CN117321013A - Method for producing float glass from raw mineral material - Google Patents
Method for producing float glass from raw mineral material Download PDFInfo
- Publication number
- CN117321013A CN117321013A CN202280031695.2A CN202280031695A CN117321013A CN 117321013 A CN117321013 A CN 117321013A CN 202280031695 A CN202280031695 A CN 202280031695A CN 117321013 A CN117321013 A CN 117321013A
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- China
- Prior art keywords
- source
- magnesium
- calcium
- raw material
- amount
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- Pending
Links
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 54
- 239000011707 mineral Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000005329 float glass Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 107
- 239000002994 raw material Substances 0.000 claims abstract description 78
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 28
- 239000011575 calcium Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000011521 glass Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000010459 dolomite Substances 0.000 claims description 12
- 229910000514 dolomite Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006063 cullet Substances 0.000 claims description 10
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000391 magnesium silicate Substances 0.000 claims description 10
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 10
- 235000019792 magnesium silicate Nutrition 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 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 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010433 feldspar Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000006060 molten glass Substances 0.000 abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000012993 chemical processing Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- -1 dolomite Chemical class 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- GSJMPHIKYICTQX-UHFFFAOYSA-N magnesium;oxosilicon Chemical compound [Mg].[Si]=O GSJMPHIKYICTQX-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 201000010001 Silicosis Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QLAAABGIYSWMHI-UHFFFAOYSA-N calcium;carbonic acid;dihydroxy(dioxido)silane Chemical compound [Ca+2].OC(O)=O.O[Si](O)([O-])[O-] QLAAABGIYSWMHI-UHFFFAOYSA-N 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- DEPUMLCRMAUJIS-UHFFFAOYSA-N dicalcium;disodium;dioxido(oxo)silane Chemical compound [Na+].[Na+].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DEPUMLCRMAUJIS-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- 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
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
Abstract
The present invention relates to a raw material mixture for producing molten glass having a target composition of float glass, comprising a raw material mixture melted to form a molten bath, wherein the raw material comprises a source of calcium and/or magnesium derived from natural mineral materials, i.e. from a raw natural geological environment.
Description
The present invention relates to the field of glass melting, in particular for the manufacture of float glass, such as in particular for the construction or automotive field.
Glass is typically produced by melting a glass comprising silica and at least one silica flux such as sodium carbonate and at least one alkaline earth metal (to impart hydrolysis resistance to the glass) such as limestone (calcium carbonate) and dolomiteStone (CaMg (CO) 3 ) 2 ) Is prepared from the raw materials of (1). During the melting process, the carbonate releases carbon dioxide, the bubbles of which assist in the mixing of the molten material. Furthermore, certain carbonates, such as dolomite, even in the release of their CO 2 The break-up into finer particles, which can be quite severe and generate dust, was previously based on the so-called bursting phenomenon, which can clog and even corrode the various pipes (chimney, regenerator, etc.) provided with the furnace. Bubble elimination in glass also typically requires the addition of a fining agent, such as sodium sulfate, from which sulfur oxides are released to carry residual bubbles of carbon dioxide and water toward the glass surface. However, sulfur oxides are a particularly corrosive gas. The addition of water to glass as a fining agent has also been proposed. In a conventional process for manufacturing soda-lime-silica glass, CO 2 The emissions are typically about 20% of the total mass of raw materials used. Furthermore, carbon dioxide is a greenhouse gas, and for environmental reasons, it is desirable to develop a process that generates as little CO as possible 2 And at the same time, a glass of good quality and acceptable cost is obtained.
For example, publication WO 2007/138109 or US 2009/01397 describes a method of using synthetic calcium magnesium aluminosilicates, the composition of which is adjusted to replace at least a portion of the calcium magnesium carbonate. Indicating CO 2 Emissions are thus reduced and the energy balance of the bath melting is also reduced. However, such conclusion does not take into account the energy consumption and the emitted CO of synthesizing the calcium magnesium alumino silicate 2 . In particular, a method for producing glass using a cement clinker type of synthetic calcium magnesium alumino silicate is described. The formation of these synthetic aluminosilicates requires a large supply of energy, which increases the CO of this process 2 And an energy footprint. Furthermore, examples given include the use of carbonaceous materials such as dolomite and sodium carbonate, the proportion of which increases during the addition of synthetic calcium magnesium aluminosilicates of the cement clinker type.
Likewise, application EP320232 describes a method for the pre-synthesis of sodium calcium silicate for introduction as a source of sodium and calcium into a raw material bath. Here again, the energy consumption and the CO emissions of the synthesis of the calcium sodium silicate must be taken into account in the overall balance 2 。
U.S. patent No. 6,271,99 describes a method of using synthetic silicate in the form of pellets in a glass forming process. Here too, the energy consumption for synthesizing the silicate and the CO emitted must be taken into account in the overall balance 2 。
Thus, except for the direct release of CO during the melting process of the raw material melt 2 In addition, it is important to consider the glass manufacturing process as a whole to take into account other factors such as the cost of raw materials, their transportation or even the energy costs of providing the raw materials.
In summary, to reduce energy costs and optimize CO 2 It is important to balance, taking into account all the steps leading to glass formation and raw material preparation, not just the final step of melting the raw material bath as described above.
The object of the present invention is to help solve the technical problem by proposing a method for manufacturing glass which is effective in reducing CO on the basis of a series of steps leading to glass formation 2 Emissions and energy footprint.
The invention relates to a raw material mixture for producing molten glass, the target composition of which corresponds to the following formulation in weight percent:
-SiO 2 between 69 and 80%, preferably between 70 and 75%,
-Na 2 o is between 8 and 20%, preferably between 10 and 20%,
CaO is present in an amount of between 5 and 20%, preferably between 5 and 15%,
MgO in an amount of between 1 and 10%, preferably between 2 and 7%,
-Al 2 O 3 between 0 and 5%, preferably between 0.5 and 3%,
-K 2 o is between 0 and 10%, preferably between 0 and 2%,
iron oxide between 0 and 15%, preferably between 0 and 10%
Other oxide(s) in total between 0 and 5%,
the balance is composed of unavoidable impurities.
This raw material mixture is intended to be heated to a specific temperature under conditions that together enable it to be melted to obtain a glass meeting the target composition.
The invention is unique in the selection of raw materials. Indeed, unlike the prejudices commonly existing in the art and illustrated by the publications cited above, it has been found possible to use natural mineral oxides, in particular natural silicates, i.e. under their initial geological composition after they are extracted from their deposits, in particular without chemical changes intended to alter their initial composition, i.e. the raw mineral material. In particular, the method according to the invention initially determines the composition of the initial melt based on the exact composition of these raw geological mineral materials as precisely determined by any suitable technique (e.g., chemical analysis, X-ray diffraction, etc.).
More precisely, based on this initial determination of the composition of the mineral material, the necessary proportions of the other components of the initial bath (such as silica, sodium carbonate or sodium hydroxide, and possibly additional limestone and/or dolomite) are calculated and adjusted to reach the target composition; thereby allowing the release of CO 2 The amount of (c) is minimized as measured in all steps leading to glass formation, not just based on the final melting of the raw material bath.
However, according to the invention, the mineral oxide may of course undergo steps prior to its use as a raw material for the melt, but not the chemical processing of the grains constituting the mineral oxide. Such a step may be crushing, screening, washing or flotation, magnetic separation or any other physical separation of impurities present between said grains of natural mineral material.
With such a mixture it is possible to significantly reduce or even eliminate CO of the raw materials 2 And (5) discharging.
The choice of the raw materials mentioned above is critical to achieving good quality of the glass, in particular after its fiber drawing. Among the properties considered to be critical, mention may be made in particular of the yield of the melt (between the quantity of glass produced and the quantity of raw material loadedIn particular SiO), the quality of the fining (which is reflected in the minimum number of residual bubbles in the glass), the homogeneity of the glass (in particular) 2 Is used) and the amount of unmelted material.
More specifically, the invention relates to a method for manufacturing glass having a target composition, comprising melting a mixture of raw materials constituting a molten bath, said target composition meeting the following criteria, in percentages by weight:
-SiO 2 between 69 and 80%, preferably between 70 and 75%,
-Na 2 o is between 8 and 20%, preferably between 10 and 20%,
CaO is present in an amount of between 5 and 20%, preferably between 5 and 15%,
MgO in an amount of between 1 and 10%, preferably between 2 and 7%,
-Al 2 O 3 between 0 and 5%, preferably between 0.5 and 3%,
-K 2 o is between 0 and 10%, preferably between 0 and 2%,
iron oxide between 0 and 15%, preferably between 0 and 10%
Other oxide(s) between 0 and 5% in total,
the balance is composed of unavoidable impurities,
the method is characterized in that it comprises the following steps:
a) Selecting a raw material for the melt from at least the following materials:
the presence of silica,
at least one sodium source, preferably chosen from sodium hydroxide NaOH, sodium carbonate Na 2 CO 3 Or sodium hydroxide NaOH and sodium carbonate Na 2 CO 3 Is a mixture of (2)
At least one source of calcium chosen from mixed oxides of calcium and at least one element chosen from Si, mg, in particular calcium silicate,
at least one magnesium source chosen from mixed oxides of magnesium and at least one element chosen from Si, ca, in particular magnesium silicate,
the calcium source and the magnesium source are natural mineral materials, i.e. raw mineral materials originating from natural geological environments,
optionally feldspar (K, na) AlSi 3 O 8 ，
-optionally limestone CaCO 3 ，
Optionally, the composition of dolomite,
optionally, recovering the cullet,
b) Determining the composition of the natural calcium source and/or magnesium source,
c) Determining the amount of said raw material necessary to obtain a glass having said target composition, based on said composition(s) determined according to point b),
d) The materials are mixed according to the amount,
e) Melting the mixture and cooling it under conditions such that the glass is obtained.
According to a particular and advantageous embodiment of the invention, they can of course be combined with one another:
-the calcium source is natural mineral calcium silicate.
-the magnesium source is a natural mineral magnesium silicate.
The raw material mixture comprises sodium hydroxide as sodium source, preferably containing less than 40% by weight of H 2 O, more preferably less than 30% by weight H 2 O。
-the calcium source is a natural mineral calcium silicate comprising, in weight percent, more than 30% SiO 2 And more than 10% CaO, preferably more than 15% CaO, caO and SiO 2 Together constituting more than 60%, or more than 70% or even more than 80% of the total weight of the source.
The magnesium source is a natural mineral magnesium silicate comprising, in weight percent, more than 30% SiO 2 And more than 10% MgO, preferably more than 15% MgO, mgO and SiO 2 Together constituting more than 60%, or more than 70% or even more than 75% of the total weight of the source.
The raw materials of the molten bath comprise a source of calcium as described above and a source of magnesium as described above.
-the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
SiO 2 between 40 and 55%, preferably between 45 and 50%,
Al 2 O 3 between 0 and 10%, for example between 1 and 10%,
MgO in an amount of between 20 and 40%, preferably between 25 and 35%
Fe 2 O 3 Between 0 and 4%, for example between 1 and 3%
Less than 5% of other oxides, preferably less than 3% of other oxides,
optionally water, which is present in particular in the form of hydroxide(s) in the source, preferably in an amount of less than 20%, in particular between 5 and 15%.
-the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
SiO 2 between 55 and 70%, preferably between 58 and 65%,
Al 2 O 3 between 0 and 10%, for example between 1 and 10%,
MgO in an amount of between 20 and 40%, preferably between 25 and 35%
Fe 2 O 3 Between 0 and 4%, for example between 0.5 and 2%,
less than 5% of other oxides, preferably less than 3% of other oxides,
optionally water, which is present in particular in the form of hydroxide(s) in the source, preferably in an amount of less than 20%, in particular between 5 and 15%.
-the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
SiO 2 between 30 and 50%, preferably between 35 and 45%,
Al 2 O 3 between 0 and 10%, for example between 1 and 5%,
MgO in an amount of between 25 and 45%, preferably between 30 and 40%,
Fe 2 O 3 between 0 and 10%, for example between 5 and 10%,
less than 5% of other oxides, preferably less than 3% of other oxides,
optionally water, which is present in particular in the form of hydroxide(s) in the source, preferably in an amount of less than 20%, in particular between 5 and 15%.
-the calcium source is a natural mineral material corresponding to the following composition, in weight percent:
SiO 2 between 30 and 50%, preferably between 35 and 45%,
CaO in an amount of between 35 and 55%, preferably between 40 and 50%,
Fe 2 O 3 between 0 and 4%, for example between 0.1 and 0.5%
Al 2 O 3 Between 0 and 5%, for example between 0.5 and 2%,
CO 2 between 0 and 20%, in particular between 5 and 15%,
less than 5% of other oxides, preferably less than 3% of other oxides.
-the magnesium source and/or the calcium source is a natural mineral material selected from brown Wu Zhiyan.
-the magnesium source and/or the calcium source is a natural mineral material corresponding to the following composition, in weight percent:
SiO 2 between 40 and 60%, preferably between 42 and 55%,
CaO in an amount of between 5 and 25%, preferably between 10 and 20%,
MgO in an amount of between 3 and 20%, preferably between 5 and 15%
Al 2 O 3 Between 0 and 20%, for example between 5 and 15%,
Fe 2 O 3 between 0 and 20%, for example between 5 and 15%
Less than 5% of other oxides, preferably less than 3% of other oxides,
between 0 and 5% of water, which is present in particular in the form of hydroxide(s) in the source.
-all silicate present in the bath constitutes more than 20%, preferably more than 25%, or even more than 40%, or even more than 45%, or even more than 50% of the total weight of the bath excluding sand and recycled cullet.
-introducing recycled cullet into the molten bath, the recycled cullet preferably constituting between 10 and 50% of the total weight of the molten bath.
The invention also relates to a raw material mixture as claimed in any of the preceding claims.
Unlike free water, which is present in the natural mineral material in the form of moisture, hydroxyl (OH) that may be present in the natural mineral material is considered to be an oxide and is considered to be part of the chemical composition of the source according to the invention.
It is also possible to obtain defect-free glass from the initial mixture according to the invention, as shown in the examples below.
Silica is typically introduced into the raw material mixture in the form of sand.
If necessary, the raw material mixture may also advantageously contain an Al support, i.e. an alumina precursor in the glass, such as feldspar, as described above.
The raw material mixture may also contain small proportions of dyes, such as iron oxide, cobalt oxide, chromium oxide.
According to the invention, as little carbonate as possible is even not introduced into the raw material mixture. Preferably, the sum of the weights of alkali metal carbonate and alkaline earth metal carbonate in the raw material mixture is less than 30 wt%, preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 1 wt%, or even zero. According to an advantageous possible embodiment, the raw material mixture does not contain any carbonate. It is advantageously able to not release any carbon oxides during its heating and melting into glass. For example, the raw material mixture may comprise between 5 and 25% by weight of alkali metal hydroxide (sum of all alkali metal hydroxides), in particular sodium hydroxide, or between 5 and 25% by weight of alkaline earth metal hydroxide (sum of all alkaline earth metal hydroxides), in particular magnesium hydroxide, in particular brucite.
For the production of glass, the Si support is introduced into the raw material mixture in the form of sand, the alkali support is advantageously introduced into the raw material mixture in the form of hydroxides such as NaOH, KOH, and the optional Al support may be introduced into the raw material mixture in the form of feldspar powder. Each raw material is introduced into the raw material mixture in such an amount that the mole% of its cations (e.g., si, na, al, fe, etc.) relative to the molar sum of all cations is the same as in the final glass. The starting materials of the mixture are selected to give a glass having a target composition within the above-described frame (percentage range of the various oxides).
The raw material mixture is typically heated in a furnace until molten glass is obtained. Depending on the quality of the glass sought, heating is carried out at either high or low temperatures or long or short, depending in particular on the tolerance for unmelted particles and bubbles. Typically, the maximum heating temperature of the molten glass is between 1200 and 1700 ℃. To convert the raw material mixture into glass, glass melting techniques well known to those skilled in the art may be used. Such processing may be performed in any type of furnace, such as an arc furnace, overhead burner furnace (overhead burner furnace), such as a cross-flame furnace or continuous furnace, submerged burner furnace.
The raw material mixture, in particular the powder material mixture, may optionally be moistened before being introduced into the furnace in order to reduce the splashing of the raw material in the furnace caused by the combustion gas flow.
For heating and melting the glass, the raw material mixture (if appropriate, moistened) can be introduced into a powder furnace, which means that each raw material contained therein is in a powder state. For heating and melting the glass, the raw material mixture (if appropriate, wetted) may be introduced into the furnace in the form of a composition comprising cullet and raw material mixture, if appropriate in powder form.
In the present invention, it is generally possible to dispense with the use of a construction (i.e. a system for shaping) system for the raw material mixture, which applies mechanical pressure, in particular using a mould to obtain calibrated agglomerates (pellets, balls, granules, pellets, etc.), such as a hoop compactor (hoop compactors). Thus, the raw material mixture may not be formed by mechanical pressure prior to introduction into the furnace. It is not necessary to use a raw material granulation technique according to which the material is rotated (in particular in a rotating drum) in the presence of a binder to produce granules (pellets).
Examples
In the following examples, various raw material mixtures were prepared to compare the mixtures currently used for glass manufacture at the same final glass composition having essentially the following composition:
TABLE 1
| Element(s) | Weight percent |
| SiO 2 | 71 |
| CaO | 9 |
| MgO | 4 |
| Al 2 O 3 | <1 |
| Fe 2 O 3 | <1 |
| Na 2 O | 13.4 |
| K 2 O | 0.3 |
Example 1 (Prior Art)
According to a first embodiment, glass corresponding to the aforementioned composition is synthesized according to the prior art.
The proportions of the various raw materials and the final composition of the mixture thus obtained are given in table 2 below:
TABLE 2
The raw material mixture was heated to 1400 ℃ for 1 hour while being exposed to air in a platinum crucible, and thereafter melted at the highest temperature at 1 hour intervals until the glass was melted at 1450 ℃. CO released 2 The amount was 204 g.
Example 2:
in this example, the raw material mixture is this time as described in table 3 below.
To replace dolomite, natural mineral material of magnesium silicon oxide taken directly from quarry located in Luzenac, france was introduced as reagent into this initial mixture. Analysis of this material by conventional chemical techniques and X-ray diffraction has shown that this mineral material consists essentially of chlorite Mg 4.882 Fe 0.22 Al 1.88 1Si 2.96 O 10 (OH) 8 (55 wt.%), talc Mg 3 Si 4 O 10 (OH) 2 (42 wt%) and less than 5 wt% dolomite.
Unlike free water (which is present in the natural mineral material in the form of moisture), hydroxyl radicals are considered to be part of the chemical composition of the source according to the invention. They are shown in the following tableIn H 2 O equivalent is expressed.
Such mineral materials, without any chemical processing and after simple grinding aimed at adjusting their particle size, are introduced directly together with the other constituents, with their proportions adjusted accordingly to obtain a glass having a composition very close to that of reference 1, and with CO 2 Release is minimized.
TABLE 3
As in example 1, the raw material mixture was heated to 1400 ℃ for 1 hour while being exposed to air in a platinum crucible, and thereafter melted at the highest temperature at 1 hour intervals until the glass was melted at 1450 ℃. CO released 2 The amount was 163 g this time, i.e. 20% reduction relative to the reference.
Example 3:
in this example, the raw material mixture is this time as described in table 4 below.
To replace dolomite, natural mineral material of magnesium silicon oxide taken directly from quarry located in Lv Cina g of france was introduced as reagent into this initial mixture.
Such materials, without any chemical processing and after simple grinding aimed at adjusting their particle size, are introduced directly in admixture with other ingredients, with their proportions adjusted accordingly to obtain glasses having a composition very close to that of reference 1.
TABLE 4
As in example 1, the raw material mixture was heated to 1400 ℃ for 1 hour while being exposed to air in a platinum crucible, and thereafter melted at the highest temperature at 1 hour intervals until the glass was melted at 1450 ℃. CO released 2 The amount was 163 g this time, i.e. 20% reduction relative to the reference.
Example 4:
in this example, the raw material mixture is this time as described in table 5 below.
To replace dolomite, another natural mineral material, magnesium silicate from the quarry located in the spanish Carino, is introduced as a reagent into this initial mixture. The analysis of this material by conventional analytical techniques is given below.
TABLE 5
As in example 1, the raw material mixture was heated to 1400 ℃ for 1 hour while being exposed to air in a platinum crucible, and thereafter melted at the highest temperature at 1 hour intervals until the glass was melted at 1450 ℃. CO released 2 The amount was this time 160 grams, i.e. 22% reduction relative to the reference.
Example 5:
in this example, the raw material mixture is this time as described in table 6 below.
To replace dolomite, another natural mineral material, namely a calcium carbonate-silicate from the quarry located in Hermosillo, mexico, is introduced as a reagent into this initial mixture. Analysis by conventional analytical techniques showed that this natural mineral material meets the composition described in table 6 below:
TABLE 6
As in example 1, the raw material mixture was heated to 1400 ℃ for 1 hour while being exposed to air in a platinum crucible, and thereafter melted at the highest temperature at 1 hour intervals until the glass was melted at 1450 ℃. CO released 2 The amount was 186 g this time, i.e. 10% reduction relative to the reference.
Example 6:
in this example, the raw material mixture is this time as described in table 7 below.
More specifically, in this example, the natural mineral material magnesium source described in example 4 was used instead of dolomite and limestone as the mineral source of magnesium and calcium, the natural mineral material magnesium source described in example 5 above was used as the calcium source, and sodium hydroxide was used instead of sodium carbonate as the sodium source.
TABLE 7
As in example 1, the raw material mixture was heated in a platinum crucible while being exposed to air until the glass melted at 1450 ℃, with a plateau of 1 hour at the highest temperature. CO released 2 The amount was 22 g this time, i.e. reduced by 90% with respect to the reference.
Example 7:
in this example, the raw material mixture is this time as described in table 8 below.
More specifically, in this example, brown Wu Zhiyan from quarries of Cluis, france was used as the mineral source.
TABLE 8
As in example 1, the raw material mixture was heated in a platinum crucible while being exposed to air until the glass melted at 1450 ℃, with a plateau of 1 hour at the highest temperature. CO released 2 The amount was 170 g this time, i.e. 17% reduction relative to the reference.
To verify the possible use of the glasses obtained according to the method of the invention, the light transmittance of the glasses according to comparative example 1 and according to example 2 was measured between 380 and 780nm on a glass having a thickness of 2cm according to standard EN410 (2011).
The light transmittance measured for examples 1 and 2 was about 80%. Therefore, the light transmittance measured for example 2 according to the present invention was still suitable for use as float glass, although the unpurified raw material according to the present invention was used.
The advantages and quality of the glasses obtained from the glass melt baths according to examples 1 (comparative) to 7 above are shown in table 9 below, in which various evaluation criteria obtained according to the following measurements are reported:
1) Yield rate
This is the ratio between the amount of glass produced and the amount of raw material loaded. The higher the ratio, the higher the amount of glass that can be produced, and the gas emissions (CO 2 、H 2 The lower O).
2) The amount of sand, which is the amount of sand used (as a weight percentage of the savings) relative to reference 1. In addition to the health considerations associated with excessive intake of sand (silicosis), the reduction in the amount of sand used, replaced by other mineral materials such as natural silicates, enables the reduction of the energy required to melt the bath, since the most refractory raw material of the bath is typically silica.
3) Energy consumed this is the amount of energy saved (as a percentage) relative to reference 1. This measurement corresponds to the energy necessary to melt the respective raw material mixture of each example.
4) Clear quality (or bubble rate):
the number of bubbles per kilogram of molten glass was measured at 1480 ℃ for 120 minutes. The higher the index, the better the clarification quality.
* Example number of bubbles/reference example 1 number of bubbles <100%
* Example number of bubbles/reference example 1 number of bubbles <50%
5)SiO 2 Uniformity:
the quality index is equal to SiO of molten glass at 1480 ℃ for 120 minutes 2 Uniformity (as measured by microprobe/EDS) is proportional.
By SiO at different points of the glass 2 A series of measurements of the quantity are used to measure uniformity and then the standard deviation is determined.
**:SiO 2 Standard deviation (measured by microprobe/EDS)>0.5％
***SiO 2 Standard deviation (measured by microprobe/EDS) of between 0.1 and 0.5%
* Standard deviation SiO2 (measured by microprobe/EDS) <0.1%
TABLE 9
Comparison of the above results shows that examples 2 to 7 according to the invention show a quality index which is generally higher than that of reference 1.
Example 3 according to the invention, in which a magnesium source consisting of the natural mineral magnesium silicate is used as a raw material in the molten bath, makes it possible to limit the uptake of sand considerably with respect to the reference method.
According to all the criteria reported in table 9 above, example 6 according to the invention, in which a calcium source consisting of the natural mineral calcium silicate and a magnesium source consisting of the natural mineral magnesium silicate are used in combination as raw material in the melt bath, appears to be particularly advantageous.
Claims (20)
1. A method of making glass having a target composition that includes melting a raw material mixture that constitutes a melt, the target composition meeting the following criteria in weight percent:
SiO 2 between 69 and 80%, preferably between 70 and 75%,
Na 2 o is between 8 and 20%, preferably between 10 and 20%,
CaO in an amount of between 5 and 20%, preferably between 5 and 15%,
MgO in an amount of between 1 and 10%, preferably between 2 and 7%,
Al 2 O 3 between 0 and 5%, preferably between 0.5 and 3%,
K 2 o is between 0 and 10%, preferably between 0 and 2%,
iron oxide, between 0 and 15%, preferably between 0 and 10%,
other oxide(s) between 0 and 5% in total,
the balance is composed of unavoidable impurities,
the method is characterized in that it comprises the following steps:
a) Selecting a raw material for the melt from at least the following materials:
the presence of silica,
at least one sodium source, preferably chosen from sodium hydroxide NaOH, sodium carbonate Na 2 CO 3 Or sodium hydroxide NaOH and sodium carbonate Na 2 CO 3 Is a mixture of (2)
At least one source of calcium chosen from mixed oxides of calcium and at least one element chosen from Si, mg, preferably calcium silicate,
at least one magnesium source selected from mixed oxides of magnesium and at least one element selected from Si, ca, preferably magnesium silicate,
the calcium source and the magnesium source are natural mineral materials, i.e. raw mineral materials originating from natural geological environments,
optionally feldspar (K, na) AlSi 3 O 8 ，
-optionally limestone CaCO 3 ，
Optionally, the composition of dolomite,
optionally, recovering the cullet,
b) Determining the composition of the natural calcium source and/or magnesium source,
c) Determining the amount of said raw material necessary to obtain a glass having said target composition, based on said composition(s) determined according to point b),
d) The materials are mixed according to the amount,
e) Melting the mixture and cooling it under conditions such that the glass is obtained.
2. The method according to the preceding claim, wherein the calcium source is natural mineral calcium silicate.
3. The method according to the preceding claim, wherein the magnesium source is a natural mineral magnesium silicate.
4. The method according to any of the preceding claims, wherein the raw material mixture comprises sodium hydroxide as sodium source.
5. The method according to any of the preceding claims, wherein the calcium source is a natural mineral calcium silicate comprising, in weight percent, more than 30% SiO 2 And more than 10% CaO, preferably more than 15% CaO, caO and SiO 2 Together constituting more than 60%, or more than 70% or even more than 80% of the total weight of the source.
6. The method according to the preceding claim, wherein the magnesium source is a natural mineral magnesium silicate comprising, in weight percent, more than 30% SiO 2 And more than 10% MgO, preferably more than 15% MgO, mgO and SiO 2 Together comprising greater than 60%, or greater than 70% or even greater than 75% of the weight of the source.
7. A method according to any one of the preceding claims, wherein the raw material of the molten bath comprises a source of calcium according to claim 5 and a source of magnesium according to claim 6.
8. A method according to any one of the preceding claims, wherein the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
-SiO 2 between 40 and 55%, preferably between 45 and 50%,
-Al 2 O 3 between 0 and 10%, for example between 1 and 10%,
MgO in an amount of between 20 and 40%, preferably between 25 and 35%,
-Fe 2 O 3 between 0 and 4%, for example between 1 and 3%,
less than 5% of other oxides, preferably less than 3% of other oxides,
-optionally water, in particular in the form of hydroxide(s), preferably in an amount of less than 20%, in particular between 5 and 15%.
9. A method according to any one of the preceding claims, wherein the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
-SiO 2 between 55 and 70%, preferably between 58 and 65%,
-Al 2 O 3 between 0 and 10%, for example between 1 and 10%,
MgO in an amount of between 20 and 40%, preferably between 25 and 35%,
-Fe 2 O 3 between 0 and 4%, for example between 0.5 and 2%,
less than 5% of other oxides, preferably less than 3% of other oxides,
-optionally water, in particular in the form of hydroxide(s), preferably in an amount of less than 20%, in particular between 5 and 15%.
10. A method according to any one of the preceding claims, wherein the magnesium source is a natural mineral material corresponding to the following composition, in weight percent:
-SiO 2 between 30 and 50%, preferably between 35 and 45%,
-Al 2 O 3 between 0 and 10%, for example between 1 and 5%,
MgO in an amount of between 25 and 45%, preferably between 30 and 40%,
-Fe 2 O 3 between 0 and 10%, for example between 5 and 10%,
less than 5% of other oxides, preferably less than 3% of other oxides,
-optionally water, in particular in the form of hydroxide(s), preferably in an amount of less than 20%, in particular between 5 and 15%.
11. A method according to any one of the preceding claims, wherein the calcium source is a natural mineral material corresponding to the following composition, in weight percent:
-SiO 2 between 30 and 50%, preferably between 35 and 45%,
CaO is present in an amount of between 35 and 55%, preferably between 40 and 50%,
-Fe 2 O 3 between 0 and 4%, for example between 0.1 and 0.5%,
-Al 2 O 3 between 0 and 5%, for example between 0.5 and 2%,
-CO 2 between 0 and 20%, in particular between 5 and 15%,
less than 5% of other oxides, preferably less than 3% of other oxides.
12. A method according to any one of the preceding claims, wherein the magnesium source and/or calcium source is a natural mineral material selected from brown Wu Zhiyan.
13. The method according to the preceding claim, wherein the magnesium source and/or calcium source is a natural mineral material corresponding to the following composition, in weight percent:
-SiO 2 between 40 and 60%, preferably between 42 and 55%,
CaO is present in an amount of between 5 and 25%, preferably between 10 and 20%,
MgO in an amount of between 3 and 20%, preferably between 5 and 15%,
-Al 2 O 3 between 0 and 20%, for example between 5 and 15%,
-Fe 2 O 3 between 0 and 20%, for example between 5 and 15%,
less than 5% of other oxides, preferably less than 3% of other oxides,
between 0 and 5% of water, which is present in particular in the form of hydroxide(s) in the source.
14. A method according to any one of the preceding claims wherein the recycled cullet is introduced into the molten bath.
15. The method according to the preceding claim, wherein the recovered cullet constitutes between 10 and 50% of the total weight of the molten bath.
16. The method according to any one of the preceding claims, wherein all silicate present in the bath constitutes more than 20% of the total weight of the bath excluding sand and recycled cullet.
17. The method according to any of the preceding claims, wherein the raw material mixture comprises between 5 and 25 wt.% of alkali metal hydroxide.
18. The method according to any one of the preceding claims, wherein the raw material mixture comprises between 5 and 25 wt.% of alkaline earth metal hydroxide.
19. A raw material mixture as claimed in any one of the preceding claims.
20. A raw material mixture comprising:
the presence of silica,
at least one sodium source, preferably chosen from sodium hydroxide NaOH, sodium carbonate Na 2 CO 3 Or sodium hydroxide NaOH and sodium carbonate Na 2 CO 3 Is used in the preparation of a mixture of (a),
at least one source of calcium chosen from mixed oxides of calcium and at least one element chosen from Si, mg, preferably calcium silicate,
at least one magnesium source selected from mixed oxides of magnesium and at least one element selected from Si, ca, preferably magnesium silicate,
the calcium source and the magnesium source are natural mineral materials, i.e. raw mineral materials originating from natural geological environments,
optionally feldspar (K, na) AlSi 3 O 8 ，
-optionally limestone CaCO 3 ，
Optionally, the composition of dolomite,
-optionally, recovering cullet.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FRFR2104436 | 2021-04-28 | ||
| FR2104436A FR3122421B3 (en) | 2021-04-28 | 2021-04-28 | PROCESS FOR MANUFACTURING FLOAT GLASS FROM UNTRANSFORMED MINERAL MATERIALS |
| PCT/FR2022/050818 WO2022229568A1 (en) | 2021-04-28 | 2022-04-28 | Method for producing float glass from unprocessed mineral materials |
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| Publication Number | Publication Date |
|---|---|
| CN117321013A true CN117321013A (en) | 2023-12-29 |
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|---|---|---|---|
| CN202280031695.2A Pending CN117321013A (en) | 2021-04-28 | 2022-04-28 | Method for producing float glass from raw mineral material |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP4330200A1 (en) |
| CN (1) | CN117321013A (en) |
| BR (1) | BR112023020594A2 (en) |
| CO (1) | CO2023013904A2 (en) |
| FR (1) | FR3122421B3 (en) |
| WO (1) | WO2022229568A1 (en) |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL120812C (en) * | 1959-07-01 | 1965-12-15 | ||
| US3296004A (en) * | 1963-08-12 | 1967-01-03 | Pittsburgh Plate Glass Co | Neutral brown heat absorbing glass composition |
| LU46426A1 (en) * | 1964-06-29 | 1972-01-01 | ||
| FR2082647A5 (en) * | 1970-03-23 | 1971-12-10 | Saint Gobain | Heat absorbing bronze glasses - for architectural use coloured with iron, cobalt, nickel,and selenium |
| US3833388A (en) * | 1972-07-26 | 1974-09-03 | Ppg Industries Inc | Method of manufacturing sheet and float glass at high production rates |
| US4138235A (en) * | 1977-05-31 | 1979-02-06 | Ppg Industries, Inc. | Method of making flat glass with lower sulfur-containing emissions |
| US4270945A (en) * | 1979-12-03 | 1981-06-02 | Ppg Industries, Inc. | Method of melting flat glass using nitrates to suppress sulfurous emissions |
| GB8728892D0 (en) | 1987-12-10 | 1988-01-27 | Pilkington Plc | Producing molten glass |
| LU88486A1 (en) * | 1994-05-11 | 1995-12-01 | Glaverbel | Soda-lime gray glass |
| LU88653A1 (en) * | 1995-09-06 | 1996-10-04 | Glaverbel | Soda-lime dark light gray glass |
| US6287378B1 (en) | 1996-09-03 | 2001-09-11 | Minerals Technologies, Inc. | Method of producing synthetic silicates and use thereof in glass production |
| CN101460417A (en) | 2006-06-01 | 2009-06-17 | 旭硝子欧洲平板玻璃股份有限公司 | Lime glass batch composition |
| US20090011397A1 (en) | 2007-07-02 | 2009-01-08 | Greg Writer | Method, system and device for managing compensated educational interaction |
| EP3708545A1 (en) * | 2019-03-11 | 2020-09-16 | Klisch spolka z ograniczona odpowiedzialnoscia | Method for granulating glass batch components |
-
2021
- 2021-04-28 FR FR2104436A patent/FR3122421B3/en active Active
-
2022
- 2022-04-28 CN CN202280031695.2A patent/CN117321013A/en active Pending
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- 2022-04-28 WO PCT/FR2022/050818 patent/WO2022229568A1/en active Application Filing
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| BR112023020594A2 (en) | 2023-12-12 |
| FR3122421A3 (en) | 2022-11-04 |
| CO2023013904A2 (en) | 2023-11-10 |
| EP4330200A1 (en) | 2024-03-06 |
| FR3122421B3 (en) | 2023-09-08 |
| WO2022229568A1 (en) | 2022-11-03 |
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