in the tantalum-niobium tailings sample 2 O 3 The content of (2) is less than 0.01% (100 ppm), the particle size is 0.1-1.5mm, and the water content is less than 5%.
2) Mixing the following raw materials:
after detecting the chemical composition in the tantalum-niobium tailing sample, calculating the SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 、ZnO、Li 2 Mixing one or more of O and MnO with the tantalum-niobium tailing sample obtained in the step 1) to obtain a mixture containing SiO 2 43％-65％，Al 2 O 3 5％-11％，CaO 14％-17％，MgO 2％-4％，Na 2 O 5％-10％，K 2 O 1％-3％，B 2 O 3 2％-5％，ZnO 0.2％-2％，Li 2 O 2％-3％,MnO 0.1％-0.5％,CeO 2 0.7％-1.8％，Na 2 Sb 2 O 7 0.9% -2.3% of glass raw material; in general industrial production, siO 2 From silica sand, al 2 O 3 From feldspar, caO from limestone, mgO from magnesite, na 2 O is from sodium carbonate, K 2 O is derived from potassium carbonate, B 2 O 3 From boric acid or borax, li 2 O is derived from lithium carbonate.
The glass raw material preferably contains SiO 2 50％-58％，Al 2 O 3 6％-10％，CaO 15％-16％，MgO 2.5％-3.5％，Na 2 O 6％-9％，K 2 O 1.5％-2.5％，B 2 O 3 3％-4％，ZnO 0.4％-1.6％，Li 2 O 2.2％-2.8％,MnO 0.2％-0.4％,CeO 2 0.9％-1.5％，Na 2 Sb 2 O 7 1.1% -2.0%; more preferably SiO-containing 2 53.9％，Al 2 O 3 8％，CaO 15.6％，MgO 3％，Na 2 O 7.5％，K 2 O 2％，B 2 O 3 3.5％，ZnO 1.0％，Li 2 O 2.5％,MnO 0.3％,CeO 2 1.2％，Na 2 Sb 2 O 7 1.5％。
3) Melting glass liquid:
melting the mixed glass raw materials in the step 2) into glass liquid at 1580-1620 ℃ generally for about 24 hours;
4) Clarifying the molten glass:
maintaining the temperature of the glass liquid obtained in the step 3) at 1600-1650 ℃ until no bubbles emerge (about 8 hours is generally needed for sufficient clarification), and finishing clarification;
5) Homogenization and cooling of molten glass:
maintaining the temperature of the glass liquid clarified in the step 4) at 1570-1605 ℃ until all parts of the glass liquid are uniform in chemical composition, and homogenizing is finished to eliminate stripes and non-uniform bodies in the glass liquid; after homogenization, the temperature of the glass liquid is reduced to 1020-1280 ℃;
6) And (5) forming:
hydraulically forming the glass into a glass ribbon with the required thickness and size by a forming pair of rollers at the temperature of 1020-1280 ℃ from the glass liquid homogenized in the step 5);
7) Primary annealing:
carrying out primary annealing on the formed glass ribbon at 630-720 ℃ by using cold air for 1.5-4 hours; the cold air temperature is-10-20 ℃, the air pressure is 20-50Pa, and the flow is 130-280Nm 3 /h。
8) Secondary annealing:
carrying out secondary annealing on the glass ribbon subjected to primary annealing at 580-650 ℃ by natural convection air for 3-6h, wherein the total time of the secondary annealing is not less than 5h until the temperature of the glass ribbon is 100-120 ℃, and obtaining the glass ribbon after the annealing is finishedThe ultra-white glass is prepared; the temperature of natural convection air is 15-40 ℃, the wind pressure is 7-18Pa, and the flow is 200-350Nm 3 /h。
The glass liquid obtained by melting the tantalum-niobium tailings serving as a part of the glass raw material has the advantages of good uniformity, no stones, no refractory matters, no stripes at high temperature, moderate viscosity, good fluidity and good forming property, and the obtained glass product has the advantages of high strength, fewer defects, white glass color and good light transmittance, so that the tantalum-niobium tailings can be used as the raw material of ultra-white glass.
The ultrawhite glass of examples 1 to 7 was prepared by the above method for producing ultrawhite glass using the above special equipment for producing ultrawhite glass and a glass raw material containing tantalum-niobium tailings. The parameters and raw material compositions for producing the ultrawhite glass of examples 1 to 7 are shown in Table 1.
TABLE 1 raw material composition and production parameters of the ultrawhite glass of example 1-example 7
Experiment:
the bending strength of the glasses obtained in examples 1 to 7 and comparative examples 1 to 4 was measured, and the glass samples were cut, ground and polished to obtain 80X 10mm strips, and a three-point bending method was used to test the DKZ-5000 type electric bending tester. The results of the performance test are shown in Table 2.
TABLE 2 Performance test results for glasses of examples 1-7 and comparative examples 1-4
Therefore, the ultra-white glass has higher strength after being chemically tempered than the common float glass, is suitable for products with thin requirements and high strength, can keep high-level strength, has good mechanical processing performance, and can be widely applied to product windows of liquid crystal displays, watches, mobile phones, flat panel displays, cameras and the like.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended by the present invention.
Claims (18)
1. The ultra-white glass is characterized by comprising the following raw materials in parts by weight: siO (SiO) 2 50wt%-58wt%，Al 2 O 3 6wt%-10wt%，CaO 15wt%-16wt%，MgO 2.5wt%-3.5wt%，Na 2 O 6wt%-9wt%，K 2 O 1.5wt%-2.5wt%，B 2 O 3 3wt%-4wt%，ZnO 0.4wt%-1.6wt%，Li 2 O 2.2wt%-2.8wt%,MnO 0.2wt%-0.4wt%,CeO 2 0.9wt%-1.5wt%，Na 2 Sb 2 O 7 1.1wt%-2.0wt%。
2. The ultra-white glass according to claim 1, wherein the raw material composition comprises: siO (SiO) 2 53.5wt%，Al 2 O 3 8wt%，CaO 15.6wt%，MgO 3wt%，Na 2 O 7.5wt%，K 2 O 2wt%，B 2 O 3 3.5wt%，ZnO 1.0wt%，Li 2 O 2.5wt%,MnO 0.3wt%,CeO 2 1.2wt%，Na 2 Sb 2 O 7 1.5wt%。
3. The ultra-white glass according to claim 1 or 2, wherein the raw materials are tantalum-niobium tailings and SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 、ZnO、Li 2 One or more of O and MnO.
4. The ultra-white glass according to claim 3, wherein the addition mass of the tantalum-niobium tailings is 32.7% -72.0% of the total mass of the raw materials.
5. The ultra-white glass according to claim 3, wherein the addition mass of the tantalum-niobium tailings is 39.3% -65.5% of the total mass of the raw materials.
6. The ultra-white glass according to claim 3, wherein the addition mass of the tantalum-niobium tailings is 52.4% of the total mass of the raw materials.
7. A special apparatus for producing the ultra-white glass according to any one of claims 1 to 6, comprising a glass melting furnace, a cooling tank, a forming zone, a primary annealing furnace and a secondary annealing furnace which are connected in sequence.
8. The special equipment according to claim 7, wherein the glass melting furnace is used for mixing and melting glass raw materials into glass liquid and clarifying to remove visible bubbles in the glass liquid;
the cooling pool is used for homogenizing and cooling the clarified glass liquid so as to ensure that the glass raw materials are uniformly mixed and cooled to the forming temperature;
the forming area is used for hydraulically forming molten glass uniformly mixed into a glass ribbon with a certain thickness, and comprises two forming pairs of rollers which are symmetrically arranged up and down, a gap is reserved between the forming pairs of rollers, and the glass ribbon is formed by pressing glass liquid through the gap between the forming pairs of rollers.
9. The special equipment according to claim 8, wherein the primary annealing furnace is a cold air annealing furnace and comprises a porous partition plate arranged above the glass ribbon, and the porous partition plate is connected with a wind barrel for introducing cold air so as to make the cold air blow on the surface of the glass ribbon uniformly; the secondary annealing kiln is a natural convection air kiln for reducing the temperature of the glass ribbon to 100-120 ℃.
10. A method for producing ultra-white glass according to any one of claims 1 to 6, characterized in that the special equipment according to any one of claims 7 to 9 is used, comprising the steps of pretreatment of tantalum-niobium tailings, mixing of raw materials, melting and clarification of molten glass, homogenization and cooling of molten glass, forming, primary annealing and secondary annealing.
11. The production method according to claim 10, wherein the pretreatment of the tantalum-niobium tailings is specifically: sequentially carrying out the procedures of grading, scrubbing, magnetic separation and acid washing on the tantalum-niobium tailings to obtain Fe 2 O 3 The content of the water is less than 0.01 percent, the grain diameter is 0.1-1.5mm, and the water content is less than 5 percent.
12. The production method according to claim 10, wherein the mixing of the raw materials is specifically:
SiO is made of 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 O、B 2 O 3 、ZnO、Li 2 Mixing one or more of O and MnO with a tantalum-niobium tailing sample obtained by pretreatment of the tantalum-niobium tailing to obtain a mixture containing SiO 2 50wt%-58wt%，Al 2 O 3 6wt%-10wt%，CaO 15wt%-16wt%，MgO 2.5wt%-3.5wt%，Na 2 O 6wt%-9wt%，K 2 O 1.5wt%-2.5wt%，B 2 O 3 3wt%-4wt%，ZnO 0.4wt%-1.6wt%，Li 2 O 2.2wt%-2.8wt%,MnO 0.2wt%-0.4wt%,CeO 2 0.9wt%-1.5wt%，Na 2 Sb 2 O 7 1.1 to 2.0 weight percent of glass raw material.
13. The production method according to claim 12, wherein the glass raw material contains SiO 2 53.9wt%，Al 2 O 3 8wt%，CaO 15.6wt%，MgO 3wt%，Na 2 O 7.5wt%，K 2 O 2wt%，B 2 O 3 3.5wt%，ZnO 1.0wt%，Li 2 O 2.5wt%,MnO 0.3wt%,CeO 2 1.2wt%，Na 2 Sb 2 O 7 1.5wt%。
14. The production method according to claim 10, wherein the melting and refining of the molten glass is specifically:
melting the mixed glass raw materials into glass liquid at 1580-1620 ℃, and keeping the temperature of the glass liquid at 1600-1650 ℃ until no bubbles emerge.
15. The production method according to claim 10, characterized in that the homogenization and cooling of the molten glass is in particular:
maintaining the temperature of the clarified glass liquid at 1570-1605 ℃ until the glass liquid is uniformly mixed, and then reducing the temperature of the glass liquid to 1020-1280 ℃.
16. The production method according to claim 10, characterized in that the shaping is in particular:
the cooled glass liquid is hydraulically pressed into glass belts with required thickness and size through forming paired rollers at the temperature of 1020-1280 ℃.
17. The production method according to any one of claims 10 to 16, wherein the primary annealing is specifically:
carrying out primary annealing on the formed glass ribbon at 630-720 ℃ by using cold air for 1.5-4 hours; the cold air temperature is-10-20deg.C, air pressure is 20-50Pa, and flow is 130-280Nm 3 /h；
The secondary annealing specifically comprises the following steps:
carrying out secondary annealing on the glass ribbon subjected to primary annealing at 580-650 ℃ by natural convection air for 3-6 hours until the temperature of the glass ribbon is 100-120 ℃ to obtain the ultrawhite glass; the natural convection air temperature is 15-40 ℃, the air pressure is 7-18Pa, and the flow is 200-350Nm 3 /h。
18. The method of claim 17, wherein the total time of the primary annealing and the secondary annealing is not less than 5 hours.
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| CN111039579A (en) * | 2019-12-31 | 2020-04-21 | 沧州天瑞星光热技术有限公司 | Low-temperature annealing process for reducing stress of glass-metal sealing structure |
| CN111943503A (en) * | 2020-08-24 | 2020-11-17 | 中国洛阳浮法玻璃集团有限责任公司 | Preparation method of high-hardness ultrathin float glass |
| CN115304258B (en) * | 2022-08-13 | 2023-12-29 | 凯盛晶华玻璃有限公司 | Cooling device for cold end plate of ultra-white float glass and use method of cooling device |
| CN117352110B (en) * | 2023-12-05 | 2024-02-13 | 江苏美特林科特殊合金股份有限公司 | System for testing high-temperature flow characteristics of tantalum melt based on rotating turbidity method |
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